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研究文章 2022 年 5 月 30 日
通过电子阻挡中间层实现的界面稳定性控制，适用于无树突和长循环的固态钠离子电池
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- 田浩晴Haoqing TianSchool of Chemical Engineering, North China University of Science and Technology, Tangshan 063009, ChinaMore by Haoqing Tian
- 戴磊Lei DaiSchool of Chemical Engineering, North China University of Science and Technology, Tangshan 063009, ChinaMore by Lei Dai
- 王玲*Ling Wang*Email: tswling@126.comSchool of Chemical Engineering, North China University of Science and Technology, Tangshan 063009, ChinaMore by Ling Wang
- 刘珊*Shan Liu*Email: sliu@ncst.edu.cnSchool of Chemical Engineering, North China University of Science and Technology, Tangshan 063009, ChinaMore by Shan Liu
摘要
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高安全性和高能量密度的固态钠离子电池（SSIBs）具有广泛的应用前景。不幸的是，钠与固体电解质之间的接触不良和 dendrite（树枝晶）生长严重阻碍了其发展。在此，设计了一种原位形成的电子阻挡中间层（EBI），该中间层位于 Na3.2Hf1.9Ca0.1Si2PO12（NHSP）表面。EBI 能够有效改善界面润湿性，并阻止电子的传输，从而确保钠与 NHSP 电解质之间的长期稳定性。具有 EBI@NHSP 电解质的电池在 0.2 mA cm–2 下能够稳定循环超过 700 小时。即使电流密度增加到 2.3 mA cm–2，电池仍然能够正常工作。与 Na3V2(PO4)3 正极配合的全电池也展现出良好的长期循环稳定性，在 0.5 C 下能够稳定循环超过 300 次，同时保持高达 99.76% 的库仑效率。该研究为防止钠 dendrite 生长和推动 SSIBs 的发展提供了一种新的可行策略。
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摘要
电子阻挡层从抑制电子传输的角度解决了固态钠离子电池中树突生长的问题。
引言
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随着对能源存储系统需求的增加，钠离子电池（SIBs）因其高能量密度和低价格而成为具有巨大开发潜力的新兴电池。(1−3) 然而，传统液体电解质（酯/醚）中的持续旁路反应和安全风险严重阻碍了 SIBs 的发展。(4,5) 固态钠离子电池（SSIBs）因其高安全性和高能量密度受到越来越多的关注。(6−8) 此外，固体电解质的应用使得使用钠金属阳极和高电压阴极成为可能，因其出色的化学稳定性，这将极大地提高电池的能量密度。(9−12)
然而，钠与固态电解质之间的接触不良和复杂的副反应使得固态钠离子电池（SSIBs）的发展面临许多不确定性。抑制副反应和枝晶生长已成为 SSIBs 发展的一个绊脚石。近年来，已经提出了几种策略来构建中间层，以改善界面润湿性和电荷传输动力学，如金属或金属氧化物涂层、聚合物中间层、无机物等。虽然这些方法已证明在界面稳定性方面具有初步效果，但抑制枝晶生长仍然是一个棘手的问题，尤其是在高电流密度下。
最近研究发现，固体电解质的高电子导电性可能是钠树枝晶生长的主要原因之一。(28,29) 研究表明，电解质的高电子导电性允许 Na+和电子渗透电解质，从而直接形成钠树枝晶（图 1a）。此外，固体电解质的相对密度也可能影响钠树枝晶的生长。然而，毫无疑问，为了持续降低电子导电性或改善电解质的密度，必须面对更多的挑战。(30) 最近的研究发现，即使电解质非常致密，当电解质的晶界具有高电子导电性时，阻止钠树枝晶的存在也是很困难的。(31,32)
图 1
图 1. NASICON 表面上 EBI 的示意图。(a) 纯钠与 NHSP 之间接触不良，这会导致局部极化并加速钠枝晶及副反应的生成。(b) EBI 不仅保证了层间的紧密接触和快速的 Na+传输，而且本质上防止了钠枝晶的形成。
本文中，设计了一种电子阻挡中间层（EBI），在 NASICON 型 Na3.2Hf1.9Ca0.1Si2PO12 (NHSP)表面通过简单的预处理方法制备。该 EBI 显著改善了界面接触和离子传输动力学，并确保在循环过程中均匀的钠沉积/溶解（图 1b）。由于设计的 EBI 几乎是电子绝缘体（1.06 × 105 Ω cm），它能够有效防止钠树枝晶的生长和副反应。使用 EBI@NHSP 电解质的电池表现出优异的长循环寿命和高倍率性能。使用 EBI@NHSP 电解质的对称电池在 0.2 mA cm–2 下稳定循环超过 700 小时。此外，室温下临界电流密度可达到 2.3 mA cm–2，几乎是同类研究中的最高值（表 S1）。此外，Na/EBI@NHSP/Na3V2(PO4)3 (NVP)的全电池在 0.5 C 下也能稳定循环超过 300 个周期，实现了 99.76%的非常高的库伦效率。
结果与讨论
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固体电解质上 EBI 的制造
EBI 是通过一个简单的原位反应获得的：SnF2 + Na → NaxSn + NaF, (33,34)，在将混合盐（SnF2/NaCl）溶液滴加到 NHSP 表面后。扫描电子显微镜（SEM）图像和能量色散光谱（EDS）映射确认混合盐均匀分布在 NHSP 表面，层间厚度约为 6 微米（图 2a-c）。混合盐修饰层中的 SnF2 和 NaCl 相由 X 射线衍射（XRD）图谱清晰显示（图 2e）。经过原位离子交换反应，混合盐从 SnF2/NaCl 转变为 NaF/NaxSn/NaCl，并且层间的颜色由白色变为黑色（图 2d 和 S1）。
图 2
图 2. EBI 的结构和形态。(a) NHSP 上混合盐层的顶部视图 SEM 图像。(b) NHSP 上混合盐层的横截面视图 SEM 图像。(c) 层间横截面 Sn 的 EDS 成像。(d) 通过溶液预处理方法形成 EBI。(e) NHSP 表面在原位反应前后的 XRD 图谱。(f) 不同比例 SnF2 和 NaCl 的层间 D.C.电导率测量。
事实上，Na/NHSP 的润湿性和离子导电性也可以通过添加单一的 SnF2 溶液来改善[形成混合离子和电子相（MIE），NaF/NaxSn]，根据之前的研究。然而，夹层中电子导电相（NaxSn）的高浓度无法抑制循环过程中的树枝晶生成，这将极大影响电池的循环寿命。在本工作中，将通过控制 SnF2 和 NaCl 的比例（SnF2:NaCl = 1:1, 1:0.67, 1:0.33 和 1:0 wt %）来调节界面电荷动力学。SnF2 将作为焊接和离子导电相，而 NaCl 将作为电子绝缘相。电化学阻抗谱（EIS）和对称电池测试证明，夹层的电子电阻率随着 NaCl 浓度的增加而增加，而比例为 1:0.33（SnF2/NaCl）溶液的夹层表现出最佳的沉积行为。与其他两个比例相比，EBI (1:0。在电解质表面均匀分散的 33)充分保护了钠阳极，使钠沉积均匀、光滑且没有树枝晶（图 S6）。通过直流电压测量对膜的绝缘电阻进行了测试（图 2f）。1:0.33 溶液的夹层电子电阻率约为 1.06 × 10^5 Ω cm，是纯 SnF2 电阻率的十分之一（图 S7）。 (41,42)
此外，我们还应注意，尽管 EBI 能够通过其高电子电阻有效抑制钠树枝晶向电解质的渗透，但这并不会严重影响界面的离子传输（见图 S8 和表 S2）。与裸 NHSP 相比，基于 EBI 和 MIE 的电池界面电阻有效降低。根据等效电路的拟合结果，高频区域出现的半圆主要是由于 NHSP 的体电阻（Rb）。EBI@NHSP 的 Rb 在循环后没有显著变化，而 MIE@NHSP 的 Rb 显著降低，这表明 MIE 层无法阻止钠金属在固体电解质中的渗透。与钠离子通过界面层的扩散和迁移相关的半圆可归因于界面电阻（Rint）和电荷转移电阻（Rct）。由于原位反应的发生，电池的 Rint 降低。 这可以归因于 NaCl 的添加通过电解液中电子和钠离子的结合避免了钠树枝晶的形成，从而大大减缓了电池的失效。然而，对于纯 SnF2，原位反应形成的混合离子电子导电中间层在长循环过程中无法有效避免树枝晶的生长。此外，NaCl 的添加使 EBI 表现出比 MIE 更大的界面电阻，但该值仍然可以接受，特别是对于电池的长循环。
探索 EBI 的无枝晶作用
钠与 EBI@NHSP 和纯 NHSP 电解质的界面稳定性通过光学和扫描电子显微镜（图 3a-h）进行了表征。与纯 NHSP 电解质相比，使用 EBI@NHSP 电解质的电池表现出优良的界面稳定性，能够保持钠与 NHSP 电解质之间的紧密接触，即使经过 100 个循环，也未观察到明显的钠树枝晶（图 3a-d）。然而，在使用纯电解质时，观察到了大量的钠树枝晶（图 3e-h）。这应归因于钠与纯 NHSP 电解质之间的接触不良，导致在长时间循环后发生持续的副反应和由于不均匀的钠沉积而随机生长的钠树枝晶。MIE@NHSP 的界面稳定性和树枝晶阻断效果也进行了测试和评估（图 S9）。如上所述，由于其高电子导电性，MIE 中间层无法有效防止持续的副反应并阻碍钠树枝晶的生长。 此外，我们还发现，使用 EBI@NHSP 电解质的电池的层间形貌在循环次数增加时并没有显著变化，这表明 EBI 表现出极高的稳定性。然而，对于使用纯 NHSP 电解质的电池，由于接触不良和持续的副反应，形成了大量的钠树枝晶。尽管 MIE 层可以保证紧密接触，但在循环过程中无法有效阻止钠树枝晶的形成，必然会影响电池的循环寿命（图 S10）。
图 3
图 3. EBI 保护固态电解质的 SEM 和光学显微镜图像。(a) 循环后 EBI@NHSP 电解质的顶视光学显微镜图像。(b) 循环后 EBI@NHSP 电解质的横截面光学显微镜图像。(c,d) 循环前后 EBI@NHSP 的横截面 SEM 图像。(e) 循环后纯 NHSP 电解质的顶视光学显微镜图像。(f) 循环后纯 NHSP 电解质的横截面光学显微镜图像。(g,h) 循环前后纯电解质的横截面 SEM 图像。(i) 循环前后 Sn 3d、F 1s 和 Cl 2p 的 XPS 图谱。(j) EBI 机制的示意图。
EBI@NHSP 的表面也通过 X 射线光电子能谱（XPS）进行了探测。如图 3i 所示，对于 EBI@NHSP 电解液，未循环前 Sn 3d 峰位于 487.05 eV 和 495.5 eV，分别对应于 Sn 3d5/2 和 Sn 3d3/2。而在循环后，这些位置分别 shifted 到 486.4 eV 和 495.3 eV，表明 SnF2 已转变为 NaxSn。(33) 同时，位于 685.3 eV 的单一 F 1s 峰对应于 F–Sn 键消失，循环后在 687.3 eV 出现了一个新峰，表明 SnF2 转变为 NaF，并伴随有界面原位反应。(26) 此外，层间中 NaCl 的存在也可以通过其在 Cl 2p 谱中的特征信号得到证明。
在循环后，电解质的表面也通过 XPS 和 XRD 进行了表征。如图 S11 所示，NHSP 的 Hf 4f 的 XPS 谱在循环后没有明显变化。结果表明，EBI@NHSP 电解质在长期循环过程中能够实现稳定并有效防止副反应。这一点可以通过 XRD 测试进一步证明（图 S12）。然而，对于裸 NHSP 电解质，在循环后，XPS 谱中出现了 Hf 4f 的额外峰，且在 XRD 谱中观察到 Na2SiO3 的额外杂质峰，这表明由于接触不良和电荷分布不均，应当存在钠与电解质之间的副反应（图 S11 和 S12）。总而言之，EBI 层卓越界面稳定性的机制可以理解为活性相（SnF2）和电子阻挡相（NaCl）的双重协同效应（图 3j）。活性相 SnF2 将在循环过程中与钠反应形成缓冲层（图 2e 和 S13）。 电池中以 SnF2 作为电极的充放电曲线清晰地总结了 Na+的嵌入过程以及 Na 与 SnF2 之间的化学反应。缓冲层中形成的 NamSnnF 和 NaF 将作为有效的钠离子导电相，促进 Na+的快速迁移。同时，少量合金元素的存在可以改善界面润湿性。此外，NaCl 的电子阻挡相将促使更多钠离子与 SnF2 反应生成 NamSnnF 或 NaF/Sn，以防止在循环过程中生成钠枝晶和副反应。 (26)
EBI 保护固体电解质的电化学性能
为了评估界面稳定性，采用 EBI@NHSP 和纯 NHSP 电解质的对称电池进行了测试。经过短暂的合金反应后，EBI@NHSP 能够在 0.2 mA cm–2 的条件下稳定循环超过 700 小时（图 4a）。不同电流密度下的长期循环也用于评估 EBI 抑制钠枝晶的能力，在高电流密度 0.4 mA cm–2 下没有出现短路现象（图 S14）。相反，使用纯 NHSP 的电池显示出较差的循环稳定性和极大的电压波动。在短周期后，由于枝晶穿透固体电解质，发生了短路（图 S15）。还测试了两个对称电池在阶梯增加电流密度过程中的时间相关电压曲线（图 4b,c）。在电流密度达到 2.3 mA cm–2 的高水平之前，使用 EBI@NHSP 的电池未观察到电压下降。然而，对于使用纯 NHSP 的电池，在 0.3 mA cm–2 开始时，电池电压因界面润湿性差和极高的界面电阻而突然下降。
图 4
图 4. EBI@NHSP 和纯 NHSP 对称电池的电化学性能。(a) EBI@NHSP 在 0.2 mA cm–2 下的电压曲线。(b,c) EBI@NHSP 和纯 NHSP 的对称电池在不同电流密度下（从 0.1 到 2.5 mA cm–2）的恒流循环。(d) EBI@NHSP 对称电池在循环前和不同循环后的电化学阻抗谱（EIS）曲线。(e) 纯 NHSP 对称电池循环前后的 EIS 曲线（插图显示了循环后 Na/NHSP/Na 的 EIS 曲线）。
使用 MIE@NHSP 电解质的电池也进行了测试。对于使用 MIE@NHSP 的电池，它在 0.2 mA cm–2 下稳定循环超过 400 小时（图 S16）。界面润湿性可以相应改善，但无法抑制在重复镀层/剥离过程中树枝晶的生长，因为界面层具有电子导电性（图 S2）。因此，MIE@NHSP 的临界电流密度只能达到 1.4 mA cm–2（图 S17）。Na/EBI@NHSP 的界面稳定性也通过 EIS 进行了测试。结果证明，含 EBI@NHSP 电解质的电池在长期循环后仍能保持较小且稳定的界面电阻（图 4d）。与新鲜的含 SnF2 和 NaCl 的电池相比，界面电阻更小，这应归因于一开始 SnF2 与钠之间的电化学反应（图 S8）。然而，对于纯 NHSP 的电池，由于钠与电解质之间的糟糕界面接触，它表现出较大的界面电阻。 此外，界面电阻接近于零，这应归因于循环后发生的短路（图 4e）。
Na/EBI@NHSP/NVP 的全电池与 MIE@NHSP 和纯 NHSP 进行了评估和比较。如图 5a 所示，搭载 EBI 的全电池展现出最佳电池性能，具有最高的比容量为 109.6 mA h g–1。相比之下，MIE 界层和纯 NHSP 表现出的容量较低且界面电阻明显更高。此外，搭载 EBI@NHSP 的电池可稳定循环超过 300 个循环。然而，MIE@NHSP 电池只能循环不到 120 个循环，且容量显著下降（图 S18）。如上所述，搭载 EBI@NHSP 的电池具有稳定的界面接触，能够有效阻挡电子传输，以确保界面的长期稳定性。对于搭载 MIE@NHSP 电解液的电池，尽管存在界面合金相，但在长期循环过程中，副反应是不可避免的。对于纯 NHSP 的电池，由于钠与 NHSP 之间的润湿性差，不仅放电容量低，而且电池容量非常不稳定。 速率性能测试还证明，使用 EBI@NHSP 的电池比其他电池具有更优越的性能（图 5b）。
图 5
图 5. Na/NVP 全电池的性能与不同电解质的电池有限元模拟。(a) 不同界面下全电池在 0.5 C 下的恒流充放电曲线。(b) 全电池从 0.5 C 到 5 C 的速率性能。有限元模拟的钠离子浓度梯度在 0.3 V 的电解质中(c) 无电子导电性和(d) 有电子导电性。
根据上述讨论，我们已确认 EBI 可以有效改善界面接触并阻止界面电子传输。为了进一步验证其对电池电化学性能的影响，通过使用 COMSOL 的有限元模拟探索了不同电解质电池的钠沉积行为的结果。（46）结果表明，使用 EBI 的电池能够稳定且均匀地沉积（图 5c）。然而，对于使用具有电子导电性的电解质的电池，将会导致局部极化和钠树枝晶的形成（图 5d）。这些结果进一步证明，通过中间层有效阻止电解质的电子导电性在实现无树枝晶生长和钠均匀沉积方面将发挥重要作用。
结论
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总之，在这项工作中，Na/NHSP 的界面电荷转移动力学通过简单的原位反应被 EBI 调节。在设计的中间层中，NaxSn/NaF 能够实现紧密的焊接和快速的电荷转移，而 NaF/NaCl 的存在则能有效抑制树枝晶的生长。基于 EBI@NHSP 电解质，对称电池在 0.2 mA cm–2 的高电流密度下能够稳定循环，超过 700 小时。即使电流密度增加到 2.3 mA cm–2，电池仍能够正常工作。此外，完整的电池在 0.5 C 的条件下在 300 个循环中展现出优异的循环稳定性，并具有出色的倍率性能。这项工作提供了一种简单有效的抑制固态离子电池中树枝晶生长的方法，并为未来固态电池的实际应用提出了新的探索。
辅助信息
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支持信息可在 https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00243 免费获得。
实验部分；固态钠离子电池的电化学性能比较；循环后钠金属的 XRD 谱图；MIE@NHSP 示意图；纯 SnF2 修饰 NHSP 的 XRD 图谱；不同浓度的 SnF2:NaCl 的 Nyquist 图、电压曲线和顶视 SEM 图像；带有和不带有 NaCl 的界面层的直流电导比较；EBI@NHSP 和 MIE@NHSP 对称电池的 EIS 比较；EBI@NHSP 和 MIE@NHSP 对称电池的阻抗分析结果；EBI@NHSP、纯 NHSP 和 MIE@NHSP 循环前后的顶视 SEM 图像；EBI@NHSP 和 MIE@NHSP 循环前后的侧视 SEM 图像；Hf 4f 的 XPS 谱图；EBI 纯 NHSP 在循环过程中的 XRD 图谱；SnF2|Na 电池的恒流充放电曲线；EBI@NHSP 的恒流循环；纯 NHSP 的电压曲线；MIE@NHSP 的电压曲线；以及 Na/NVP 全电池的长循环（PDF）
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Author Information
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- Shan Liu - School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009, China;
https://orcid.org/0000-0002-8554-6306;
Acknowledgments
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The authors appreciate the support from the Natural Science Foundation of China (Grant nos. 52004092 and 51872090) and the Ph.D. Research Startup Foundation of North China University of Science and Technology (no. BS2019001).
References
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This article references 46 other publications.
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- 6Zhao, Y.; Adair, K. R.; Sun, X. Recent Developments and Insights into the Understanding of Na Metal Anodes for Na-metal Batteries. Energy Environ. Sci. 2018, 11, 2673– 2695, DOI: 10.1039/c8ee01373jGoogle Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVSqs7nP&md5=d33a49fc969a36f1b793f8ac12951c58Recent developments and insights into the understanding of Na metal anodes for Na-metal batteriesZhao, Yang; Adair, Keegan R.; Sun, XueliangEnergy & Environmental Science (2018), 11 (10), 2673-2695CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Rechargeable Na-based battery systems, including Na-ion batteries, room temp. Na-S, Na-O2, Na-CO2, and all-solid-state Na metal batteries, have attracted significant attention due to the high energy d., abundance, low cost, and suitable redox potential of Na metal. However, the Na metal anode faces several challenges, including: (1) the formation of Na dendrites and short circuiting; (2) low Coulombic efficiency (CE) and poor cycling performance; and (3) an infinite vol. change due to its hostless nature. Furthermore, the issues assocd. with Na metal anodes have also been noticed in practical Na metal batteries (NMBs). In recent years, the importance of the Na metal anode has been highlighted and many studies have provided potential solns. to address the issues of its use. This review article focuses on the recent developments of Na metal anodes, including insight into the fundamental understanding of its electrochem. processes, novel characterization methods, approaches for protecting the anode and future perspectives. Our review will accelerate further improvement in the characterization and application of Na metal anodes for next-generation NMB systems.
- 7Oh, J. A. S.; He, L.; Chua, B.; Zeng, K.; Lu, L. Inorganic Sodium Solid-state Electrolyte and Interface with Sodium Metal for Room-temperature Metal Solid-state Batteries. Energy Storage Mater. 2021, 34, 28– 44, DOI: 10.1016/j.ensm.2020.08.037Google ScholarThere is no corresponding record for this reference.
- 8Xu, L.; Li, J.; Liu, C.; Zou, G.; Hou, H.; Ji, X. Research Progress in Inorganic Solid-State Electrolytes for Sodium-Ion Batteries. Acta Phys.-Chim. Sin. 2020, 36, 1905013, DOI: 10.3866/pku.Whxb201905013Google ScholarThere is no corresponding record for this reference.
- 9Zhou, C.; Bag, S.; Thangadurai, V. Engineering Materials for Progressive All-Solid-State Na Batteries. ACS Energy Lett. 2018, 3, 2181– 2198, DOI: 10.1021/acsenergylett.8b00948Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVemtLrL&md5=dc1af0c07b0da8d83637a05ac82fbd1eEngineering Materials for Progressive All-Solid-State Na BatteriesZhou, Chengtian; Bag, Sourav; Thangadurai, VenkataramanACS Energy Letters (2018), 3 (9), 2181-2198CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Following the prevalence of the Li-ion battery for elec. energy storage systems (EESs), the world is looking toward alternative, cost-effective, elec. EESs for portable electronics, elec. vehicles, and grid storage from renewable sources. Na-based batteries are the most promising candidates and show similar chem. as Li-based batteries. All-solid-state sodium batteries (AS3Bs) have attracted great attention due to safe operation, high energy d., and wide operational temp. Herein, current development of solid-state cryst. borate- and chalcogenide-based Na-ion conductors is discussed together with historically important Na-β-alumina and Na superionic conductors (NASICONs). Furthermore, we report on engineering a ceramic Na-ion electrolyte and electrode interface, which is considered a bottleneck for practical applications of solid-state electrolytes in AS3Bs. A soft Na-ion conducting interlayer is crit. to suppress the interfacial Na-ion charge transfer resistance between the solid electrolyte and electrode. Several Na-ion conducting ionic liqs., polymers, gels, cryst. plastics interlayers, and other interfacial modification strategies have been effectively employed in advanced AS3Bs.
- 10Gao, Z.; Yang, J.; Yuan, H.; Fu, H.; Li, Y.; Li, Y.; Ferber, T.; Guhl, C.; Sun, H.; Jaegermann, W.; Hausbrand, R.; Huang, Y. Stabilizing Na3Zr2Si2PO12/Na Interfacial Performance by Introducing a Clean and Na-Deficient Surface. Chem. Mater. 2020, 32, 3970– 3979, DOI: 10.1021/acs.chemmater.0c00474Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnt1SrsLo%253D&md5=6cdcc62fd6c1b6d2a45b6652733df624Stabilizing Na3Zr2Si2PO12/Na Interfacial Performance by Introducing a Clean and Na-Deficient SurfaceGao, Zhonghui; Yang, Jiayi; Yuan, Haiyang; Fu, Haoyu; Li, Yutao; Li, Yuyu; Ferber, Thimo; Guhl, Conrad; Sun, Huabin; Jaegermann, Wolfram; Hausbrand, Rene; Huang, YunhuiChemistry of Materials (2020), 32 (9), 3970-3979CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Most Li+/Na+-conducting solid electrolytes are unstable in moisture, and the formed hydroxides and carbonates on their surfaces result in the increase of the interfacial resistance between solid electrolytes and alkali metal anodes. In this study, heat treatment was used to remove the byproduct coating on the surface of Na3Zr2Si2PO12 (NZSP) that also leads to the generation of Na-ion deficient surface simultaneously. This surface chem. approach was used to reduce the interfacial resistance and suppress Na-dendrite growth during Na plating. A combination of the metallic Na wetting test, d. functional theory, and electrochem. measurement was employed to investigate the origins of ultralow interfacial resistance and mechanism between the Na-ion deficient surface and the metallic Na anode. The anal. demonstrates that the Na-ion-deficient surface effectively improves the contact between NZSP and the metallic Na anode. Moreover, an ultrathin passivating layer involving Na2O was formed between NZSP with metallic Na that protected the NZSP electrolyte from the redn. by metallic Na. This study not only motivates the need for further understanding of the surface chem. of NZSP but also provides guidelines for the future design of the Na-ion solid-electrolyte interface.
- 11Wang, C.; Sun, Z.; Zhao, Y.; Wang, B.; Shao, C.; Sun, C.; Zhao, Y.; Li, J.; Jin, H.; Qu, L. Grain Boundary Design of Solid Electrolyte Actualizing Stable All-Solid-State Sodium Batteries. Small 2021, 17, 2103819, DOI: 10.1002/smll.202103819Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFGmsb%252FO&md5=f28ab54df470d176091ccc32380a5051Grain Boundary Design of Solid Electrolyte Actualizing Stable All-Solid-State Sodium BatteriesWang, Chengzhi; Sun, Zheng; Zhao, Yongjie; Wang, Boyu; Shao, Changxiang; Sun, Chen; Zhao, Yang; Li, Jingbo; Jin, Haibo; Qu, LiangtiSmall (2021), 17 (40), 2103819CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)Advanced inorg. solid electrolytes (SEs) are crit. for all-solid-state alk. metal batteries with high safety and high energy densities. A new interphase design to address the urgent interfacial stability issues against all-solid-state sodium metal batteries (ASSMBs) is proposed. The grain boundary phase of a Mg2+-doped Na3Zr2Si2PO12 conductor (denoted as NZSP-xMg) is manipulated to introduce a favorable Na3-2δMgδPO4-dominant interphase which facilitates its intimate contact with Na metal and works as an electron barrier to suppress Na metal dendrite penetration into the electrolyte bulk. The optimal NZSP-0.2Mg electrolyte endows a low interfacial resistance of 93 Ω cm2 at room temp., over 16 times smaller than that of Na3Zr2Si2PO12. The Na plating/stripping with small polarization is retained under 0.3 mA cm-2 for more than 290 days (7000 h), representing a record high cycling stability of SEs for ASSMBs. An all-solid-state NaCrO2//Na battery is accordingly assembled manifesting a high capacity of 110 mA h g-1 at 1 C for 1755 cycles with almost no capacity decay. Excellent rate capability at 5 C is realized with a high Coulombic efficiency of 99.8%, signifying promising application in solid-state electrochem. energy storage systems.
- 12Zhang, Z.; Zhang, Q.; Shi, J.; Chu, Y. S.; Yu, X.; Xu, K.; Ge, M.; Yan, H.; Li, W.; Gu, L.; Hu, Y.-S.; Li, H.; Yang, X.-Q.; Chen, L.; Huang, X. A Self-Forming Composite Electrolyte for Solid-State Sodium Battery with Ultralong Cycle Life. Adv. Energy Mater. 2017, 7, 1601196, DOI: 10.1002/aenm.201601196Google ScholarThere is no corresponding record for this reference.
- 13Li, Z.; Zhu, K.; Liu, P.; Jiao, L. 3D Confinement Strategy for Dendrite-Free Sodium Metal Batteries. Adv. Energy Mater. 2021, 12, 2100359, DOI: 10.1002/aenm.202100359Google ScholarThere is no corresponding record for this reference.
- 14Lou, S.; Zhang, F.; Fu, C.; Chen, M.; Ma, Y.; Yin, G.; Wang, J. Interface Issues and Challenges in All-Solid-State Batteries: Lithium, Sodium, and Beyond. Adv. Mater. 2021, 33, 2000721, DOI: 10.1002/adma.202000721Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsVClt7zM&md5=a6b03c7d6b94b527daae04f5299c2f02Interface Issues and Challenges in All-Solid-State Batteries: Lithium, Sodium, and BeyondLou, Shuaifeng; Zhang, Fang; Fu, Chuankai; Chen, Ming; Ma, Yulin; Yin, Geping; Wang, JiajunAdvanced Materials (Weinheim, Germany) (2021), 33 (6), 2000721CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Owing to the promise of high safety and energy d., all-solid-state batteries are attracting incremental interest as one of the most promising next-generation energy storage systems. However, their widespread applications are inhibited by many tech. challenges, including low-cond. electrolytes, dendrite growth, and poor cycle/rate properties. Particularly, the interfacial dynamics between the solid electrolyte and the electrode is considered as a crucial factor in detg. solid-state battery performance. In recent years, intensive research efforts have been devoted to understanding the interfacial behavior and strategies to overcome these challenges for all-solid-state batteries. Here, the interfacial principle and engineering in a variety of solid-state batteries, including solid-state lithium/sodium batteries and emerging batteries (lithium-sulfur, lithium-air, etc.), are discussed. Specific attention is paid to interface physics (contact and wettability) and interface chem. (passivation layer, ionic transport, dendrite growth), as well as the strategies to address the above concerns. The purpose here is to outline the current interface issues and challenges, allowing for target-oriented research for solid-state electrochem. energy storage. Current trends and future perspectives in interfacial engineering are also presented.
- 15Zhang, Z.; Wenzel, S.; Zhu, Y.; Sann, J.; Shen, L.; Yang, J.; Yao, X.; Hu, Y.-S.; Wolverton, C.; Li, H.; Chen, L.; Janek, J. Na3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries. ACS Appl. Energy Mater. 2020, 3, 7427– 7437, DOI: 10.1021/acsaem.0c00820Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1eqt7vN&md5=1d1e3b6eab1b8fe2ea14b4d6f557f5eaNa3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State BatteriesZhang, Zhizhen; Wenzel, Sebastian; Zhu, Yizhou; Sann, Joachim; Shen, Lin; Yang, Jing; Yao, Xiayin; Hu, Yong-Sheng; Wolverton, Christopher; Li, Hong; Chen, Liquan; Janek, JurgenACS Applied Energy Materials (2020), 3 (8), 7427-7437CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Solid electrolytes (SEs) offer great potential as the basis for safer rechargeable batteries with high energy d. Aside from excellent ion cond., the stability of SEs against the highly reactive metal anode is also a prerequisite to achieve good performance in solid-state batteries (SSBs). Yet, most SEs are found to have limited thermodn. stability and are unstable against Li/Na metal. With the combination of AC impedance spectroscopy, first-principles calcns., and in situ XPS, we unequivocally reveal that a NaSICON-structured Na3Zr2Si2PO12 electrolyte forms a kinetically stable interface against sodium metal. Prolonged galvanostatic cycling of sym. Na|Na3Zr2Si2PO12|Na cells shows stable plating/stripping behavior of sodium metal at a c.d. of 0.1 mA cm-2 and an areal capacity of 0.5 mA h cm-2 at room temp. Evaluation of Na3Zr2Si2PO12 as an electrolyte in SSBs further demonstrates its good cycling stability for over 120 cycles with very limited capacity degrdn. This work provides strong evidence that Na3Zr2Si2PO12 is one of the few electrolytes that simultaneously achieve superionic cond. and excellent chem./electrochem. stability, making it a very promising alternative to liq. electrolytes. Our findings open up a fertile avenue of exploration for SSBs based on Na3Zr2Si2PO12 and related SEs.
- 16Hou, W.; Guo, X.; Shen, X.; Amine, K.; Yu, H.; Lu, J. Solid Electrolytes and Interfaces in All-solid-state Sodium Batteries: Progress and Perspective. Nano Energy 2018, 52, 279– 291, DOI: 10.1016/j.nanoen.2018.07.036Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVCgurnF&md5=4555cb61bf61c88d2bcfdf86c897b888Solid electrolytes and interfaces in all-solid-state sodium batteries: Progress and perspectiveHou, Wenru; Guo, Xianwei; Shen, Xuyang; Amine, Khali; Yu, Haijun; Lu, JunNano Energy (2018), 52 (), 279-291CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)All-solid-state sodium batteries are promising candidates for the next generation of energy storage with exceptional safety, reliability and stability. The solid electrolytes are key components for enabling all-solid-state sodium batteries with high electrochem. performances. This Review discusses the current developments on inorg. and org. sodium ions solid electrolytes, including β/β''-alumina, NASICON, sulfides, polymers and others. In particular, the structures, ionic conductivities and fabrications as well as electrochem./chem. stabilities of solid electrolytes are discussed. The effective approaches for forming intimate interfaces between solid electrolytes and electrodes are also reviewed. And perspectives on future developments in the field of solid electrolytes and possible directions to improve interfacial contacts for future practical applications of all-solid-state sodium batteries are included.
- 17Uchida, Y.; Hasegawa, G.; Shima, K.; Inada, M.; Enomoto, N.; Akamatsu, H.; Hayashi, K. Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression. ACS Appl. Energy Mater. 2019, 2, 2913– 2920, DOI: 10.1021/acsaem.9b00250Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmsFegur0%253D&md5=bab5654226d744c8ea156b6f611f660aInsights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial CompressionUchida, Yasuhiro; Hasegawa, George; Shima, Kazunari; Inada, Miki; Enomoto, Naoya; Akamatsu, Hirofumi; Hayashi, KatsuroACS Applied Energy Materials (2019), 2 (4), 2913-2920CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)A robust ceramic solid electrolyte with high ionic cond. is a key component for all-solid-state batteries (ASSBs). In terms of the demand for high-energy-d. storage, researchers have been tackling various challenges to use metal anodes, where a fundamental understanding on the metal/solid electrolyte interface is of particular importance. The Na+ superionic conductor, so-called NASICON, has high potential for application to ASSBs with a Na anode due to its high Na+ ion cond. at room temp., which has, however, faced a daunting issue of the significantly large interfacial resistance between Na and NASICON. In this work, we have successfully reduced the interfacial resistance as low as 14 Ω cm2 at room temp. by a simple mech. compression of a Na/NASICON assembly. We also demonstrate a fundamental study of the Na/NASICON interface in comparison with the Na/β''-alumina counterpart by means of the electrochem. impedance technique, which elucidates a stark difference between the activation energies for interfacial charge transfer: ∼0.6 eV for Na/NASICON and ∼0.3 eV for Na/β''-alumina. This result suggests the formation of a Na+-conductive interphase layer in pressing Na metal on the NASICON surface at room temp.
- 18Oh, J. A. S.; Wang, Y.; Zeng, Q.; Sun, J.; Sun, Q.; Goh, M.; Chua, B.; Zeng, K.; Lu, L. Intrinsic Low Sodium/NASICON Interfacial Resistance Paving the Way for Room Temperature Sodium-metal Battery. J. Colloid Interface Sci. 2021, 601, 418– 426, DOI: 10.1016/j.jcis.2021.05.123Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1SktLbI&md5=c885321186dcb7c48c65cbd6774887dbIntrinsic low sodium/NASICON interfacial resistance paving the way for room temperature sodium-metal batteryOh, Jin An Sam; Wang, Yumei; Zeng, Qibin; Sun, Jianguo; Sun, Qiaomei; Goh, Minhao; Chua, Bengwah; Zeng, Kaiyang; Lu, LiJournal of Colloid and Interface Science (2021), 601 (), 418-426CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)Sodium-metal batteries have strong potential to be utilized as stationary high energy d. storage devices. Owing to its high ionic cond., low electronic cond. and relatively easy fabrication, NASICON-structure electrolyte (Na3Zr2Si2PO12) is one of the potential candidates to be considered in the solid-state sodium-metal batteries at room temp. However, the large interfacial resistance between the solid-state electrolyte and the metallic sodium is known to limit the crit. c.d. (CCD) of the cell. In this study, a simple and cost-effective annealing process is introduced to the electrolyte prepn. to improves its interface with metallic sodium. XPS and scanning probe microscopy show that Si forms bonds with the surface functional groups when exposed to the ambient condition. With the removal of surface contamination as well as a partially reduced electrolyte surface, the annealed electrolyte shows an extremely small interfacial resistance of 11 Ω cm2 and a high CCD of 0.9 mA cm-2. This study provides an insight on the electrolyte surface prepn. and its significant in a sodium-metal solid-state battery.
- 19He, M.; Cui, Z.; Chen, C.; Li, Y.; Guo, X. Formation of Self-limited, Stable and Conductive Interfaces between Garnet Electrolytes and Lithium Anodes for Reversible Lithium Cycling in Solid-state Batteries. J. Mater. Chem. A 2018, 6, 11463– 11470, DOI: 10.1039/c8ta02276cGoogle Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpslSrtrw%253D&md5=a4af208ef6a2f8f74c514c528aa449daFormation of self-limited, stable and conductive interfaces between garnet electrolytes and lithium anodes for reversible lithium cycling in solid-state batteriesHe, Minghui; Cui, Zhonghui; Chen, Cheng; Li, Yiqiu; Guo, XiangxinJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (24), 11463-11470CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid-state batteries (SSBs) have already attracted significant attention due to their potential to offer high energy d. and excellent safety as compared to the currently used lithium-ion batteries with liq. electrolytes. The use of a lithium anode in SSBs is extremely important to realize these advantages. Starting from the synthesis of a highly conductive cubic garnet solid electrolyte (Li6.375La3Zr1.375Nb0.625O12, LLZNO) using Nb as a structure stabilizer, in this study, we demonstrated the resoln. of interfacial problems between the garnet electrolyte and lithium anode and the integration of the lithium anode into garnet-based SSBs by modifying the as-synthesized LLZNO with a Sn thin film. Due to the Sn modification, the interfacial resistances between the garnet electrolyte and the lithium anode decreased approx. 20 times to only 46.6 Ω cm2. The fast and reversible lithium plating/stripping under high current densities and the excellent battery performance of Li/Sn-LLZNO/LiFePO4 full cells were achieved. This improvement is ascribed to the formation of a Li-Sn alloy interlayer, which severs as a self-limited stable and conductive interface, bridging the garnet electrolyte and the lithium anode and enabling fast and stable lithium transport. As a proof-of-concept, this effective surface modification method will offer inspirations to researchers for overcoming the interfacial problems and promoting the development of high-performance SSBs.
- 20Hao, X.; Zhao, Q.; Su, S.; Zhang, S.; Ma, J.; Shen, L.; Yu, Q.; Zhao, L.; Liu, Y.; Kang, F.; He, Y. B. Constructing Multifunctional Interphase between Li1.4Al0.4Ti1.6(PO4)3 and Li Metal by Magnetron Sputtering for Highly Stable Solid-State Lithium Metal Batteries. Adv. Energy Mater. 2019, 9, 1901604, DOI: 10.1002/aenm.201901604Google ScholarThere is no corresponding record for this reference.
- 21Yang, J.; Gao, Z.; Ferber, T.; Zhang, H.; Guhl, C.; Yang, L.; Li, Y.; Deng, Z.; Liu, P.; Cheng, C.; Che, R.; Jaegermann, W.; RenéHausbrand; Huang, Y. Guided-formation of a Favorable Interface for Stabilizing Na Metal Solid-state Batteries. J. Mater. Chem. A 2020, 8, 7828– 7835, DOI: 10.1039/d0ta01498bGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlt1Gitrk%253D&md5=27cf4043b5abb5ba6c29e83ce4073de2Guided-formation of a favorable interface for stabilizing Na metal solid-state batteriesYang, Jiayi; Gao, Zhonghui; Ferber, Thimo; Zhang, Haifeng; Guhl, Conrad; Yang, Liting; Li, Yuyu; Deng, Zhi; Liu, Porun; Cheng, Chuanwei; Che, Renchao; Jaegermann, Wolfram; ReneHausbrand; Huang, YunhuiJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (16), 7828-7835CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The sodium (Na) anode suffers severe interfacial resistance and dendrite issues in a classic NASICON-type Na3Zr2Si2PO12 (NZSP) electrolyte, resulting in poor electrochem. performance for solid-state Na metal batteries. There has been little success in the redn. of interfacial resistance in recent years. The exact mechanism of this resistance has not been fully understood because of little information about the interface. In this work, the large interfacial resistance issue and the metal dendrite problem between the Na anode and NZSP are effectively addressed by introducing a TiO2 film as an active interphase. Quasiinsitu XPS is employed to uncover the interphase formation mechanism at the Na/TiO2-NZSP electrolyte interface. The quasiinsitu XPS results confirm the formation of a sodiated-TiO2 interphase upon stepwise Na evapn. on the surface of the NZSP electrolyte. Further investigation by molten Na contact angle measurements, impedance spectroscopy and DFT calcns. demonstrates that the sodiated-TiO2 interphase promotes Na ion transport between the Na anode and NZSP electrolyte. Moreover, the electrostatic potential formed at the NZSP/NaxTiO2 interface can effectively reduce electronic cond. at the interface and hence prevent the growth of sodium dendrites. A representative paradigm for interphase design is provided to address the interface contact for developing stable solid-state batteries with high performance.
- 22Yang, J.; Xu, H.; Wu, J.; Gao, Z.; Hu, F.; Wei, Y.; Li, Y.; Liu, D.; Li, Z.; Huang, Y. Improving Na/Na3Zr2Si2PO12 Interface via SnOx/Sn Film for High-Performance Solid-State Sodium Metal Batteries. Small Methods 2021, 5, 2100339, DOI: 10.1002/smtd.202100339Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvVKks7o%253D&md5=39b17fb96700d176b611f8763fc13e11Improving Na/Na3Zr2Si2PO12 Interface via SnOx/Sn Film for High-Performance Solid-State Sodium Metal BatteriesYang, Jiayi; Xu, Henghui; Wu, Jingyi; Gao, Zhonghui; Hu, Fei; Wei, Ying; Li, Yuyu; Liu, Dezhong; Li, Zhen; Huang, YunhuiSmall Methods (2021), 5 (9), 2100339CODEN: SMMECI; ISSN:2366-9608. (Wiley-VCH Verlag GmbH & Co. KGaA)Sodium (Na) metal batteries have attracted much attention due to their rich resources, low cost, and high energy d. As a promising solid electrolyte, Na3Zr2Si2PO12 (NZSP) is expected to be used in solid-state Na metal batteries addressing the safety concerns. However, due to the poor contact between NZSP and the Na metal, the interfacial resistance is too large to gain proper performance for practical solid-state batteries (SSBs) application. Here, a SnOx/Sn film is successfully introduced to improve the interface between Na and NZSP for enhancing the electrochem. performance of SSBs. As a result, the Na/NZSP interfacial resistance is dramatically reduced from 581 to 3 Ω cm2. The modified Na||Na sym. cell keeps cycling over 1500 h with an overpotential of 40 mV at 0.1 mA cm-2 at room temp. Even at current densities of 0.3 and 0.5 mA cm-2, the cell still maintains an excellent cyclability. When coupled with NaTi2(PO4)3 and a Na3V2(PO4)3 cathode, the full-cell demonstrates a good performance at 0.2 C and 1°C, resp. The present work provides an effective way to solve the interface issue of SSBs.
- 23Gao, H.; Xue, L.; Xin, S.; Park, K.; Goodenough, J. B. A Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium Batteries. Angew. Chem., Int. Ed. Engl. 2017, 56, 5541– 5545, DOI: 10.1002/anie.201702003Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1cvntFemtw%253D%253D&md5=d0a306f7920ff90f30e6a04c2ae79a1fA Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium BatteriesGao Hongcai; Xue Leigang; Xin Sen; Park Kyusung; Goodenough John BAngewandte Chemie (International ed. in English) (2017), 56 (20), 5541-5545 ISSN:.The development of all-solid-state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge-discharge cycle. The introduction of a plastic-crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid-state sodium cells with 1) solid electrolyte Na3 Zr2 (Si2 PO4 ) particles versus 2) plastic-crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic-crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all-solid-state battery cells.
- 24Xu, Y.; Wang, C.; Matios, E.; Luo, J.; Hu, X.; Yue, Q.; Kang, Y.; Li, W. Sodium Deposition with a Controlled Location and Orientation for Dendrite-Free Sodium Metal Batteries. Adv. Energy Mater. 2020, 10, 2002308, DOI: 10.1002/aenm.202002308Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVylsbbF&md5=ec4a7e511c150ec2d432a673fceba435Sodium Deposition with a Controlled Location and Orientation for Dendrite-Free Sodium Metal BatteriesXu, Ying; Wang, Chuanlong; Matios, Edward; Luo, Jianmin; Hu, Xiaofei; Yue, Qin; Kang, Yijin; Li, WeiyangAdvanced Energy Materials (2020), 10 (44), 2002308CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Sodium is one of the most promising alternatives to lithium as an anode material for next-generation batteries. However, severe Na dendrite growth hinders its practical implementation. Here, a polyacrylonitrile (PAN) fiber film coated with a thin layer of tin on the bottom side (closing to battery case) serves as a scaffold for Na deposition. Due to the low nucleation barrier enabled by the Sn layer, Na deposition spontaneously occurs at the bottom of the scaffold, and then is homogeneously confined within its 3D network because of the decreased local c.d. caused by 3D structure and uniform Na+ distribution regulated by the sodiophilic PAN. With this well-controlled orientation of Na deposition, the Na-PAN/Sn electrode delivers a high Coulombic efficiency of 99.5% in Na plating/stripping at 5 mA cm-2, stable operation for over 2500 h in sym. batteries at 2 mA cm-2, and excellent cyclic stability and rate capability in Na metal full batteries.
- 25Zhang, Q.; Lu, Y.; Guo, W.; Shao, Y.; Liu, L.; Lu, J.; Rong, X.; Han, X.; Li, H.; Chen, L.; Hu, Y.-S. Hunting Sodium Dendrites in NASICON-Based Solid-State Electrolytes. Energy Mater. Adv. 2021, 2021, 1, DOI: 10.34133/2021/9870879Google ScholarThere is no corresponding record for this reference.
- 26Miao, X.; Di, H.; Ge, X.; Zhao, D.; Wang, P.; Wang, R.; Wang, C.; Yin, L. AlF3-modified Anode-electrolyte Interface for Effective Na Dendrites Restriction in NASICON-based Solid-state Electrolyte. Energy Storage Mater. 2020, 30, 170– 178, DOI: 10.1016/j.ensm.2020.05.011Google ScholarThere is no corresponding record for this reference.
- 27Lu, Y.; Alonso, J. A.; Yi, Q.; Lu, L.; Wang, Z. L.; Sun, C. A High-Performance Monolithic Solid-State Sodium Battery with Ca2+ Doped Na3Zr2Si2PO12 Electrolyte. Adv. Energy Mater. 2019, 9, 1901205, DOI: 10.1002/aenm.201901205Google ScholarThere is no corresponding record for this reference.
- 28Han, F.; Westover, A. S.; Yue, J.; Fan, X.; Wang, F.; Chi, M.; Leonard, D. N.; Dudney, N. J.; Wang, H.; Wang, C. High Electronic Conductivity as the Origin of Lithium Dendrite Formation within Solid Electrolytes. Nat. Energy 2019, 4, 187– 196, DOI: 10.1038/s41560-018-0312-zGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmslGktbc%253D&md5=bc9f7d5bd77f27144060254fea0474f1High electronic conductivity as the origin of lithium dendrite formation within solid electrolytesHan, Fudong; Westover, Andrew S.; Yue, Jie; Fan, Xiulin; Wang, Fei; Chi, Miaofang; Leonard, Donovan N.; Dudney, Nancy J.; Wang, Howard; Wang, ChunshengNature Energy (2019), 4 (3), 187-196CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Solid electrolytes (SEs) are widely considered as an 'enabler' of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S-P2S5 is actually much easier than that in liq. electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concn. profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concn. in LiPON can be obsd., we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic cond. of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic cond., rather than further increasing the ionic cond. of SEs, is therefore crit. for the success of all-solid-state Li batteries.
- 29Tu, Q.; Shi, T.; Chakravarthy, S.; Ceder, G. Understanding Metal Propagation in Solid Electrolytes Due to Mixed Ionic-electronic Conduction. Matter 2021, 4, 3248– 3268, DOI: 10.1016/j.matt.2021.08.004Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xislyhsbw%253D&md5=420566d1ad838466a9c7fad90678041fUnderstanding metal propagation in solid electrolytes due to mixed ionic-electronic conductionTu, Qingsong; Shi, Tan; Chakravarthy, Srinath; Ceder, GerbrandMatter (2021), 4 (10), 3248-3268CODEN: MATTCG; ISSN:2590-2385. (Elsevier Inc.)Metal penetration into a solid electrolyte (SE) is one of the crit. problems impeding the practical application of solid-state batteries. In this study, we investigate the conditions under which electronic cond. of the SE can lead to metal deposition and fracture within the SE. Three different stages for void filling (metal plating initiation, metal growth, and metal compression) in the SE are identified. We show that a micron-size isolated void in the SE near the anode can be quickly filled in by metal and fractured when the developed pressure in the void grows larger than the max. pressure the SE material can sustain. We find that the anode voltage and applied c.d. play a significant role in detg. the vulnerability to metal deposition. We discuss several strategies to prevent electronic cond.-driven metal propagation in electrolytes that are not fully dense, including the densified layers between the anode and SE.
- 30Ping, W.; Wang, C.; Lin, Z.; Hitz, E.; Yang, C.; Wang, H.; Hu, L. Reversible Short-Circuit Behaviors in Garnet-Based Solid-State Batteries. Adv. Energy Mater. 2020, 10, 2000702, DOI: 10.1002/aenm.202000702Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptlKqu70%253D&md5=bb2e893b64c37040488744a6e8f82e71Reversible Short-Circuit Behaviors in Garnet-Based Solid-State BatteriesPing, Weiwei; Wang, Chengwei; Lin, Zhiwei; Hitz, Emily; Yang, Chunpeng; Wang, Howard; Hu, LiangbingAdvanced Energy Materials (2020), 10 (25), 2000702CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Garnet-based solid-state electrolytes (SSEs) are attractive for solid-state lithium metal batteries due to their wide electrochem. window, high cond., and excellent stability against lithium metal. However, the risk of short-circuit encumbers the cycle life and capacity of garnet-based solid-state batteries without clear reason or mechanism. Here, reversible short-circuit behavior in the garnet-based solid-state batteries, which differs from the short-circuit in liq. cells, is reported for the first time. In situ neutron depth profiling is adopted to quant. measure Li transport, which helps forecast and confirm the reversible nature of the short-circuit in garnet-based batteries. A real-time Li accumulation monitoring system of NMC//CNT/garnet/Li cell is designed to reveal the Li dendrite formation mechanism. The voltage drops of the CNT monitoring electrode during the charging process indicate the formation of Li dendrites inside the garnet bulk, while the smooth voltage profile during the discharging process demonstrates the disappearance of the short-circuit. This is the first confirmation of short-circuit behavior that provides clarification of the Li dendrite formation mechanism in garnet-based solid-state batteries, which is shown to be a reversible process caused by the low ionic cond. and non-negligible electronic cond. of garnet SSEs.
- 31Gao, B.; Jalem, R.; Tian, H. K.; Tateyama, Y. Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte. Adv. Energy Mater. 2022, 12, 2102151, DOI: 10.1002/aenm.202102151Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXis12lu7jL&md5=a9fd48dd2f10160e7563a7ed3f08fbecRevealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid ElectrolyteGao, Bo; Jalem, Randy; Tian, Hong-Kang; Tateyama, YoshitakaAdvanced Energy Materials (2022), 12 (3), 2102151CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)For real applications of all-solid-state batteries (ASSBs) to be realized, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the at.-scale defect stabilities and transport of ions around GBs is still far from understood. Here, a first-principles investigation on the promising garnet Li7La3Zr2O12 (LLZO) solid electrolyte (SE) GBs is carried out. The study reveals a GB-dependent behavior for the Li-ion transport correlated to the diffusion network. Of particular note, the Σ3(112) tilt GB model exhibits a quite high Li-ion cond. comparable to that in bulk, and a fast intergranular diffusion, contrary to former discovered. Moreover, the uncovered preferential electron localization at the Σ3(112) GB leads to an increase in the electronic cond. at the GB, and the Li accumulation at the coarse GBs is revealed from the neg. Li interstitial formation energies. These factors play important roles in the dendrite formation along the GBs during Li plating in the LLZO|Li cell. These findings suggest strategies for the optimization of synthesis conditions and coating materials at the interface for preventing dendrite formation. The present comprehensive simulations provide new insights into the GB effect and engineering of the SE in ASSBs.
- 32Huo, H.; Gao, J.; Zhao, N.; Zhang, D.; Holmes, N. G.; Li, X.; Sun, Y.; Fu, J.; Li, R.; Guo, X.; Sun, X. A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries. Nat. Commun. 2021, 12, 176, DOI: 10.1038/s41467-020-20463-yGoogle Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhtF2gu7Y%253D&md5=e26bd5e66afda0fc3090244e6e8d883bA flexible electron-blocking interfacial shield for dendrite-free solid lithium metal batteriesHuo, Hanyu; Gao, Jian; Zhao, Ning; Zhang, Dongxing; Holmes, Nathaniel Graham; Li, Xiaona; Sun, Yipeng; Fu, Jiamin; Li, Ruying; Guo, Xiangxin; Sun, XueliangNature Communications (2021), 12 (1), 176CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technol. due to their enhanced energy d. and safety. However, the high electronic cond. of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven elec.-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, we propose a flexible electron-blocking interfacial shield (EBS) to protect garnet electrolytes from the electronic degrdn. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li vol. change, maintaining the integrity of the interface during repeated cycling. D. functional theory calcns. show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved crit. c.d. of 1.2 mA cm-2 and stable cycling for over 400 h at 1 mA cm-2 (1 mAh cm-2) at room temp. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.
- 33Guo, W.; Han, Q.; Jiao, J.; Wu, W.; Zhu, X.; Chen, Z.; Zhao, Y. In situ Construction of Robust Biphasic Surface Layers on Lithium Metal for Lithium-Sulfide Batteries with Long Cycle Life. Angew. Chem., Int. Ed. Engl. 2021, 60, 7267– 7274, DOI: 10.1002/anie.202015049Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3svivFWmtA%253D%253D&md5=404bf9a416299d8efbe48670f871c92eIn situ Construction of Robust Biphasic Surface Layers on Lithium Metal for Lithium-Sulfide Batteries with Long Cycle LifeGuo Wei; Han Qing; Jiao Junrong; Wu Wenhao; Zhu Xuebing; Chen Zhonghui; Zhao YongAngewandte Chemie (International ed. in English) (2021), 60 (13), 7267-7274 ISSN:.Lithium-sulfur (Li-S) batteries have potential in high energy density battery systems. However, intermediates of lithium polysulfides (LiPSs) can easily shuttle to the Li anode and react with Li metal to deplete the active materials and cause rapid failure of the battery. A facile solution pretreatment method for Li anodes involving a solution of metal fluorides/dimethylsulfoxide was developed to construct robust biphasic surface layers (BSLs) in situ. The BSLs consist of lithiophilic alloy (Lix M) and LiF phases on Li metal, which inhibit the shuttle effect and increase the cycle life of Li-S batteries. The BSLs allow Li(+) transport and they inhibit dendrite growth and shield the Li anodes from corrosive reaction with LiPSs. Li-S batteries containing BSLs-Li anodes demonstrate excellent cycling over 1000 cycles at 1 C and simultaneously maintain a high coulombic efficiency of 98.2 %. Based on our experimental and theoretical results, we propose a strategy for inhibition of the shuttle effect that produces high stability Li-S batteries.
- 34Li, W.; Gao, J.; Tian, H.; Li, X.; He, S.; Li, J.; Wang, W.; Li, L.; Li, H.; Qiu, J.; Zhou, W. SnF2-Catalyzed Formation of Polymerized Dioxolane as Solid Electrolyte and its Thermal Decomposition Behavior. Angew. Chem., Int. Ed. Engl. 2021, 61, e202114805 DOI: 10.1002/anie.202114805Google ScholarThere is no corresponding record for this reference.
- 35Pathak, R.; Chen, K.; Gurung, A.; Reza, K. M.; Bahrami, B.; Pokharel, J.; Baniya, A.; He, W.; Wu, F.; Zhou, Y.; Xu, K.; Qiao, Q. Fluorinated Hybrid Solid-electrolyte-interphase for Dendrite-free Lithium Deposition. Nat. Commun. 2020, 11, 93, DOI: 10.1038/s41467-019-13774-2Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlslWjtg%253D%253D&md5=b3cc4ece7d7a6287dc716f618f6c5672Fluorinated hybrid solid-electrolyte-interphase for dendrite-free lithium depositionPathak, Rajesh; Chen, Ke; Gurung, Ashim; Reza, Khan Mamun; Bahrami, Behzad; Pokharel, Jyotshna; Baniya, Abiral; He, Wei; Wu, Fan; Zhou, Yue; Xu, Kang; Qiao, QiquanNature Communications (2020), 11 (1), 93CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Lithium metal anodes have attracted extensive attention owing to their high theor. specific capacity. However, the notorious reactivity of lithium prevents their practical applications, as evidenced by the undesired lithium dendrite growth and unstable solid electrolyte interphase formation. Here, we develop a facile, cost-effective and one-step approach to create an artificial lithium metal/electrolyte interphase by treating the lithium anode with a tin-contg. electrolyte. As a result, an artificial solid electrolyte interphase composed of lithium fluoride, tin, and the tin-lithium alloy is formed, which not only ensures fast lithium-ion diffusion and suppresses lithium dendrite growth but also brings a synergistic effect of storing lithium via a reversible tin-lithium alloy formation and enabling lithium plating underneath it. With such an artificial solid electrolyte interphase, lithium sym. cells show outstanding plating/stripping cycles, and the full cell exhibits remarkably better cycling stability and capacity retention as well as capacity utilization at high rates compared to bare lithium.
- 36Wang, J.; Zhang, Z.; Ying, H.; Han, G.; Han, W.-Q. In-situ Formation of LiF-rich Composite Interlayer for Dendrite-free All-solid-state Lithium Batteries. Chem. Eng. J. 2021, 411, 128534, DOI: 10.1016/j.cej.2021.128534Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvF2iu7o%253D&md5=af1dc43df553b2f5214ff6244746b32eIn-situ formation of LiF-rich composite interlayer for dendrite-free all-solid-state lithium batteriesWang, Jianli; Zhang, Zhao; Ying, Hangjun; Han, Gaorong; Han, Wei-QiangChemical Engineering Journal (Amsterdam, Netherlands) (2021), 411 (), 128534CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)Polyethylene oxide (PEO)-based composite electrolytes are considered as competent candidates to achieve high energy d. all-solid-state lithium batteries (ASSLBs) due to good flexibility, which can effectively solve the problem of large interfacial resistance with electrodes. However, poor mech. strength and low Li+ transference no. can't restrain the formation and growth of Li dendrites, leading to parasitic reaction between electrolyte and Li anode and unsatisfied coulombic efficiency. Herein, Li metal is pre-treated by poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP)/CuF2 composite to form a stable interlayer on the anode. In-situ reaction of CuF2 with Li greatly improves the contact between PVDF-HFP layer and Li anode, forming a LiF-rich modified layer. The interlayer with high mech. strength and ionic cond. can not only suppress the formation of Li dendrites, but also achieve the growth restriction and elimination of dendrites. Moreover, excellent elasticity and strong adhesion with Li anode can ensure the structure stability of modified layer during dynamic plating/stripping of Li. Applied in ASSLBs with PEO-based electrolyte, PVDF-HFP/CuF2 modified sym. Li cells demonstrate increased crit. c.d. and extended cycle life than that of bare Li or single CuF2 treated Li. Furtherly, the ASSLBs with LiFePO4 cathode show excellent cycle stability and high coulombic efficiency over 1000 cycles at 1 C.
- 37Gross, M. M.; Small, L. J.; Peretti, A. S.; Percival, S. J.; Rodriguez, M. A.; Spoerke, E. D. Tin-based Ionic Chaperone Phases to Improve Low Temperature Molten Sodium-NaSICON Interfaces. J. Mater. Chem. A 2020, 8, 17012– 17018, DOI: 10.1039/d0ta03571hGoogle Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFertL7M&md5=7b2bca49d74a8866d408b9c30f7ab248Tin-based ionic chaperone phases to improve low temperature molten sodium-NaSICON interfacesGross, Martha M.; Small, Leo J.; Peretti, Amanda S.; Percival, Stephen J.; Rodriguez, Mark A.; Spoerke, Erik D.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17012-17018CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)High temp. operation of molten sodium batteries impacts cost, reliability, and lifetime, and has limited the widespread adoption of these grid-scale energy storage technologies. Poor charge transfer and high interfacial resistance between molten sodium and solid-state electrolytes, however, prevents the operation of molten sodium batteries at low temps. Here, in situ formation of tin-based chaperone phases on solid state NaSICON ion conductor surfaces is shown in this work to greatly improve charge transfer and lower interfacial resistance in sodium sym. cells operated at 110°C at current densities up to an aggressive 50 mA cm-2. It is shown that static wetting testing, as measured by the contact angle of molten sodium on NaSICON, does not accurately predict battery performance due to the dynamic formation of a chaperone NaSn phase during cycling. This work demonstrates the promise of sodium intermetallic-forming coatings for the advancement of low temp. molten sodium batteries by improved mating of sodium-NaSICON surfaces and reduced interfacial resistance.
- 38Chi, X.; Hao, F.; Zhang, J.; Wu, X.; Zhang, Y.; Gheytani, S.; Wen, Z.; Yao, Y. A High-energy Quinone-based All-solid-state Sodium Metal Battery. Nano Energy 2019, 62, 718– 724, DOI: 10.1016/j.nanoen.2019.06.005Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFOksbbI&md5=dfcd1dd53235201dcb03758c30929209A high-energy quinone-based all-solid-state sodium metal batteryChi, Xiaowei; Hao, Fang; Zhang, Jibo; Wu, Xiangwei; Zhang, Ye; Gheytani, Saman; Wen, Zhaoyin; Yao, YanNano Energy (2019), 62 (), 718-724CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)Redox-active org. electrode materials show great promise as an addn. to inorg. electrode materials for grid-scale energy storage due to their ability to store various cations, moderate operating potentials, and relatively high theor. specific capacities. However, most org. compds. when reduced suffer from dissoln. in org. liq. electrolytes, resulting in poor cycling stability. Herein, we show for the first time an all-solid-state battery based on an oxide-based solid electrolyte, beta-alumina solid electrolyte (BASE), that not only enables stable cycling of an org. quinone-based compd. (pyrene-4,5,9,10-tetraone, PTO) with high specific energy (∼900 Wh kg-1) at the material level but also demonstrates the best cycling stability (1000 h at 0.5 mA cm-2) with a sodium metal anode among any reported all-solid-state sodium metal batteries (ASSMBs). Anode-electrolyte interfacial resistance was successfully reduced by introducing a Sn thin film between the Na anode and BASE. The cathode-electrolyte interfacial barrier was overcome with a mech. compliant PTO-poly(ethylene oxide)-carbon composite cathode that forms interpenetrating ionic and electronic pathways which favor full utilization of PTO. This proof-of-concept demonstration combining org. electrode materials with an oxide-based solid electrolyte and the interface modification strategies pave the way for ASSMBs with higher capacity and cycling stability.
- 39Liang, X.; Pang, Q.; Kochetkov, I. R.; Sempere, M. S.; Huang, H.; Sun, X.; Nazar, L. F. A Facile Surface Chemistry Route to a Stabilized Lithium Metal Anode. Nat. Energy 2017, 2, 17119, DOI: 10.1038/nenergy.2017.119Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVehtLk%253D&md5=5be4236643323e51b90ddb41154284e7A facile surface chemistry route to a stabilized lithium metal anodeLiang, Xiao; Pang, Quan; Kochetkov, Ivan R.; Sempere, Marina Safont; Huang, He; Sun, Xiaoqi; Nazar, Linda F.Nature Energy (2017), 2 (9), 17119CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Lithium metal is a highly desirable anode for lithium rechargeable batteries, having the highest theor. specific capacity and lowest electrochem. potential of all material candidates. Its most notable problem is dendritic growth upon Li plating, which is a major safety concern and exacerbates reactivity with the electrolyte. Here we report that Li-rich composite alloy films synthesized in situ on lithium by a simple and low-cost methodol. effectively prevent dendrite growth. This is attributed to the synergy of fast lithium ion migration through Li-rich ion conductive alloys coupled with an electronically insulating surface component. The protected lithium is stabilized to sustain electrodeposition over 700 cycles (1,400 h) of repeated plating/stripping at a practical c.d. of 2 mA cm-2 and a 1,500 cycle-life is realized for a cell paired with a Li4Ti5O12 pos. electrode. These findings open up a promising avenue to stabilize lithium metal with surface layers having targeted properties.
- 40Chu, I.-H.; Kompella, C. S.; Nguyen, H.; Zhu, Z.; Hy, S.; Deng, Z.; Meng, Y. S.; Ong, S. P. Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor. Sci. Rep. 2016, 6, 33733, DOI: 10.1038/srep33733Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFGrsb3K&md5=4c0f43f314bd6495f2bacfefc8d4bf80Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic ConductorChu, Iek-Heng; Kompella, Christopher S.; Nguyen, Han; Zhu, Zhuoying; Hy, Sunny; Deng, Zhi; Meng, Ying Shirley; Ong, Shyue PingScientific Reports (2016), 6 (), 33733CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)All-solid-state sodium-ion batteries are promising candidates for large-scale energy storage applications. The key enabler for an all-solid-state architecture is a sodium solid electrolyte that exhibits high Na+ cond. at ambient temps., as well as excellent phase and electrochem. stability. In this work, we present a first-principles-guided discovery and synthesis of a novel Cl-doped tetragonal Na3PS4 (t-Na3-xPS4-xClx) solid electrolyte with a room-temp. Na+ cond. exceeding 1 mS cm-1. We demonstrate that an all-solid-state TiS2/t-Na3-xPS4-xClx/Na cell utilizing this solid electrolyte can be cycled at room-temp. at a rate of C/10 with a capacity of about 80 mAh g-1 over 10 cycles. We provide evidence from d. functional theory calcns. that this excellent electrochem. performance is not only due to the high Na+ cond. of the solid electrolyte, but also due to the effect that "salting" Na3PS4 has on the formation of an electronically insulating, ionically conducting solid electrolyte interphase.
- 41Hu, P.; Zhang, Y.; Chi, X.; Kumar Rao, K.; Hao, F.; Dong, H.; Guo, F.; Ren, Y.; Grabow, L. C.; Yao, Y. Stabilizing the Interface between Sodium Metal Anode and Sulfide-Based Solid-State Electrolyte with an Electron-Blocking Interlayer. ACS Appl. Mater. Interfaces 2019, 11, 9672– 9678, DOI: 10.1021/acsami.8b19984Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjvFyjsbo%253D&md5=fe453f83c2453443bde2decba11aa4dbStabilizing the Interface between Sodium Metal Anode and Sulfide-Based Solid-State Electrolyte with an Electron-Blocking InterlayerHu, Pu; Zhang, Ye; Chi, Xiaowei; Kumar Rao, Karun; Hao, Fang; Dong, Hui; Guo, Fangmin; Ren, Yang; Grabow, Lars C.; Yao, YanACS Applied Materials & Interfaces (2019), 11 (10), 9672-9678CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Sulfide-based Na-ion conductors are promising electrolytes for all-solid-state sodium batteries (ASSSBs) because of high ionic cond. and favorable formability. However, no effective strategy has been reported for long-duration Na cycling with sulfide-based electrolytes because of interfacial challenges. Here it is demonstrated that a cellulose-poly(ethylene oxide) (CPEO) interlayer can stabilize the interface between sulfide electrolyte (Na3SbS4) and Na by shutting off the electron pathway of the electrolyte decompn. reaction. As a result, stable Na plating/stripping is achieved for 800 cycles at 0.1 mA cm-2 in all-solid-state devices at 60°.
- 42Zheng, G.; Lee, S. W.; Liang, Z.; Lee, H.-W.; Yan, K.; Yao, H.; Wang, H.; Li, W.; Chu, S.; Cui, Y. Interconnected Hollow Carbon Nanospheres for Stable Lithium Metal Anodes. Nat. Nanotechnol. 2014, 9, 618– 623, DOI: 10.1038/nnano.2014.152Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1ait77L&md5=0778b04fefcd0b158df78c2d7bfc3633Interconnected hollow carbon nanospheres for stable lithium metal anodesZheng, Guangyuan; Lee, Seok Woo; Liang, Zheng; Lee, Hyun-Wook; Yan, Kai; Yao, Hongbin; Wang, Haotian; Li, Weiyang; Chu, Steven; Cui, YiNature Nanotechnology (2014), 9 (8), 618-623CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)For future applications in portable electronics, elec. vehicles and grid storage, batteries with higher energy storage d. than existing lithium ion batteries need to be developed. Recent efforts in this direction have focused on high-capacity electrode materials such as lithium metal, silicon and tin as anodes, and sulfur and oxygen as cathodes. Lithium metal would be the optimal choice as an anode material, because it has the highest specific capacity (3,860 mAh g-1) and the lowest anode potential of all. However, the lithium anode forms dendritic and mossy metal deposits, leading to serious safety concerns and low Coulombic efficiency during charge/discharge cycles. Although advanced characterization techniques have helped shed light on the lithium growth process, effective strategies to improve lithium metal anode cycling remain elusive. Here, we show that coating the lithium metal anode with a monolayer of interconnected amorphous hollow carbon nanospheres helps isolate the lithium metal depositions and facilitates the formation of a stable solid electrolyte interphase. We show that lithium dendrites do not form up to a practical c.d. of 1 mA cm-2. The Coulombic efficiency improves to ∼99% for more than 150 cycles. This is significantly better than the bare unmodified samples, which usually show rapid Coulombic efficiency decay in fewer than 100 cycles. Our results indicate that nanoscale interfacial engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes.
- 43Xu, M.; Li, Y.; Ihsan-Ul-Haq, M.; Mubarak, N.; Liu, Z.; Wu, J.; Luo, Z.; Kim, J. K. NaF-rich Solid Electrolyte Interphase for Dendrite-free Sodium Metal Batteries. Energy Storage Mater. 2022, 44, 477– 486, DOI: 10.1016/j.ensm.2021.10.038Google ScholarThere is no corresponding record for this reference.
- 44Yan, C.; Cheng, X.-B.; Yao, Y.-X.; Shen, X.; Li, B.-Q.; Li, W.-J.; Zhang, R.; Huang, J.-Q.; Li, H.; Zhang, Q. An Armored Mixed Conductor Interphase on a Dendrite-Free Lithium-Metal Anode. Adv. Mater. 2018, 30, 1804461, DOI: 10.1002/adma.201804461Google ScholarThere is no corresponding record for this reference.
- 45Tian, H.; Liu, S.; Deng, L.; Wang, L.; Dai, L. New-type Hf-based NASICON Electrolyte for Solid-state Na-ion Batteries with Superior Long-cycling Stability and Rate Capability. Energy Storage Mater. 2021, 39, 232– 238, DOI: 10.1016/j.ensm.2021.04.026Google ScholarThere is no corresponding record for this reference.
- 46Tamwattana, O.; Park, H.; Kim, J.; Hwang, I.; Yoon, G.; Hwang, T.-h.; Kang, Y.-S.; Park, J.; Meethong, N.; Kang, K. High-Dielectric Polymer Coating for Uniform Lithium Deposition in Anode-Free Lithium Batteries. ACS Energy Lett. 2021, 6, 4416– 4425, DOI: 10.1021/acsenergylett.1c02224Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisFSgtbbP&md5=843c3bb5011b28729b34dc2725b6bc79High-Dielectric Polymer Coating for Uniform Lithium Deposition in Anode-Free Lithium BatteriesTamwattana, Orapa; Park, Hyeokjun; Kim, Jihyeon; Hwang, Insang; Yoon, Gabin; Hwang, Tae-hyun; Kang, Yoon-Sok; Park, Jinhwan; Meethong, Nonglak; Kang, KisukACS Energy Letters (2021), 6 (12), 4416-4425CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)The use of lithium metal either in an anode or anode-free configuration is envisaged as the most promising way to boost the energy d. of the current lithium-ion battery system. Nevertheless, the uncontrolled lithium dendritic growth inhibits practical utilization of lithium metal as an anode due to safety concerns and low Coulombic efficiency. In this work, we show that when a high-dielec. SEI is coated on a current collector, it can effectively promote a uniform lithium deposition by decreasing the overpotential between the surfaces, lowering the local c.d. and suppressing lithium protrusions. Using a PVDF (polyvinylidene difluoride)-based dielec. medium, it is demonstrated that varying the dielec. properties of PVDF by crystallinity control can regulate the lithium deposition mechanisms. Moreover, when the dielec. properties of PVDF film are tailored by the inclusion of dielec. nanoparticles, a selective formation of high-dielec. β-PVDF phase is induced during its film formation (LiF@PVDF), which synergistically promotes uniform lithium deposition/stripping in an anode-free half-cell setup.
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Abstract
Figure 1
Figure 1. Schematic diagram of the EBI on the surface of NASICON. (a) There is poor contact between pure sodium and NHSP, which will cause local polarization and accelerate the generation of sodium dendrites and side reactions. (b) The EBI not only guarantees a close contact and a fast Na+ transmission through the interlayer but also prevents the formation of sodium dendrites essentially.
Figure 2
Figure 2. Structure and morphology of the EBI. (a) Top-view SEM image of the mixed salt layer on NHSP. (b) Cross-sectional view SEM image of the mixed salt layer on NHSP. (c) EDS mapping of Sn of cross section of the interlayer. (d) Formation of EBI by the solution pretreatment method. (e) XRD pattern of the surface of NHSP before and after the in situ reaction. (f) Measurements of D.C. conductivity of interlayers with different ratios of SnF2 and NaCl.
Figure 3
Figure 3. SEM and optical microscopy of the EBI-protected solid electrolyte. (a) Top-view optical microscopy image of the EBI@NHSP electrolyte after cycling. (b) Cross-sectional optical microscopy image of the EBI@NHSP electrolyte after cycling. (c,d) Cross-sectional SEM images of the EBI@NHSP before and after cycling. (e) Top-view optical microscopy image of the pure NHSP electrolyte after cycling. (f) Cross-sectional optical microscopy image of the pure NHSP electrolyte after cycling. (g,h) Cross-sectional SEM images of the pure electrolyte before and after cycling. (i) XPS patterns of Sn 3d, F 1s, and Cl 2p before and after cycling. (j) Schematic diagram of the mechanism of EBI.
Figure 4
Figure 4. Electrochemical performance of symmetric cells with EBI@NHSP and pure NHSP. (a) Voltage profile of EBI@NHSP at 0.2 mA cm–2. (b,c) Galvanostatic cycling of symmetric cells with EBI@NHSP and pure NHSP at different current densities from 0.1 to 2.5 mA cm–2. (d) EIS curves of the symmetric cell with EBI@NHSP before cycling and after different cycles. (e) EIS curves of the symmetric cell with pure NHSP before and after cycling (the inset shows the EIS curve of Na/NHSP/Na after cycling).
Figure 5
Figure 5. Performance of the full cell of Na/NVP and finite element simulation of batteries with various electrolytes. (a) Galvanostatic charge/discharge profiles of full cells with different interfaces at 0.5 C. (b) Rate performance of the full cell from 0.5 to 5 C. Finite element simulation of the sodium-ion concentration gradient with a potential of 0.3 V within the electrolyte (c) without electronic conductivity and (d) with electronic conductivity.
References
This article references 46 other publications.
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- 3Chu, C.; Li, R.; Cai, F.; Bai, Z.; Wang, Y.; Xu, X.; Wang, N.; Yang, J.; Dou, S. Recent Advanced Skeletons in Sodium Metal Anodes. Energy Environ. Sci. 2021, 14, 4318– 4340, DOI: 10.1039/d1ee01341f3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhtlGlt7bN&md5=233e3e77b9aeb55803b0d379a4f5ecf3Recent advanced skeletons in sodium metal anodesChu, Chenxiao; Li, Rui; Cai, Feipeng; Bai, Zhongchao; Wang, Yunxiao; Xu, Xun; Wang, Nana; Yang, Jian; Dou, ShiXueEnergy & Environmental Science (2021), 14 (8), 4318-4340CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. The sodium metal anode exhibits great potential in next-generation high-energy-d. batteries due to its high theor. capacity (1165 mA h g-1) at low redox potential (-2.71 V vs. std. hydrogen electrode) as well as the high natural abundance and low cost of Na resources. However, its practical application in rechargeable batteries is hindered by uncontrollable dendrite growth that leads to poor coulombic efficiency, short lifespan, infinite vol. change and even safety issues during plating/stripping processes. Among various strategies, the application of skeletons for Na metal anodes demonstrates a pos. influence on reducing local c.d., inhibiting dendrite growth, and alleviating vol. expansion. This work reviews the research progress of various skeleton materials for sodium metal anodes in recent years, including carbon-based skeletons, alloy-based skeletons, metallic skeletons and MXene-based skeletons. Simultaneously, the recent technol. advances and strategies are summarized and categorized. Finally, we discuss the development prospects and research strategies of skeleton materials in sodium metal anodes from the perspective of basic research and practical applications.
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- 5Chen, R.; Li, Q.; Yu, X.; Chen, L.; Li, H. Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces. Chem. Rev. 2020, 120, 6820– 6877, DOI: 10.1021/acs.chemrev.9b002685https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit1Sls73I&md5=3815702575eb5c35199afe7459308888Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and InterfacesChen, Rusong; Li, Qinghao; Yu, Xiqian; Chen, Liquan; Li, HongChemical Reviews (Washington, DC, United States) (2020), 120 (14), 6820-6877CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Solid-state batteries were attracting wide attention for next generation energy storage devices due to the probability to realize higher energy d. and superior safety performance compared with the state-of-the-art lithium ion batteries. However, there are still intimidating challenges for developing low cost and industrially scalable solid-state batteries with high energy d. and stable cycling life for large-scale energy storage and elec. vehicle applications. This review presents an overview on the scientific challenges, fundamental mechanisms, and design strategies for solid-state batteries, specifically focusing on the stability issues of solid-state electrolytes and the assocd. interfaces with both cathode and anode electrodes. First, the authors give a brief overview on the history of solid-state battery technologies, followed by introduction and discussion on different types of solid-state electrolytes. Then, the assocd. stability issues, from phenomena to fundamental understandings, are intensively discussed, including chem., electrochem., mech., and thermal stability issues; effective optimization strategies are also summarized. State-of-the-art characterization techniques and in situ and operando measurement methods deployed and developed to study the aforementioned issues are summarized as well. Following the obtained insights, perspectives are given in the end on how to design practically accessible solid-state batteries in the future.
- 6Zhao, Y.; Adair, K. R.; Sun, X. Recent Developments and Insights into the Understanding of Na Metal Anodes for Na-metal Batteries. Energy Environ. Sci. 2018, 11, 2673– 2695, DOI: 10.1039/c8ee01373j6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVSqs7nP&md5=d33a49fc969a36f1b793f8ac12951c58Recent developments and insights into the understanding of Na metal anodes for Na-metal batteriesZhao, Yang; Adair, Keegan R.; Sun, XueliangEnergy & Environmental Science (2018), 11 (10), 2673-2695CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Rechargeable Na-based battery systems, including Na-ion batteries, room temp. Na-S, Na-O2, Na-CO2, and all-solid-state Na metal batteries, have attracted significant attention due to the high energy d., abundance, low cost, and suitable redox potential of Na metal. However, the Na metal anode faces several challenges, including: (1) the formation of Na dendrites and short circuiting; (2) low Coulombic efficiency (CE) and poor cycling performance; and (3) an infinite vol. change due to its hostless nature. Furthermore, the issues assocd. with Na metal anodes have also been noticed in practical Na metal batteries (NMBs). In recent years, the importance of the Na metal anode has been highlighted and many studies have provided potential solns. to address the issues of its use. This review article focuses on the recent developments of Na metal anodes, including insight into the fundamental understanding of its electrochem. processes, novel characterization methods, approaches for protecting the anode and future perspectives. Our review will accelerate further improvement in the characterization and application of Na metal anodes for next-generation NMB systems.
- 7Oh, J. A. S.; He, L.; Chua, B.; Zeng, K.; Lu, L. Inorganic Sodium Solid-state Electrolyte and Interface with Sodium Metal for Room-temperature Metal Solid-state Batteries. Energy Storage Mater. 2021, 34, 28– 44, DOI: 10.1016/j.ensm.2020.08.037There is no corresponding record for this reference.
- 8Xu, L.; Li, J.; Liu, C.; Zou, G.; Hou, H.; Ji, X. Research Progress in Inorganic Solid-State Electrolytes for Sodium-Ion Batteries. Acta Phys.-Chim. Sin. 2020, 36, 1905013, DOI: 10.3866/pku.Whxb201905013There is no corresponding record for this reference.
- 9Zhou, C.; Bag, S.; Thangadurai, V. Engineering Materials for Progressive All-Solid-State Na Batteries. ACS Energy Lett. 2018, 3, 2181– 2198, DOI: 10.1021/acsenergylett.8b009489https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVemtLrL&md5=dc1af0c07b0da8d83637a05ac82fbd1eEngineering Materials for Progressive All-Solid-State Na BatteriesZhou, Chengtian; Bag, Sourav; Thangadurai, VenkataramanACS Energy Letters (2018), 3 (9), 2181-2198CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Following the prevalence of the Li-ion battery for elec. energy storage systems (EESs), the world is looking toward alternative, cost-effective, elec. EESs for portable electronics, elec. vehicles, and grid storage from renewable sources. Na-based batteries are the most promising candidates and show similar chem. as Li-based batteries. All-solid-state sodium batteries (AS3Bs) have attracted great attention due to safe operation, high energy d., and wide operational temp. Herein, current development of solid-state cryst. borate- and chalcogenide-based Na-ion conductors is discussed together with historically important Na-β-alumina and Na superionic conductors (NASICONs). Furthermore, we report on engineering a ceramic Na-ion electrolyte and electrode interface, which is considered a bottleneck for practical applications of solid-state electrolytes in AS3Bs. A soft Na-ion conducting interlayer is crit. to suppress the interfacial Na-ion charge transfer resistance between the solid electrolyte and electrode. Several Na-ion conducting ionic liqs., polymers, gels, cryst. plastics interlayers, and other interfacial modification strategies have been effectively employed in advanced AS3Bs.
- 10Gao, Z.; Yang, J.; Yuan, H.; Fu, H.; Li, Y.; Li, Y.; Ferber, T.; Guhl, C.; Sun, H.; Jaegermann, W.; Hausbrand, R.; Huang, Y. Stabilizing Na3Zr2Si2PO12/Na Interfacial Performance by Introducing a Clean and Na-Deficient Surface. Chem. Mater. 2020, 32, 3970– 3979, DOI: 10.1021/acs.chemmater.0c0047410https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnt1SrsLo%253D&md5=6cdcc62fd6c1b6d2a45b6652733df624Stabilizing Na3Zr2Si2PO12/Na Interfacial Performance by Introducing a Clean and Na-Deficient SurfaceGao, Zhonghui; Yang, Jiayi; Yuan, Haiyang; Fu, Haoyu; Li, Yutao; Li, Yuyu; Ferber, Thimo; Guhl, Conrad; Sun, Huabin; Jaegermann, Wolfram; Hausbrand, Rene; Huang, YunhuiChemistry of Materials (2020), 32 (9), 3970-3979CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Most Li+/Na+-conducting solid electrolytes are unstable in moisture, and the formed hydroxides and carbonates on their surfaces result in the increase of the interfacial resistance between solid electrolytes and alkali metal anodes. In this study, heat treatment was used to remove the byproduct coating on the surface of Na3Zr2Si2PO12 (NZSP) that also leads to the generation of Na-ion deficient surface simultaneously. This surface chem. approach was used to reduce the interfacial resistance and suppress Na-dendrite growth during Na plating. A combination of the metallic Na wetting test, d. functional theory, and electrochem. measurement was employed to investigate the origins of ultralow interfacial resistance and mechanism between the Na-ion deficient surface and the metallic Na anode. The anal. demonstrates that the Na-ion-deficient surface effectively improves the contact between NZSP and the metallic Na anode. Moreover, an ultrathin passivating layer involving Na2O was formed between NZSP with metallic Na that protected the NZSP electrolyte from the redn. by metallic Na. This study not only motivates the need for further understanding of the surface chem. of NZSP but also provides guidelines for the future design of the Na-ion solid-electrolyte interface.
- 11Wang, C.; Sun, Z.; Zhao, Y.; Wang, B.; Shao, C.; Sun, C.; Zhao, Y.; Li, J.; Jin, H.; Qu, L. Grain Boundary Design of Solid Electrolyte Actualizing Stable All-Solid-State Sodium Batteries. Small 2021, 17, 2103819, DOI: 10.1002/smll.20210381911https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFGmsb%252FO&md5=f28ab54df470d176091ccc32380a5051Grain Boundary Design of Solid Electrolyte Actualizing Stable All-Solid-State Sodium BatteriesWang, Chengzhi; Sun, Zheng; Zhao, Yongjie; Wang, Boyu; Shao, Changxiang; Sun, Chen; Zhao, Yang; Li, Jingbo; Jin, Haibo; Qu, LiangtiSmall (2021), 17 (40), 2103819CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)Advanced inorg. solid electrolytes (SEs) are crit. for all-solid-state alk. metal batteries with high safety and high energy densities. A new interphase design to address the urgent interfacial stability issues against all-solid-state sodium metal batteries (ASSMBs) is proposed. The grain boundary phase of a Mg2+-doped Na3Zr2Si2PO12 conductor (denoted as NZSP-xMg) is manipulated to introduce a favorable Na3-2δMgδPO4-dominant interphase which facilitates its intimate contact with Na metal and works as an electron barrier to suppress Na metal dendrite penetration into the electrolyte bulk. The optimal NZSP-0.2Mg electrolyte endows a low interfacial resistance of 93 Ω cm2 at room temp., over 16 times smaller than that of Na3Zr2Si2PO12. The Na plating/stripping with small polarization is retained under 0.3 mA cm-2 for more than 290 days (7000 h), representing a record high cycling stability of SEs for ASSMBs. An all-solid-state NaCrO2//Na battery is accordingly assembled manifesting a high capacity of 110 mA h g-1 at 1 C for 1755 cycles with almost no capacity decay. Excellent rate capability at 5 C is realized with a high Coulombic efficiency of 99.8%, signifying promising application in solid-state electrochem. energy storage systems.
- 12Zhang, Z.; Zhang, Q.; Shi, J.; Chu, Y. S.; Yu, X.; Xu, K.; Ge, M.; Yan, H.; Li, W.; Gu, L.; Hu, Y.-S.; Li, H.; Yang, X.-Q.; Chen, L.; Huang, X. A Self-Forming Composite Electrolyte for Solid-State Sodium Battery with Ultralong Cycle Life. Adv. Energy Mater. 2017, 7, 1601196, DOI: 10.1002/aenm.201601196There is no corresponding record for this reference.
- 13Li, Z.; Zhu, K.; Liu, P.; Jiao, L. 3D Confinement Strategy for Dendrite-Free Sodium Metal Batteries. Adv. Energy Mater. 2021, 12, 2100359, DOI: 10.1002/aenm.202100359There is no corresponding record for this reference.
- 14Lou, S.; Zhang, F.; Fu, C.; Chen, M.; Ma, Y.; Yin, G.; Wang, J. Interface Issues and Challenges in All-Solid-State Batteries: Lithium, Sodium, and Beyond. Adv. Mater. 2021, 33, 2000721, DOI: 10.1002/adma.20200072114https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsVClt7zM&md5=a6b03c7d6b94b527daae04f5299c2f02Interface Issues and Challenges in All-Solid-State Batteries: Lithium, Sodium, and BeyondLou, Shuaifeng; Zhang, Fang; Fu, Chuankai; Chen, Ming; Ma, Yulin; Yin, Geping; Wang, JiajunAdvanced Materials (Weinheim, Germany) (2021), 33 (6), 2000721CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Owing to the promise of high safety and energy d., all-solid-state batteries are attracting incremental interest as one of the most promising next-generation energy storage systems. However, their widespread applications are inhibited by many tech. challenges, including low-cond. electrolytes, dendrite growth, and poor cycle/rate properties. Particularly, the interfacial dynamics between the solid electrolyte and the electrode is considered as a crucial factor in detg. solid-state battery performance. In recent years, intensive research efforts have been devoted to understanding the interfacial behavior and strategies to overcome these challenges for all-solid-state batteries. Here, the interfacial principle and engineering in a variety of solid-state batteries, including solid-state lithium/sodium batteries and emerging batteries (lithium-sulfur, lithium-air, etc.), are discussed. Specific attention is paid to interface physics (contact and wettability) and interface chem. (passivation layer, ionic transport, dendrite growth), as well as the strategies to address the above concerns. The purpose here is to outline the current interface issues and challenges, allowing for target-oriented research for solid-state electrochem. energy storage. Current trends and future perspectives in interfacial engineering are also presented.
- 15Zhang, Z.; Wenzel, S.; Zhu, Y.; Sann, J.; Shen, L.; Yang, J.; Yao, X.; Hu, Y.-S.; Wolverton, C.; Li, H.; Chen, L.; Janek, J. Na3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries. ACS Appl. Energy Mater. 2020, 3, 7427– 7437, DOI: 10.1021/acsaem.0c0082015https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1eqt7vN&md5=1d1e3b6eab1b8fe2ea14b4d6f557f5eaNa3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State BatteriesZhang, Zhizhen; Wenzel, Sebastian; Zhu, Yizhou; Sann, Joachim; Shen, Lin; Yang, Jing; Yao, Xiayin; Hu, Yong-Sheng; Wolverton, Christopher; Li, Hong; Chen, Liquan; Janek, JurgenACS Applied Energy Materials (2020), 3 (8), 7427-7437CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Solid electrolytes (SEs) offer great potential as the basis for safer rechargeable batteries with high energy d. Aside from excellent ion cond., the stability of SEs against the highly reactive metal anode is also a prerequisite to achieve good performance in solid-state batteries (SSBs). Yet, most SEs are found to have limited thermodn. stability and are unstable against Li/Na metal. With the combination of AC impedance spectroscopy, first-principles calcns., and in situ XPS, we unequivocally reveal that a NaSICON-structured Na3Zr2Si2PO12 electrolyte forms a kinetically stable interface against sodium metal. Prolonged galvanostatic cycling of sym. Na|Na3Zr2Si2PO12|Na cells shows stable plating/stripping behavior of sodium metal at a c.d. of 0.1 mA cm-2 and an areal capacity of 0.5 mA h cm-2 at room temp. Evaluation of Na3Zr2Si2PO12 as an electrolyte in SSBs further demonstrates its good cycling stability for over 120 cycles with very limited capacity degrdn. This work provides strong evidence that Na3Zr2Si2PO12 is one of the few electrolytes that simultaneously achieve superionic cond. and excellent chem./electrochem. stability, making it a very promising alternative to liq. electrolytes. Our findings open up a fertile avenue of exploration for SSBs based on Na3Zr2Si2PO12 and related SEs.
- 16Hou, W.; Guo, X.; Shen, X.; Amine, K.; Yu, H.; Lu, J. Solid Electrolytes and Interfaces in All-solid-state Sodium Batteries: Progress and Perspective. Nano Energy 2018, 52, 279– 291, DOI: 10.1016/j.nanoen.2018.07.03616https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVCgurnF&md5=4555cb61bf61c88d2bcfdf86c897b888Solid electrolytes and interfaces in all-solid-state sodium batteries: Progress and perspectiveHou, Wenru; Guo, Xianwei; Shen, Xuyang; Amine, Khali; Yu, Haijun; Lu, JunNano Energy (2018), 52 (), 279-291CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)All-solid-state sodium batteries are promising candidates for the next generation of energy storage with exceptional safety, reliability and stability. The solid electrolytes are key components for enabling all-solid-state sodium batteries with high electrochem. performances. This Review discusses the current developments on inorg. and org. sodium ions solid electrolytes, including β/β''-alumina, NASICON, sulfides, polymers and others. In particular, the structures, ionic conductivities and fabrications as well as electrochem./chem. stabilities of solid electrolytes are discussed. The effective approaches for forming intimate interfaces between solid electrolytes and electrodes are also reviewed. And perspectives on future developments in the field of solid electrolytes and possible directions to improve interfacial contacts for future practical applications of all-solid-state sodium batteries are included.
- 17Uchida, Y.; Hasegawa, G.; Shima, K.; Inada, M.; Enomoto, N.; Akamatsu, H.; Hayashi, K. Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression. ACS Appl. Energy Mater. 2019, 2, 2913– 2920, DOI: 10.1021/acsaem.9b0025017https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmsFegur0%253D&md5=bab5654226d744c8ea156b6f611f660aInsights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial CompressionUchida, Yasuhiro; Hasegawa, George; Shima, Kazunari; Inada, Miki; Enomoto, Naoya; Akamatsu, Hirofumi; Hayashi, KatsuroACS Applied Energy Materials (2019), 2 (4), 2913-2920CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)A robust ceramic solid electrolyte with high ionic cond. is a key component for all-solid-state batteries (ASSBs). In terms of the demand for high-energy-d. storage, researchers have been tackling various challenges to use metal anodes, where a fundamental understanding on the metal/solid electrolyte interface is of particular importance. The Na+ superionic conductor, so-called NASICON, has high potential for application to ASSBs with a Na anode due to its high Na+ ion cond. at room temp., which has, however, faced a daunting issue of the significantly large interfacial resistance between Na and NASICON. In this work, we have successfully reduced the interfacial resistance as low as 14 Ω cm2 at room temp. by a simple mech. compression of a Na/NASICON assembly. We also demonstrate a fundamental study of the Na/NASICON interface in comparison with the Na/β''-alumina counterpart by means of the electrochem. impedance technique, which elucidates a stark difference between the activation energies for interfacial charge transfer: ∼0.6 eV for Na/NASICON and ∼0.3 eV for Na/β''-alumina. This result suggests the formation of a Na+-conductive interphase layer in pressing Na metal on the NASICON surface at room temp.
- 18Oh, J. A. S.; Wang, Y.; Zeng, Q.; Sun, J.; Sun, Q.; Goh, M.; Chua, B.; Zeng, K.; Lu, L. Intrinsic Low Sodium/NASICON Interfacial Resistance Paving the Way for Room Temperature Sodium-metal Battery. J. Colloid Interface Sci. 2021, 601, 418– 426, DOI: 10.1016/j.jcis.2021.05.12318https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1SktLbI&md5=c885321186dcb7c48c65cbd6774887dbIntrinsic low sodium/NASICON interfacial resistance paving the way for room temperature sodium-metal batteryOh, Jin An Sam; Wang, Yumei; Zeng, Qibin; Sun, Jianguo; Sun, Qiaomei; Goh, Minhao; Chua, Bengwah; Zeng, Kaiyang; Lu, LiJournal of Colloid and Interface Science (2021), 601 (), 418-426CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)Sodium-metal batteries have strong potential to be utilized as stationary high energy d. storage devices. Owing to its high ionic cond., low electronic cond. and relatively easy fabrication, NASICON-structure electrolyte (Na3Zr2Si2PO12) is one of the potential candidates to be considered in the solid-state sodium-metal batteries at room temp. However, the large interfacial resistance between the solid-state electrolyte and the metallic sodium is known to limit the crit. c.d. (CCD) of the cell. In this study, a simple and cost-effective annealing process is introduced to the electrolyte prepn. to improves its interface with metallic sodium. XPS and scanning probe microscopy show that Si forms bonds with the surface functional groups when exposed to the ambient condition. With the removal of surface contamination as well as a partially reduced electrolyte surface, the annealed electrolyte shows an extremely small interfacial resistance of 11 Ω cm2 and a high CCD of 0.9 mA cm-2. This study provides an insight on the electrolyte surface prepn. and its significant in a sodium-metal solid-state battery.
- 19He, M.; Cui, Z.; Chen, C.; Li, Y.; Guo, X. Formation of Self-limited, Stable and Conductive Interfaces between Garnet Electrolytes and Lithium Anodes for Reversible Lithium Cycling in Solid-state Batteries. J. Mater. Chem. A 2018, 6, 11463– 11470, DOI: 10.1039/c8ta02276c19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpslSrtrw%253D&md5=a4af208ef6a2f8f74c514c528aa449daFormation of self-limited, stable and conductive interfaces between garnet electrolytes and lithium anodes for reversible lithium cycling in solid-state batteriesHe, Minghui; Cui, Zhonghui; Chen, Cheng; Li, Yiqiu; Guo, XiangxinJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (24), 11463-11470CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid-state batteries (SSBs) have already attracted significant attention due to their potential to offer high energy d. and excellent safety as compared to the currently used lithium-ion batteries with liq. electrolytes. The use of a lithium anode in SSBs is extremely important to realize these advantages. Starting from the synthesis of a highly conductive cubic garnet solid electrolyte (Li6.375La3Zr1.375Nb0.625O12, LLZNO) using Nb as a structure stabilizer, in this study, we demonstrated the resoln. of interfacial problems between the garnet electrolyte and lithium anode and the integration of the lithium anode into garnet-based SSBs by modifying the as-synthesized LLZNO with a Sn thin film. Due to the Sn modification, the interfacial resistances between the garnet electrolyte and the lithium anode decreased approx. 20 times to only 46.6 Ω cm2. The fast and reversible lithium plating/stripping under high current densities and the excellent battery performance of Li/Sn-LLZNO/LiFePO4 full cells were achieved. This improvement is ascribed to the formation of a Li-Sn alloy interlayer, which severs as a self-limited stable and conductive interface, bridging the garnet electrolyte and the lithium anode and enabling fast and stable lithium transport. As a proof-of-concept, this effective surface modification method will offer inspirations to researchers for overcoming the interfacial problems and promoting the development of high-performance SSBs.
- 20Hao, X.; Zhao, Q.; Su, S.; Zhang, S.; Ma, J.; Shen, L.; Yu, Q.; Zhao, L.; Liu, Y.; Kang, F.; He, Y. B. Constructing Multifunctional Interphase between Li1.4Al0.4Ti1.6(PO4)3 and Li Metal by Magnetron Sputtering for Highly Stable Solid-State Lithium Metal Batteries. Adv. Energy Mater. 2019, 9, 1901604, DOI: 10.1002/aenm.201901604There is no corresponding record for this reference.
- 21Yang, J.; Gao, Z.; Ferber, T.; Zhang, H.; Guhl, C.; Yang, L.; Li, Y.; Deng, Z.; Liu, P.; Cheng, C.; Che, R.; Jaegermann, W.; RenéHausbrand; Huang, Y. Guided-formation of a Favorable Interface for Stabilizing Na Metal Solid-state Batteries. J. Mater. Chem. A 2020, 8, 7828– 7835, DOI: 10.1039/d0ta01498b21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlt1Gitrk%253D&md5=27cf4043b5abb5ba6c29e83ce4073de2Guided-formation of a favorable interface for stabilizing Na metal solid-state batteriesYang, Jiayi; Gao, Zhonghui; Ferber, Thimo; Zhang, Haifeng; Guhl, Conrad; Yang, Liting; Li, Yuyu; Deng, Zhi; Liu, Porun; Cheng, Chuanwei; Che, Renchao; Jaegermann, Wolfram; ReneHausbrand; Huang, YunhuiJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (16), 7828-7835CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The sodium (Na) anode suffers severe interfacial resistance and dendrite issues in a classic NASICON-type Na3Zr2Si2PO12 (NZSP) electrolyte, resulting in poor electrochem. performance for solid-state Na metal batteries. There has been little success in the redn. of interfacial resistance in recent years. The exact mechanism of this resistance has not been fully understood because of little information about the interface. In this work, the large interfacial resistance issue and the metal dendrite problem between the Na anode and NZSP are effectively addressed by introducing a TiO2 film as an active interphase. Quasiinsitu XPS is employed to uncover the interphase formation mechanism at the Na/TiO2-NZSP electrolyte interface. The quasiinsitu XPS results confirm the formation of a sodiated-TiO2 interphase upon stepwise Na evapn. on the surface of the NZSP electrolyte. Further investigation by molten Na contact angle measurements, impedance spectroscopy and DFT calcns. demonstrates that the sodiated-TiO2 interphase promotes Na ion transport between the Na anode and NZSP electrolyte. Moreover, the electrostatic potential formed at the NZSP/NaxTiO2 interface can effectively reduce electronic cond. at the interface and hence prevent the growth of sodium dendrites. A representative paradigm for interphase design is provided to address the interface contact for developing stable solid-state batteries with high performance.
- 22Yang, J.; Xu, H.; Wu, J.; Gao, Z.; Hu, F.; Wei, Y.; Li, Y.; Liu, D.; Li, Z.; Huang, Y. Improving Na/Na3Zr2Si2PO12 Interface via SnOx/Sn Film for High-Performance Solid-State Sodium Metal Batteries. Small Methods 2021, 5, 2100339, DOI: 10.1002/smtd.20210033922https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvVKks7o%253D&md5=39b17fb96700d176b611f8763fc13e11Improving Na/Na3Zr2Si2PO12 Interface via SnOx/Sn Film for High-Performance Solid-State Sodium Metal BatteriesYang, Jiayi; Xu, Henghui; Wu, Jingyi; Gao, Zhonghui; Hu, Fei; Wei, Ying; Li, Yuyu; Liu, Dezhong; Li, Zhen; Huang, YunhuiSmall Methods (2021), 5 (9), 2100339CODEN: SMMECI; ISSN:2366-9608. (Wiley-VCH Verlag GmbH & Co. KGaA)Sodium (Na) metal batteries have attracted much attention due to their rich resources, low cost, and high energy d. As a promising solid electrolyte, Na3Zr2Si2PO12 (NZSP) is expected to be used in solid-state Na metal batteries addressing the safety concerns. However, due to the poor contact between NZSP and the Na metal, the interfacial resistance is too large to gain proper performance for practical solid-state batteries (SSBs) application. Here, a SnOx/Sn film is successfully introduced to improve the interface between Na and NZSP for enhancing the electrochem. performance of SSBs. As a result, the Na/NZSP interfacial resistance is dramatically reduced from 581 to 3 Ω cm2. The modified Na||Na sym. cell keeps cycling over 1500 h with an overpotential of 40 mV at 0.1 mA cm-2 at room temp. Even at current densities of 0.3 and 0.5 mA cm-2, the cell still maintains an excellent cyclability. When coupled with NaTi2(PO4)3 and a Na3V2(PO4)3 cathode, the full-cell demonstrates a good performance at 0.2 C and 1°C, resp. The present work provides an effective way to solve the interface issue of SSBs.
- 23Gao, H.; Xue, L.; Xin, S.; Park, K.; Goodenough, J. B. A Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium Batteries. Angew. Chem., Int. Ed. Engl. 2017, 56, 5541– 5545, DOI: 10.1002/anie.20170200323https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1cvntFemtw%253D%253D&md5=d0a306f7920ff90f30e6a04c2ae79a1fA Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium BatteriesGao Hongcai; Xue Leigang; Xin Sen; Park Kyusung; Goodenough John BAngewandte Chemie (International ed. in English) (2017), 56 (20), 5541-5545 ISSN:.The development of all-solid-state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge-discharge cycle. The introduction of a plastic-crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid-state sodium cells with 1) solid electrolyte Na3 Zr2 (Si2 PO4 ) particles versus 2) plastic-crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic-crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all-solid-state battery cells.
- 24Xu, Y.; Wang, C.; Matios, E.; Luo, J.; Hu, X.; Yue, Q.; Kang, Y.; Li, W. Sodium Deposition with a Controlled Location and Orientation for Dendrite-Free Sodium Metal Batteries. Adv. Energy Mater. 2020, 10, 2002308, DOI: 10.1002/aenm.20200230824https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVylsbbF&md5=ec4a7e511c150ec2d432a673fceba435Sodium Deposition with a Controlled Location and Orientation for Dendrite-Free Sodium Metal BatteriesXu, Ying; Wang, Chuanlong; Matios, Edward; Luo, Jianmin; Hu, Xiaofei; Yue, Qin; Kang, Yijin; Li, WeiyangAdvanced Energy Materials (2020), 10 (44), 2002308CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Sodium is one of the most promising alternatives to lithium as an anode material for next-generation batteries. However, severe Na dendrite growth hinders its practical implementation. Here, a polyacrylonitrile (PAN) fiber film coated with a thin layer of tin on the bottom side (closing to battery case) serves as a scaffold for Na deposition. Due to the low nucleation barrier enabled by the Sn layer, Na deposition spontaneously occurs at the bottom of the scaffold, and then is homogeneously confined within its 3D network because of the decreased local c.d. caused by 3D structure and uniform Na+ distribution regulated by the sodiophilic PAN. With this well-controlled orientation of Na deposition, the Na-PAN/Sn electrode delivers a high Coulombic efficiency of 99.5% in Na plating/stripping at 5 mA cm-2, stable operation for over 2500 h in sym. batteries at 2 mA cm-2, and excellent cyclic stability and rate capability in Na metal full batteries.
- 25Zhang, Q.; Lu, Y.; Guo, W.; Shao, Y.; Liu, L.; Lu, J.; Rong, X.; Han, X.; Li, H.; Chen, L.; Hu, Y.-S. Hunting Sodium Dendrites in NASICON-Based Solid-State Electrolytes. Energy Mater. Adv. 2021, 2021, 1, DOI: 10.34133/2021/9870879There is no corresponding record for this reference.
- 26Miao, X.; Di, H.; Ge, X.; Zhao, D.; Wang, P.; Wang, R.; Wang, C.; Yin, L. AlF3-modified Anode-electrolyte Interface for Effective Na Dendrites Restriction in NASICON-based Solid-state Electrolyte. Energy Storage Mater. 2020, 30, 170– 178, DOI: 10.1016/j.ensm.2020.05.011There is no corresponding record for this reference.
- 27Lu, Y.; Alonso, J. A.; Yi, Q.; Lu, L.; Wang, Z. L.; Sun, C. A High-Performance Monolithic Solid-State Sodium Battery with Ca2+ Doped Na3Zr2Si2PO12 Electrolyte. Adv. Energy Mater. 2019, 9, 1901205, DOI: 10.1002/aenm.201901205There is no corresponding record for this reference.
- 28Han, F.; Westover, A. S.; Yue, J.; Fan, X.; Wang, F.; Chi, M.; Leonard, D. N.; Dudney, N. J.; Wang, H.; Wang, C. High Electronic Conductivity as the Origin of Lithium Dendrite Formation within Solid Electrolytes. Nat. Energy 2019, 4, 187– 196, DOI: 10.1038/s41560-018-0312-z28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmslGktbc%253D&md5=bc9f7d5bd77f27144060254fea0474f1High electronic conductivity as the origin of lithium dendrite formation within solid electrolytesHan, Fudong; Westover, Andrew S.; Yue, Jie; Fan, Xiulin; Wang, Fei; Chi, Miaofang; Leonard, Donovan N.; Dudney, Nancy J.; Wang, Howard; Wang, ChunshengNature Energy (2019), 4 (3), 187-196CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Solid electrolytes (SEs) are widely considered as an 'enabler' of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S-P2S5 is actually much easier than that in liq. electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concn. profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concn. in LiPON can be obsd., we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic cond. of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic cond., rather than further increasing the ionic cond. of SEs, is therefore crit. for the success of all-solid-state Li batteries.
- 29Tu, Q.; Shi, T.; Chakravarthy, S.; Ceder, G. Understanding Metal Propagation in Solid Electrolytes Due to Mixed Ionic-electronic Conduction. Matter 2021, 4, 3248– 3268, DOI: 10.1016/j.matt.2021.08.00429https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xislyhsbw%253D&md5=420566d1ad838466a9c7fad90678041fUnderstanding metal propagation in solid electrolytes due to mixed ionic-electronic conductionTu, Qingsong; Shi, Tan; Chakravarthy, Srinath; Ceder, GerbrandMatter (2021), 4 (10), 3248-3268CODEN: MATTCG; ISSN:2590-2385. (Elsevier Inc.)Metal penetration into a solid electrolyte (SE) is one of the crit. problems impeding the practical application of solid-state batteries. In this study, we investigate the conditions under which electronic cond. of the SE can lead to metal deposition and fracture within the SE. Three different stages for void filling (metal plating initiation, metal growth, and metal compression) in the SE are identified. We show that a micron-size isolated void in the SE near the anode can be quickly filled in by metal and fractured when the developed pressure in the void grows larger than the max. pressure the SE material can sustain. We find that the anode voltage and applied c.d. play a significant role in detg. the vulnerability to metal deposition. We discuss several strategies to prevent electronic cond.-driven metal propagation in electrolytes that are not fully dense, including the densified layers between the anode and SE.
- 30Ping, W.; Wang, C.; Lin, Z.; Hitz, E.; Yang, C.; Wang, H.; Hu, L. Reversible Short-Circuit Behaviors in Garnet-Based Solid-State Batteries. Adv. Energy Mater. 2020, 10, 2000702, DOI: 10.1002/aenm.20200070230https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptlKqu70%253D&md5=bb2e893b64c37040488744a6e8f82e71Reversible Short-Circuit Behaviors in Garnet-Based Solid-State BatteriesPing, Weiwei; Wang, Chengwei; Lin, Zhiwei; Hitz, Emily; Yang, Chunpeng; Wang, Howard; Hu, LiangbingAdvanced Energy Materials (2020), 10 (25), 2000702CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Garnet-based solid-state electrolytes (SSEs) are attractive for solid-state lithium metal batteries due to their wide electrochem. window, high cond., and excellent stability against lithium metal. However, the risk of short-circuit encumbers the cycle life and capacity of garnet-based solid-state batteries without clear reason or mechanism. Here, reversible short-circuit behavior in the garnet-based solid-state batteries, which differs from the short-circuit in liq. cells, is reported for the first time. In situ neutron depth profiling is adopted to quant. measure Li transport, which helps forecast and confirm the reversible nature of the short-circuit in garnet-based batteries. A real-time Li accumulation monitoring system of NMC//CNT/garnet/Li cell is designed to reveal the Li dendrite formation mechanism. The voltage drops of the CNT monitoring electrode during the charging process indicate the formation of Li dendrites inside the garnet bulk, while the smooth voltage profile during the discharging process demonstrates the disappearance of the short-circuit. This is the first confirmation of short-circuit behavior that provides clarification of the Li dendrite formation mechanism in garnet-based solid-state batteries, which is shown to be a reversible process caused by the low ionic cond. and non-negligible electronic cond. of garnet SSEs.
- 31Gao, B.; Jalem, R.; Tian, H. K.; Tateyama, Y. Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte. Adv. Energy Mater. 2022, 12, 2102151, DOI: 10.1002/aenm.20210215131https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXis12lu7jL&md5=a9fd48dd2f10160e7563a7ed3f08fbecRevealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid ElectrolyteGao, Bo; Jalem, Randy; Tian, Hong-Kang; Tateyama, YoshitakaAdvanced Energy Materials (2022), 12 (3), 2102151CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)For real applications of all-solid-state batteries (ASSBs) to be realized, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the at.-scale defect stabilities and transport of ions around GBs is still far from understood. Here, a first-principles investigation on the promising garnet Li7La3Zr2O12 (LLZO) solid electrolyte (SE) GBs is carried out. The study reveals a GB-dependent behavior for the Li-ion transport correlated to the diffusion network. Of particular note, the Σ3(112) tilt GB model exhibits a quite high Li-ion cond. comparable to that in bulk, and a fast intergranular diffusion, contrary to former discovered. Moreover, the uncovered preferential electron localization at the Σ3(112) GB leads to an increase in the electronic cond. at the GB, and the Li accumulation at the coarse GBs is revealed from the neg. Li interstitial formation energies. These factors play important roles in the dendrite formation along the GBs during Li plating in the LLZO|Li cell. These findings suggest strategies for the optimization of synthesis conditions and coating materials at the interface for preventing dendrite formation. The present comprehensive simulations provide new insights into the GB effect and engineering of the SE in ASSBs.
- 32Huo, H.; Gao, J.; Zhao, N.; Zhang, D.; Holmes, N. G.; Li, X.; Sun, Y.; Fu, J.; Li, R.; Guo, X.; Sun, X. A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries. Nat. Commun. 2021, 12, 176, DOI: 10.1038/s41467-020-20463-y32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhtF2gu7Y%253D&md5=e26bd5e66afda0fc3090244e6e8d883bA flexible electron-blocking interfacial shield for dendrite-free solid lithium metal batteriesHuo, Hanyu; Gao, Jian; Zhao, Ning; Zhang, Dongxing; Holmes, Nathaniel Graham; Li, Xiaona; Sun, Yipeng; Fu, Jiamin; Li, Ruying; Guo, Xiangxin; Sun, XueliangNature Communications (2021), 12 (1), 176CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technol. due to their enhanced energy d. and safety. However, the high electronic cond. of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven elec.-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, we propose a flexible electron-blocking interfacial shield (EBS) to protect garnet electrolytes from the electronic degrdn. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li vol. change, maintaining the integrity of the interface during repeated cycling. D. functional theory calcns. show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved crit. c.d. of 1.2 mA cm-2 and stable cycling for over 400 h at 1 mA cm-2 (1 mAh cm-2) at room temp. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.
- 33Guo, W.; Han, Q.; Jiao, J.; Wu, W.; Zhu, X.; Chen, Z.; Zhao, Y. In situ Construction of Robust Biphasic Surface Layers on Lithium Metal for Lithium-Sulfide Batteries with Long Cycle Life. Angew. Chem., Int. Ed. Engl. 2021, 60, 7267– 7274, DOI: 10.1002/anie.20201504933https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3svivFWmtA%253D%253D&md5=404bf9a416299d8efbe48670f871c92eIn situ Construction of Robust Biphasic Surface Layers on Lithium Metal for Lithium-Sulfide Batteries with Long Cycle LifeGuo Wei; Han Qing; Jiao Junrong; Wu Wenhao; Zhu Xuebing; Chen Zhonghui; Zhao YongAngewandte Chemie (International ed. in English) (2021), 60 (13), 7267-7274 ISSN:.Lithium-sulfur (Li-S) batteries have potential in high energy density battery systems. However, intermediates of lithium polysulfides (LiPSs) can easily shuttle to the Li anode and react with Li metal to deplete the active materials and cause rapid failure of the battery. A facile solution pretreatment method for Li anodes involving a solution of metal fluorides/dimethylsulfoxide was developed to construct robust biphasic surface layers (BSLs) in situ. The BSLs consist of lithiophilic alloy (Lix M) and LiF phases on Li metal, which inhibit the shuttle effect and increase the cycle life of Li-S batteries. The BSLs allow Li(+) transport and they inhibit dendrite growth and shield the Li anodes from corrosive reaction with LiPSs. Li-S batteries containing BSLs-Li anodes demonstrate excellent cycling over 1000 cycles at 1 C and simultaneously maintain a high coulombic efficiency of 98.2 %. Based on our experimental and theoretical results, we propose a strategy for inhibition of the shuttle effect that produces high stability Li-S batteries.
- 34Li, W.; Gao, J.; Tian, H.; Li, X.; He, S.; Li, J.; Wang, W.; Li, L.; Li, H.; Qiu, J.; Zhou, W. SnF2-Catalyzed Formation of Polymerized Dioxolane as Solid Electrolyte and its Thermal Decomposition Behavior. Angew. Chem., Int. Ed. Engl. 2021, 61, e202114805 DOI: 10.1002/anie.202114805There is no corresponding record for this reference.
- 35Pathak, R.; Chen, K.; Gurung, A.; Reza, K. M.; Bahrami, B.; Pokharel, J.; Baniya, A.; He, W.; Wu, F.; Zhou, Y.; Xu, K.; Qiao, Q. Fluorinated Hybrid Solid-electrolyte-interphase for Dendrite-free Lithium Deposition. Nat. Commun. 2020, 11, 93, DOI: 10.1038/s41467-019-13774-235https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlslWjtg%253D%253D&md5=b3cc4ece7d7a6287dc716f618f6c5672Fluorinated hybrid solid-electrolyte-interphase for dendrite-free lithium depositionPathak, Rajesh; Chen, Ke; Gurung, Ashim; Reza, Khan Mamun; Bahrami, Behzad; Pokharel, Jyotshna; Baniya, Abiral; He, Wei; Wu, Fan; Zhou, Yue; Xu, Kang; Qiao, QiquanNature Communications (2020), 11 (1), 93CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Lithium metal anodes have attracted extensive attention owing to their high theor. specific capacity. However, the notorious reactivity of lithium prevents their practical applications, as evidenced by the undesired lithium dendrite growth and unstable solid electrolyte interphase formation. Here, we develop a facile, cost-effective and one-step approach to create an artificial lithium metal/electrolyte interphase by treating the lithium anode with a tin-contg. electrolyte. As a result, an artificial solid electrolyte interphase composed of lithium fluoride, tin, and the tin-lithium alloy is formed, which not only ensures fast lithium-ion diffusion and suppresses lithium dendrite growth but also brings a synergistic effect of storing lithium via a reversible tin-lithium alloy formation and enabling lithium plating underneath it. With such an artificial solid electrolyte interphase, lithium sym. cells show outstanding plating/stripping cycles, and the full cell exhibits remarkably better cycling stability and capacity retention as well as capacity utilization at high rates compared to bare lithium.
- 36Wang, J.; Zhang, Z.; Ying, H.; Han, G.; Han, W.-Q. In-situ Formation of LiF-rich Composite Interlayer for Dendrite-free All-solid-state Lithium Batteries. Chem. Eng. J. 2021, 411, 128534, DOI: 10.1016/j.cej.2021.12853436https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvF2iu7o%253D&md5=af1dc43df553b2f5214ff6244746b32eIn-situ formation of LiF-rich composite interlayer for dendrite-free all-solid-state lithium batteriesWang, Jianli; Zhang, Zhao; Ying, Hangjun; Han, Gaorong; Han, Wei-QiangChemical Engineering Journal (Amsterdam, Netherlands) (2021), 411 (), 128534CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)Polyethylene oxide (PEO)-based composite electrolytes are considered as competent candidates to achieve high energy d. all-solid-state lithium batteries (ASSLBs) due to good flexibility, which can effectively solve the problem of large interfacial resistance with electrodes. However, poor mech. strength and low Li+ transference no. can't restrain the formation and growth of Li dendrites, leading to parasitic reaction between electrolyte and Li anode and unsatisfied coulombic efficiency. Herein, Li metal is pre-treated by poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP)/CuF2 composite to form a stable interlayer on the anode. In-situ reaction of CuF2 with Li greatly improves the contact between PVDF-HFP layer and Li anode, forming a LiF-rich modified layer. The interlayer with high mech. strength and ionic cond. can not only suppress the formation of Li dendrites, but also achieve the growth restriction and elimination of dendrites. Moreover, excellent elasticity and strong adhesion with Li anode can ensure the structure stability of modified layer during dynamic plating/stripping of Li. Applied in ASSLBs with PEO-based electrolyte, PVDF-HFP/CuF2 modified sym. Li cells demonstrate increased crit. c.d. and extended cycle life than that of bare Li or single CuF2 treated Li. Furtherly, the ASSLBs with LiFePO4 cathode show excellent cycle stability and high coulombic efficiency over 1000 cycles at 1 C.
- 37Gross, M. M.; Small, L. J.; Peretti, A. S.; Percival, S. J.; Rodriguez, M. A.; Spoerke, E. D. Tin-based Ionic Chaperone Phases to Improve Low Temperature Molten Sodium-NaSICON Interfaces. J. Mater. Chem. A 2020, 8, 17012– 17018, DOI: 10.1039/d0ta03571h37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFertL7M&md5=7b2bca49d74a8866d408b9c30f7ab248Tin-based ionic chaperone phases to improve low temperature molten sodium-NaSICON interfacesGross, Martha M.; Small, Leo J.; Peretti, Amanda S.; Percival, Stephen J.; Rodriguez, Mark A.; Spoerke, Erik D.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17012-17018CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)High temp. operation of molten sodium batteries impacts cost, reliability, and lifetime, and has limited the widespread adoption of these grid-scale energy storage technologies. Poor charge transfer and high interfacial resistance between molten sodium and solid-state electrolytes, however, prevents the operation of molten sodium batteries at low temps. Here, in situ formation of tin-based chaperone phases on solid state NaSICON ion conductor surfaces is shown in this work to greatly improve charge transfer and lower interfacial resistance in sodium sym. cells operated at 110°C at current densities up to an aggressive 50 mA cm-2. It is shown that static wetting testing, as measured by the contact angle of molten sodium on NaSICON, does not accurately predict battery performance due to the dynamic formation of a chaperone NaSn phase during cycling. This work demonstrates the promise of sodium intermetallic-forming coatings for the advancement of low temp. molten sodium batteries by improved mating of sodium-NaSICON surfaces and reduced interfacial resistance.
- 38Chi, X.; Hao, F.; Zhang, J.; Wu, X.; Zhang, Y.; Gheytani, S.; Wen, Z.; Yao, Y. A High-energy Quinone-based All-solid-state Sodium Metal Battery. Nano Energy 2019, 62, 718– 724, DOI: 10.1016/j.nanoen.2019.06.00538https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFOksbbI&md5=dfcd1dd53235201dcb03758c30929209A high-energy quinone-based all-solid-state sodium metal batteryChi, Xiaowei; Hao, Fang; Zhang, Jibo; Wu, Xiangwei; Zhang, Ye; Gheytani, Saman; Wen, Zhaoyin; Yao, YanNano Energy (2019), 62 (), 718-724CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)Redox-active org. electrode materials show great promise as an addn. to inorg. electrode materials for grid-scale energy storage due to their ability to store various cations, moderate operating potentials, and relatively high theor. specific capacities. However, most org. compds. when reduced suffer from dissoln. in org. liq. electrolytes, resulting in poor cycling stability. Herein, we show for the first time an all-solid-state battery based on an oxide-based solid electrolyte, beta-alumina solid electrolyte (BASE), that not only enables stable cycling of an org. quinone-based compd. (pyrene-4,5,9,10-tetraone, PTO) with high specific energy (∼900 Wh kg-1) at the material level but also demonstrates the best cycling stability (1000 h at 0.5 mA cm-2) with a sodium metal anode among any reported all-solid-state sodium metal batteries (ASSMBs). Anode-electrolyte interfacial resistance was successfully reduced by introducing a Sn thin film between the Na anode and BASE. The cathode-electrolyte interfacial barrier was overcome with a mech. compliant PTO-poly(ethylene oxide)-carbon composite cathode that forms interpenetrating ionic and electronic pathways which favor full utilization of PTO. This proof-of-concept demonstration combining org. electrode materials with an oxide-based solid electrolyte and the interface modification strategies pave the way for ASSMBs with higher capacity and cycling stability.
- 39Liang, X.; Pang, Q.; Kochetkov, I. R.; Sempere, M. S.; Huang, H.; Sun, X.; Nazar, L. F. A Facile Surface Chemistry Route to a Stabilized Lithium Metal Anode. Nat. Energy 2017, 2, 17119, DOI: 10.1038/nenergy.2017.11939https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVehtLk%253D&md5=5be4236643323e51b90ddb41154284e7A facile surface chemistry route to a stabilized lithium metal anodeLiang, Xiao; Pang, Quan; Kochetkov, Ivan R.; Sempere, Marina Safont; Huang, He; Sun, Xiaoqi; Nazar, Linda F.Nature Energy (2017), 2 (9), 17119CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Lithium metal is a highly desirable anode for lithium rechargeable batteries, having the highest theor. specific capacity and lowest electrochem. potential of all material candidates. Its most notable problem is dendritic growth upon Li plating, which is a major safety concern and exacerbates reactivity with the electrolyte. Here we report that Li-rich composite alloy films synthesized in situ on lithium by a simple and low-cost methodol. effectively prevent dendrite growth. This is attributed to the synergy of fast lithium ion migration through Li-rich ion conductive alloys coupled with an electronically insulating surface component. The protected lithium is stabilized to sustain electrodeposition over 700 cycles (1,400 h) of repeated plating/stripping at a practical c.d. of 2 mA cm-2 and a 1,500 cycle-life is realized for a cell paired with a Li4Ti5O12 pos. electrode. These findings open up a promising avenue to stabilize lithium metal with surface layers having targeted properties.
- 40Chu, I.-H.; Kompella, C. S.; Nguyen, H.; Zhu, Z.; Hy, S.; Deng, Z.; Meng, Y. S.; Ong, S. P. Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor. Sci. Rep. 2016, 6, 33733, DOI: 10.1038/srep3373340https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFGrsb3K&md5=4c0f43f314bd6495f2bacfefc8d4bf80Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic ConductorChu, Iek-Heng; Kompella, Christopher S.; Nguyen, Han; Zhu, Zhuoying; Hy, Sunny; Deng, Zhi; Meng, Ying Shirley; Ong, Shyue PingScientific Reports (2016), 6 (), 33733CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)All-solid-state sodium-ion batteries are promising candidates for large-scale energy storage applications. The key enabler for an all-solid-state architecture is a sodium solid electrolyte that exhibits high Na+ cond. at ambient temps., as well as excellent phase and electrochem. stability. In this work, we present a first-principles-guided discovery and synthesis of a novel Cl-doped tetragonal Na3PS4 (t-Na3-xPS4-xClx) solid electrolyte with a room-temp. Na+ cond. exceeding 1 mS cm-1. We demonstrate that an all-solid-state TiS2/t-Na3-xPS4-xClx/Na cell utilizing this solid electrolyte can be cycled at room-temp. at a rate of C/10 with a capacity of about 80 mAh g-1 over 10 cycles. We provide evidence from d. functional theory calcns. that this excellent electrochem. performance is not only due to the high Na+ cond. of the solid electrolyte, but also due to the effect that "salting" Na3PS4 has on the formation of an electronically insulating, ionically conducting solid electrolyte interphase.
- 41Hu, P.; Zhang, Y.; Chi, X.; Kumar Rao, K.; Hao, F.; Dong, H.; Guo, F.; Ren, Y.; Grabow, L. C.; Yao, Y. Stabilizing the Interface between Sodium Metal Anode and Sulfide-Based Solid-State Electrolyte with an Electron-Blocking Interlayer. ACS Appl. Mater. Interfaces 2019, 11, 9672– 9678, DOI: 10.1021/acsami.8b1998441https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjvFyjsbo%253D&md5=fe453f83c2453443bde2decba11aa4dbStabilizing the Interface between Sodium Metal Anode and Sulfide-Based Solid-State Electrolyte with an Electron-Blocking InterlayerHu, Pu; Zhang, Ye; Chi, Xiaowei; Kumar Rao, Karun; Hao, Fang; Dong, Hui; Guo, Fangmin; Ren, Yang; Grabow, Lars C.; Yao, YanACS Applied Materials & Interfaces (2019), 11 (10), 9672-9678CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Sulfide-based Na-ion conductors are promising electrolytes for all-solid-state sodium batteries (ASSSBs) because of high ionic cond. and favorable formability. However, no effective strategy has been reported for long-duration Na cycling with sulfide-based electrolytes because of interfacial challenges. Here it is demonstrated that a cellulose-poly(ethylene oxide) (CPEO) interlayer can stabilize the interface between sulfide electrolyte (Na3SbS4) and Na by shutting off the electron pathway of the electrolyte decompn. reaction. As a result, stable Na plating/stripping is achieved for 800 cycles at 0.1 mA cm-2 in all-solid-state devices at 60°.
- 42Zheng, G.; Lee, S. W.; Liang, Z.; Lee, H.-W.; Yan, K.; Yao, H.; Wang, H.; Li, W.; Chu, S.; Cui, Y. Interconnected Hollow Carbon Nanospheres for Stable Lithium Metal Anodes. Nat. Nanotechnol. 2014, 9, 618– 623, DOI: 10.1038/nnano.2014.15242https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1ait77L&md5=0778b04fefcd0b158df78c2d7bfc3633Interconnected hollow carbon nanospheres for stable lithium metal anodesZheng, Guangyuan; Lee, Seok Woo; Liang, Zheng; Lee, Hyun-Wook; Yan, Kai; Yao, Hongbin; Wang, Haotian; Li, Weiyang; Chu, Steven; Cui, YiNature Nanotechnology (2014), 9 (8), 618-623CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)For future applications in portable electronics, elec. vehicles and grid storage, batteries with higher energy storage d. than existing lithium ion batteries need to be developed. Recent efforts in this direction have focused on high-capacity electrode materials such as lithium metal, silicon and tin as anodes, and sulfur and oxygen as cathodes. Lithium metal would be the optimal choice as an anode material, because it has the highest specific capacity (3,860 mAh g-1) and the lowest anode potential of all. However, the lithium anode forms dendritic and mossy metal deposits, leading to serious safety concerns and low Coulombic efficiency during charge/discharge cycles. Although advanced characterization techniques have helped shed light on the lithium growth process, effective strategies to improve lithium metal anode cycling remain elusive. Here, we show that coating the lithium metal anode with a monolayer of interconnected amorphous hollow carbon nanospheres helps isolate the lithium metal depositions and facilitates the formation of a stable solid electrolyte interphase. We show that lithium dendrites do not form up to a practical c.d. of 1 mA cm-2. The Coulombic efficiency improves to ∼99% for more than 150 cycles. This is significantly better than the bare unmodified samples, which usually show rapid Coulombic efficiency decay in fewer than 100 cycles. Our results indicate that nanoscale interfacial engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes.
- 43Xu, M.; Li, Y.; Ihsan-Ul-Haq, M.; Mubarak, N.; Liu, Z.; Wu, J.; Luo, Z.; Kim, J. K. NaF-rich Solid Electrolyte Interphase for Dendrite-free Sodium Metal Batteries. Energy Storage Mater. 2022, 44, 477– 486, DOI: 10.1016/j.ensm.2021.10.038There is no corresponding record for this reference.
- 44Yan, C.; Cheng, X.-B.; Yao, Y.-X.; Shen, X.; Li, B.-Q.; Li, W.-J.; Zhang, R.; Huang, J.-Q.; Li, H.; Zhang, Q. An Armored Mixed Conductor Interphase on a Dendrite-Free Lithium-Metal Anode. Adv. Mater. 2018, 30, 1804461, DOI: 10.1002/adma.201804461There is no corresponding record for this reference.
- 45Tian, H.; Liu, S.; Deng, L.; Wang, L.; Dai, L. New-type Hf-based NASICON Electrolyte for Solid-state Na-ion Batteries with Superior Long-cycling Stability and Rate Capability. Energy Storage Mater. 2021, 39, 232– 238, DOI: 10.1016/j.ensm.2021.04.026There is no corresponding record for this reference.
- 46Tamwattana, O.; Park, H.; Kim, J.; Hwang, I.; Yoon, G.; Hwang, T.-h.; Kang, Y.-S.; Park, J.; Meethong, N.; Kang, K. High-Dielectric Polymer Coating for Uniform Lithium Deposition in Anode-Free Lithium Batteries. ACS Energy Lett. 2021, 6, 4416– 4425, DOI: 10.1021/acsenergylett.1c0222446https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisFSgtbbP&md5=843c3bb5011b28729b34dc2725b6bc79High-Dielectric Polymer Coating for Uniform Lithium Deposition in Anode-Free Lithium BatteriesTamwattana, Orapa; Park, Hyeokjun; Kim, Jihyeon; Hwang, Insang; Yoon, Gabin; Hwang, Tae-hyun; Kang, Yoon-Sok; Park, Jinhwan; Meethong, Nonglak; Kang, KisukACS Energy Letters (2021), 6 (12), 4416-4425CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)The use of lithium metal either in an anode or anode-free configuration is envisaged as the most promising way to boost the energy d. of the current lithium-ion battery system. Nevertheless, the uncontrolled lithium dendritic growth inhibits practical utilization of lithium metal as an anode due to safety concerns and low Coulombic efficiency. In this work, we show that when a high-dielec. SEI is coated on a current collector, it can effectively promote a uniform lithium deposition by decreasing the overpotential between the surfaces, lowering the local c.d. and suppressing lithium protrusions. Using a PVDF (polyvinylidene difluoride)-based dielec. medium, it is demonstrated that varying the dielec. properties of PVDF by crystallinity control can regulate the lithium deposition mechanisms. Moreover, when the dielec. properties of PVDF film are tailored by the inclusion of dielec. nanoparticles, a selective formation of high-dielec. β-PVDF phase is induced during its film formation (LiF@PVDF), which synergistically promotes uniform lithium deposition/stripping in an anode-free half-cell setup.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00243.
Experimental section; comparison of electrochemical performance of solid sodium-ion batteries; XRD spectra of sodium metal after cycling; schematic diagram of MIE@NHSP; XRD pattern of pure SnF2-modified NHSP; Nyquist plots, voltage profiles, and top-view SEM images with different concentrations of SnF2:NaCl; comparison of DC conductivity of interface layers with and without NaCl; EIS comparison of symmetric cells with EBI@NHSP and MIE@NHSP; impedance analysis results of EBI@NHSP and MIE@NHSP symmetric cells; top-view SEM images of EBI@NHSP, pure NHSP and MIE@NHSP before and after cycling; side-view SEM images of EBI@NHSP and MIE@NHSP before and after cycling; XPS spectra of Hf 4f; XRD pattern of EBI pure NHSP during cycling; galvanostatic charge/discharge profiles of the SnF2|Na battery; galvanostatic cycling of EBI@NHSP; voltage profile of pure NHSP; voltage profile of MIE@NHSP; and long-cycle of the full cell of Na/NVP (PDF)
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