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  5. 硫化物固态电解质界面稳定性：机制、挑战与协同工程策略

硫化物固态电解质界面稳定性：机制、挑战与协同工程策略

文献检索匿名用户发表于 2026年05月21日 17:1527阅读
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硫化物固态电解质界面稳定性综述框架

摘要 (Abstract)

  • 简要介绍硫化物固态电解质（SSEs）在全固态电池（ASSBs）中的重要性。
  • 指出SSEs面临的关键挑战，特别是界面稳定性和由此产生的电池性能问题。
  • 概述本综述的结构和主要内容，包括对界面问题的深入分析、现有解决方案、未来方向。

1. 引言 (Introduction)

  • 1.1. 锂离子电池的局限性与全固态电池的兴起
    • 传统液态锂离子电池的优势及其在能量密度、安全性方面的固有局限性（例如，有机液态电解质的易燃性，枝晶生长问题）。
    • 引出全固态电池作为下一代能源存储技术，其高安全性、高能量密度、简单封装和宽工作温度范围的优势。
  • 1.2. 固态电解质的重要性与硫化物固态电解质的优势
    • 强调固态电解质是ASSBs的核心组成部分。
    • 介绍不同类型的固态电解质（聚合物基、氧化物基、硫化物基）。
    • 突出硫化物固态电解质的独特优势：
      • 高离子电导率，甚至可与商业有机液态电解质媲美或更高。
      • 良好的机械特性，适合层压加工。
      • 较小的电负性和对Li离子的结合能，以及较大的原子半径，有利于高离子电导率。
  • 1.3. 硫化物固态电解质面临的挑战：聚焦界面问题
    • 尽管有诸多优势，硫化物固态电解质仍面临几个关键挑战：
      • 窄的电化学稳定窗口。
      • 与电极之间不稳定的界面（这是本综述的重点）。
      • 锂枝晶形成（特别是在与锂金属阳极接触时）。
      • 空气稳定性差（与湿气反应生成H2S）。
    • 明确本综述的目标：深入探讨硫化物固态电解质与电极之间的界面问题，分析其产生机制，总结现有解决方案，并展望未来研究方向。
  • 1.4. 综述结构
    • 简要介绍后续章节将涵盖的内容（例如，阳极/SSE界面、阴极/SSE界面、通用界面稳定策略、未来展望）。

2. 硫化物固态电解质的特性与合成 (Properties and Synthesis of Sulfide Solid Electrolytes)

  • 2.1. 结构与离子传输机制
    • 介绍常见的硫化物电解质类型，例如Li-P-S体系（如Li3PS4, Li6PS5Cl, Li7P3S11）和Li-Sn-S, Li-Si-S体系。
    • 简述离子电导率的决定因素，例如晶格结构、缺陷、Li离子迁移路径等。
    • 讨论无序结构对化学键合、电化学性能和界面稳定性的影响。
  • 2.2. 合成方法
    • 简要提及常见的合成方法（例如，机械球磨、固态反应、溶剂热法等）。
    • 讨论不同合成方法对材料结构和性能的影响。
  • 2.3. 固有稳定性问题
    • 电化学稳定窗口： 硫化物电解质的氧化还原稳定性限制，在低电位下易被还原，在高电位下易被氧化。
    • 空气/湿气稳定性： 硫化物电解质（如Li6PS5Cl）在潮湿空气中易发生水解和水合反应，导致H2S气体生成，并形成LiCl, Li2S, Li3PO4, 氧化硫化物等产物，增加界面阻抗。
      • 例如，Li6PS5Cl暴露于湿气会发生水解和水合，通过热处理可部分恢复，但水解导致不可逆的硫损失，形成LiCl、Li2S、Li3PO4和氧化硫化物。
      • 在-40°C露点干燥室环境中，(Li2S)75(P2S5)25 + 20 mol% LiI粉末暴露30分钟后，会产生0.1 cc/g H2S，离子电导率下降超过50%。然而，如果SSE粉末以十二烷载体浆料形式暴露，H2S生成量为0 cc/g，离子电导率仅下降14%，表明适当加工可改善湿气稳定性。

3. 硫化物固态电解质与阳极的界面稳定性 (Interfacial Stability between Sulfide Solid Electrolytes and Anodes)

  • 3.1. 锂金属阳极
    • 优势与挑战： 锂金属是理想的阳极材料，但其与硫化物电解质的界面反应和锂枝晶生长是主要挑战。
    • 界面反应机理： 硫化物电解质（如Li6PS5Cl）与锂金属阳极直接接触时，容易发生还原反应，形成高阻抗的固态电解质界面（SEI）层，阻碍锂离子传输。
    • 锂枝晶生长： 锂离子在充电过程中不均匀沉积，导致枝晶穿透固态电解质，引发短路和安全问题。
    • 代表文献：
      • ：指出了硫化物电解质中锂枝晶形成的问题。
      • ：提出g-C3N4涂层可降低Li6PS5Cl的电子电导率，并通过促进Li/Li6PS5Cl界面原位形成离子导电的Li3N来提高界面稳定性，同时减少H2S的形成，从而实现Li-Li对称电池的稳定循环。
      • ：通过在Li6PS5Cl中引入锑（Sb）形成Li-Sb合金，在阳极界面形成Li-Sb合金，促进均匀锂沉积，提高了界面稳定性，实现了14.5 mA cm-2的最高临界电流密度，且无锂枝晶穿透。
  • 3.2. 硅基阳极
    • 优势与挑战： 硅因其高比容量、低锂化电位和低锂枝晶风险而被认为是极具前景的阳极材料。然而，其电化学性能差（实际比容量低、容量衰减快）阻碍了实际应用。
    • 界面反应机理： 硅阳极与硫化物固态电解质（如Li6PS5Cl）复合时，固态电解质界面（SEI）的生长导致复合阳极的电阻显著增加，解释了其容量快速衰减。
    • 体积膨胀问题： 硅在锂化过程中体积膨胀巨大，导致电极结构破坏和与固态电解质的界面接触丧失，尤其是在低堆叠压力下。
    • 代表文献：
      • ：揭示了在低堆叠压力下，仅低体积膨胀不足以实现良好的循环稳定性，必须考虑紧密的硅阳极-固态电解质界面接触，这受硅机械变形的影响。该研究发现，微粒状SiO x阳极在有机/无机复合固态电解质下表现出良好的界面兼容性，而SiO x和Si的混合物与硫化物固态电解质结合，可在低堆叠压力下提供优异的循环稳定性。
      • ：揭示了复合Si/Li6PS5Cl阳极中，固态电解质界面的生长导致电阻显著增加，是容量快速衰减的原因。固态电解质-free硅阳极虽然具有高比容量，但脱锂过程中微孔形成导致二维界面处的机械应力更大。
      • ：通过硫化物固态电解质的界面钝化特性，实现了99.9wt%微硅阳极的稳定运行，消除了持续的界面生长和不可逆的锂损失。

4. 硫化物固态电解质与阴极的界面稳定性 (Interfacial Stability between Sulfide Solid Electrolytes and Cathodes)

  • 4.1. 富镍氧化物阴极 (Ni-rich Layered Oxide Cathodes)
    • 优势与挑战： 富镍层状氧化物（NRLO）阴极因其高比容量和低成本，是高能量密度锂离子电池和全固态电池中最有前景的阴极材料之一。然而，它们面临结构和界面不稳定性挑战，尤其是在与硫化物电解质匹配时。
    • 界面反应机理：
      • 在充电状态下，阴极/硫化物电解质界面处会形成富锂耗尽层，导致硫化物侧Li耗尽和氧化，从而产生高界面电阻。
      • Ni-rich材料中的级联反应和阴极与固态电解质之间的化学机械降解会降低循环寿命。
      • 高电位下，富镍阴极释放的氧气会攻击硫化物电解质，导致界面分解和性能衰减。
    • 代表文献：
      • ：通过引入异原子化学竞争扩散策略，稳定了富镍阴极与固态电解质的接触面，异原子作为“氧锚”缓解了氧的过度氧化，并形成离子“扩散调节器”，改善了界面兼容性，削弱了空间电荷层。
      • ：通过高熵掺杂（Mg, Al, Ti, Nb, Mo）LiNi0.8Co0.1Mn0.05Mg0.01Al0.01Ti0.01Nb0.01Mo0.01O2（HE-NCM）来稳定富镍阴极，缓解H2-H3相变，减少晶格体积变化，改善本体/界面稳定性。与硫化物固态电解质匹配时，HE-NCM@LiNbO3在1700次循环后仍保持84.5%的容量保持率。
      • ：首次通过DFT+U框架计算，理论阐明了氧化物阴极与硫化物电解质之间空间电荷层（SCL）的特性及其对电池性能的影响，并证明LiNbO3缓冲层的插入可抑制SCL的生长。
      • ：综述了富镍阴极/硫化物固态电解质界面存在的问题及改善界面稳定性的策略。
      • ：理论研究表明，LiFePO4/Li3PS4界面在充电状态下不稳定，Li在界面附近的硫化物侧耗尽和氧化，与氧化物界面形成对比，这暗示了Li耗尽层的形成并支持插入氧化物缓冲层以降低界面电阻的有效性。
      • ：使用原位低温电子显微镜直接观察到LiNi0.5Co0.2Mn0.3O2/Li6PS5Cl界面在充电过程中形成约50 nm厚的Li耗尽的阴极-电解质界面层，Li浓度降低导致固态电解质完全非晶化，增加Li离子迁移势垒，这是界面电阻的根源。LiNbOy涂层界面则没有明显的Li耗尽或非晶化。
  • 4.2. 其他氧化物阴极
    • 例如LiCoO2等，其与硫化物电解质的界面也存在空间电荷层效应。
    • 代表文献：
      • ：探讨了LiCoO2阴极与β-Li3PS4固态电解质（LCO/LPS）界面的空间电荷层效应，以及LiNbO3缓冲层（LCO/LNO/LPS）的插入作用。LNO的插入抑制了SCL的生长并提供了平滑的Li传输路径。

5. 硫化物固态电解质界面稳定化策略 (Strategies for Stabilizing Sulfide Solid Electrolyte Interfaces)

  • 5.1. 界面涂层/缓冲层 (Interfacial Coatings/Buffer Layers)
    • 目的： 阻止电极与硫化物电解质的直接接触，降低界面反应，减少空间电荷层效应，促进离子传输。
    • 针对阳极：
      • 例如g-C3N4涂层在Li6PS5Cl表面，可降低电子电导率，促进Li3N的形成，提高Li/Li6PS5Cl界面稳定性，并减少H2S形成。
      • 通过Li-Sb合金形成策略，在阳极界面形成Li-Sb合金，促进均匀锂沉积，提高长期稳定性。
    • 针对阴极：
      • 氧化物缓冲层： 例如LiNbO3、Li2ZrO3等，可有效隔离阴极与硫化物电解质，抑制有害副反应。
        • LiNbO3缓冲层被证实可抑制空间电荷层生长，改善LiCoO2/LPS界面的Li传输。
        • LiNbOy涂层界面没有明显的Li耗尽或非晶化，即使涂层厚度仅为5 nm，有效阐明了其缓冲机制。
        • LiNbO3涂层的LiNi0.6Mn0.2Co0.2O2在ASSLMBs中表现出优异的容量保持率。
        • Li2ZrO3（LZONPs）纳米结构颗粒通过成本效益高的干法涂覆工艺，可显著降低阴极电荷转移电阻，提高LiNi0.70Mn0.15Co0.15O2的循环稳定性。
      • 异原子掺杂/高熵掺杂： 通过在阴极材料中引入异原子（如Mg, Al, Ti, Nb, Mo）进行高熵掺杂，可以稳定阴极结构，缓解相变，减少晶格体积变化，从而改善本体/界面稳定性。
    • 代表文献：
      • ：异原子化学竞争扩散策略稳定Ni-rich阴极/固态电解质界面。
      • ：g-C3N4涂层改善硫化物SE的空气稳定性和锂兼容性。
      • ：高熵掺杂Ni-rich阴极与LiNbO3涂层在硫化物固态电解质中显示出优异的性能。
      • ：LiNbO3缓冲层抑制空间电荷层生长。
      • ：LiNbOy涂层缓解Li耗尽和非晶化。
      • ：Li-Sb合金形成策略改善阳极界面稳定性。
      • ：通过干法涂覆Li2ZrO3功能化LiNi0.70Co0.15Mn0.15O2阴极，提高固态电池性能。
  • 5.2. 新型复合电解质设计 (Novel Composite Electrolyte Design)
    • 目的： 结合不同材料的优势，改善电解质的综合性能，包括离子电导率、机械性能和界面稳定性。
    • 例如，Na3SbS4 (NSS) 和氧化硫化物玻璃组成的复合SE，其中氧化硫化物中的P2S7-aOa单元通过释放O离子与阳极反应形成氧化物，改善界面稳定性；PS4-aOa单元稳定离子传输网络；NSS作为枝晶捕食者与渗透的Na反应。
    • 代表文献：
      • ：O-Tailored微结构工程界面用于先进室温全固态钠电池。
  • 5.3. 界面工程与工艺优化 (Interface Engineering and Process Optimization)
    • 堆叠压力优化： 适当的堆叠压力对于维持硅阳极与硫化物固态电解质的紧密接触至关重要，尤其是在低膨胀阳极材料中。
    • 电解质结构调控： 通过控制硫化物电解质的成分和结构，例如75 mol% Li2S和Li2O共改性剂可改善湿气稳定性。
    • 原位界面形成： 某些涂层可以促进原位形成离子导电的界面层，如g-C3N4促进Li3N的形成。
    • 代表文献：
      • ：机械影响机制探讨硅阳极在低堆叠压力下的固态电池中的应用。
      • ：硫化物固态电解质在干燥室环境下的湿气稳定性研究。

6. 关键争议与未解决问题 (Key Controversies and Unresolved Issues)

  • 6.1. 界面反应的精确机制与产物识别： 尽管已有很多研究，但界面反应（特别是复杂的多组分体系）的原子级精确机制和产物类型仍需更深入的表征和理解。
  • 6.2. 空间电荷层效应的定量评估： 空间电荷层对界面电阻的具体贡献和其随电池循环的演变机制，仍需更准确的实验验证和理论模型。
  • 6.3. 湿气稳定性的根本解决与大规模生产： 硫化物电解质的空气/湿气稳定性是其商业化的主要障碍。虽然有改善策略，但如何在实际大规模生产中（例如，-40°C露点干燥室）实现完全稳定仍是挑战。
  • 6.4. 枝晶生长抑制的长期有效性： 尽管各种策略（如合金形成、涂层）显示出对锂枝晶生长的抑制作用，但其在长期循环和高电流密度下的有效性仍需进一步验证。
  • 6.5. 界面工程的普适性与成本效益： 许多界面稳定化策略虽然有效，但其普适性、复杂性和成本效益（尤其是在大规模生产中）需要进一步考量。

7. 建议图表 (Suggested Figures)

  • 图1：全固态电池与传统锂离子电池的结构对比图。 突出固态电解质在安全性方面的优势。
  • 图2：硫化物固态电解质的典型晶体结构示意图（例如，Argyrodite Li6PS5Cl），并示意Li离子传输路径。
  • 图3：硫化物固态电解质与锂金属阳极界面失效机制示意图。 包括SEI形成、锂枝晶生长。
  • 图4：硫化物固态电解质与硅基阳极界面失效机制示意图。 包括体积膨胀导致的界面脱离、SEI生长。
  • 图5：硫化物固态电解质与富镍阴极界面失效机制示意图。 包括Li耗尽层形成、阴极降解、氧气释放对SSE的攻击、空间电荷层。
  • 图6：界面稳定化策略示意图。 包含缓冲层（氧化物、氮化物）、复合电解质、合金化阳极等。
  • 图7：不同界面稳定化策略的代表性电化学性能对比图。 例如，循环稳定性、倍率性能等。
  • 图8：硫化物固态电解质在不同湿气环境下的H2S释放量和离子电导率衰减对比图。

8. 未来展望 (Future Outlook)

  • 8.1. 多维度界面表征技术的融合： 结合原位/操作条件下的先进表征技术（如冷冻透射电镜、同步辐射X射线衍射、核磁共振、电化学阻抗谱）以更深入地理解界面演变过程，特别是原子尺度和动态过程。
  • 8.2. 理论计算与机器学习的指导作用： 利用密度泛函理论（DFT）、分子动力学模拟（MD）和机器学习等计算方法，预测界面结构、反应路径和材料性能，加速新材料和界面设计。
  • 8.3. 智能界面材料的设计： 开发具有自修复、自适应功能的智能界面材料，能够响应电池内部环境变化，自动调节界面性能。
  • 8.4. 多组分复合电解质的协同效应： 探索将硫化物、氧化物、聚合物等多种组分复合，以实现高离子电导率、良好机械性能、优异界面稳定性及空气稳定性的综合优势。例如，氧化硫化物玻璃与Na3SbS4的复合SE。
  • 8.5. 可扩展制造工艺的开发： 聚焦低成本、环境友好的大规模生产方法，以实现硫化物ASSBs的商业化应用。例如，干法涂覆工艺。
  • 8.6. 新型阳极和阴极材料的探索： 除了锂金属和硅，探索其他高容量、高稳定性的阳极材料，以及能更好地与硫化物电解质兼容的阴极材料。

9. 结论 (Conclusion)

  • 总结硫化物固态电解质在ASSBs中的关键作用和面临的界面挑战。
  • 重申本综述所讨论的界面失效机制和稳定化策略的重要性。
  • 强调界面工程是实现高性能硫化物ASSBs的关键。
  • 再次展望未来研究方向，强调多学科交叉合作的重要性。

适合投稿的文章角度 (Suitable Article Angle for Submission) 考虑到当前研究的深度和广度，以及关键挑战的存在，以下几个文章角度可能更具吸引力：

  1. “硫化物固态电解质界面化学与力学耦合失效机制及协同工程策略”： 强调界面问题的复杂性，不仅仅是化学反应，还包括机械应力、体积变化等因素的协同作用。综述应深入探讨化学（如SEI形成、Li耗尽、氧化还原反应）和机械（如体积膨胀、界面脱离、枝晶穿透）在不同电极界面的具体表现，并提出多尺度、多物理场耦合的协同界面工程策略。

    • 核心关键词： 界面化学、界面力学、协同工程、多尺度、原子级机制。
    • 优势： 深入挖掘问题本质，提出更全面的解决方案，而非仅仅罗列策略。

  2. “从原子尺度理解硫化物固态电解质界面：原位表征与理论计算的视角”： 侧重于利用最新的先进原位表征技术（如原位低温电镜）和理论计算方法（如DFT、MD）来揭示界面在原子尺度上的动态演变过程和机理。这篇综述可以强调这些技术如何帮助我们更精确地理解界面反应产物、空间电荷层、离子传输路径和失效机理，并指出未来这些技术融合应用的前景。

    • 核心关键词： 原子尺度、原位表征、理论计算、冷冻电镜、DFT、分子动力学。
    • 优势： 突出前沿研究方法，提供对微观机制的深度洞察。

  3. “面向大规模制造的硫化物固态电解质界面稳定性挑战与解决方案”： 将重心放在硫化物固态电解质在实际工业应用和大规模制造中遇到的界面稳定性问题（例如，湿气稳定性、成本效益、可扩展的涂覆技术）。这篇综述不仅讨论科学问题，更要关注技术可行性、经济性和环境影响，并提出符合工业标准的界面工程解决方案。

    • 核心关键词： 大规模制造、工业化、湿气稳定性、成本效益、干法工艺。
    • 优势： 结合实际应用需求，具有较强的工程和产业指导意义。

建议投稿期刊：

  • 高影响力综合期刊： Advanced Materials, Nature Materials, Science (如果内容极具突破性)
  • 材料科学与电化学专业期刊： Advanced Functional Materials, Journal of the American Chemical Society, Energy & Environmental Science, ACS Nano, Chemistry of Materials, Journal of Power Sources, ACS Applied Materials & Interfaces

这个框架旨在全面覆盖硫化物固态电解质界面稳定性的各个方面，并提供深入的思考方向。希望对您撰写综述有所帮助！

References

1O‐Tailored Microstructure‐Engineered Interface toward Advanced Room Temperature All‐Solid‐State Na BatteriesOpenAlex

Lin Li, Ruonan Xu, Long Zhang, et al.
Abstract The severe parasitic interface reaction and dendrite growth retard the practical applications of all‐solid‐state (ASS) Na batteries with sulfide solid electrolytes (SEs). Here, a novel composite SE is proposed, with a high ionic conductivity, composed of Na 3 SbS 4 (NSS) and oxysulfide glass. The study reveals that the P 2 S 7‐ a O a and PS 4‐ a O a units in oxysulfide play various roles: The former is deoxidized to release free O ions, which reacts with the anode via migrating to form oxides, favoring an improved interface stability. The latter is highly stable upon cycling, thereby maintaining an ion transport network. Meanwhile, NSS acts as a dendrite predator via reacting with penetrated Na. These advantages enable the resulting ASS Na battery with superior long‐term cycling performance at a high current density at room temperature, one of the best results so far. This discovery sheds light on innovative advanced SE materials through an oxysulfide‐based composite design.

2Mechanical influence mechanisms of silicon anodes in solid-state batteries under low stack pressureOpenAlex

Fei Yang, Qian Xu, Xin Qin, et al.
Microparticulate silicon (Si) has been successfully used in solid lithium-ion battery anodes due to its strength in high gravimetric/volumetric capacity and low risk of dendrite growth. Nevertheless, the operation condition of low stack pressure challenges the cycle life of the assembled microparticulate Si-based solid-state batteries. In this work, we unveiled that solely low volume expansion of the Si anode is insufficient to achieve good cyclic stability for solid-state batteries under low stack pressure, and the intimate Si anode-solid electrolyte interfacial contact must be considered, which is found to be influenced by the mechanical deformation of Si. As a result, for the batteries with organic/inorganic composite solid-state electrolytes, the low-expansion microparticulate silicon oxide (SiO x ) anode is employed and achieves stable cycling performance and high areal capacity (23 mAh cm −2 ) with good interfacial compatibility under 0 MPa stack pressure. For all-solid-state batteries using sulfide solid-state electrolyte, the hybrid of microparticulate SiO x and Si combined with the low expansion of SiO x and good plastic deformation ability of Si is applied and affords superior cyclic stability under decreased stack pressure. This work refreshes the understanding of the anode design principle for low-stack-pressure solid-state batteries using organic/inorganic composite solid-state electrolytes or sulfide solid-state electrolytes. • The SiO x anode achieves high areal capacity with organic/inorganic SSE. • The μSi anode exhibits superior interface stability with sulfide SSE. • The hybrid SiO x and μSi anode combines low expansion and plastic deformation.

3Lithium/Sulfide All‐Solid‐State Batteries using Sulfide ElectrolytesOpenAlex

Jinghua Wu, Sufu Liu, Fudong Han, et al.
All-solid-state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide operable temperature range. The critical component in ASSLBs is the solid-state electrolyte. Among all solid-state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur-based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted. The opportunities for sulfide-based ASSLBs are also discussed.

4Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State BatteriesOpenAlex

Qing Zhang, Daxian Cao, Yi Ma, et al.
Due to their high ionic conductivity and adeciduate mechanical features for lamination, sulfide composites have received increasing attention as solid electrolyte in all-solid-state batteries. Their smaller electronegativity and binding energy to Li ions and bigger atomic radius provide high ionic conductivity and make them attractive for practical applications. In recent years, noticeable efforts have been made to develop high-performance sulfide solid-state electrolytes. However, sulfide solid-state electrolytes still face numerous challenges including: 1) the need for a higher stability voltage window, 2) a better electrode-electrolyte interface and air stability, and 3) a cost-effective approach for large-scale manufacturing. Herein, a comprehensive update on the properties (structural and chemical), synthesis of sulfide solid-state electrolytes, and the development of sulfide-based all-solid-state batteries is provided, including electrochemical and chemical stability, interface stabilization, and their applications in high performance and safe energy storage.

5Chemical Competing Diffusion for Practical All-Solid-State BatteriesOpenAlex

Zhongsheng Dai, Xuan Sun, Renjie Chen, et al.
The thermal safety issues of currently available Ni-rich cathode-based power supplies brought in the development of all-solid-state batteries, yet the cascade reactions in Ni-rich materials and the chemo-mechanical degradation between the cathode and solid electrolyte diminished the cycle life. Here, by introducing a new heteroatom chemical competing diffusion strategy, we successfully stabilize the Ni-rich cathode and the contact face with an solid electrolyte. Combining extensive explorations in theoretical calculation and multiscale in/ex situ characterization, we elucidate the atomic-level chemical competing diffusion upon the topological lithiation of layered materials. The heteroatoms with higher binding energy to the coordinated oxygen served as the "oxygen anchor" in the bulk and alleviated the excessive oxygen oxidation through charge compensation, thus easing the chemical aggression of the solid electrolyte by evolved oxygen. Comparably, others were enriched in the surface and formed an ionic "diffusion regulator" with residual lithium, and the special ionic transfer regulation mechanism of the piezoelectric layer validly improved the interface compatibility with the solid electrolyte and weakened the space-charge layer in solid-state batteries. This helped the designed Ni-rich cathode-based sulfide solid-state battery exhibit excellent cyclability under 4.5 V (97.3% after 120 cycles). Our findings unlocked the structure-function relationship between the polarization field generated by the piezoelectric material and the electrode.

6Surface Coating Enabling Sulfide Solid Electrolytes with Excellent Air Stability and Lithium CompatibilityOpenAlex

Min Luo, Changhong Wang, Yi Duan, et al.
All‐solid‐state lithium metal batteries (ASSLMBs) featuring sulfide solid electrolytes (SEs) are recognized as the most promising next‐generation energy storage technology because of their exceptional safety and much‐improved energy density. However, lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide‐based ASSLMBs. Here, a thin layer (approximately 5 nm) of g‐C 3 N 4 is coated on the surface of a sulfide SE (Li 6 PS 5 Cl), which not only lowers the electronic conductivity of Li 6 PS 5 Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion‐conductive Li 3 N at the Li/Li 6 PS 5 Cl interface. Additionally, the g‐C 3 N 4 coating on the surface can substantially reduce the formation of H 2 S when Li 6 PS 5 Cl is exposed to humid air. As a result, Li–Li symmetrical cells using g‐C 3 N 4 ‐coated Li 6 PS 5 Cl stably cycle for 1000 h with a current density of 0.2 mA cm −2 . ASSLMBs paired with LiNbO 3 ‐coated LiNi 0.6 Mn 0.2 Co 0.2 O 2 exhibit a capacity of 132.8 mAh g −1 at 0.1 C and a high‐capacity retention of 99.1% after 200 cycles. Furthermore, g‐C 3 N 4 ‐coated Li 6 PS 5 Cl effectively mitigates the self‐discharge behavior observed in ASSLMBs. This surface‐coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide‐based ASSLMBs.

7High-Entropy Doped Ni-Rich Oxide Cathodes with Alleviated H2–H3 Phase Transition for Li-Ion and All-Solid-State Li BatteriesOpenAlex

Maosheng Gong, Yadong Wei, Hongzhou Zhang, et al.
High-capacity Ni-rich cathodes hold considerable promise in advancing both high-energy Li-ion batteries (LIBs) and all-solid-state Li batteries (ASSLBs). Yet, lattice volume changes induced by the H2–H3 phase transition lead to structural degradation. It has been demonstrated that doping approaches can enhance structural stability. Nevertheless, the selection of an appropriate dopant is of considerable importance for the design of high-performance Ni-rich materials with high-entropy doping. Furthermore, the feasibility of high-entropy doped Ni-rich cathodes in ASSLBs has not been reported to date. In this study, leveraging the chemically competitive doping mechanism of Mg, Al, Ti, Nb, and Mo elements, we propose a high-entropy doped LiNi0.8Co0.1Mn0.05Mg0.01Al0.01Ti0.01Nb0.01Mo0.01O2 (HE-NCM) to stabilize Ni-rich cathodes. In-situ X-ray diffraction confirms that the synergistic effect of multiple dopants in high-entropy doping significantly alleviates the H2–H3 phase transition and reduces lattice volume changes, which contribute to the absence of microcracks and improved bulk/interface stability. In ASSLBs, the HE-NCM@LiNbO3 maintains an outstanding capacity retention of 84.5% even after 1700 cycles, demonstrating the feasibility of high-entropy doped Ni-rich cathodes when matched with a sulfide solid-state electrolyte. The application of high-entropy doping methodology for the development of advanced rechargeable batteries has been shown to provide a novel perspective on the improvement of the structural robustness and interfacial compatibility of Ni-rich cathode materials.

8Space–Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion BatteryOpenAlex

Jun Haruyama, Keitaro Sodeyama, Liyuan Han, et al.
We theoretically elucidated the characteristics of the space–charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state lithium-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the first time, via the calculations with density functional theory (DFT) + U framework. As a most representative system, we examined the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calculations, coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calculated energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the atomic scale will give a useful perspective for the further improvement of the ASS-LIB performance.

9Review on Interface and Interphase Issues in Sulfide Solid-State Electrolytes for All-Solid-State Li-Metal BatteriesOpenAlex

Young‐Woon Byeon, Haegyeom Kim
All-solid-state batteries have emerged as promising alternatives to conventional Li-ion batteries owing to their higher energy density and safety, which stem from their use of inorganic solid-state electrolytes instead of flammable organic liquid electrolytes. Among various candidates, sulfide solid-state electrolytes are particularly promising for the development of high-energy all-solid-state Li metal batteries because of their high ionic conductivity and deformability. However, a significant challenge remains as their inherent instability in contact with electrodes forms unstable interfaces and interphases, leading to degradation of the battery performance. In this review article, we provide an overview of the key issues for the interfaces and interphases of sulfide solid-state electrolyte systems as well as recent progress in understanding such interface and interphase formation and potential solutions to stabilize them. In addition, we provide perspectives on future research directions in this field.

10Chemo-mechanical failure mechanisms of the silicon anode in solid-state batteriesOpenAlex

Hanyu Huo, Ming Jiang, Yang Bai, et al.
Abstract Silicon is a promising anode material due to its high theoretical specific capacity, low lithiation potential and low lithium dendrite risk. Yet, the electrochemical performance of silicon anodes in solid-state batteries is still poor (for example, low actual specific capacity and fast capacity decay), hindering practical applications. Here the chemo-mechanical failure mechanisms of composite Si/Li 6 PS 5 Cl and solid-electrolyte-free silicon anodes are revealed by combining structural and chemical characterizations with theoretical simulations. The growth of the solid electrolyte interphase at the Si|Li 6 PS 5 Cl interface causes severe resistance increase in composite anodes, explaining their fast capacity decay. Solid-electrolyte-free silicon anodes show sufficient ionic and electronic conductivities, enabling a high specific capacity. However, microscale void formation during delithiation causes larger mechanical stress at the two-dimensional interfaces of these anodes than in composite anodes. Understanding these chemo-mechanical failure mechanisms of different anode architectures and the role of interphase formation helps to provide guidelines for the design of improved electrode materials.

11Ni-Rich Layered Oxide Cathodes/Sulfide Electrolyte Interface in Solid-State Lithium BatteryOpenAlex

Yiman Feng, Zhixing Wang, Duo Deng, et al.
Because of the high specific capacity and low cost, Ni-rich layered oxide (NRLO) cathodes are one of the most promising cathode candidates for the next high-energy-density lithium-ion batteries. However, they face structure and interface instability challenges, especially the battery safety risk caused by using an intrinsic flammable organic liquid electrolyte. In this regard, a solid electrolyte with high safety is of great significance to promote the development of energy storage. Among them, sulfide electrolytes are considered to be the most potential substitutes for liquid electrolytes because of their high ionic conductivity and good processing properties. Nevertheless, the interfacial incompatibility between the sulfide electrolyte and NRLO cathode is the critical challenge for high-performance sulfide all-solid-state lithium batteries (ASSLBs). In this review, we summarize the problems of the Ni-rich cathode/sulfide solid electrolyte interface and the strategies to improve the interface stability. On the basis of these insights, we highlight the scientific problems and technological challenges that need to be resolved urgently and propose several potential directions to further improve the interface stability. The objective of this study is to provide a comprehensive understanding and insightful recommendations for the enhancement of the sulfide ASSLBs with NRLO cathode.

12Cooperative Transport of Lithium in Disordered Li<sub>10</sub>MP<sub>2</sub>S<sub>12</sub> (M = Sn, Si) Electrolytes for Li-Ion BatteriesOpenAlex

Vinay Maithani, Sumantra Das, Sankha Mukherjee
Disorder in sulfide solid-state electrolytes significantly impacts chemical bonding, affecting electrochemical properties and interface stability. Li10GeP2S12, a prominent sulfide electrolyte, is expensive and has limited interfacial stability, so substituting Ge with earth-abundant elements, such as Sn and Si, could be more practical. However, a thorough understanding of the kinetics and chemical bonding nature of Li in the Sn/Si-substituted systems is missing owing to the complexity associated with disordered sublattice in these materials. We use isothermal–isobaric ensemble Car–Parrinello molecular dynamics to evaluate configuration-dependent tracer and charged diffusivities and activation energies for lithium-ion migration in disordered configurations of Li10SiP2S12 (LSiPS) and Li10SnP2S12 (LSnPS) obtained using ensemble statistics. The study uses Li-ion probability density and maximally localized Wannier orbital analysis to determine how temperature and Sn and Si cations affect Li-ion migration. Our findings indicate that higher temperatures enhance Li-ion mobility by enabling more diffusion pathways. The disordered LSiPS and LSnPS electronic structure shows a Kohn–Sham band gap of 2.4 eV for LSiPS and 2 eV for LSnPS, of the most probable configuration across 500 configurations, suggesting a wider electrolyte window for LSiPS. Additionally, Wannier function visualizations demonstrated the significant impact of locality and temperature on the dynamic nature of bonding states of migrating Li ions.

13Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion BatteriesOpenAlex

Masato Sumita, Yoshinori Tanaka, Minoru Ikeda, et al.
Interfaces between cathodes and sulfide electrolytes exhibit high resistance in all-solid-state lithium ion batteries. In this paper, to elucidate the origin of the high interface resistance we have theoretically investigated the properties of the cathode interfaces with the sulfide electrolyte and oxide electrolyte for comparison. From the density functional molecular dynamics simulations of the LiFePO4/Li3PS4 interface in both discharged and charged states, we have demonstrated the instability of the sulfide interface in the charged state, that is, the lithium depletion and oxidation on the sulfide side near the interface, in contrast to the oxide interfaces. The obtained results imply the formation of a Li-depleted layer around the sulfide interfaces during charging and support the validity of the insertion of oxide buffer layers at the interface to reduce the interface resistance.

14Investigating dry room compatibility of sulfide solid-state electrolytes for scalable manufacturingOpenAlex

Yu‐Ting Chen, Maxwell A. T. Marple, Darren H. S. Tan, et al.
When exposed to moisture, Li 6 PS 5 Cl undergoes both hydrolysis and hydration reactions. It can be partially recovered by heat treatment, but hydrolysis causes the formation of LiCl, Li 2 S, Li 3 PO 4 , and oxysulfides due to the irreversible sulfur loss.

15Visualizing a Li-depleted amorphous cathode–electrolyte interphase in sulfide solid-state batteries using in situ cryogenic electron microscopyOpenAlex

Yuki Nomura, Ryoma Sasaki, Huu Duc Luong, et al.
Electrochemical degradation at the cathode/solid-electrolyte interface critically limits the performance of sulfide-based solid-state batteries; however, its nanoscale origin remains unclear. Here, we directly visualize the structural and chemical evolutions of the LiNi 0.5 Co 0.2 Mn 0.3 O 2 /Li 6 PS 5 Cl interface during charging using in situ scanning transmission electron microscopy combined with electron energy-loss spectroscopy and energy-filtered nanobeam electron diffraction. A potential-controlled sample-preparation protocol is developed to preserve the native interphase structure during sample preparation, and low-dose-rate cryogenic electron microscopy suppresses electron-beam-induced damage. At the uncoated interface, charging induced the formation of a ~50-nm-thick Li-depleted cathode–electrolyte interphase. In regions within ~20 nm of the interface, the Li concentration decreased to below x = 4 in Li x PS 5 Cl, leading to complete amorphization of the solid electrolyte. Machine-learning-potential molecular dynamics simulations reveal that Li depletion destabilizes the argyrodite Li 6 PS 5 Cl framework and increases the Li-ion migration barrier, thereby identifying the origin of interfacial resistance. Conversely, LiNbO y -coated interfaces exhibited neither pronounced Li depletion nor significant amorphization, even with coating thicknesses as small as 5 nm, thereby elucidating the buffering mechanism of LiNbO y at the cathode/sulfide-solid-electrolyte interface. These results establish Li-depletion-induced structural disorder as a fundamental transport-limiting mechanism at cathode interfaces employing sulfide solid electrolytes, providing a framework for interface engineering.

16Li–Sb Alloy Formation Strategy to Improve Interfacial Stability of All‐Solid‐State Lithium BatteriesOpenAlex

Berhanu Degagsa Dandena, Wei‐Nien Su, Dah‐Shyang Tsai, et al.
Abstract The solid electrolyte is anticipated to prevent lithium dendrite formation. However, preventing interface reactions and the development of undesirable lithium metal deposition during cycling are difficult and remain unresolved. Here, to comprehend these occurrences better, this study reports an alloy formation strategy for enhanced interface stability by incorporating antimony (Sb) in the lithium argyrodite solid electrolyte Li 6 PS 5 Cl (LPSC‐P) to form Li–Sb alloy. The Li–Sb alloy emergence at the anodic interface is crucial in facilitating uniform lithium deposition, resulting in excellent long‐term stability, and achieving the highest critical current density of 14.5 mA cm −2 (among the reported sulfide solid electrolytes) without lithium dendrite penetration. Furthermore, Li–Sb alloy formation maintain interfacial contact, even, after several plating and stripping. The Li–Sb alloy formation is confirmed by XRD, Raman, and XPS. The work demonstrates the prospect of utilizing alloy‐forming electrolytes for advanced solid‐state batteries.

17Advancements and Challenges in Solid-State Battery Technology: An In-Depth Review of Solid Electrolytes and Anode InnovationsOpenAlex

Abniel Machín, Carmen Morant, Francisco Márquez
The primary goal of this review is to provide a comprehensive overview of the state-of-the-art in solid-state batteries (SSBs), with a focus on recent advancements in solid electrolytes and anodes. The paper begins with a background on the evolution from liquid electrolyte lithium-ion batteries to advanced SSBs, highlighting their enhanced safety and energy density. It addresses the increasing demand for efficient, safe energy storage in applications like electric vehicles and portable electronics. A major part of the paper analyzes solid electrolytes, key to SSB technology. It classifies solid electrolytes as polymer-based, oxide-based, and sulfide-based, discussing their distinct properties and application suitability. The review also covers advancements in anode materials for SSBs, exploring materials like lithium metal, silicon, and intermetallic compounds, focusing on their capacity, durability, and compatibility with solid electrolytes. It addresses challenges in integrating these anode materials, like the interface stability and lithium dendrite growth. This review includes a discussion on the latest analytical techniques, experimental studies, and computational models to understand and improve the anode–solid electrolyte interface. These are crucial for tackling interfacial resistance and ensuring SSBs’ long-term stability and efficiency. Concluding, the paper suggests future research and development directions, highlighting SSBs’ potential in revolutionizing energy storage technologies. This review serves as a vital resource for academics, researchers, and industry professionals in advanced battery technology development. It offers a detailed overview of materials and technologies shaping SSBs’ future, providing insights into current challenges and potential solutions in this rapidly evolving field.

18Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytesOpenAlex

Darren H. S. Tan, Yu‐Ting Chen, Hedi Yang, et al.
The development of silicon anodes for lithium-ion batteries has been largely impeded by poor interfacial stability against liquid electrolytes. Here, we enabled the stable operation of a 99.9 weight % microsilicon anode by using the interface passivating properties of sulfide solid electrolytes. Bulk and surface characterization, and quantification of interfacial components, showed that such an approach eliminates continuous interfacial growth and irreversible lithium losses. Microsilicon full cells were assembled and found to achieve high areal current density, wide operating temperature range, and high areal loadings for the different cells. The promising performance can be attributed to both the desirable interfacial property between microsilicon and sulfide electrolytes and the distinctive chemomechanical behavior of the lithium-silicon alloy.

19Moisture Stability of Sulfide Solid-State ElectrolytesOpenAlex

Thomas A. Yersak, Yubin Zhang, Fang Hao, et al.
In this report we detail a comprehensive study on the moisture stability of sulfide solid-state electrolytes in dry room environments. Although sulfide SSEs have many favorable attributes, this class of materials suffers from poor stability with water. Sulfide SSEs react with water to form gaseous H 2 S and a variety of solid byproducts like Li 3 PO 4 and LiOH, which go on to increase the interfacial impedance of solid-state batteries. Lab-scale research typically utilizes gloveboxes with &amp;lt;1 ppm water, however, the large-scale manufacturing of Li-ion batteries occurs in −40°C dewpoint dry rooms with around 126 ppm water. Consequently, the moisture stability of sulfide SSEs must be addressed if the manufacture of solid-state batteries based on sulfide SSEs is to be scaled up. Here, we are the first to characterize the moisture stability of sulfide SSEs according to both H 2 S and the degradation of ionic conductivity at different moisture setpoints ranging from −76°C to −40°C dewpoint. A variety of different SSE compositions are studied; namely, (Li 2 S) 75 (P 2 S 5 ) 25 , (Li 2 S) 70 (P 2 S 5 ) 30 , (Li 2 O) 7 (Li 2 S) 68 (P 2 S 5 ) 25 , (Li 2 O) 7 (Li 2 S) 63 (P 2 S 5 ) 30 , and (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI. We find that moisture stability improves with 75 mol% Li 2 S modifier content and the introduction of a Li 2 O co-modifier. After a 30 min exposure in a −40°C dewpoint dry room environment we found that (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI powder generated 0.1 cc/g H 2 S and its ionic conductivity decreased by over 50%. However, when SSE powder was exposed as a slurry in a dodecane carrier the same SSE composition generated 0 cc/g H 2 S and its ionic conductivity only dropped by 14%. Our results show that sulfide SSEs have acceptable moisture stability when appropriately processed in a dry room environment.

20Surface Functionalization of LiNi<sub>7.0</sub>Co<sub>0.15</sub>Mn<sub>0.15</sub>O<sub>2</sub> with Fumed Li<sub>2</sub>ZrO<sub>3</sub> via a Cost‐Effective Dry‐Coating Process for Enhanced Performance in Solid‐State BatteriesOpenAlex

Şahin Cangaz, Felix Hippauf, Ryo Takata, et al.
Abstract Applying a thin film coating is a vital strategy to enhance long term and interface stability of Ni‐rich layered oxide cathode materials (NRLOs), especially when they are matched with sulfidic solid electrolytes (SSEs) in solid‐state batteries (SSBs). The coating prevents direct contact between the cathode active material (CAM) and the SSE, shielding against parasitic side reactions at the cathode electrolyte interface (CEI). Conventional coatings are based on wet‐chemical methods and therefore harmful to the environment and require long‐lasting processing and high costs. In this study, we present a versatile, facile and highly‐scalable dry‐coating method (with suitable equipment up to 500 kg per batch) successfully employed for both multi ‐ and single ‐crystalline LiNi 0.70 Mn 0.15 Co 0.15 O 2 (NCM70) particles by fumed Li 2 ZrO 3 nanostructured particles (LZONPs) via high intensity mixing process. The resulting porous coating layer stays firmly attached at the CAM particle surface without a need of post ‐calcination step at elevated temperatures. The electrochemical testing results signify enhanced rate capability up to 1.5 mA cm −2 for both particle types and cyclic stability up to 650 cycles with a capacity retention of 86.1 % for single ‐crystalline NCM70. We attribute the enhanced performance to the reduced CEI reactions as cathodic charge transfer resistance depressed significantly after dry‐coating by LZONPs, being an important step towards sulfidic solid‐state batteries.
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