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硫化物固态电解质界面稳定性提升策略对比
硫化物固态电解质（SSEs）因其高离子电导率和优异的延展性，在全固态电池（ASSBs）中展现出巨大的应用潜力。然而，硫化物固态电解质与电极之间复杂的固-固界面问题，包括界面副反应、接触不良以及锂枝晶形成等，严重阻碍了其性能的提升和实际应用。为了解决这些挑战，研究人员已经开发出多种策略来提高硫化物固态电解质的界面稳定性。以下将对这些主要策略进行详细对比分析：
1. 界面保护层/涂层策略
界面保护层或涂层是一种常用的策略，旨在防止固态电解质与电极直接接触，从而抑制界面副反应的发生，并改善界面接触。
1.1. 氧化物涂层
- LiNbO3 (LNO) 涂层： LNO 涂层已被提出用于高压氧化物正极，以提高其与硫化物固态电解质（如 Li6PS5Cl (LPSCl)）的界面稳定性。研究表明，LNO 涂层能够改善正极材料与LPSCl之间的热力学稳定性，并促进LPSCl电化学分解的原位钝化效应，从而在首次充电循环时形成稳定的界面，实现ASSBs的长期循环。
- 富集异质原子涂层 (Heteroatom Chemical Competing Diffusion Strategy)： 通过引入具有更高结合能的异质原子（如“氧锚定”原子和形成离子“扩散调节器”的表面富集原子）来稳定富镍正极与固态电解质的界面。这种策略通过缓解过度氧氧化、减弱空间电荷层效应和提高界面兼容性，使富镍硫化物固态电池在4.5V下表现出优异的循环性能（120次循环后容量保持率达97.3%）。
- Li2ZrO3 纳米颗粒（LZONPs）干法涂层： 将烟熏 Li2ZrO3 纳米颗粒通过高强度混合干法涂覆到 Ni 含量高的层状氧化物正极材料（NRLOs）表面，形成多孔涂层。这种方法能够有效减少阴极电解质界面的副反应，显著降低阴极电荷转移电阻，从而提高倍率性能和循环稳定性。与湿法化学方法相比，干法涂层更具成本效益、环境友好且易于大规模生产。
- Li2ZrCl5F 保护层： 在复合正极中引入氧化稳定性的 Li2ZrCl5F，可以提升硫化物固态电池的循环性能和快速充电能力，实现高能量密度（354.4 Wh kg⁻¹）。
1.2. 聚合物涂层
- 离子导电聚合物（PILs）涂层： 使用含有锂盐的离子导电聚合物作为多功能涂层，可显著提高富镍正极硫化物固态电池在环境温度下的性能。这种涂层能够实现高容量（>150 mAh g⁻¹ at 0.1C）和优异的容量保持率（在0.2C和20°C下循环500次后仍保持82.7%）。
- 聚(乙烯醋酸酯) (PEVA) 支架和聚四氟乙烯 (PTFE) 粘合剂： 利用多孔粘性 PEVA 支架和 PTFE 粘合剂将硫化物固态电解质编织成超薄自支撑膜，厚度仅为 40 µm，同时保持高离子电导率（1.1 mS cm⁻¹）和高拉伸强度（74 MPa）。为了缓解 PTFE 粘合剂与锂金属负极之间的还原反应，通过原位形成富含 Li3N 的固体电解质界面（SEI），对称电池在0.2 mA cm⁻²的电流密度下展现出800小时的优异循环稳定性。
1.3. 锂丰富过渡金属硫化物（Li1.2Ti0.8S2）正极：
- 研究发现，采用锂丰富硫化物正极（Li1.2Ti0.8S2）与硫银锗矿电解质（Li5.7PS4.7Cl1.3）组成的ASSB系统，在不使用任何保护涂层的情况下，正极/电解质界面在20次循环后未检测到明显降解。这表明钛和硫物种均参与电化学过程，且此类全硫化物系统的电化学性能不受正极/电解质反应活性的限制，为开发与硫化物电解质兼容的特定正极材料提供了新的方向。
2. 固态电解质界面（SEI）工程
SEI的形成对于锂金属电池的性能至关重要，特别是为了抑制锂枝晶生长和稳定界面。
- 预锂化三硫氰尿酸 (Li3TCA) 作为有机添加剂： 将预锂化三硫氰尿酸 (Li3TCA) 与 Li6PS5Cl 混合，可以在硫化物固态电解质和锂金属负极之间建立稳定的界面，同时保持高离子电导率。添加2.5 wt%的 Li3TCA 可减轻电解质在锂金属界面的分解，减少SEI中 Li2S 的含量，从而形成更稳定的界面。这种策略将临界电流密度从1.0 mA cm⁻²提高到1.9 mA cm⁻²，并在1.0 mA cm⁻²的高电流密度下实现了750小时以上的稳定循环。在全电池中，Li|NbO-NCM811 电池在0.3 C下可循环超过500次。
- 原位形成富含Li3N的SEI： 如前所述，在PEVA/PTFE基硫化物固态电解质薄膜中，通过在锂金属负极上原位形成富含Li3N的SEI，可以有效缓解PTFE与锂金属的还原反应，提高对称电池的循环稳定性。
- 聚合物-固态电解质复合材料： 通过低温溶液沉淀法制备的聚合物-硫化锂磷复合电解质，具有更均匀的聚合物分布，增强了机械强度并降低了电子传导性，从而改善了对枝晶形成的稳定性。这种复合材料在锂剥离/沉积循环中表现出更高的稳定性，优于其他制备方法（如机械混合和溶液分散）获得的类似复合材料。
- 硅负极中的SEI生长： 对于复合Si/Li6PS5Cl硅负极，SEI的生长会导致界面电阻显著增加，进而引起容量快速衰减。因此，调控SEI的形成和稳定性是改善硅负极性能的关键。
3. 固态电解质材料改性
通过对硫化物固态电解质本身进行改性，可以提高其本征稳定性和与电极的兼容性。
- Cl 掺杂 Li10SnP2S12 (LSPS)： Cl 掺杂 LSPS 可提高其离子电导率和对负极的电化学稳定性。例如，Li9.9SnP2S11.9Cl0.1 具有 2.62 mS cm⁻¹ 的高离子电导率和更低的活化能。X射线衍射Rietveld精修结果表明，Cl成功取代S进入LSPS晶格，增加了锂离子空位，并缩短了沿c轴分布的相邻锂离子之间的距离，有利于锂离子传输。Cl掺杂还促进了LSPS与锂金属负极界面的稳定性，从而提高了全固态电池的比容量和循环寿命。
- 表面分子工程： 采用可逆的表面修饰策略，例如使用长链烷基硫醇（1-undecanethiol）处理硫化物固态电解质（如 Li6PS5Cl），可以使其在潮湿环境中进行加工。硫醇基团锚定在SSE表面，疏水性烃尾通过排斥水提供保护，使Li6PS5Cl在相对湿度33%的环境中暴露时间延长100倍以上，同时保持高于1 mS cm⁻¹的电导率。这种修饰后的SSE在Li0.5In||LiNi0.8Co0.1Mn0.1O2 ASSB中表现出良好的功能，为硫化物SSE的大规模、低成本制造提供了可能。
4. 电池结构和制造工艺优化
优化电池的结构设计和制造工艺也有助于改善界面接触和稳定性。
- 超薄固态电解质膜： 减薄固态电解质膜可以降低电池内阻、提升能量密度和优化界面接触。然而，膜体的减薄会导致离子电导率、致密度、机械强度和抗枝晶能力的下降。因此，在超薄化过程中需要优化结构以提高致密性和机械性能。
- 共辊干法工艺： 这种干法工艺通过共辊压厚固态电解质和正极层，同时实现了均匀、薄（50 µm）的SSE层和高负载（5 mAh cm⁻²）的正极层，且活性材料比例高达80 wt%。共辊压过程构建了增强且紧密的SSE-正极界面，使得SSE-正极集成薄膜表现出增强的物理性能和在低堆叠压力（2 MPa）下的循环稳定性（500次循环后容量保持率>80%）。这种方法还实现了具有高堆叠级能量密度（310 Wh kg⁻¹）和比能量（805 Wh L⁻¹）的全固态软包电池，在30°C和5 MPa下运行。
- 整体电池设计评估： 硫化物基全固态电池的循环性能对正极活性材料的化学机械性能、SEI的形成以及锂在复合正极和空间电荷层中的扩散过程高度敏感。通过多构型方法和电化学阻抗信号的分布弛豫时间解卷积，可以解耦电池组件中复杂的界面过程，从而促进硫化物固态电池的设计并为电池老化评估提供方法学输入。
5. 挑战与展望
尽管上述策略在提升硫化物固态电解质界面稳定性方面取得了显著进展，但仍面临一些共性挑战：
- 界面副反应： 硫化物固态电解质的窄电化学稳定性窗口和与锂金属负极的化学反应性仍是导致界面降解和电化学性能差的主要原因。特别是在高电压下，正极材料中的Ni会引发级联反应，加剧正极与固态电解质之间的化学机械降解。
- 固-固接触不良： 固态电解质与电极之间的物理接触不良会导致高界面阻抗，阻碍电荷传输并加剧锂的不均匀沉积，最终导致容量利用率不足和循环稳定性差。
- 锂枝晶问题： 锂枝晶的形成会穿透电解质，导致短路和安全问题，限制了电池的寿命和安全性。
- 大规模制造和成本： 硫化物固态电解质对湿气的高度敏感性要求在非兼容传统锂离子电池制造基础设施的环境中进行加工。传统的湿法涂层方法对环境有害且成本高昂。
- 薄膜化挑战： 固态电解质膜的减薄虽然有利于提高能量密度，但会降低离子电导率、致密度、机械强度和抗枝晶能力，影响电池的寿命和安全性。
未来的研究需要继续深入理解复杂的固-固界面现象，特别是原子级别的化学反应和力学行为。同时，开发更高效、更经济、更环境友好的界面工程策略，以及可实现大规模生产的制造工艺，将是推动硫化物全固态电池商业化的关键。结合多尺度表征和理论计算的方法，有助于解锁材料的结构-功能关系，为设计高性能全固态电池提供指导。
References
1Research progress on the application of ultra-thin solid electrolytes in high-energy-density solid-state lithium batteriesOpenAlex
Nan Wang, Ning Zhao, Xiangxin Guo
在固态电池的研究中, 超薄固态电解质膜因在降低电池内阻、提升能量密度以及优化界面接触等方面的优势受到广泛关注. 然而, 膜体的减薄带来离子电导率、致密度、机械强度以及耐枝晶能力的下降, 进而影响电芯的寿命和安全性. 本文围绕固态电解质膜减薄过程中的共性挑战展开讨论, 系统综述不同类型超薄电解质的研究进展, 主要包括氧化物、硫化物以及复合电解质三个材料体系. 首先, 探讨超薄化对电解质离子传输及结构稳定性的影响, 分析制备过程中结构优化对提高致密性和机械性能的重要作用; 其次, 针对不同材料体系, 梳理制备工艺、性能调控及界面匹配等方面取得的关键进展并探讨发展趋势; 最后, 对超薄固态电解质膜的产业化现状、规模化制备技术以及实际应用中面临的工程化瓶颈进行了评述
2Understanding Interfaces at the Positive and Negative Electrodes on Sulfide-Based Solid-State BatteriesOpenAlex
Ander Orue, Manar Cheddadi, Artur Tron, et al.
Despite the high ionic conductivity and attractive mechanical properties of sulfide-based solid-state batteries, this chemistry still faces key challenges to encompass fast rate and long cycling performance, mainly arising from dynamic and complex solid–solid interfaces. This work provides a comprehensive assessment of the cell performance-determining factors ascribed to the multiple sources of impedance from the individual processes taking place at the composite cathode with high-voltage LiNi0.6Mn0.2Co0.2O2, the sulfide argyrodite Li6PS5Cl separator, and the Li metal anode. From a multiconfigurational approach and an advanced deconvolution of electrochemical impedance signals into distribution of relaxation times, we disentangle intricate underlying interfacial processes taking place at the battery components that play a major role on the overall performance. For the Li metal solid-state batteries, the cycling performance is highly sensitive to the chemomechanical properties of the cathode active material, formation of the SEI, and processes ascribed to Li diffusion in the cathode composite and in the space-charge layer. The outcomes of this work aim to facilitate the design of sulfide solid-state batteries and provide methodological inputs for battery aging assessment.
3Interfacial Stabilization by Prelithiated Trithiocyanuric Acid as an Organic Additive in Sulfide‐Based All‐Solid‐State Lithium Metal BatteriesOpenAlex
Leonie Braks, Jinsong Zhang, Alexander Forster, et al.
Abstract Sulfide‐based all‐solid‐state battery (ASSB) with a lithium metal anode (LMA) is a promising candidate to surpass conventional Li‐ion batteries owing to their inherent safety against fire hazards and potential to achieve a higher energy density. However, the narrow electrochemical stability window and chemical reactivity of the sulfide solid electrolyte towards the LMA results in interfacial degradation and poor electrochemical performance. In this direction, we introduce an organic additive approach, that is the mixing of prelithiated trithiocyanuric acid, Li 3 TCA, with Li 6 PS 5 Cl, to establish a stable interface while preserving high ionic conductivity. Including 2.5 wt % Li 3 TCA alleviates the decomposition of the electrolyte on the lithium metal interface, decreasing the Li 2 S content in the solid‐electrolyte interface (SEI) thus forming a more stable interface. In Li|Li symmetric cells, this strategy enables a rise in the critical current density from 1.0 to 1.9 mA cm −2 and stable cycling for over 750 hours at a high current density of 1.0 mA cm −2 . This approach also enables Li|NbO‐NCM811 full cell to operate more than 500 cycles at 0.3 C.
4Chemical 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.
5A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur BatteriesOpenAlex
Bingxin Qi, Xinyue Hong, Ying Jiang, et al.
The utilization of solid-state electrolytes (SSEs) presents a promising solution to the issues of safety concern and shuttle effect in Li-S batteries, which has garnered significant interest recently. However, the high interfacial impedances existing between the SSEs and the electrodes (both lithium anodes and sulfur cathodes) hinder the charge transfer and intensify the uneven deposition of lithium, which ultimately result in insufficient capacity utilization and poor cycling stability. Hence, the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries. In this review, we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes, and summarize recent progresses of their applications in solid-state Li-S batteries. Moreover, the challenges and perspectives of rational interfacial design in practical solid-state Li-S batteries are outlined as well. We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.
6Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State BatteriesOpenAlex
Abhik Banerjee, Hanmei Tang, Xuefeng Wang, et al.
Enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against sulfide solid electrolytes. While protective oxide coating layers such as LiNbO3 (LNO) have been proposed, its precise working mechanisms are still not fully understood. Existing literature attributes reductions in interfacial impedance growth to the coating’s ability to prevent interfacial reactions. However, its true nature is more complex, with cathode interfacial reactions and electrolyte electrochemical decomposition occurring simultaneously, making it difficult to decouple each effect. Herein, we utilized various advanced characterization tools and first-principles calculations to probe the interfacial phenomenon between solid electrolyte Li6PS5Cl (LPSCl) and high-voltage cathode LiNi0.85Co0.1Al0.05O2 (NCA). We segregated the effects of spontaneous reaction between LPSCl and NCA at the interface and quantified the intrinsic electrochemical decomposition of LPSCl during cell cycling. Both experimental and computational results demonstrated improved thermodynamic stability between NCA and LPSCl after incorporation of the LNO coating. Additionally, we revealed the in situ passivation effect of LPSCl electrochemical decomposition. When combined, both these phenomena occurring at the first charge cycle result in a stabilized interface, enabling long cyclability of all-solid-state batteries.
7Surface 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.
8High Ionic Conductive, Mechanical Robust Sulfide Solid Electrolyte Films and Interface Design for All‐Solid‐State Lithium Metal BatteriesOpenAlex
Dabing Li, Hong Liu, Chao Wang, et al.
Abstract All‐solid‐state lithium batteries (ASSLBs) are considered a promising technology for next‐generation energy storage systems due to their inherent safety. However, the conventional laboratory‐scale ASSLBs reported to date are based on pellet‐type structures with thick solid electrolyte layers, leading to challenges related to low energy densities and poor electrochemical performance. In this study, porous adhesive poly(ethylene vinyl acetate) (PEVA) scaffolds and polytetrafluoroethylene (PTFE) binders are utilized to interweave sulfide solid electrolytes into freestanding films with an ultra‐low thickness of 40 µm, high ionic conductivity of 1.1 mS cm −1 , and a high tensile strength of 74 MPa. To mitigate the reduction reaction between the PTFE binder and the lithium metal anode, a Li 3 N‐rich solid electrolyte interphase (SEI) in situ on lithium metal is formed, and the assembled symmetric cell shows excellent cycling stability within 800 h at the current density of 0.2 mA cm −2 and room temperature. Additionally, the ASSLBs using oxidatively stable Li 2 ZrCl 5 F in the composite cathode and the prepared solid electrolyte film demonstrate exceptional cycling performance and fast‐charging capability, with a high cell‐level energy density of 354.4 Wh kg −1 . The ASSLBs prepared by coupling E‐LPSCl film and stable interface design exhibit excellent electrochemical performance and a high cell‐level energy density.
9Chemo-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.
10Lithium Phosphorus Sulfide Chloride–Polymer Composite via the Solution–Precipitation Process for Improving Stability toward Dendrite Formation of Li-Ion Solid ElectrolyteOpenAlex
Piyachai Khomein, Young‐Woon Byeon, Dongye Liu, et al.
Improving the mechanical strength of ceramic solid electrolytes such as lithium phosphorus sulfide families for pressure-driven dendrite blocking as well as reducing the electronic conductivity to prevent a dendrite formation inside the electrolytes are very important to extend the lifespan of all-solid-state lithium-metal batteries. Here, we propose a low-temperature solution-precipitation process to prepare polymer-solid electrolyte composites for a highly uniform polymer distribution in the electrolyte to enhance their mechanical strength and reduce their electronic conduction. The composites with up to 12 wt % of polymer are prepared, and the composites exhibit high ionic conductivities of up to 0.3 mS/cm. Furthermore, the electrochemical stability of the electrolyte composites on Li striping/plating cycles is investigated. We confirm that the proposed solution-precipitation process makes the composite much more stable than the bare solid electrolyte and causes them to outperform similar composites from the other existing preparation methods, such as mechanical mixing and solution dispersion.
11Interfacial challenges for all-solid-state batteries based on sulfide solid electrolytesOpenAlex
Shuo Wang, Ruyi Fang, Yutao Li, et al.
Sulfide solid electrolytes (e.g., lithium thiophosphates) have the highest room-temperature ionic conductivity (∼10−2 S cm−1) among solid Li-ion conductors so far, and thus have attracted ever-increasing attention for high energy-density and safety all-solid-state batteries (ASSBs). However, interfacial issues between sulfide electrolytes and electrodes have been the main challenges for their applications in ASSBs. The interfacial instabilities would occur due to side reactions of sulfides with electrodes, poor solid-solid contact, and lithium dendrites during charge/discharge cycling. In this review, we analyze the interfacial issues in ASSBs based on sulfide electrolytes, and in particular, discuss strategies for solving these interfacial issues and stabilize the electrode-electrolyte interfaces. Moreover, a perspective of the interfacial engineering for sulfide-based ASSBs is provided.
12Study of the Cathode/Electrolyte Interface in an All-Sulfide-Solid-State Battery Using Lithium-Rich Transition Metal SulfideOpenAlex
Mathieu Caspar, Yohan Biecher, Yann Tison, et al.
All-solid-state lithium batteries (ASSBs) are among the most promising energy storage technologies, particularly for electric vehicles, due to their enhanced safety. However, performances of these systems are still hindered by interfacial side reactions at electrode/electrolyte interfaces, especially when sulfide electrolytes are used, and additional issues of mechanical nature. In this work, an ASSB system composed of an argyrodite (Li5.7PS4.7Cl1.3) electrolyte, a lithium-rich sulfide cathode (Li1.2Ti0.8S2) operating at moderate voltage, and a lithium metal anode is investigated. The positive electrode/electrolyte interface is scrutinized during several battery cycles using X-ray photoelectron spectroscopy (XPS) via two complementary approaches (ex situ and in situ). We show that both titanium and sulfur species contribute to the electrochemical process without any detectable degradation of the electrolyte after 20 cycles and without the use of any protective coating. These results suggest that the electrochemical performances of such an all-sulfide system are not limited by the cathode/electrolyte reactivity, opening a promising route for the development of specific cathode materials adapted to sulfide electrolytes.
13Cl-Doped Li<sub>10</sub>SnP<sub>2</sub>S<sub>12</sub> with Enhanced Ionic Conductivity and Lower Li-Ion Migration BarrierOpenAlex
Qingtao Wang, Dongxu Liu, Xuefang Ma, et al.
All-solid-state lithium batteries based on sulfide solid electrolytes have attracted much attention because of their high ionic conductivity. Li10SnP2S12 (LSPS) has the same structure as Li10GeP2S12, and there is little difference in ionic conductivity between them, but the preparation cost of LSPS is lower. Here, Cl doping is used to improve the electrochemical stability of the LSPS to the anode and the Li-ion transport performance. Among them, Li9.9SnP2S11.9Cl0.1 had a high ion conductivity of 2.62 mS cm–1 after cold pressure. On the crystal structure, X-ray diffraction Rietveld refinement indicated that the Cl-substituted portion S is successfully incorporated into the lattice of the LSPS, increasing Li-ion vacancies and reducing the distance between adjacent Li-ion distributed along the c-axis, these are conducive to Li-ion transmission. The temperature-dependent AC impedance experiment and density functional theory calculation show that doping with Cl makes Li9.9SnP2S11.9Cl0.1 have a lower activation energy. The assembled lithium symmetric batteries show that the doping of Cl promotes the stability of the interface between LSPS and the lithium metal anode. The charge–discharge tests of all-solid-state batteries using Li9.9SnP2S11.9Cl0.1 as electrolyte have confirmed that Cl doping can improve the electrochemical performance of LSPS, which have a higher specific capacity and cycle life.
14Surface molecular engineering to enable processing of sulfide solid electrolytes in humid ambient airOpenAlex
Mengchen Liu, Jessica J. Hong, Elias Sebti, et al.
Abstract Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today’s lithium-ion battery manufacturing infrastructure. Herein, we present a reversible surface modification strategy that enables the processability of sulfide SSEs (e. g., Li 6 PS 5 Cl) under humid ambient air. We demonstrate that a long chain alkyl thiol, 1-undecanethiol, is chemically compatible with the electrolyte with negligible impact on its ion conductivity. Importantly, the thiol modification extends the amount of time that the sulfide SSE can be exposed to air with 33% relative humidity (33% RH) with limited degradation of its structure while retaining a conductivity of above 1 mS cm -1 for up to 2 days, a more than 100-fold improvement in protection time over competing approaches. Experimental and computational results reveal that the thiol group anchors to the SSE surface, while the hydrophobic hydrocarbon tail provides protection by repelling water. The modified Li 6 PS 5 Cl SSE maintains its function after exposure to ambient humidity when implemented in a Li 0.5 In | |LiNi 0.8 Co 0.1 Mn 0.1 O 2 ASSB. The proposed protection strategy based on surface molecular interactions represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications.
15Large-scale manufacturing of solid-state electrolytes: Challenges, progress, and prospectsOpenAlex
Justyna Minkiewicz, Gareth M. Jones, Shaghayegh Ghanizadeh, et al.
Solid-state electrolytes (SSEs) are vital components in solid-state lithium batteries, which hold significant promise for energy storage applications. This review provides an overview of solid-state batteries (SSBs) and discusses the classification of electrolytes, with a focus on the challenges associated with oxide- and sulphide-based SSEs, particularly concerning interfaces and chemical stability. This review also explores methods employed to form and sinter SSEs in large-scale manufacturing, including both established and novel techniques for producing dense oxide- and sulphide-based films. Additionally, the potential application of additive manufacturing (AM) in SSE production is discussed. Lastly, the paper summarises the mass manufacturing of SSEs and provides an outlook for sustainable SSB development goals. The insights presented in this review contribute to the understanding and progress of SSE technology for solid-state lithium batteries.
17Multifunctional ion-conductive polymer coatings for high-performance sulfide solid-state batteries with Ni-rich cathodesOpenAlex
Pranav Karanth, Jelle H Prins, Ajay Gautam, et al.
for uncoated at 0.1C) and a remarkable capacity retention of 82.7% after 500 cycles at 0.2C and ambient conditions (20 °C) are observed. These results emphasize the effectiveness of PILs with Li salts as multifunctional coatings that enable high-performance sulfide-based SSBs with Ni-rich cathode materials at ambient temperature.
18Electrochemical Stability of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub> and Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Solid ElectrolytesOpenAlex
Fudong Han, Yizhou Zhu, Xingfeng He, et al.
The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk‐type solid‐state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemical stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte‐carbon cell. The most promising solid electrolytes, Li 10 GeP 2 S 12 and cubic Li‐garnet Li 7 La 3 Zr 2 O 12 , are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high‐performance solid‐state batteries.
19Robust interface and reduced operation pressure enabled by co-rolling dry-process for stable all-solid-state batteriesOpenAlex
Dong Ju Lee, Yuju Jeon, Jung-Pil Lee, et al.
Abstract The dry-process is a sustainable and promising fabrication method for all-solid-state batteries by eliminating solvents. However, a pragmatic fabrication design for thin and robust solid-state electrolyte (SSE) layers has not been established. Herein, we report a dry-process approach that enhances mechanical stability of SSE layers from film fabrication to cell operation. By co-rolling thick SSE and positive electrode feeds, a uniform, thin SSE layer (50 µm) and a high loading positive electrode layer (5 mAh cm −2 ) with high active material ratio (80 wt%) are simultaneously achieved. This SSE-positive electrode integrated film exhibits enhanced physical properties and cyclability (> 80% retention after 500 cycles) at low stack pressure (2 MPa) compared to the freestanding counterparts, attributed to reinforced and intimate SSE-positive electrode interface constructed during co-rolling process. Additionally, an all-solid-state pouch cell with high stack-level specific energy (310 Wh kg −1 ) and energy density (805 Wh L −1 ) operating at 30 °C and 5 MPa is demonstrated.
20Solid-State Electrolyte for Lithium-Air Batteries: A ReviewOpenAlex
Qian‐Cheng Zhu, Jie Ma, Shujian Li, et al.
Traditional lithium-air batteries (LABs) have been seriously affected by cycle performance and safety issues due to many problems such as the volatility and leakage of liquid organic electrolyte, the generation of interface byproducts, and short circuits caused by the penetration of anode lithium dendrite, which has hindered its commercial application and development. In recent years, the emergence of solid-state electrolytes (SSEs) for LABs well alleviated the above problems. SSEs can prevent moisture, oxygen, and other contaminants from reaching the lithium metal anode, and their inherent performance can solve the generation of lithium dendrites, making them potential candidates for the development of high energy density and safety LABs. This paper mainly reviews the research progress of SSEs for LABs, the challenges and opportunities for synthesis and characterization, and future strategies are addressed.