Practical Application of Li-Rich Materials in Halide All-Solid-State Batteries and Interfacial Reactions between Cathodes and Electrolytes

Zhang, Anbang; Wang, Jing; Yu, Ruizhi; Zhuo, Haoxiang; Wang, Changhong; Ren, Zhimin; Wang, Jiantao

doi:10.1021/acsami.2c21569

Cited by 9 publications

(8 citation statements)

References 41 publications

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“…The R 1 and R 2 peaks represent the charge transfer resistance at the cathode/LPSCl interface. [31,32] Since LLO consists of two phases, it is reasonable that the two peaks observed in DRT analysis correspond to R 1 and R 2 . [33] The R 3 peak is attributed to the solid-phase diffusion of cathodes.…”

Section: Electrochemical Propertiesmentioning

confidence: 99%

Dual‐Function Modifications for High‐Stability Li‐Rich Cathode Toward Sulfide All‐Solid‐State Batteries

Wang,

Wu,

Chen

et al. 2023

Adv Funct Materials

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With the growing demand for high‐energy‐density lithium‐ion batteries, Li‐rich Mn‐based layered oxide (LLO) cathodes with high specific capacity and low cost receive significant attention in conventional liquid lithium‐ion batteries. However, LLO is rarely used in sulfide all‐solid‐state lithium batteries (ASSLBs) because of severe interfacial side reactions with sulfide solid electrolytes (SEs), especially at a high operation voltage of 4.8 V (vs Li/Li+). In this work, a dual‐function modification strategy is proposed to enable electrochemically stable LLO in sulfide ASSLBs. The covalent Ru─O bond formed by Ru‐doping can not only stabilize lattice oxygen, preventing further interfacial decomposition involving oxygen, but also enhance the ability of Li diffusion in Li2MnO3 component, and then stimulate the activation of Li2MnO3 phase. Meanwhile, the surface sulfidation strategy establishes a highly stable interface, contributing to the rapid ionic transport at LLO/LPSCl interface. Results show that the modified LLO in sulfide ASSLBs delivers two times higher initial discharge capacity and an extra‐long life of 2022 cycles of up to 4.2 V (vs Li–In) (with >70% capacity retention at 1 C). This research enriches the strategies for improving interfacial compatibility between LLO cathodes and sulfide SEs, thus providing new inspiration for guiding the application of LLO in sulfide ASSLBs.

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Section: Electrochemical Propertiesmentioning

confidence: 99%

Dual‐Function Modifications for High‐Stability Li‐Rich Cathode Toward Sulfide All‐Solid‐State Batteries

Wang,

Wu,

Chen

et al. 2023

Adv Funct Materials

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“…Wh kg -1 以上的高能量密度发展目标，而且有机电解液易泄露、易腐蚀、易燃烧等特性也导致液态锂电池存在严重的安全隐患 [3,4] 。与液态锂电池相比，采用固态电解质的全固态锂电池(All-soild-state lithium battery，ASSLB)具有高安全性、高能量密度、长寿命等优点，有望解决目前液态锂电池存在的上述问题，是实现 2025年单体电池能量密度达到500 Wh kg -1 目标的关键技术之一 [5,6] 。目前，正极材料仍然是决定全固态锂电池能量密度的关键因素。因此，选择更高容量的正极材料对于提高全固态锂电池的能量密度至关重要 [7,8] 。富锂锰基层状氧化物正极材料(1-x)LiTMO 2 • xLi 2 MnO 3 (0< x≤ 1，TM=Ni，Co，Mn)的阴离子和阳离子可以在高工作电压下协同参与氧化还原反应，能提供高放电比容量(> 250 mAh g -1 )和能量密度(> 900 Wh kg -1 ) ，并且还具有热稳定性更高、原料成本低等优点 [9,10] 。此外，通过取代 Li 2 TMO 3 (TM=Ti [11] ，Zr [12] ，Ir [13] ，Ru [14] ) 中的 TM 元素，也可以获得不同类型的高容量富锂层状氧化物正极材料。近年来，图1 富锂正极材料在全固态锂电池中的发展历史概览 [18][19][20][21][22][23][24][25][26][27][28][29][30] Fig. 1.…”

Section: 引言unclassified

“…1. Development history of lithium-rich cathodes in all-solid-state lithium batteries [18][19][20][21][22][23][24][25][26][27][28][29][30] .…”

Section: 引言mentioning

confidence: 99%

“…V(vs Li/Li + )， 0.1 mV s -1 下初始四个循环期间的 CV 曲线；(d) Pt|LLO|LPSCl|Pt 的原位加电装置图和原位电荷密度分布 [19] corresponds to the oxidized oxygen triggered by oxygen redox reaction at the charged state) [18] ; (b) Electronic conductivity, ionic conductivity and C2/m phase content of LRCox and LRCo10@yLN cathodes [20] 和Li 2 MoO 4 等 [50][51][52] 。 Sun等 [21] 首次报道了Li 1.17 循环寿命。Zhang等 [22] ；(b) 采用 LNO 离子导电涂层材料对 LRM 进行表面化学修饰 [23] ；(c) 通过 S-O 键以稳定 LRMO/SE 界面 [22] Fig. 4.…”

Section: 富锂全固态锂电池研究进展unclassified

“…4. Lithium-rich cathode halide ASSLB: (a) Schematic illustration of ASSLB consisting of carbon additives and coated-LPO LLO [21] ; (b) Surface chemistry modification of LRM with an ionic conductive coating material of LNO [23] ; (c) Stabilization of LRMO/SE interface by S-O 13 bonding [22] .…”

Section: 富锂全固态锂电池研究进展mentioning

confidence: 99%

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Research advance of lithium-rich cathode materials in all-solid-state lithium batteries

Yang¹,

Hu²,

Jin³

et al. 2023

Acta Phys. Sin.

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The development of all-solid-state lithium batteries with high energy density, long cycle life, low cost and high safety is one of the important directions for the development of next-generation lithium-ion batteries. Lithium-rich cathode materials have been widely used in liquid lithium batteries for their higher discharge specific capacity (> 250 mAh g-1) and energy density (> 900 Wh kg-1), due to the synergistic redox of anions and cations, as well as their high thermal stability and low raw material cost. With the rapid development of high-performance lithium-rich cathode materials and solid-state electrolytes in all-solid-state lithium batteries, the application of lithium-rich cathode materials in all-solid-state lithium batteries is expected to break through to the target of 500 W h kg-1 energy density of lithium-ion batteries. In this review, we firstly elaborate the failure mechanism of lithium-rich cathode materials in all-solid-state lithium batteries. The poor electronic conductivity, irreversible redox reaction of anionic oxygen and structute transformation during the electrochemical cycling of lithium-rich cathode materials lead to the low initial coulomb efficiency, poor cycling stability and voltage decay. In addition, the high operating voltage of lithium-rich cathode materials (> 4.5 V vs. Li/Li+) exposes the cathode/electrolyte to not only conventional interfacial chemical reactions, but the released oxygen also aggravates the interfacial electrochemical reactions, which put higher demands on the interfacial stability of the cathode/electrolyte. Therefore, the intrinsic characteristics of lithium-rich cathode materials and the severe interfacial reaction of lithium-rich cathode/electrolyte greatly limit the application of lithium-rich cathode materials in all-solid-state lithium batteries. Then, we review the research progress of lithium-rich cathode materials in various solid-state electrolyte systems in recent years. The higher room temperature ionic conductivity and wider voltage window of inorganic solid-state electrolytes provide opportunities for the application of lithium-rich cathode materials in all-solid-state lithium batteries. At present, the application of lithium-rich cathode materials in all-solid-state lithium batteries has been initially explored on the basis of sulfide, halide and oxide solid-state electrolyte systems, and important progress has been made in studies including composite cathode preparation methods, interfacial reaction mechanisms and activation mechanisms. Finally, we summarize the current research focus of lithium-rich cathode all-solid-state lithium batteries and propose several strategies for their future outlook. Strategies such as the regulation of cathode material components, the construction of lithium ion and electron transport pathways within the composite cathode, and the interfacial modification of cathode materials have been shown to have significant effects in solving the failure problem.

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Unraveling the Spatial Asynchronous Activation Mechanism of Oxygen Redox‐Involved Cathode for High‐Voltage Solid‐State Batteries

Hu,

Zhang,

Yang

et al. 2024

Advanced Energy Materials

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Li‐rich layered oxides (LRLO) exhibit significant potential for use in all‐solid‐state lithium batteries (ASSLBs) owing to their high capacities and wide range of operating voltages. However, the practical application of LRLO in ASSLBs is hindered by the severe failure of carrier transport at the solid–solid interface, which subsequently limits the electrochemical activity of these batteries. Here, the spatially asynchronous activation mechanism of the LRLO in ASSLBs is presented. A spectroscopic study extending from the surface into the bulk interior of LRLO indicates that the activation kinetics of anionic oxygen prefers hysteretic delivery over uniform delivery and fast transition metals (TMs) activation. This spatial hetero activation is dominated by the failure of carrier transport at the interface, which is induced by microstructural defects in the composite cathode. This study is expected to facilitate the microstructural design of high‐performance LRLO‐based ASSLBs.

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Practical Application of Li-Rich Materials in Halide All-Solid-State Batteries and Interfacial Reactions between Cathodes and Electrolytes

Cited by 9 publications

References 41 publications

Dual‐Function Modifications for High‐Stability Li‐Rich Cathode Toward Sulfide All‐Solid‐State Batteries

Dual‐Function Modifications for High‐Stability Li‐Rich Cathode Toward Sulfide All‐Solid‐State Batteries

Research advance of lithium-rich cathode materials in all-solid-state lithium batteries

Unraveling the Spatial Asynchronous Activation Mechanism of Oxygen Redox‐Involved Cathode for High‐Voltage Solid‐State Batteries

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