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CHINESE CHEMICAL LETTERS · 2021 ·Vol. 33 ·期 10 ·4635-4639 · IF 6.779

Enabling ultrafast lithium-ion conductivity of Li2ZrCl6 by indium doping

Shuai Chen,Chuang Yu,Shaoqing Chen,Linfeng Peng,Cong Liao,Chaochao Wei,Zhongkai Wu,Shijie Cheng,Jia Xie

Solid-state batteries with high energy density and safety are promising next-generation battery systems. However, lithium oxide and lithium sulfide electrolytes suffer low ionic conductivity and poor electrochemical stability, respectively. Lithium halide solid electrolyte shows high conductivity and good compatibility with the pristine high-voltage cathode but limited applications due to the high price of rare metal. Zr-based lithium halides with low cost and high stability possess great potential. Herein, a small amount of In 3+ is introduced in Li 2 ZrCl 6 to synthesize Li 2.25 Zr 0.75 In 0.25 Cl 6 electrolytes with a high room temperature Li-ion conductivity of 1.08 mS/cm. Solid-state batteries using Li 2.25 Zr 0.75 In 0.25 Cl 6 /Li 5.5 PS 4.5 Cl 1.5 bilayer solid electrolytes combined with Li-In anode and pristine LiNi 0.7 Mn 0.2 Co 0.1 O 2 cathode deliver high initial discharge capacities under different cut-off voltages. This work provides an effective strategy for enhancing the conductivity of Li 2 ZrCl 6 electrolytes, promoting their applications in solid-state batteries.

研究领域: 材料科学 · 电化学 · 固体离子学 · 能源存储 · 无机非金属材料 · 电池技术
✓ 已验证 DOI 高影响因子
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Journal of Materials Chemistry A · 2019 ·Vol. 7 ·期 31 ·18612-18618 · IF 10.733

High-performance Li6PS5Cl-based all-solid-state lithium-ion batteries

Shuo Wang,Xiaofu Xu,Xue Zhang,Chengzhou Xin,Bingqing Xu,Liangliang Li,Yuan-Hua Lin,Yang Shen,Baohua Li,Ce-Wen Nan

All-solid-state lithium-ion batteries (ASSLIBs) owing to their advantage of enhanced safety are considered to be a promising candidate for next-generation energy storage devices. However, the poor cycling performance and low areal capacities of ASSLIBs with S, Li2S or traditional oxide cathodes hinder the development of high-energy-density ASSLIBs. Herein, a Li6PS5Cl solid-state electrolyte has been systematically investigated for use as a cathode active material in ASSLIBs for the first time. ASSLIBs employing Li6PS5Cl as both the active material and electrolyte with a Li–In alloy anode are fabricated. A Li6PS5Cl-based cell with an active material loading of 3.1 mg cm−2 exhibits a high discharge capacity of around 535 mA h g−1 after 650 cycles at 56 mA g−1 (∼0.1C) at room temperature, which is the highest value among ASSLIBs using sulfide SSEs as active materials and is even comparable with those of cells with S, Li2S or transition metal sulfides as the active material. This superior long-term cycling performance is attributed to the highly reversible electrochemical activity of Li6PS5Cl revealed by ex situ XRD and XPS analyses.

研究领域: 电化学 · 能源材料 · 固态离子学 · 储能技术 · 材料科学
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Journal of Energy Chemistry · 2020 · IF 7.216

Enabling high-performance all-solid-state lithium batteries with high ionic conductive sulfide-based composite solid electrolyte and ex-situ artificial SEI film

Jingguang Yi,Dan Zhou,Yuhao Liang,Hong Liu,Haifang Ni,Li-Zhen Fan

All-solid-state lithium batteries (ASSLBs) employing sulfide electrolyte and lithium (Li) anode have received increasing attention due to the intrinsic safety and high energy density. However, the thick electrolyte layer and lithium dendrites formed at the electrolyte/Li anode interface hinder the realization of high-performance ASSLBs . Herein, a novel membrane consisting of Li 6 PS 5 Cl (LPSCl), poly(ethylene oxide) (PEO) and Li-salt (LiTFSI) was prepared as sulfide-based composite solid electrolyte (LPSCl-PEO3-LiTFSI) (LPSCl:PEO = 97:3 wt/wt; EO:Li = 8:1 mol/mol), which delivers high ionic conductivity (1.1 × 10 −3 S cm −1 ) and wide electrochemical window (4.9 V vs. Li + /Li) at 25 °C. In addition, an ex-situ artificial solid electrolyte interphase (SEI) film enriched with LiF and Li 3 N was designed as a protective layer on Li anode (Li(SEI)) to suppress the growth of lithium dendrites. Benefiting from the synergy of sulfide-based composite solid electrolyte and ex-situ artificial SEI, cells of S-CNTs/LPSCl-PEO3-LiTFSI/Li(SEI) and Al 2 O 3 @LiNi 0.5 Co 0.3 Mn 0.2 O 2 /LPSCl-PEO3-LiTFSI/Li(SEI) are assembled and both exhibit high initial discharge capacity of 1221.1 mAh g −1 (135.8 mAh g −1 ) and enhanced cycling   stability with 81.6% capacity retention over 200 cycles at 0.05 C (89.2% over 100 cycles at 0.1 C). This work provides a new insight into the synergy of composite solid electrolyte and artificial SEI for achieving high-performance ASSLBs .

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 界面工程
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Inhibition of lithium dendrites by a LiPON interlayer with Li+ conductive and electron non-conductive dynamic properties based on Li7La3Zr2O12 solid electrolyte

Yanhua Zhang,Yuhang Mei,Xinglong Gao,Yumei Xiao,Zijun Tang,Xing Xiang,Jiadong Deng

The lithium dendrite problem of Li 7 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) solid electrolyte restricts the practical application and development of all-solid-state lithium batteries (ASSLBs). Herein, a LiPON interlayer with Li + conductive and electron non-conductive dynamic properties is constructed at the Li/LLZTO interface. Results show that the electronic conductivity of solid electrolyte after LiPON modification decreased by nearly three orders of magnitude, indicating that it has good ability to hinder electron conduction . The interlayer enhances the wettability between the Li metal anode and LLZTO, resulting in a decrease of battery resistance from 3400 Ω to 700 Ω. The critical current density of the ASSLBs increase from 0.1 mA cm −2 to 1.2 mA cm −2 at room temperature, and the battery cycle number increase from 31 h to over 1000 h. XPS deep etching results show that the LiPON/LLZTO interface has good electrochemical stability. The Kelvin probe force microscope displays a sharp increase in potential within the LiPON interlayer, indicating its successful hindrance of electron conduction to the solid electrolyte. The effective inhibition of lithium dendrites growth is due to LiPON can promote the Li + transmission from LLZTO solid electrolyte to Li anode, and also hinder the electron conduction to LLZTO to form lithium dendrites.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 界面工程
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

Indium doped sulfide solid electrolyte with tamed lithium dendrite and improved ionic conductivity for all-solid-state battery applications

Yuanyuan Li,Jun Cheng,Jianwei Li,Zhen Zeng,Yixuan Guo,Hongqiang Zhang,Hongbin Liu,Xiao Xu,Yiwei Rao,Deping Li,Lijie Ci

Sulfide solid state electrolytes capture much attention owing to their high conductivity and decent mechanical property. Nevertheless, the moisture instability and poor interfacial compatibility against lithium metal anode remain challenging and hinder the practical application. Herein, we report a novel indium (In) doping strategy based on the hard-soft-acid-base theory to tackle these issues. Optimized Li 7 P 2.9 S 10.9 In 0.1 electrolyte exhibits a high ionic conductivity of 4.1 × 10 −3  S cm −1 and achieves an enhanced interfacial compatibility. Importantly, as In partially replaces the phosphorus (P), the amount of released hydrogen sulfide can be significantly decreased and the air stability is improved. The all-solid-state battery assembled with the Li 7 P 2.9 S 10.9 In 0.1 electrolyte demonstrates a high discharge capacity and a good cycling stability under a high current density of 1.0 C. This work provides a practical and effective method to design sulfide-based solid-state electrolyte with high ionic conductivity and enhanced air stability for all-solid-state battery applications.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 电池技术
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Science China-Materials · 2021 ·Vol. 64 ·期 6 ·1378-1385 · IF 8.273

Interplay between Li3YX6 (X = Cl or Br) solid electrolytes and the Li metal anode

Fu Yuanyuan,Ma Cheng

The interplay between solid electrolytes and electrodes is of vital importance to the performance of all-solid-state Li batteries. Recently, halide superionic conductors have emerged as a new family of high-performance solid electrolytes, but their compatibility with Li metal, i.e., the anode with the highest theoretical capacity, has not been systematically studied. Here, we investigate the interaction between Li metal and two representative halide solid electrolytes: Li 3 YCl 6 and Li 3 YBr 6 . Both materials are found to form interphases with Li, similar to most solid electrolytes. However, the interphases observed here contain electronic conducting components, which are detrimental to their compatibility with Li. By elucidating this phenomenon, the present study provides guiding principles for improving the Li compatibility of halide solid electrolytes.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 电池技术
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2019 · IF 7.467

Smart construction of intimate interface between solid polymer electrolyte and 3D-array electrode for quasi-solid-state lithium ion batteries

S.Z. Zhang,X.L. Wang,X.H. Xia,Z.J. Yao,Y.J. Xu,D.H. Wang,D. Xie,J.B. Wu,C.D. Gu,J.P. Tu

Interfacial issues have been the main obstacle to the development of solid-state batteries . In this work, we design a solid hybrid polymer electrolyte based on poly-(ethylene glycol) diacrylate and succinonitrile (PSSE) with a liquid state precursor. An intimate interface between PSSE and Li 4 Ti 5 O 12 @vertical graphene (LTO@VG) electrode with three-dimensional array structure is cleverly constructed by infiltrating fluid precursor of PSSE into vertical pores of LTO@VG followed by polymerization and solidification of PSSE. The quasi-solid-state LTO@VG//PSSE//Li and LiFePO 4 //PSSE//LTO@VG full cells exhibit superior electrochemical performance since the active materials are closely contacted by the conductive skeleton and ion-conductive electrolyte. The LTO@VG//PSSE//Li cells maintain 85.7% capacity retention after 400 cycles at 2 C and the LFP//PSSE//LTO@VG full cells still reach 99.0% capacity retention after 200 cycles at 0.5 C. This novel strategy for interface engineering paves the way for achieving high-performance solid-state batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子化学 · 纳米材料 · 界面科学
✓ 已验证 DOI 高影响因子
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Enhanced ionic conductivity and lithium dendrite suppression of polymer solid electrolytes by alumina nanorods and interfacial graphite modification

Xin-yu Hu,Mao-xiang Jing,Hua Yang,Quan-yao Liu,Fei Chen,Wei-yong Yuan,Le Kang,Dong-hong Li,Xiang-qian Shen

Poor room-temperature ionic conductivity and lithium dendrite formation are the main issues of solid electrolytes. In this work, rod-shaped alumina incorporation and graphite coating were simultaneously applied to poly (propylene carbonate) (PPC)-based polymer solid electrolytes (Wang et al., 2018). The obtained alumina modified solid electrolyte membrane (Al-SE) achieves a high ionic conductivity of 3.48 × 10 −4 S/cm at room temperature with a wide electrochemical window of 4.6 V. The assembled NCM622/Al-SE/Li solid-state battery exhibits initial discharge capacities of 198.2 mAh/g and 177.5 mAh/g at the current density of 0.1 C and 0.5 C, with the remaining capacities of 165.8 mAh/g and 161.3 mAh/g after 100 cycles respectively. The rod-shaped structure of Al 2 O 3 provides fast transport channels for lithium ions and its Lewis acidity promotes the dissociation of lithium salts and release of free lithium ions. The lithiophilic Al 2 O 3 and Graphite form intimate contact with metallic Li and create fast Li + conductive layers of Li-Al-O layer and LiC 6 layer, thus facilitating the uniform deposition of Li and inhibiting Li dendrite formation during long-term cycling. This kind of composite Al-SE is expected to provide a promising alternative for practical application in solid electrolytes.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 纳米复合材料 · 锂金属电池
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IONICS · 2016 ·Vol. 23 ·期 10 ·2603-2611 · IF 2.119

Hybrid solid electrolytes with excellent electrochemical properties and their applications in all-solid-state cells

Chen Shaojie,Zhao Yanran,Yang Jing,Yao Lili,Xu Xiaoxiong

Three types of inorganic electrolytes [Li 10 GeP 2 S 12 (LGPS), 75Li 2 S·24P 2 S 5 ·1P 2 O 5 (LPOS), Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP)] with different particle sizes and electrochemical properties are selected as active fillers incorporated into poly(ethylene oxide) (PEO) matrix to fabricate hybrid solid electrolytes. The optimum composition of each filler is found in consideration of ionic conductivity. Their electrochemical characteristics are investigated. The optimal conductivities are 1.60 × 10 −5 , 1.18 × 10 −5 , and 2.12 × 10 −5  S cm −1 at room temperature for PEO-1%LGPS, PEO-1%LPOS, and PEO-20%LAGP, respectively. The electrochemical stability windows of these hybrid solid electrolytes are all above 5 V (vs. Li + /Li). The results show that these fillers have positive effects on the ionic conductivity, lithium ion transference number, and electrochemical stability. The relationship between the type of filler and electrochemical properties has been investigated. All-solid-state cells LiFePO 4 /Li are fabricated and present fascinating electrochemical performance with high capacity retention and good cycling stability. This work provides promising electrolytes prepared by a simple method.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 功能材料 · 锂电池技术
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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

A simple approach through reduction of Na2SO4 to prepare high-purity Na2S for sulfide electrolytes toward all-solid-state sodium batteries

Yufen Yan,Yayu Guo,Huadong Zheng,Liang Qi,Yutao Yang,Yanli Miao,Xixi Shi,Lianqi Zhang,Chunliang Li,Dawei Song

Development of sulfide solid-state electrolytes (SSEs) with high ionic conductivity plays a leading role in achieving all-solid-state sodium batteries (ASSSBs). As an important raw material for synthesizing sulfide SSEs, the purity of Na 2 S significantly affects the ionic conductivity and electrochemical properties of sulfide SSEs. In order to obtain high-purity and low-cost Na 2 S, a hydrogen reduction of industrial grade Na 2 SO 4 followed by ethanol purification has been successfully employed to synthesize and purify Na 2 S, which possesses a high purity of 98 %. Na 3 SbS 4 has been synthesized by as-synthesized Na 2 S (A-Na 2 S) and commercial Na 2 S (C–Na 2 S) by liquid-phase synthesis and solid-state reaction methods, respectively. The electrochemical properties indicate that Na 3 SbS 4 samples synthesized by A-Na 2 S possess higher ionic conductivity and lower Ea, and the assembled ASSSBs exhibit higher specific capacities, superior cycle and rate performance. At 0.5C, the assembled TiS 2 /Na 3 SbS 4 /NaSn ASSSB exhibits a high initial capacity of 211.4 mAh g −1 with capacity retention of 96.2 % after 360 cycles at room temperature. This work provides a simple approach for synthesizing high-purity Na 2 S at low cost, enabling the large-scale application of sulfide SSEs for ASSSBs.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 无机合成 · 电池技术
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TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA · 2025 ·Vol. 35 ·期 7 ·2341-2353 · IF 4.7

High-performance Li3YCl3Br3 halide solid electrolyte synthesized using wet-chemistry route for all-solid-state battery

Han-zhou LIU,Yan-chen LIU,Sheng-hao JING,Ya-qi HU,Zong-liang ZHANG,Si-liang LIU,Yang LIU,Zhi ZHUANG,Fan-qun LI,Fang-yang LIU

A dual-halide solid electrolyte, Li 3 YCl 3 Br 3 , was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route. Li 3 YCl 3 B r3 exhibits an ion conductivity of 2.08 mS/cm and an electro- chemical stability window of 3.8 V. Additionally, an all-solid-state lithium-ion battery using Li 3 YCl 3 Br 3 and LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM811) as the cathode material achieves a capacity retention of 93% after 200 cycles at 0.3 C and maintains a specific capacity of 115 mA·h/g during 2 C cycling. This exceptional performance is attributed to the high oxidative stability of Li 3 YCl 3 Br 3 and the in-situ formation of Y 2 O 3 inert protective layer on the NCM811 surface under high voltage. Consequently, the study demonstrates the feasibility of a simple, cost-effective wet-chemistry route for synthesizing multi-component halides, highlighting its potential for large-scale production of halide solid electrolytes for practical applications.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 电池技术 · 无机非金属材料 · 纳米材料应用
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Small · 2024 ·Vol. 20 ·期 31 ·2310912 · IF 13

Vertically-Aligned Card-House Structure for Composite Solid Polymer Electrolyte with Fast and Stable Ion Transport Channels

Xunzhi Miao,Jianhe Hong,Shuo Huang,Liye Ding,Fang Wang,Min Liu,Quanquan Zhang,Hongyun Jin

All-solid-state lithium batteries (ASSLBs) are highly promising as next-generation energy storage devices owing to their potential for great safety and high energy density. This work demonstrates that composite solid polymer electrolyte with vertically-aligned card-house structure can simultaneously improve the high rate and long-term cycling performance of ASSLBs. The vertical alignment of laponite nanosheets creates fast and uniform Li + ion transport channels at the nanosheets/polymer interphase, resulting in high ionic conductivity of 8.9 × 10 −4 S cm −1 and Li + transference number of 0.32 at 60 °C, as well as uniformly distributed solid electrolyte interphase. Such electrolyte is characterized by high mechanical strength, low flammability, excellent structural stability and stable ion transport channels. In addition, the ASSLB cell with the electrolyte and LiFePO 4 cathode delivers a high discharge specific capacity of 124.8 mAh g −1 , which accounts for 85.6% of its initial capacity after 500 cycles at 1C. The reasonable design through structural control strategy by interconnecting the vertically-aligned nanosheets open a way to fabricate high performance composite solid polymer electrolytes.

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子科学 · 纳米材料 · 电池技术
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