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Regulating surface base of LiCoO_(2) to inhibit side reactions between LiCoO_(2) and sulfide electrolyte

Rare Metals 2023年第12期42卷 4128-4141页

作者： Kai Yang Rong-Zheng Tian Zhen-Yu Wang Hong-Zhou Zhang Yue Ma Xi-Xi Shi Da-Wei Song Lian-Qi Zhang Ling-Yun Zhu School of Materials Science and Engineering Tianjin University of TechnologyTianjin 300384China Guilin Electrical Equipment Scientifie Research Institute Co.Lud Guilin 541004China Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Nankai UniversityTianjin 300071China School of Materials Science and Engineering Anhui UniversityHefei 230601China

The interface instability between layered oxide cathode and sulfide electrolyte is a key point affecting the perform ance of sulfide-based all-solid-state lithium batteries.Coating with fast-ionic conductor and constructing core-shell structure can effectively alleviate the interfacial side reactions and improve the interfacial stability between layered oxide and sulfide electrolyte.However,what have been neglected is the surface base(including Li_(2)CO_(3) and LiOH)of layered oxide can also affect the interfacial stability.To clarify this point clearly and improve the interfacial stability,the surface base of LiCoO_(2)(LCO)is regulated and investigated in this work.First,LCO with surface base Li_(2)CO_(3)(LCO@Li_(2)CO_(3))is prepared by the reaction of Co_(3)O_4 and excess Li_(2)CO_(3).Then,the bare LCO is obtained after LCO@Li_(2)CO_(3) is washed with deionized water and calcined again.Besides,LCO with surface base Li_(2)O(LCO@Li_(2)O)is also prepared with the bare LCO and LiOH.As a result,the electrochemical performances of LCO@Li_(2)O are significantly improved and much higher than those of LCO@Li_(2)CO_(3) and the bare LCO electrodes.In particular,LCO@Li_(2)O-2 cathode display the most outstanding electrochemical performances(discharge capacity138.4 mAh·g^(-1)at 0.2C,105 mAh·g^(-1)at 2C and a capacity retention of 95.4%after 150 cycles at 0.5C).The high discharge capacity and excellent cycle stability of LCO@Li_(2)O electrode confirm the effectiveness of regulating the surface base of layered oxide from Li_(2)CO_(3) to Li_(2)O.The surface base regulating is expected to be a simple but effective strategy to construct the stable interface between the cathode and the sulfide electrolyte of the all-solid-state lithium batteries.

关键词： All-solid-state lithium battery sulfide electrolyte LiCoO_(2) Surface base Interfacial stability

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Optimization on transport of charge carriers in cathode of sulfide electrolyte-based solid-state lithium-sulfur batteries

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Nano Research 2023年第6期16卷 8139-8158页

作者： Zengqi Zhang Yantao Wang Tao Liu Gang Li Jun Ma Jianjun Zhang Pengxian Han Shanmu Dong Xuedong Yan Yue Tang Guanglei Cui Qingdao Industrial Energy Storage Research Institute Qingdao Institute of Bioenergy and Bioprocess TechnologyChinese Academy of SciencesQingdao 266101China School of Future Technology University of Chinese Academy of SciencesBeijing 100049China College of Chemical Engineering Ningbo PolytechnicNingbo 315800China The Biodesign Institute and School of Molecular Sciences Arizona State University TempeArizona 85287USA

Lithium-sulfur(Li-S)batteries are considered as promising candidates for novel energy storage technology that achieves energy density of 500 Wh·kg^(−1).However,poor cycle stability resulting from notorious shuttle effect and the safety concerns deriving from flammability of ether-based electrolyte hinder the practical application of Li-S batteries.Because of low solubility to polysulfide,high ionic conductivity,and safety property,sulfide-based electrolytes can fundamentally address above issues.It is widely known that the effective transports of both electrons and ions are basic requirement for redox reaction of active materials in cathode.Thereby,construction of fast and stable ionic and electronic transport paths in cathode is especially pivotal for cycle stability of solid-state Li-S batteries(SSLSBs).In this review,we provide research progresses on facilitating transport of charge carriers in composite cathode of SSLSBs.From perspective of materials,intrinsically conductivity of electrolyte and carbon shows dramatic effect on migration of charge carriers in cathode of SSLSBs,thereby the conductive additives are summarized in the manuscript.Additionally,the charge transport in cathode of SSLSBs fully depends on the physical contact between active materials and conductive additives,therefore we summarized the strategies optimizing interfacial contact and reducing interfacial resistance.Finally,potential future research directions and prospects for SSLSBs with improved energy density and cycle performance are also proposed.

关键词： sulfide electrolyte charge transport composite cathode solid-state lithium-sulfur battery

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Toward Practical All-solid-state Batteries with sulfide electrolyte: A Review

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Chemical Research in Chinese Universities 2020年第3期36卷 377-385页

作者： YUAN Hong LIU Jia LU Yang ZHAO Chcnzi CHENG Xinbing NAN Haoxiong LIU Quanbing HUANG Jiaqi ZHANG Qiang Advanced Research Institute of Multidisciplinary Science Beijing Institute of Technology Beijing 100081P.R.China Beijing Key Laboratory of Green Chemical Reaction Engineering and TechnologyDepartment of Chemical EngineeringTsinghua UniversityBeijing 100084R R.China Beijing Key Laboratory of Ligtiocellulosic Chemistty Beijing Fotvstry UniversityBeijing 100083P.R.China School of Chemical Engineering and Light lndustty Guangdong University of TechnologyGuangzhou 510006P.R.China

sulfide-based solid-state electrolytes with ultrahigh lithium ion conductivities have been considered as the most promising electrolyte system to enable practical all-solid-state batteries.However,the practical applications of the sulfide-based all-solid-state batteries are hindered by severe interfacial issues as well as large-scale material preparation and battery fabrication problems.Liquid-involved interfacial treatments and preparation processes compatible with current battery manufacturing capable of improving electrode/electrolyte interface contacts and realizing the mass production of sulfide electrolytes and the scalable fabrication of sulfide-based battery component have attracted considerable attention.In this perspective,the current advances in liquid-involved treatments and processes in sulfide-based all-solid-state batteries are summarized.Then relative chemical mechanisms and existing challenges are included.Finally,future guidance is also proposed for sulfide-based batteries.Focusing on the sulfide-based all-solid-state batteries,we aim at providing a fresh insight on understandings towards liquid-involved processes and promoting the development of all-solid-state batteries with higher energy density and better safety.

关键词： sulfide electrolyte All-solid-state battery Compsite electrode Liquid-involved materials processing Energy material

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A facile path from fast synthesis of Li-argyrodite conductor to dry forming ultrathin electrolyte membrane for high-energy-density allsolid-state lithium batteries

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Journal of Energy Chemistry 2022年第11期31卷 309-316,I0008页

作者： Zhao Jiang Hongling Peng Jingru Li Yu Liu Yu Zhong Changdong Gu Xiuli Wang Xinhui Xia Jiangping Tu State Key Laboratory of Silicon Materials Key Laboratory of Advanced Materials and Applications for Batteries of Zhejiang Provinceand School of Materials Science and EngineeringZhejiang UniversityHangzhou 310027ZhejiangChina CCTEG Chongqing Research Institute Chongqing 400039China

All-solid-state lithium batteries(ASSLBs),utilizing sulfide solid electrolyte,are considered as the promising design on account of their superior safety and high energy density,whereas the time-consuming preparation process of sulfide electrolyte powders and the thickness of electrolyte layer hinder their practical application.Herein,an innovative ultimate-energy mechanical alloying plus rapid thermal processing approach is employed to rapidly synthesize the crystalline Argyrodite-type conductor Li_(5.3)PS_(4.3)ClBr_(0.7)(LPSCIBr)with superior ionic conductivity(11.7 mS cm^(-1)).Furthermore,to realize the higher energy density of the battery,an ultrathin LPSCIBr sulfide electrolyte membrane with superior ionic conductivity of 6.5 mS cm^(-1)is fabricated with the aid of polytetrafluoroethylene(PTFE)binder and the reinforced cellulose mesh.Moreover,a simple solid electrolyte interphase(SEI)is constructed on the surface of lithium metal to enhance anodic stability.Benefiting from the joint efforts of these merits,the modified ASSLBs with a high cell-level energy density of 311 Wh kg^(-1) show an excellent cyclic stability.The assembled all-solid-state Li_(2) S/Li pouch cell can operate even under the severe conditions of bending and cutting,demonstrating the enormous potential of the sulfide electrolyte membrane for ASSLBs application.

关键词： sulfide electrolyte Thermal processing Ultrathin membrane Ionic conductivity All-solid-state lithium battery

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Stable all-solid-state battery enabled with Li_(6.25)PS_(5.25)Cl_(0.75) as fast ion-conducting electrolyte

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Journal of Energy Chemistry 2021年第2期30卷 147-154,I0006页

作者： Weidong Xiao Hongjie Xu Minjie Xuan Zhiheng Wu Yongshang Zhang Xiangdan Zhang Shijie Zhang Yonglong Shen Guosheng Shao School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001HenanChina Centre for International Cooperation on Designer Low-carbon Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001HenanChina Zhengzhou Materials Genome Institute(ZMGI) Zhengzhou 450100HenanChina

All-solid-state batteries(ASSB) with lithium anode have attracted ever-increasing attention towards developing safer batteries with high energy densities.While great advancement has been achieved in developing solid electrolytes(SE) with superb ionic conductivity rivalling that of the current liquid technology,it has yet been very difficult in their successful application to ASSBs with sustaining rate and cyclic performances.Here in this work,we have realized a stable ASSB using the Li_(6.25)PS_(5.25)Cl_(0.75) fast ionconducting electrolyte together with LiNbO_3 coated LiCoO_2 as cathode and lithium foil as the anode.The effective diffusion coefficient of Li-ions in the battery is higher than 10^(-12) cm~2 s^(-1),and the significantly enhanced electrochemical matching at the cathode-electrolyte interface was essential to enable long-term stability against high oxidation potential,with the LCO@LNO/Li_(6.25)PS_(5.25)Cl_(0.75)/Li battery to retain 74.12% capacity after 430 cycles at 100 μA cm-2 and 59.7% of capacity after 800 cycles at 50 μA cm^(-2),at a high charging cut-off voltage of 4.2 V.This demonstrates that the Li_(6.25)PS_(5.25)Cl_(0.75) can be an excellent electrolyte for the realization of stable ASSBs with high-voltage cathodes and metallic lithium as anode,once the electrochemical compatibility between cathode and electrolyte can be addressed with a suitable buffer coating.

关键词： All-solid-state batteries sulfide electrolyte Li_(6.25)PS_(5.25)Cl_(0.75) LiNbO_(3)coating Lithium anode Long-term stability

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LiNbO3-coated LiNi0.8Co0.1Mn0.1O2 cathode with high discharge capacity and rate performance for all-solid-state lithium battery

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Journal of Energy Chemistry 2020年第1期29卷 39-45,I0002页

作者： Xuelei Li Liubing Jin Dawei Song Hongzhou Zhang Xixi Shi Zhenyu Wang Lianqi Zhang Lingyun Zhu Tianjin Key Laboratory for Photoelectric Materials and Devices School of Materials Science and EngineeringTianjin University of TechnologyTianjin 300384China Guilin Electrical Equipment Scientific Research Institute Co.Ltd. Guilin 541004GuangxiChina

In order to obtain high power density,energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products,oxide cathodes have been widely explored in all-solidstate lithium batteries(ASSLB)using sulfide solid electrolyte.However,the electrochemical performances are still not satisfactory,due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode,especially Ni-rich oxide cathodes,in charge-discharge process.Ni-rich LiNi0.8Co0.1Mn0.1O2(NCM811)material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg^-1 in liquid LIB,but rarely investigated in ASSLB using sulfide electrolyte.To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary.In this work,in view of our previous work,LiNbO3 coating with about 1 wt% content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li10GeP2S12 solid electrolyte.Consequently,LiNbO3-coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.

关键词： All-solid-state lithium battery sulfide electrolyte LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 LiNbO_3 Electrochemical performances

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First principle study of LiXS_2(X=Ga, In) as cathode materials for Li ion batteries

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Chinese Physics B 2016年第2期25卷 522-527页

作者：饶凤雅宁芳华蒋礼威曾祥明吴木生徐波欧阳楚英 Department of Physics Laboratory of Computational Materials Physics Jiangxi Normal University School of New Energy Science and Engineering Xinyu University

From first principle calculations, we demonstrate that LiXS_2（X = Ga, In） compounds have potential applications as cathode materials for Li ion batteries. It is shown that Li can be extracted from the LiXS_2 lattice with relatively small volume change and the XS_4 tetrahedron structure framework remains stable upon delithiation. The theoretical capacity and average intercalation potential of the LiGaS_2（LiInS_2） cathode are 190.4（144._2） m Ah/g and 3.50 V（3.53 V）. The electronic structures of the LiXS_2 are insulating with band gaps of _2.88 eV and 1.99 eV for X = Ga and In, respectively.However, Li vacancies, which are formed through delithiation, change the electronic structure substantially from insulating to metallic structure, indicating that the electrical conductivities of the LiXS_2 compounds should be good during cycling.Li ion migration energy barriers are also calculated, and the results show that Li ion diffusions in the LiXS_2 compounds can be as good as those in the currently widely used electrode materials.

关键词： lithium batteries sulfide electrolyte cathode materials first principle calculations

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