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A gelatin-based artificial sei for lithium deposition regulation and polysulfide shuttle suppression in lithium-sulfur batteries

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Journal of Energy Chemistry 2021年第1期30卷 310-317,I0010页

作者： Naseem Akhtar Xiaogang Sun Muhammad Yasir Akram Fakhar Zaman Weikun Wang Anbang Wang Long Chen Hao Zhang Yuepeng Guan Yaqin Huang Beijing Key Laboratory of Electrochemical Process and Technology for Materials Key Laboratory of Biomedical Materials of Natural MacromoleculesMinistry of EducationBeijing Advanced Innovation Center for Soft Matter Science and EngineeringBeijing University of Chemical TechnologyBeijing 100029China Research Institute of Chemical Defense Beijing 100191China

Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.

关键词： Bifunctional layer Gelatin-based fibers Shuttle effect artificial sei Lithium-sulfur battery

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

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Journal of Energy Chemistry 2021年第7期30卷 17-24页

作者： Jingguang Yi Dan Zhou Yuhao Liang Hong Liu Haifang Ni Li-Zhen Fan Beijing Advanced Innovation Center for Materials Genome Engineering Beijing Key Laboratory for Advanced Energy Materials and TechnologiesUniversity of Science and Technology BeijingBeijing 100083China

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 ℃.In addition,an ex-situ artificial solid electrolyte interphase(sei) film enriched with LiF and Li3 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/LPSCI-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.

关键词： All-solid-state lithium batteries High-performance Composite solid electrolyte Ionic conductivity artificial sei Cycling stability

Solid Electrolyte Interface in Zn-Based Battery Systems

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Nano-Micro Letters 2022年第12期14卷 286-309页

作者： Xinyu Wang Xiaomin Li Huiqing Fan Longtao Ma Frontiers Science Center for Flexible Electronics Institute of Flexible ElectronicsNorthwestern Polytechnical UniversityXi’an 710072People’s Republic of China State Key Laboratory of Solidification Processing School of Materials Science and EngineeringNorthwestern Polytechnical UniversityXi’an 710072People’s Republic of China

Due to its high theoretical capacity(820 mAh g^(−1)),low standard electrode potential(−0.76 V vs.SHE),excellent stability in aqueous solutions,low cost,environmental friendliness and intrinsically high safety,zinc(Zn)-based batteries have attracted much attention in developing new energy storage devices.In Zn battery system,the battery performance is significantly affected by the solid electrolyte interface(sei),which is controlled by electrode and electrolyte,and attracts dendrite growth,electrochemical stability window range,metallic Zn anode corrosion and passivation,and electrolyte mutations.Therefore,the design of sei is decisive for the overall performance of Zn battery systems.This paper summarizes the formation mechanism,the types and characteristics,and the characterization techniques associated with sei.Meanwhile,we analyze the influence of sei on battery performance,and put forward the design strategies of sei.Finally,the future research of sei in Zn battery system is prospected to seize the nature of sei,improve the battery performance and promote the large-scale application.

关键词： Solid electrolyte interface Zn-based battery Solvated structure artificial sei In situ sei

Lithiophilicity: The key to efficient lithium metal anodes for lithium batteries

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Journal of Energy Chemistry 2023年第2期77卷 123-136,I0004页

作者： Yahao Li Yue Li Lulu Zhang Huachao Tao Qingyu Li Jiujun Zhang Xuelin Yang Hubei Provincial Collaborative Innovation Center for New Energy Microgrid College of Electrical Engineering&New EnergyChina Three Gorges UniversityYichang 443002HubeiChina Guangxi Key Laboratory of Low Carbon Energy Materials School of Chemical and Pharmaceutical ScienceGuangxi Normal UniversityGuilin 541004GuangxiChina College of Materials Sciences and Engineering Fuzhou UniversityFuzhou 350108FujianChina Department of Chemical and Biochemical Engineering University of British ColumbiaVancouverBC V6T 1W5Canada

Lithium metal anode of lithium batteries,including lithium-ion batteries,has been considered the anode for next-generation batteries with desired high energy densities due to its high theoretical specific capacity(3860 mA h g^(-1))and low standards electrode potential(-3.04 V vs.SHE).However,the highly reactive nature of metallic lithium and its direct contact with the electrolyte could lead to severe chemical reactions,leading to the continuous consumption of the electrolyte and a reduction in the cycle life and Coulombic efficiency.In addition,the solid electrolyte interface formed during battery cycling is mainly inorganic,which is too fragile to withstand the extreme volume change during the plating and stripping of lithium.The uneven flux of lithium ions could lead to excessive lithium deposition at local points,resulting in needle-like lithium dendrites,which could pierce the separator and cause short circuits,battery failure,and safety issues.In the last five years,tremendous efforts have been dedicated to addressing these issues,and the most successful improvements have been related to lithiophilicity optimizations.Thus,this paper comprehensively reviewed the lithiophilicity regulation in lithium metal anode modifications and highlighted the vital effect of lithiophilicity.The remaining challenges faced by the lithiophilicity optimization for lithium metal anodes are discussed with the proposed research directions for overcoming the technical challenges in this subject.

关键词： Lithium metal anode Lithiophilicity optimization Host artificial sei Nucleation sites Dendrite growth

A flexible artificial solid-electrolyte interlayer supported by compactness-tailored carbon nanotube network for dendrite-free lithium metal anode

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Journal of Energy Chemistry 2022年第6期31卷 421-427,I0012页

作者： Haowen Liu Jifang Zhang Yang Liu Yang Wei Shuaiyang Ren Ludi Pan Yi Su Jianhua Xiao Haiyan Fan Yitao Lin Yipeng Su Yuegang Zhang State Key Laboratory of Low-Dimensional Quantum Physics and Department of Physics Tsinghua UniversityBeijing 100084China

A dendrite-free lithium metal anode requires a stable interface designed for efficient and reversible lithium plating and stripping. In this work, we have devised a mechanically flexible artificial Li_(3)N solid-electrolyte interlayer supported by a dual-layer compactness-tailored carbon nanotube fiber network. The more compact side of the network ensures a full coverage of Li_(3)N, which prevents the reaction between electrolyte and lithium. The other side, with sparsely distributed nanotube fibers, provides mechanical flexibility for the film, and induces three-dimensional lithium deposition along its structure without any dendrite formation. The resulting full cell with NCM811 cathode has a high capacity retention of 95.1% for 160 cycles compared with less than 80% for the control.

关键词： Lithium metal anode artificial sei CNT network 3D deposition

Ultralong-life lithium metal batteries enabled by decorating robust hybrid interphases on 3D layered framworks

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Chinese Chemical Letters 2023年第5期34卷 610-615页

作者： Qiongjie Ke Qingshuai Xu Xuejun Lai Xianfeng Yang Huichun Gao Zaisheng Wang Yongcai Qiu School of Environment and Energy State Key Laboratory of Luminescent Materials and DeviceGuangdong Provincial Key Laboratory of Atmospheric Environment and Pollution ControlSouth China University of TechnologyGuangzhou 510000China EVE Energy Co. Ltd.Huizhou 516000China

Stable solid-electrolyte interphase(sei)is crucial for advanced development of lithium metal batteries.However,the continuous collapse and reconstruction of sei will deplete fresh Li and electrolytes upon cycling,leading to irreversible capacity loss.Herein,we addressed this issue by pre-formation of artificial robust hybrid interphase on a 3D layered graphene/lithium metal framework,in which is constructed by LiF associated with Li2TiF 6generated by the in-situ reaction between the surfacial lithium and titanium fluoride contained electrolytes.The as-obtained interphase can maintain the structure integrality and avoid continuous consumption of the fresh Li and electrolytes.As a consequence,the Li symmetric cells achieve high-efficiency Li deposition and stable cycling over 3600 h.When paired with LiFePO_(4)cathodes,the coin cells exhibit long lifespan(>800 cycles)with almost 88.3%retention of the initial capacity.

关键词： Lithium metal battery TiF_4 artificial sei Dendrite free 3D frameworks