Engineering Ferroelectric Interlayer between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)and Lithium Metal for Stable Solid-State Batteries Operating at Room Temperature

The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP in high-energy density solid-state Li metal batteries.In this work,a multifunctional ferroelectric BaTiO_(3)(BTO)/poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene)(P[VDF-TrFE-CTFE])composite interlayer(B-TERB)is constructed between LATP and Li metal anode,which not only suppresses the Li dendrite growth,but also improves the interfacial stability and maintains the intimate interfacial contact to significantly decrease the interfacial resistance by two orders of magnitude.The B-TERB interlayer generates a uniform electric field to induce a uniform and lateral Li deposition,and therefore avoids the side reactions between Li metal and LATP achieving excellent interface stability.As a result,the Li/LATP@B-TERB/Li symmetrical batteries can stably cycle for 1800 h at 0.2 mA cm^(-2)and 1000 h at 0.5 mA cm^(-2).The solid-state LiFePO_(4)/LATP@B-TERB/Li full batteries also exhibit excellent cycle performance for 250 cycles at 0.5 C and room temperature.This work proposes a novel strategy to design multifunctional ferroelectric interlayer between ceramic electrolytes and Li metal to enable stable room-temperature cycling performance.

Design of advanced porous silver powder with high-sintering activity to improve silicon solar cells

Silver(Ag)paste is widely used in semiconductor metallization,especially in silicon solar cells.Ag powder is the material with the highest proportion in Ag paste.The morphology and structure of Ag powder are crucial which determine its characteristics,especially for the sintering activity.In this work,a simple method was developed to synthesize a type of microcrystalline spherical Ag particles(SP-A)with internal pores and the structural changes and sintering behavior were thoroughly studied by combining ultra-small-angle X-ray scattering(USAXS),small-angle X-ray scattering(SAXS),in-situ heating X-ray diffraction(XRD),focused ion beam(FIB),and thermal analysis measurement.Due to the unique internal pores,the grain size of SP-A is smaller,and the coefficient of thermal expansion(CTE)is higher than that of traditional solid Ag particles.As a result,the sintering activity of SP-A is excellent,which can form a denser sintered body and form silver nanoparticles at the Ag–Si interface to improve silver silicon contact.Polycrystalline silicon solar cell built with SP-A obtained a low series resistance(Rs)and a high photoelectric conversion efficiency(PCE)of 19.26%.These fill a gap in Ag particle structure research,which is significant for the development of high-performance electronic Ag particles and efficient semiconductor devices.

Progress and perspectives of in situ polymerization method for lithium-based batteries

The application of lithium-based batteries is challenged by the safety issues of leakage and flammability of liquid electrolytes.Polymer electrolytes(PEs)can address issues to promote the practical use of lithium metal batteries.However,the traditional preparation of PEs such as the solution-casting method requires a complicated preparation process,especially resulting in side solvents evaporation issues.The large thickness of traditional PEs reduces the energy density of the battery and increases the transport bottlenecks of lithium-ion.Meanwhile,it is difficult to fill the voids of electrodes to achieve good contact between electrolyte and electrode.In situ polymerization appears as a facile method to prepare PEs possessing excellent interfacial compatibility with electrodes.Thus,thin and uniform electrolytes can be obtained.The interfacial impedance can be reduced,and the lithium-ion transport throughput at the interface can be increased.The typical in situ polymerization process is to implant a precursor solution containing monomers into the cell and then in situ solidify the precursor under specific initiating conditions,and has been widely applied for the preparation of PEs and battery assembly.In this review,we focus on the preparation and application of in situ polymerization method in gel polymer electrolytes,solid polymer electrolytes,and composite polymer electrolytes,in which different kinds of monomers and reactions for in situ polymerization are discussed.In addition,the various compositions and structures of inorganic fillers,and their effects on the electrochemical properties are summarized.Finally,challenges and perspectives for the practical application of in situ polymerization methods in solid-state lithium-based batteries are reviewed.

铌酸锂调控固态电解质电场结构促进锂离子高效传输

聚合物基固态电解质得益于其易加工性,最有希望应用于下一代固态锂金属电池.目前,聚合物基态电解质的离子电导率提升策略多为加入导锂陶瓷以构建离子传输通道,其提升程度有限.电场在锂离子输运过程中存在重要影响,目前研究中有关电场对锂离子传输的影响机制尚不明确.本文将兼具高离子电导率和高介电常数的铌酸锂嵌入聚偏氟乙烯基体中,设计了一种新型复合固态电解质.铌酸锂颗粒有效调节电解质内部电场结构,增强了离子输运方向电场强度,实现了离子电导率的大幅提升(7.39×10^(-4)S cm^(-1),25℃).该电解质匹配高镍正极和锂金属负极的固态电池可稳定循环1000次以上,容量保持率为72%.该研究为设计下一代固态锂电池用高离子电导复合固态电解质提供了新的策略.

Progress and perspective of Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3) ceramic electrolyte in lithium batteries

The replacement of liquid organic electrolytes with solid-state electrolytes(SSEs)is a feasible way to solve the safety issues and improve the energy density of lithium batteries.Developing SSEs materials that can well match with high-voltage cathodes and lithium metal anode is quite significant to develop high-energy-density lithium batteries.Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)SSE with NASICON structure exhibits high ionic conductivity,low cost and superior air stability,which enable it as one of the most hopeful candidates for all-solidstate batteries(ASSBs).However,the high interfacial impedance between LATP and electrodes,and the severe interfacial side reactions with the lithium metal greatly limit its applications in ASSBs.This review introduces the crystal structure and ion transport mechanisms of LATP and summarizes the key factors affecting the ionic conductivity.The side reaction mechanisms of LATP with Li metal and the promising strategies for optimizing interfacial compatibility are reviewed.We also summarize the applications of LATP including as surface coatings of cathode particles,ion transport network additives and inorganic fillers of composite polymer electrolytes.At last,this review proposes the challenges and the future development directions of LATP in SSBs.

Building better solid-state batteries with silicon-based anodes

Silicon(Si)-based solid-state batteries(Si-SSBs)are attracting tremendous attention because of their high energy density and unprecedented safety,making them become promising candidates for next-generation energy storage systems.Nevertheless,the commercialization of Si-SSBs is significantly impeded by enormous challenges including large volume variation,severe interfacial problems,elusive fundamental mechanisms,and unsatisfied electrochemical performance.Besides,some unknown electrochemical processes in Si-based anode,solid-state electrolytes(SSEs),and Si-based anode/SSE interfaces are still needed to be explored,while an in-depth understanding of solid–solid interfacial chemistry is insufficient in Si-SSBs.This review aims to summarize the current scientific and technological advances and insights into tackling challenges to promote the deployment of Si-SSBs.First,the differences between various conventional liquid electrolyte-dominated Si-based lithium-ion batteries(LIBs)with Si-SSBs are discussed.Subsequently,the interfacial mechanical contact model,chemical reaction properties,and charge transfer kinetics(mechanical–chemical kinetics)between Si-based anode and three different SSEs(inorganic(oxides)SSEs,organic–inorganic composite SSEs,and inorganic(sulfides)SSEs)are systemically reviewed,respectively.Moreover,the progress for promising inorganic(sulfides)SSE-based Si-SSBs on the aspects of electrode constitution,three-dimensional structured electrodes,and external stack pressure is highlighted,respectively.Finally,future research directions and prospects in the development of Si-SSBs are proposed.

Lithium-ion spontaneous exchange and synergistic transport in ceramic-liquid hybrid electrolytes for highly efficient lithium-ion transfer

Ceramic electrolytes are important in ceramic-liquid hybrid electrolytes(CLHEs),which can effectively solve the interfacial issues between the electrolyte and electrodes in solid-state batteries and provide a highly efficient Li-ion transfer for solid–liquid Li metal batteries.Understanding the ionic transport mechanisms in CLHEs and the corresponding role of ceramic electrolytes is crucial for a rational design strategy.Herein,the Li-ion transfer in the ceramic electrolytes of CLHEs was confirmed by tracking the 6Li and 7Li substitution behavior through solid-state nuclear magnetic resonance spectroscopy.The ceramic and liquid electrolytes simultaneously participate in Li-ion transport to achieve highly efficient Li-ion transfer in CLHEs.A spontaneous Li-ion exchange was also observed between ceramic and liquid electrolytes,which serves as a bridge that connects the ceramic and liquid electrolytes,thereby greatly strengthening the continuity of Li-ion pathways in CLHEs and improving the kinetics of Li-ion transfer.The importance of an abundant solid–liquid interface for CLHEs was further verified by the enhanced electrochemical performance in LiFePO4/Li and LiNi0.8Co0.1Mn0.1O2/Li batteries from the generated interface.This work provides a clear understanding of the Li-ion transport pathway in CLHEs that serves as a basis to build a universal Li-ion transport model of CLHEs.

Grain boundaries contribute to highly efficient lithium-ion transport in advanced LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)secondary sphere with compact structure

LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)secondary particles with high tap density have a great potential for high volumetric energy density lithium(Li)-ion power bat-tery.However,the ionic conductivity mechanism of NCA with compact structure is still a suspense,especially the function of grain boundaries.Herein,we sys-tematically investigate the Li-ion transport behavior in both the primitive NCA(PNCA)secondary sphere densely grown by single-crystal primary grains and ball-milled NCA(MNCA)nanosized particle to reveal the role of grain bound-aries for Li-ion transport.The PNCA and MNCA have comparable Li-ion dif-fusion coefficients and rate performance.Moreover,the graphene nanosheet conductive additive only mildly affects the Li-ion diffusion in PNCA cathode,while which severely blocks the Li-ion transport in MNCA cathode.Through high-resolution transmission electron microscopy and electron energy loss spec-troscopy,we clearly observe Li-ion depletion at lower state of charge(SOC)and Li-ion aggregation at high SOC along the grain boundaries of PNCA secondary particles during high-rate lithiation process.The grain boundaries can construct an interconnected Li-ion transport network for highly efficient Li-ion transport,which contributes to excellent high-rate performance of compact PNCA sec-ondary particles.These findings present new strategy and deep insight in design-ing compact materials with excellent high-rate performance.