Heterogeneous electrolyte membranes enabling double-side stable interfaces for solid lithium batteries

The solid polymer electrolyte(SPE) is one of the most promising candidates for building solid lithium batteries with high energy density and safety due to its advantages of flexibility and light-weight.However,the conventional monolayered electrolytes usually exhibit unstable contacts with either high-voltage cathodes or Li-metal anodes during cell operation.Herein,heterogeneous dual-layered electrolyte membranes(HDEMs) consisting of the specific functional polymer matrixes united with the designed solid ceramic fillers are constructed to address the crucial issues of interfacial instability.The electrolyte layers composed of the high-conductivity and oxidation-resistance polyacrylonitrile(PAN) combined with Li_(0.33)La_(0.557)TiO_(3) nanofibers are in contact with the high-voltage cathodes,achieving the compatible interface between the cathodes and the electrolytes.Meanwhile,the electrolyte layers composed of the highstability and dendrite-resistance polyethylene oxide(PEO) with Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12) nanoparticles are in contact with the Li-metal anodes,aiming to suppress the dendrite growth,as well as avoid the passivation between the PAN and the Li-metal.Consequently,the solid LiNi_(0.6)Co_(0.2)Mn_(0.2)O2‖Li full cells based on the designed HDEMs show the good rate and cycling performance,i.e.the discharge capacity of 170.1 mAh g^(-1) with a capacity retention of 78.2% after 100 cycles at 0.1 C and 30℃.The results provide an effective strategy to construct the heterogeneous electrolyte membranes with double-side stable electrode/-electrolyte interfaces for the high-voltage and dendrite-free solid lithium batteries.

A review of Al-based material dopants for high-performance solid state lithium metal batteries

As the world transitions to green energy, there is a growing focus among many researchers on the requirement for high-efficient and safe batteries. Solid-state lithium metal batteries(SSLMBs) have emerged as a promising alternative to traditional liquid lithium-ion batteries(LIBs), offering higher energy density, enhanced safety, and longer lifespan. The rise of SSLMBs has brought about a transformation in energy storage, with aluminum(Al)-based material dopants playing a crucial role in advancing the next generation of batteries. The review highlights the significance of Al-based material dopants in SSLMBs applications, particularly its contributions to solid-state electrolytes(SSEs), cathodes, anodes,and other components of SSLMBs. Some studies have also shown that Al-based material dopants effectively enhance SSE ion conductivity, stabilize electrode and SSE interfaces, and suppress lithium dendrite growth, thereby enhancing the electrochemical performance of SSLMBs. Despite the above mentioned progresses, there are still problems and challenges need to be addressed. The review offers a comprehensive insight into the important role of Al in SSLMBs and addresses some of the issues related to its applications, endowing valuable support for the practical implementation of SSLMBs.

A homogenous solid polymer electrolyte prepared by facile spray drying method is used for room-temperature solid lithium metal batteries

The aggregation of inorganic particles with high mass ratio will form a heterogeneous electric field in the solid polymer electrolytes(SPEs),which is difficult to be compatible with lithium anode,leading to inadequate ionic conductivity.Herein,a facile spray drying method is adopted to increase the mass ratio of inorganic particles and solve the aggregation problems of fillers simultaneously.The polyvinylidene fluoride(PVDF)with lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)covers the surface of each Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)granules during the nebulization process,then forming flat solid electrolytes via layer-by-layer deposition.Characterized by the atomic force microscope,the obtained solid electrolytes achieve a homogenous dispersion of Young’s modulus and surface electric field.As a result,the as-prepared SPEs present high tensile strength of 7.1 MPa,high ionic conductivity of 1.86×10^(−4)S·cm^(−1)at room temperature,and wide electrochemical window up to 5.0 V,demonstrating increased mechanical strength and uniform lithium-ion migration channels for SPEs.Thanks to the as-prepared SPEs,the lithiumsymmetrical cells show a highly stable Li plating/stripping cycling for over 1,000 h at 0.1 mA·cm^(−2).The corresponding Li/LCoO_(2)batteries also present good rate capability and excellent cyclic performance with capacity retention of 80%after 100 cycles at room temperature.

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

All-solid-state lithium batteries with inorganic solid electrolytes:Review of fundamental science

The scientific basis of all-solid-state lithium batteries with inorganic solid electrolytes is reviewed briefly, touching upon solid electrolytes, electrode materials, electrolyte/electrode interface phenomena, fabrication, and evaluation. The challenges and prospects are outlined as well.

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

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.

Lithium–matrix composite anode protected by a solid electrolyte layer for stable lithium metal batteries

Lithium (Li) metal with an ultrahigh specific theoretical capacity and the lowest reduction potential is strongly considered as a promising anode for high-energy-density batteries. However, uncontrolled lithium dendrites and infinite volume change during repeated plating/stripping cycles hinder its practical applications immensely. Herein, a house-like Li anode (housed Li) was designed to circumvent the above issues. The house matrix was composed of carbon fiber matrix and affords a stable structure to relieve the volume change. An artificial solid electrolyte layer was formed on composite Li metal, just like the roof of a house, which facilitates uniform Li ions diffusion and serves as a physical barrier against electrolyte corrosion. With the combination of solid electrolyte layer and matrix in the composite Li metal anode, both dendrite growth and volume expansion are remarkably inhibited. The housed Li|LiFePO4 batteries exhibited over 95% capacity retention after 500 cycles at 1.0 C in coin cell and 85% capacity retention after 80 cycles at 0.5 C in pouch cell. The rationally combination of solid electrolyte layer protection and housed framework in one Li metal anode sheds fresh insights on the design principle of a safe and long-lifespan Li metal anode for Li metal batteries.

CNTs@S composite as cathode for all-solid-state lithium-sulfur batteries with ultralong cycle life

The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite formation.All-solid-state lithium-sulfur batteries have been proposed to solve the shuttle effect and prevent short circuits.However,solid-solid contacts between the electrodes and the electrolyte increase the interface resistance and stress/strain,which could result in the limited electrochemical performances.In this work,the cathode of all-solid-state lithium-sulfur batteries is prepared by depositing sulfur on the surface of the carbon nanotubes(CNTs@S)and further mixing with Li10GeP2S12 electrolyte and acetylene black agents.At 60℃,CNTs@S electrode exhibits superior electrochemical performance,delivering the reversible discharge capacities of 1193.3,959.5,813.1,569.6 and 395.5 mAhg^-1 at the rate of 0.1,0.5,1,2 and 5 C,respectively.Moreover,the CNTs@S is able to demonstrate superior high-rate capability of 660.3 mAhg^-1 and cycling stability of 400 cycles at a high rate of 1.0 C.Such uniform distribution of the CNTs,S and Li10GeP2S12 electrolyte increase the electronic and ionic conductivity between the cathode and the electrolyte hence improves the rate performance and capacity retention.

Self-assembly synthesis of solid polymer electrolyte with carbonate terminated poly (ethylene glycol) matrix and its application for solid state lithium battery

A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.

Lithium-ion transport in inorganic solid state electrolyte

An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and de signing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell （to convey ions while isolate electrons）, and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state elec- trolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.

PIM-1 as an artificial solid electrolyte interphase for stable lithium metal anode in high-performance batteries

Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithium,limits its commercial application.PIM-1(PIM:polymer of intrinsic microporosity),which is a polymer with abundant micropores,exhibits high rigidity and flexibility with contorted spirocenters in the backbone,and is an ideal candidate for artificial solid electrolyte interphases(SEI).In this work,a PIM-1 membrane was synthesized and fabricated as a protective membrane on the surface of an electrode to facilitate the uniform flux of Li ions and act as a stable interface for the lithium plating/stripping process.Nodule-like lithium with rounded edges was observed under the PIM-1 membrane.The Li@PIM-1 electrode delivered a high average Coulombic efficiency(99.7%),excellent cyclability(80%capacity retention rate after 600 cycles at 1 C),and superior rate capability(125.3 m Ah g-1 at 10 C).Electrochemical impedance spectrum(EIS)showed that the PIM-1 membrane could lower the diffusion rate of Li+significantly and change the rate-determining step from charge transfer to Li+diffusion.Thus,the PIM-1 membrane is proven to act as an artificial SEI to facilitate uniform and stable deposition of lithium,in favor of obtaining a compact and dense Li-plating pattern.This work extends the application of PIMs in the field of lithium batteries and provides ideas for the construction of artificial SEI.

Effect of lithium content on the electrochemical properties of solid-state-synthesized spinel Li_xMn_2O_4

Lithium-substituted LixMn2O4 （x = 0.98, 1.03, 1.08） spinel samples were synthesized by solid-state reaction. X-ray diffraction （XRD） patterns show that the prepared samples have a spinel structure with a space group of Fd 3 m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. Li1.03Mn2O4 shows high capacity at both low and high current densities, while Lil.08Mn2O4shows good cycling performance but relatively low capacity when cycled at both room and elevated temperatures. A variety of electrochemical methods were employed to investigate the electrochemical properties of these series of spinel LixMn2O4.

Solid-State Electrolytes for Lithium-Sulfur Batteries

Secondary lithium-sulfur batteries have attracted extensive attention due to their high energy density,low cost and environment friendly.However,the"shuttle effect"of polysulfides dissolved in liquid electrolytes leads to a decrease of the cell Coulomb efficiency(CE).Therefore,researchers have used solid electrolytes instead of traditional liquid electrolytes and separators to suppress the"shuttle effect"of polysulfides and the growth of lithium dendrites.The progress in electrolytes for solid-state lithium-sulfur batteries including solid-state polymer,inorganic,and composite electrolytes to solve the issues is summarized.

Artificial solid electrolyte interphase based on polyacrylonitrile for homogenous and dendrite-free deposition of lithium metal

High chemical reactivity, large volume changes, and uncontrollable lithium dendrite growth have always been the key problems of lithium metal anodes.Coating has been demonstrated as an effective strategy to protect the lithium metal.In this work, the effects of polyacrylonitrile(PAN)-based coatings on electrodeposited lithium have been studied.Our results show that a PAN coating layer provides uniform and dendrite-free lithium deposition as well as better cycling performance with carbonate electrolyte.Notably, heat treatment of the PAN coating layer promotes the formation of larger deposit particle size and higher coulombic efficiency(85%).The compact coating layer of heat-treated PAN with a large Young modulus(82.7 GPa) may provide stable protection for the active lithium.Improved homogeneity of morphology and mechanical properties of heat-treated PAN contribute to the larger deposit particles.This work provides new feasibility to optimize the polymer coating through rational modification of polymers.

Synthesis, Characterization and Performance Evaluation of an Advanced Solid Electrolyte and Air Cathode for Rechargeable Lithium-Air Batteries

Synthesis and characterization of a tri-layered solid electrolyte and oxygen permeable solid air cathode for lithium-air battery cells were carried out in this investigation. Detailed fabrication procedures for solid electrolyte, air cathode and real-world lithium-air battery cell are described. Materials characterizations were performed through FTIR and TGA measurement. Based on the experimental four-probe conductivity measurement, it was found that the tri-layered solid electrolyte has a very high conductivity at room temperature, 23。C, and it can be reached up to 6 times higher at 100。C. Fabrication of real-world lithium-air button cells was performed using the synthesized tri-layered solid electrolyte, an oxygen permeable air cathode, and a metallic lithium anode. The lithium-air button cells were tested under dry air with 0.1 mA - 0.2 mA discharge/ charge current at elevated temperatures. Experimental results showed that the lithium-air cell performance is very sensitive to the oxygen concentration in the air cathode. The experimental results also revealed that the cell resistance was very large at room temperature but decreased rapidly with increasing temperatures. It was found that the cell resistance was the prime cause to show any significant discharge capacity at room temperature. Experimental results suggested that the lack of robust interfacial contact among solid electrolyte, air cathode and lithium metal anode were the primary factors for the cell’s high internal resistances. It was also found that once the cell internal resistance issues were resolved, the discharge curve of the battery cell was much smoother and the cell was able to discharge at above 2.0 V for up to 40 hours. It indicated that in order to have better performing lithium-air battery cell, interfacial contact resistances issue must have to be resolved very efficiently.

Interfacial Issues of All Solid State Lithium Batteries

All solid state lithium battery is a promising next generation battery system with improved cycle life, en ergy density, especially safety. However, its development is greatly hampered by a large impedance between the solid state electrolyte/electrode interface. How to build an ideal electrolyte/electrode interface to improve the inter facial stability and reduce the interracial resistance is a huge challenge for improving battery performance. This pa per reviews interracial problems and introduces the formation mechanism of different interface layers between elec trodes and electrolytes. In addition, the strategies for improving interracial contact and reducing interracial resist ance are described in detail. Finally, the research directions for engineering interfaces in all solid state lithium bat teries are proposed.

Tuning hybrid liquid/solid electrolytes by lowering Li salt concentration for lithium batteries

Hybrid liquid/solid electrolytes（HLSEs） consisting of conventional organic liquid electrolyte（LE）, polyacrylonitrile（PAN）, and ceramic lithium ion conductor Li（1.5）Al（0.5）Ge（1.5）（PO4）3（LAGP） are proposed and investigated. The HLSE has a high ionic conductivity of over 2.25 × 10^（-3） S/cm at 25？C, and an extended electrochemical window of up to 4.8 V versus Li/Li＋. The Li｜HLSE｜Li symmetric cells and Li｜HLSE｜Li FePO4 cells exhibit small interfacial area specific resistances（ASRs） comparable to that of LE while much smaller than that of ceramic LAGP electrolyte, and excellent performance at room temperature. Bis（trifluoromethane sulfonimide） salt in HLSE significantly affects the properties and electrochemical behaviors. Side reactions can be effectively suppressed by lowering the concentration of Li salt. It is a feasible strategy for pursuing the high energy density batteries with higher safety.

固态电池关键材料体系发展研究

固态电池技术是发展兼具高能量密度、高安全性、长寿命和低成本的下一代电池的重要保证,当前全球主要国家及地区均在加快布局固态电池研发和产业化。本文从固态电池关键材料的技术体系、产业体系和支撑体系3个方面着手,综述了国际固态电池关键材料体系的发展现状,分析了美国、欧洲、日本、韩国等国家和地区的固态电池技术发展路径、产业规模和支撑体系建设情况,梳理了我国固态电池关键材料体系的发展现状并提出了发展目标。研究发现,我国固态电池正处于推广发展期,在关键原材料、关键科学技术瓶颈突破、规模化量产及产业化应用等方面面临挑战。研究建议,坚持分步发展固态电池的总体策略,设立国家级固态电池发展规划和重大科技专项,推动固态电池技术研发机构建设,促进固态电池市场化应用及产业转型,优化固态电池生态环境建设,实现我国固态电池产业领跑世界。

树枝状磺化聚醚砜纤维基复合固态电解质的制备及其性能

为解决应用于全固态锂金属电池中固态有机电解质离子电导率较低和力学性能较弱的问题,采用静电纺丝技术制备了树枝状磺化聚醚砜(SPES)纳米纤维膜,将其与聚氧化乙烯(PEO)结合制备复合固态电解质,并应用于全固态锂金属电池中。探讨了纺丝工艺对纳米纤维形貌的影响,在最佳的静电纺丝工艺参数下,研究了SPES纳米纤维膜对复合固态电解质结晶度、离子电导率、力学性能以及电化学性能的影响。结果表明:在四丁基六氟磷酸铵质量分数为2%,静电纺丝电压为30 kV,接收距离为15 cm时,制备的树枝状SPES纳米纤维膜具有最好的形貌,将PEO浇筑在该纳米纤维膜上获得的复合固态电解质其离子电导率为8.13×10^(-5)S/cm(30℃),断裂强度为5.1 MPa,且可使对称电池在0.1 mA·h/cm^(2)下稳定循环198 h,使LiFePO_(4)/Li电池在循环400圈后仍保持着128.6 mA·h/g的放电比容量;SPES纳米纤维膜因破坏PEO的结晶区且能构成三维离子传输路径,不仅提高了复合固态电解质的离子电导率,还使复合固态电解质具有优异的力学强度,可满足高性能全固态锂金属电池的应用需求。

基于专利数据挖掘的固态锂电池关键材料分析

固态锂电池作为下一代高性能储能技术,其关键材料的研发对于提高固态锂电池的能量密度、稳定性和安全性至关重要。本文以全球固态锂电池专利为研究对象,基于文本挖掘方法提取和整理固态锂电池专利文献中的材料信息,通过主要材料分布和共现网络重点分析了固态锂电池的材料分布特点和潜在研发材料,通过机构-材料的分布和共现网络重点分析了主要研发机构的材料布局和研发重点,梳理了2021年以来固态锂电池专利中出现的新材料及其研发机构,揭示了固态锂电池材料领域的现有研究热点和未来发展趋势。研究结果显示,锂、铝、镧、磷、硫化物等材料在固态锂电池专利中占据重要地位;大部分机构围绕核心材料进行创新和合作,在材料开发和应用方面具有相似的策略;少数重要机构积极开发固态锂电池的新材料并广泛布局相关专利,对固态锂电池的材料开发、技术创新和商业化有推动作用。本文为固态锂电池材料的分析和挖掘提供了新的方法,为固态锂电池的材料研发和技术创新提供参考。