Single-Phase Ternary Compounds with a Disordered Lattice and Liquid Metal Phase for High-Performance Li-Ion Battery Anodes

Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.

Sb-Cu alloy cathode with a novel lithiation mechanism of ternary intermetallic formation: Enabling high energy density and superior rate capability of liquid metal battery

Antimony(Sb) is an attractive cathode for liquid metal batteries(LMBs) because of its high theoretical voltage and low cost.The main obstacles associated with the Sb-based cathodes are unsatisfactory energy density and poor rate-capability.Herein,we propose a novel Sb_(64)Cu_(36)cathode that effectively tackles these issues.The Sb_(64)Cu_(36)(melting point:525℃) cathode presents a novel lithiation mechanism involving sequentially the generation of Li_(2)CuSb,the formation of Li_(3)Sb,and the conversion reaction of Li_(2)CuSb to Li_(3)Sb and Cu.The generated intermetallic compounds show a unique microstructure of the upper floated Li_(2)CuSb layer and the below cross-linked structure with interpenetrated Li_(2)CuSb and Li_(3)Sb phases.Compared with Li_(3)Sb,the lower Li migration energy barrier(0.188 eV) of Li_(2)CuSb significantly facilitates the lithium diffusion across the intermediate compounds and accelerates the reaction kinetics.Consequently,the Li‖Sb_(64)Cu_(36)cell delivers a more excellent electrochemical performance(energy density:353 W h kg^(-1)at 0.4 A cm^(-2);rate capability:0.59 V at 2.0 A cm^(-2)),and a much lower energy storage cost of only 38.45 $ kW h^(-1)than other previously reported Sb-based LMBs.This work provides a novel cathode design concept for the development of high-performance LMBs in applications for large-scale energy storage.

Designing Advanced Liquid Electrolytes for Alkali Metal Batteries:Principles,Progress,and Perspectives

The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.

Self-discharge mitigation in a liquid metal displacement battery

Recently,a disruptive idea was reported about the discovery of a new type of battery named Liquid Displacement Battery(LDB)comprising liquid metal electrodes and molten salt electrolyte.This cell featured a novel concept of a porous electronically conductive faradaic membrane instead of the traditional ion-selective ceramic membrane.LDBs are attractive for stationary storage applications but need mitigation against self-discharge.In the instant battery chemistry,Li|LiCl-PbCl_(2)|Pb,reducing the diffusion coefficient of lead ions can be a way forward and a solution can be the addition of Pb O to the electrolyte.The latter acts as a supplementary barrier and complements the function of the faradaic membrane.The remedial actions improved the cell’s coulombic efficiency from 92%to 97%without affecting the voltage efficiency.In addition,the limiting current density of a 500 m Ah cell increased from 575 to 831 m A cm;and the limiting power from 2.53 to 3.66 W.Finally,the effect of Pb O on the impedance and polarization of the cell was also studied.

Anode reaction mechanisms of Na|NaCl-CaCl2|Zn liquid metal battery

Na|NaCl-CaCl_(2)|Zn liquid metal battery is regarded as a promising energy storage system for power grids.Despite intensive attempts to present a real mechanism of metal electrodes reaction, those for Na||Zn LMBs are not clear yet. Herein, the anode reactions for the multiple discharge potential plateaus were deduced by means of FactSage thermochemical software, which were subsequently validated by X-ray diffraction analysis and the modeling of phase transformation in the cooling process. A pre-treatment process was proposed for the analysis of anode product composition using the atomic absorption spectrometry method, and the anode states at working temperature(560 ℃) were obtained by the Na-CaZn ternary phase for the first time. The results indicate the discharge of Na and Ca led to the formation of Ca-Zn intermetallic compounds, whilst the extraction of Ca in Ca-Zn intermetallic compounds was responsible for the multiple discharge plateaus. Moreover, it was found that the charging product was in electrochemical double liquid metal layers, which are composed of Na and Ca with dissolved Zn respectively.

Arbitrary skin metallization by pencil-writing inspired solid-ink rubbing for advanced energy storage and harvesting

The development of a durable metallic coating on diverse substrates is both intriguing and challenging,particularly in the research of metal-conductive materials for applications such as batteries,soft electronics,and beyond.Herein,by learning from the pencil-writing process,a facile solid-ink rubbing technology(SIR-tech)is invented to address the above challenge.The solid-ink is exampled by rational combination of liquid metal and graphite particles.By harnessing the synergistic effects between rubbing and adhesion,controllable metallic skin is successfully formed onto metals,woods,ceramics,and plastics without limitation in size and shape.Moreover,outperforming pure liquid-metal coating,the composite metallic skin by SIR-tech is very robust due to the self-lamination of graphite nanoplate exfoliated by liquid-metal rubbing.The critical factors controlling the structures-properties of the composite metallic skin have been systematically investigated as well.For applications,the SIR-tech is demonstrated to fabricate high-performance composite current collectors for next-generation batteries without traditional metal foils.Meanwhile,advanced skin-electrodes are further demonstrated for stable triboelectricity generation even under temperature fluctuation from-196 to 120℃.This facile and highly-flexible SIR-tech may work as a powerful platform for the studies on functional coatings by liquid metals and beyond.

Ionic liquids for high performance lithium metal batteries

The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.

Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode

Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.

Bifunctional Liquid Metals Allow Electrical Insulating Phase Change Materials to Dual-Mode Thermal Manage the Li-Ion Batteries

Phase change materials(PCMs)are expected to achieve dual-mode thermal management for heating and cooling Li-ion batteries(LIBs)according to real-time thermal conditions,guaranteeing the reliable operation of LIBs in both cold and hot environments.Herein,we report a liquid metal(LM)modified polyethylene glycol/LM/boron nitride PCM,capable of dual-mode thermal managing the LIBs through photothermal effect and passive thermal conduction.Its geometrical conformation and thermal pathways fabricated through ice-template strategy are conformable to the LIB’s structure and heat-conduction characteristic.Typically,soft and deformable LMs are modified on the boron nitride surface,serving as thermal bridges to reduce the contact thermal resistance among adjacent fillers to realize high thermal conductivity of 8.8 and 7.6 W m^(−1) K^(−1) in the vertical and in-plane directions,respectively.In addition,LM with excellent photothermal performance provides the PCM with efficient battery heating capability if employing a controllable lighting system.As a proof-of-concept,this PCM is manifested to heat battery to an appropriate temperature range in a cold environment and lower the working temperature of the LIBs by more than 10℃ at high charging/discharging rate,opening opportunities for LIBs with durable working performance and evitable risk of thermal runaway.

A self-healing liquid metal anode for lithium-ion batteries

The gallium-based liquid metal as one of the self-healing materials has gained wide attention, especially in the energy storage system. However, volume expansion with the ‘‘liquid-solid-liquid”transformation process still leads to un-controlled electrode failure, which stimulates the irreversibility of liquid metal and hinders their self-healing effect as the anode for lithium-ion batteries. Herein, the polypyrrole(PPy) with highly conductive and adhesive features is first introduced to fasten the liquid metal nanoparticles(gallium-tin alloy, EGaSn) in the integrated electrode and applied as the anode for lithium-ion batteries. A tightly PPy wrapped EGaSn nanoparticles structure is formed during the in-situ polymerization synthesis process, which effectively avoids the detachment of solid alloyed products. Based on the features of PPy, polyacrylic acid is added to facilitate strengthening the integrity of the electrode by constructing the hydrogen bond. The ‘‘dual-insurance” design endows the EGaSn to exhibit superior electrochemical kinetics and an astonishing self-healing effect. As a result, the customized anode displays superior cycling stability(499.8 mAh g^(-1) after 500 cycles at 1.0 A g^(-1))and rate capability(350 mAh g^(-1) at 2.0 A g^(-1)).This work enriches the electrode engineering technology of liquid metal nanoparticles and opens up a new way to customize the self-healing anode for lithium-ion batteries.

A stable anthraquinone-derivative cathode to develop sodium metal batteries: The role of ammoniates as electrolytes

Rechargeable sodium metal batteries constitute a cost-effective option for energy storage although sodium shows some drawbacks in terms of reactivity with organic solvents and dendritic growth.Here we demonstrate that an organic dye,indanthrone blue,behaves as an efficient cathode material for the development of secondary sodium metal batteries when combined with novel inorganic electrolytes.These electrolytes are ammonia solvates,known as liquid ammoniates,which can be formulated as NaI·3.3NH_(3) and NaBF_(4)·2.5NH_(3).They impart excellent stability to sodium metal,and they favor sodium non-dendritic growth linked to their exceedingly high sodium ion concentration.This advantage is complemented by a high specific conductivity.The battery described here can last hundreds of cycles at 10 C while keeping a Coulombic efficiency of 99%from the first cycle.Because of the high capacity of the cathode and the superior physicochemical properties of the electrolytes,the battery can reach a specific energy value as high as 210 W h kgIB^(-1),and a high specific power of 2.2 kW kgIB^(-1),even at below room temperature(4℃).Importantly,the battery is based on abundant and cost-effective materials,bearing promise for its application in large-scale energy storage.

Self-healing Ga-based liquid metal/alloy anodes for rechargeable batteries

With the rapid development of electronics,electric vehicles,and grid energy storage stations,higher requirements have been put forward for advanced secondary batteries.Liquid metal/alloy electrodes have been considered as a promising development direction to achieve excellent electrochemical performance in metal-ion batteries,due to their specific advantages including the excellent electrode kinetics and self-healing ability against microstructural electrode damage.For conventional liquid batteries,high temperatures are needed to keep electrode liquid and ensure the high conductivity of molten salt electrolytes,which also brings the corrosion and safety issues.Ga-based metal/alloys,which can be operated at or near room temperature,are potential candidates to circumvent the above problems.In this review,the properties and advantages of Ga-based metal/alloys are summarized.Then,Ga-based liquid metal/alloys as anodes in various metal-ion batteries are reviewed in terms of their self-healing ability,battery configurations,working mechanisms,and so on.Furthermore,some views on the future development of Ga-based electrodes in batteries are provided.

储能电池建模与状态估计研究进展

储能电池具有能够平滑可再生能源输出,提高电力系统灵活性和应对电力需求峰谷等优势,有助于推动可再生能源发展,从而应对环境污染和能源紧缺的双重压力。目前市场主流的储能电池为锂离子电池,具有高比能特性,同时新型储能电池也在蓬勃发展,其中全钒液流电池具有高安全性的优势,液态金属电池具有超长循环寿命,在电力储能领域具有重要应用前景。储能电池的建模和状态估计对提高储能电池系统性能,确保其安全性以及优化维护效率至关重要,因此文中对锂离子电池、全钒液流电池和液态金属电池的建模和状态估计进行综述。首先,介绍了储能电池状态估计的整体框架,对基于实验的方法、基于模型的方法和基于数据驱动的方法进行整体介绍,并对荷电状态(state of charge,SOC)、健康状态(state of health,SOH)和剩余使用寿命(remaining useful life,RUL)进行概括;然后,从原理出发,分别总结了不同储能电池体系的内部工作过程、模型构建、状态估计与电池管理过程;最后,对不同储能电池体系的主要工作特性进行横向对比和总结,旨在为储能电池选择和发展提供启示。

脱合金纳米材料的制备及其在碱金属离子电池负极中的应用进展

碱金属离子电池包括锂离子电池、钠离子电池和钾离子电池等,是一种非常有应用前景的电化学储能装置.在“双碳”背景下,随着电动汽车的快速普及,对电池的能量密度提出了更高的要求.硅、锗、锡、锑、铋等因具有高的理论比容量有望实现在高能量密度电池中的应用.由于具有成本低、结构可控和工业应用潜力大等特点,脱合金技术常用来制备硅、锗、锑等负极材料,并实现对硅、锗、锑等脱合金材料的结构、形态和空间排列的动态控制.本文阐述了脱合金技术的常见分类和代表性研究进展,重点讨论了由脱合金技术制备多种维度的纳米材料以及它们在碱金属离子电池等储能领域的应用情况,最后对脱合金技术的发展趋势以及脱合金技术在储能领域的应用前景进行了展望.

基于锂负极的液态金属电池研究进展

液态金属电池由于具有低成本、易于组装和扩容等优点,且在充放电过程中能够有效地避免枝晶生长和电极结构变形等问题,在规模化电网储能领域具有显著优势。本文系统地综述了液体金属电池的工作原理、优缺点、电池材料(包括电极和电解质)的选取原则以及近期液态金属电池电极材料的研究进展,着重介绍了Li‖Te体系、Li‖Bi体系、Li‖Sb体系、Li‖Sb-X(X=Pb,Sn)体系以及Li‖Bi-X(X=Sn,Pb)体系等以金属锂为负极的液态金属电池关键材料体系,重点分析了上述材料体系的电化学储能特性、安全性、循环稳定性以及性能提升策略,并对比分析了上述材料体系在大规模储能应用时存在的优势与不足。此外,综述了Li基液态金属电池在熔盐电解质、高温密封及腐蚀防护、电池热管理等方面存在的问题以及面临的技术难题。最后,展望了液态金属电池正、负极材料的主要发展方向。综合分析表明,基于Li负极的液态金属电池具有低熔点、低成本、高库仑效率以及高放电电压等优点。

并网型风光氢储微电网容量优化配置研究

本文以并网型风光氢储微电网为研究对象,在满足年制氢量任务的前提下建立了以系统年收益最大为目标的经济优化模型,对不同储能容量方案采用含罚函数的粒子群算法进行优化调度求解。最后对液态金属电池、液态金属电池-铅酸电池、锂电池、锂电池-铅酸电池四种储能配置方案进行对比研究,发现液态金属电池现阶段因价格高单独使用时优势不明显,而在混合储能系统中可以与铅酸电池优势互补。

Liquid metal welding enabling high loading binder/carbon-free layered oxide cathode toward high-performance liquid and solid-state battery

High loading cathode with high active material proportion is a practical demand but far below the desirable value to achieve high energy density lithium-ion batteries(LIBs).Normally,the Li^(+)/electron transport between active materials and electrolyte/c arbon,however,it is poor and areal resistance is extremely high for a high loading/thick cathode.In this manuscript,taking high-voltage lithium cobalt oxide LiCoO_(2)(LCO)as an example,we design a facile liquid metal welding method enabled by a low melting-point indium-tin oxide In_(2)O_(3)/SnO_(2)(ITO)during a thermal treatment process,the strongly adhesion active particles show robust mechanical property for the free-standing LCO cathode with a pellet architecture.We also demonstrate that the O_(2)atmosphere plays a critical role on the interfacial property,that is preventing the layered structure to rock-salt Co_(3)O_(4)as well as further enhancing the interfacial mechanical integration.As expected,the LCO-ITO free-standing cathode not only shows robust mechanical property with densely packed configuration but also provides a fast Li^(+)/electron pathway at the interface.Consequently,the LCO-ITO composite cathode exhibits excellent electrochemical cycling performance in both liquid and solid-state cells.For example,even at a high active material mass of 56 mg·cm^(-2),the LCO cathode still delivers a specific capacity of 151 mAh·g^(-1)and maintains132.5 mAh·g^(-1)(corresponding to 7.4 mAh·cm^(-2))after 80cycles.The LCO-ITO-O_(2)cathode is also applicable to a solidstate cell,which exhibits a high capacity of 100.4 mAh·g^(-1)after 200 cycles of long-term cycling.The excellent electrochemical of the LCO-ITO-O_(2)reveals the successful engineering mechanical architecture and interfacial carriers transport,which may be expected as an alternative approach to achieve high energy density LIBs.

Recent progress in rechargeable alkali metal-air batteries

Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.

Advances on Na-K liquid alloy-based batteries

Sodium-potassium(Na^(-)K)liquid alloys attract increasing research attention,as an ideal alternative of Li metal for metal-based batteries,attributing to their high abundance,low redox potential,high capacity,and dendrite-free properties.In addition,the liquid and self-healing features of Na^(-)K alloys endow good electrode/electrolyte interfacial contact.The recent advances on the Na^(-)K liquid alloy-based batteries(NKBs)are reviewed herein.The anode designs for immobilization of the liquid alloy are introduced.The influences of the electrolyte and cathode materials on the battery performances are discussed.In addition,considering the co-existence of both K^(+)and Na^(+)in the electrolyte,the working mechanisms of the NKBs are elaborated.We also show that despite the improvement,challenges of the NKBs remain.The compatibility between Na^(-)K liquid alloy and electrolyte,as well as disputed working mechanisms,request detailed surface analyses of the liquid alloy and local element distribution evolution in the battery.This review would shed light on the fundamental understanding of Na^(-)K alloy electrochemistry and the development of dendrite-free metal-based energy storage systems with high energy density.

离子液体在电池电解质中的应用现状

离子液体根据阳离子的结构特点,可分为咪唑类、吡咯类、季铵盐类和聚合物类等。离子液体具有很好的理化性质,在电池电解质中应用广泛。结合离子液体应用于金属空气电池电解质、超级电容器电解质、燃料电池电解质的研究实例和离子液体的理化性质,剖析将离子液体应用到各电池电解质中的优缺点,以改善和解决上述电池传统电解质存在的析氢腐蚀、副反应产物、室温下不稳定及环境污染等问题。对于离子液体的发展和改善,提出引入官能团和添加金属盐的设想。