Prussian Blue Analogue‑Templated Nanocomposites for Alkali‑Ion Batteries:Progress and Perspective

Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO_(2)cathode material

With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Photo‑Energized MoS_(2)/CNT Cathode for High‑Performance Li–CO_(2)Batteries in a Wide‑Temperature Range

Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.

Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Construction of 3D porous Cu_(1.81)S/nitrogen-doped carbon frameworks for ultrafast and long-cycle life sodium-ion storage

Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.

Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

增程式电动拖拉机动力电池供电系统研究

增程式电动拖拉机具有节能减排、续航时间长等优点,但现有动力电池组电压等级较低,无法满足增程式电动拖拉机整机直流母线电压需求。为此,针对增程式电动拖拉机整机500 V电压平台需求,研究了其动力电池供电系统,完成了动力电池供电系统硬件设计和控制设计,最终利用MatLab/Simulink进行了仿真验证。仿真试验方面,所设计的动力电池供电系统实现了从320 V到500 V良好的升压稳压控制与闭环直流电源供电效果,能够适应与增程器等其他电源并联均流供电需求,动力电池供电系统具有良好的动态性能和稳态性能,满足稳定供电需求。

二维TiS_(2)/TiO_(2)杂化纳米片储钠性质的第一性原理研究

二维TiS_(2)是一种具有较大应用前景的钠离子电池负极材料.然而,二维TiS_(2)负极材料钠离子扩散动力学性能不佳大大限制了其在钠离子电池领域的大规模应用.本文利用基于密度泛函理论的第一性原理计算方法,探究了二维TiO_(2)/TiS_(2)杂化单层上钠原子吸附和扩散的热力学和动力学性质.研究结果表明,二维TiO_(2)/TiS_(2)杂化单层结构具有较高的动力学和热力学稳定性.此外,钠原子倾向于吸附在二维TiO_(2)/TiS_(2)杂化单层硫-硫-氧穴位(S-S-O)的顶部,沿穴位-钛顶位-穴位方向(H_(CC)^(1)-T_(T)-H_(CC)^(1′))具有较低的扩散能垒(0.19 eV).与纯相二维TiS_(2)单层相比,钠原子更容易在二维TiO_(2)/TiS_(2)杂化单层上迁移.本文通过对钠原子在二维TiO_(2)/TiS_(2)杂化单层上的结构稳定性、优选吸附位点和扩散路径的全面研究,揭示了二维TiO_(2)/TiS_(2)杂化单层的结构性质和钠输运特性,为设计高性能的钛基钠离子电池负极材料提供了理论支撑.

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。

储能锂电池系统综合管理研究进展

锂电池系统是新型储能系统的重要组成部分,电池管理技术对确保电池系统的安全、高效运行和延长使用寿命具有重要意义。从电池系统的模型、状态、故障、一致性、热管理等层面出发,综述了锂电池管理的研究进展。在电池模型方面,分析总结了电池在电、热、力等特性的建模及高效计算方法。对于电池的状态估计,总结了基于模型、数据驱动以及两者相结合的状态估计方法以及各自的优缺点,分析了构建数据驱动与电池领域知识融合框架的未来发展前景。在电池故障方面,分析了电池系统不同故障特征、类型、触发机制和诊断方法,对电池系统在早期故障预警、故障检测灵敏度提升等方面进行了展望。对于电池系统的一致性,总结分析了在均衡拓扑和均衡策略两个方面的研究现状,并对电池重构在均衡、快充、能量利用提升、故障隔离等方面的应用进行了分析。在电池热管理方面,分析了高温冷却以及低温加热的方法,并对热管理系统的优化设计和控制策略进行了总结,对开发高效换热、轻量化以及低能耗的先进热管理系统进行了探讨。此外,对电池管理系统的新技术和应用场景进行了概述,分析了数字孪生技术以及储能综合管理在电池系统上的应用,为未来电池管理的发展提供了参考。

锂电池回收产出的碳酸锂制备单水氢氧化锂工艺分析与探讨

锂元素的回收是电池回收工艺中的关键步骤,目前一般采用湿法浸出技术将有价元素从锂电池黑粉中转移到溶液中,然后经过除杂净化得到精制的硫酸锂溶液,加入碳酸钠制备成工业级碳酸锂或者碳酸锂粗品,再经精制除杂得到碳酸锂产品返回电池生产过程。随着氢氧化锂市场需求的提高,如何将碳酸锂经济高效地转化为氢氧化锂也成为重要环节。针对电池回收产生的工业级碳酸锂转化为氢氧化锂的工艺过程,详细分析了不同工艺路线的原料选择、工艺过程、产品及副产品产出以及能源消耗等关键因素,通过对比不同工艺路线的优劣势,总结出不同企业状态适用的工艺路线,旨在为优化生产流程、提高回收产业链附加值提供有价值的参考。研究结果将有助于指导电池回收企业在选择氢氧化锂生产工艺时作出决策,同时也为盐湖提锂和矿石提锂产生的碳酸锂生产氢氧化锂提供借鉴。

锂离子电池电解液安全性的影响因素及改进措施

锂离子电池由于能量密度高、高电压和维护成本低等优点而被大家使用.但在使用它们的过程中存在燃烧、爆炸等安全问题.电解液是锂离子电池中最易燃的组分,所以其与锂电池的安全性息息相关.改进电解液是提高锂离子电池安全性的关键方法.首先探讨了影响锂离子电池电解液安全性的因素,然后提出了改善措施,主要包括添加阻燃剂和抗过充添加剂来降低风险.

锂离子电池健康状态估计及寿命预测研究进展综述

随着锂离子电池的应用越来越广泛,锂电池健康状态的精确估计和剩余寿命的实时预测对于锂电池系统的安全运行和降低运维成本具有重要意义。锂电池内部复杂的物理化学反应和外部复杂工作条件,使得实现精准的健康状态估计和寿命预测具有挑战性。该文综述近年来锂电池健康状态估计和剩余使用寿命预测方法的研究现状,分析基于物理/数学模型、数据驱动、模型法和数据驱动融合,以及多种数据驱动融合的锂电池健康状态估计方法的优缺点及适用条件,并对比分析不同数据驱动类型的锂电池寿命预测方法。指出锂电池健康状态估计及寿命预测尚存在的问题,并对未来研究方向进行展望,对完善锂电池健康状态估计和寿命预测算法理论体系、指导实际应用技术具有重要意义。

从电池管理到电化学数字电源

电源技术的发展对绿色交通、规模化储能、智慧电网等领域具有重要作用。以电化学器件为代表的电化学电源具有反应机理复杂、多物理场、多尺度特性,同时工作过程中表现出强非线性、时变性及空间分布等特点,为电源的管理带来了挑战。本文以动力电池为对象,分别从模型、测量和管理三个方面阐述当前电池管理技术的研究现状及发展趋势,认为局限于本地的管理技术将逐渐走向全局的数字化管控,提出电化学数字电源的概念并诠释其内涵,旨在助力新能源汽车、氢电储能、新型电网、充电基础设施等电化学电源应用场景的发展。

基于安全、轻量化、可靠性多目标的新能源汽车电池包壳体开发

电池包作为新能源汽车的动力源,是新能源汽车最重要的部件之一,而电池包壳体对电池包乃至整车起重要保护作用,是新能源汽车的关键部件。电池包壳体质量占整车的2%~6%,电池包壳体对汽车轻量化同样起到重要作用。基于全球汽车产业的节能减排发展目标,从安全性、轻量化、可靠性3个角度出发,论述了新能源汽车电池包壳体开发的行业发展现状,展望其未来的发展趋势,同时针对这一领域存在的共性关键技术问题进行了讨论。

基于电化学阻抗谱的锂电池过充电阻抗特性与检测方法研究

目前以锂电池为主的电化学储能单元及系统应用日益广泛,而锂电池在实际使用中频发因过充电滥用引发电池故障的情况,因此实际电池的过充电状态准确检测一直是该领域的难点和瓶颈问题。针对此,该文采用电化学阻抗谱技术对单体电池过充电行为及过程开展检测研究,在实验室设计并制定电池过充电模拟循环实验,利用弛豫时间分布法对锂电池阻抗特性进行分析;在获得电池阻抗特性的基础上,对电池弛豫时间分布曲线进行解析;最后筛选阻抗特征参量为模型输入量,构建支持向量机模型进行电池过充电检测。结果表明,弛豫时间分布曲线中的极化峰P1对应锂离子在固态电解质界面(solid electrolyte interphase,SEI)膜中的扩散过程、极化峰P2对应电子在正极材料中的扩散过程、极化峰P3对应锂离子在电极界面的氧化还原反应。过充电会导致电池欧姆内阻、SEI膜内阻与电荷转移电阻的增长速率最大为正常循环的266%、360%和182%,其中固态电解质界面SEI膜内阻为主要因素。电化学阻抗谱的阻抗特征参量以及支持向量机模型可以用于锂电池过充电检测,估计精度达93.24%。不仅可掌握电池的运行状态,还可对过充电进行有效辨识。

双金属MOFs碳化材料的结构对锂硫电池正极性能的影响

利用硝酸钴和铁氰化钾在水溶液中沉淀反应以及ZIF-8在水溶液中的部分分解,分别制备了2种组成相近但结构不同的双金属有机框架前驱体Co-Fe precursor和ZCF precursor。经过多巴胺包覆,对2种产品在氩气气氛下退火获得碳化产物。将碳化产物与纳米硫粉混合得到的碳/硫复合材料(E-CoFeCN@C/S、E-ZCF@C/S)分别作为正极,组装扣式锂硫电池并测试电化学性能。利用X射线衍射仪、扫描电子显微镜、透射电子显微镜、热重分析仪进行形貌和结构分析。在组成相似的情况下,核壳结构碳载体(E-CoFeCN@C)与发散式结构碳载体(E-ZCF@C)对锂硫电池性能的影响呈现出“此消彼长”的特点:E-ZCF@C/S在循环伏安测试中表现出更小的极化以及更强的电流响应,在电化学阻抗测试中表现出更低的电荷转移阻抗,表明该材料有利于促进正极电荷传递过程,即加快电极反应动力学。E-ZCF@C/S在0.2C倍率下放电初始比容量为1211.3mAh/g,在2C倍率下放电初始比容量为794mAh/g,均优于E-CoFeCN@C/S。而核壳结构的优势主要体现在容量衰减方面,E-CoFeCN@C/S在0.2C倍率下经过100次循环后平均衰减率为0.074%(E-ZCF@C/S为0.26%),在2C倍率下循环300次后平均衰减率为0.047%(E-ZCF@C/S为0.13%),说明核壳结构对活性物质的锚固作用明显而对电荷转移不利。

响应曲面法优化废旧三元锂电池黑粉酸浸工艺

使用盐酸直接浸出废旧三元锂电池黑粉中的锂、镍、钴、锰,采用基于Box-Behnken设计的响应曲面法,考察反应温度、酸浓度、时间对4种元素浸出率的影响。结果表明,直接酸浸法最佳工艺条件为:酸浓度6 mol/L,固液比250 g/L,反应温度60℃,反应时间7 h,2次浸出后,锂浸出率为99.96%,镍浸出率为99.73%,钴浸出率99.90%,锰含量为99.82%。