Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

Enhanced structural stability and durability in lithium-rich manganese-based oxide via surface double-coupling engineering

Lithium-rich manganese-based oxides(LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore,this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring threedimensional(3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li_(3)PO_(4) coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li_(3)PO_(4) to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 m V per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.

Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.

Lithiophilic Li-Si alloy-solid electrolyte interface enabled by high-concentration dual salt-reinforced quasi-solid-state electrolyte

Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.

Enhanced high-temperature performance of Li-rich layered oxide via surface heterophase coating

Li-rich layered oxides have become one of the most concerned cathode materials for high-energy lithiumion batteries, but they still suffer from poor cycling stability and detrimental voltage decay, especially at elevated temperature. Herein, we proposed a surface heterophase coating engineering based on amorphous/crystalline Li3 PO4 to address these issues for Li-rich layered oxides via a facile wet chemical method. The heterophase coating layer combines the advantages of physical barrier effect achieved by amorphous Li3 PO4 with facilitated Li+diffusion stemmed from crystalline Li3 PO4. Consequently, the modified Li(1.2) Ni(0.2) Mn(0.6) O2 delivers higher initial coulombic efficiency of 92% with enhanced cycling stability at 55 °C(192.9 mAh/g after 100 cycles at 1 C). More importantly, the intrinsic voltage decay has been inhibited as well, i.e. the average potential drop per cycle decreases from 5.96 mV to 2.99 mV. This surface heterophase coating engineering provides an effective strategy to enhance the high-temperature electrochemical performances of Li-rich layered oxides and guides the direction of surface modification strategies for cathode materials in the future.

Reversible cationic-anionic redox in disordered rocksalt cathodes enabled by fluorination-induced integrated structure design

Cation-disordered rocksalt oxides(DRX)have been identified as promising cathode materials for high energy density applications owing to their variable elemental composition and cationic-anionic redox activity.However,their practical implementation has been impeded by unwanted phenomena such as irrepressible transition metal migration/dissolution and O_(2)/CO_(2)evolution,which arise due to parasitic reactions and densification-degradation mechanisms during extended cycling.To address these issues,a micron-sized DRX cathode Li_(1.2)Ni_(1/3)Ti_(1/3)W_(2/15)O_(1.85)F_(0.15)(SLNTWOF)with F substitution and ultrathin LiF coating layer is developed by alcohols assisted sol-gel method.Within this fluorination-induced integrated structure design(FISD)strategy,in-situ F substitution modifies the activity/reversibility of the cationic-anionic redox reaction,while the ultrathin LiF coating and single-crystal structure synergistically mitigate the cathode/electrolyte parasitic reaction and densification-degradation mechanism.Attributed to the multiple modifications and size effect in the FISD strategy,the SLNTWOF sample exhibits reversible cationic-anionic redox chemistry with a meliorated reversible capacity of 290.3 mA h g^(-1)at 0.05C(1C=200 mA g^(-1)),improved cycling stability of 78.5%capacity retention after 50 cycles at 0.5 C,and modified rate capability of 102.8 mA h g^(-1)at 2 C.This work reveals that the synergistic effects between bulk structure modification,surface regulation,and engineering particle size can effectively modulate the distribution and evolution of cationic-anionic redox activities in DRX cathodes.

Machine learning and neural network supported state of health simulation and forecasting model for lithium-ion battery

As the intersection of disciplines deepens,the field of battery modeling is increasingly employing various artificial intelligence(AI)approaches to improve the efficiency of battery management and enhance the stability and reliability of battery operation.This paper reviews the value of AI methods in lithium-ion battery health management and in particular analyses the application of machine learning(ML),one of the many branches of AI,to lithium-ion battery state of health(SOH),focusing on the advantages and strengths of neural network(NN)methods in ML for lithium-ion battery SOH simulation and prediction.NN is one of the important branches of ML,in which the application of NNs such as backpropagation NN,convolutional NN,and long short-term memory NN in SOH estimation of lithium-ion batteries has received wide attention.Reports so far have shown that the utilization of NN to model the SOH of lithium-ion batteries has the advantages of high efficiency,low energy consumption,high robustness,and scalable models.In the future,NN can make a greater contribution to lithium-ion battery management by,first,utilizing more field data to play a more practical role in health feature screening and model building,and second,by enhancing the intelligent screening and combination of battery parameters to characterize the actual lithium-ion battery SOH to a greater extent.The in-depth application of NN in lithium-ion battery SOH will certainly further enhance the science,reliability,stability,and robustness of lithium-ion battery management.

ZrO_(2)包覆高镍LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)正极材料提高其循环稳定性的作用机理

高镍三元材料作为一种锂离子电池正极材料,因其较高的放电比容量而得到科学界和工业界的广泛关注。研究表明,高镍三元材料的比容量与材料中的Ni含量呈正相关,但Ni含量的增加也会加剧循环过程中的界面副反应,材料表面释氧以及结构转变等问题。本文采用ZrO_(2)包覆LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)材料,利用X射线衍射证明,在高温处理下ZrO_(2)包覆物中的Zr^(4+)会掺杂进LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)材料表面晶格中,使得X射线衍射谱中的(003)衍射峰左移。电化学测试证明在4.3和4.5 V的截止电压下,改性最优的材料在1C循环100周后容量保持率分别从84.89%和75.60%提高到97.61%和81.37%,同时发现循环稳定性的提升主要来自材料表面的Zr^(4+)掺杂。X射线光电子能谱证明Zr^(4+)表层掺杂后材料的Ni化合价由Ni3+向Ni^(2+)转变,透射电子显微镜观察到Zr^(4+)的表层掺杂使得材料表面的层状结构发生重构,从而稳定了材料体相结构,提高了材料整体的循环稳定性。

The mechanism of side reaction induced capacity fading of Ni-rich cathode materials for lithium ion batteries

Ni-rich cathode materials show great potential of applying in high-energy lithium ion batteries,but their inferior cycling stability hinders this process.Study on the electrode/electrolyte interfacial reaction is indispensable to understand the capacity failure mechanism of Ni-rich cathode materials and further address this issue.This work demonstrates the domain size effects on interfacial side reactions firstly,and further analyzes the inherent mechanism of side reaction induced capacity decay through comparing the interfacial behaviors before and after MgO coating.It has been determined that LiF deposition caused thicker SEI films may not increase the surface film resistance,while HF erosion induced surface phase transition will increase the charge transfer resistance,and the later plays the dominant factor to declined capacity of Ni-rich cathode materials.This work suggests strategies to suppress the capacity decay of layered cathode materials and provides a guidance for the domain size control to match the various applications under different current rates.

Unrevealing the effects of low temperature on cycling life of 21700-type cylindrical Li-ion batteries

The low-temperature performance of Li-ion batteries(LIBs) has important impacts on their commercial applications. Besides the metallic lithium deposition, which is regarded as one of the main failure mechanisms of the LIBs at low temperatures, the synergistic effects originating from the cathode, anode, electrolyte, and separators to the batteries are still not clear. Here, the 21700-type cylindrical batteries were evaluated at a wide range of temperatures to investigate the failure mechanism of batteries. Voltage relaxation, and the post-mortem analysis combined with the electrochemical tests, unravel that the capacity degradation of batteries at low temperature is related to the lithium plating at graphite anodes,the formation of unsatisfied solid deposited/decomposed electrolyte mixture phase on the anode, the precipitation of solvent in the electrolytes and the block of separator pores, and the uneven dissolved transition metal-ions from the cathode. We hope this finding may open up a new avenue to alleviate the capacity degradation of advanced LIBs at low temperatures and shed light on the development of outstanding low-temperature LIBs via simultaneous optimization of all the components including electrodes, electrolytes and separators.

Stress accumulation in Ni-rich layered oxide cathodes:Origin,impact,and resolution

LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1)is one of the most promising cathode candidates for high energy density lithium-ion batteries(LIBs).Due to the potential in enhancing energy density and cyclic life of LIBs,Ni-rich layered NCM(NCM,x≥0.6)have garnered significant research attention.However,improved specific capacity lead to severer expansion and shrinkage of layered lattice,accelerating the stress generation and accumulation even microcracks formation in NCM materials.The microcracks can promote the electrolyte permeation and decomposition,which can consequently reduce cyclic stabilities.Therefore,it is significant to provide an in-depth insight into the origin and impacts of stress accumulation,and the available modification strategies for the future development of NCM materials.In this review,we will first summarize the origin of stress accumulation in NCM materials.Next,we discuss the impact of stress accumulation.The electrolyte permeation along microcracks can enhance the extent of side reaction at the interface,trigger phase transformation and consequential capacity fading.To cushion the impact of stress accumulation,we will review five main strategies.Finally,concise perspectives to reduce stress accumulation and enhance particle strength in further works will be presented.

The nature of irreversible phase transformation propagation in nickel-rich layered cathode for lithium-ion batteries

Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory (DFT) results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.

Urea-assisted mixed gas treatment on Li-Rich layered oxide with enhanced electrochemical performance

Lithium-rich manganese-based oxides(LRMOs)have been considered as one of the most promising cathode materials owing to their superior specific capacity and high operating voltage.However,their largescale commercial applications are limited due to problems such as structural instability,voltage decay,and poor cycle stability.Herein,pre-generated oxygen vacancies and oxygen-deficient phase were introduced to Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)(LMNO)using a facile urea-assisted mixed gas treatment(UMGT)method for facilitating electronic and ionic conductivity,reducing the surface oxygen partial pressure,and suppressing the release of lattice oxygen.Compared with the pristine LMNO material,the UMGT sample modified at 200℃exhibited enhanced discharge capacity,capacity retention,and rate capability.In addition,the Li+diffusion coefficient significantly improved by 50%than that of the reference LMNO.More importantly,the voltage decay was effectively suppressed,with average potential decreasing from 0.53 V(LMNO)to 0.39 V(UMGT-200)after 200 cycles at 1 C.The proposed UMGT method provides an effective strategy to alleviate the phase transition and improve the electrochemical performance for lithium-rich materials,and identifies a promising research direction to inhibit the voltage decay of layered anion redox cathode materials.

UiO-66 type metal-organic framework as a multifunctional additive to enhance the interfacial stability of Ni-rich layered cathode material

To effectively alleviate the surface structure degradation caused by electrolyte corrosion and transition metal(TM) dissolution for Ni-rich(Ni content > 0.6) cathode materials, porous Zirconium based metalorganic frameworks(Zr-MOFs, UiO-66) material is utilized herein as a positive electrode additive. UiO-66 owns tunable attachment sites and strong binding affinity, making itself an efficient defluorination agent to suppress the undesirable reactions caused by fluorine species. Besides, it can also relieve TMs dissolution and block the migration of TMs toward anode side since it’s a multifarious metal ions adsorbent,realizing both cathode and anode interface protection. Benefiting from these advantages, the UiO-66 assistant Ni-rich cathode achieves superior cycling stability. Particularly in full cell, the positive effects of this multifunctional additive are more pronounced than in the half-cell, that is after 400 cycles at 2 C,the capacity retention has doubled with the addition of UiO-66. More broadly, this unique application of functional additive provides new insight into the degradation mechanism of layered cathode materials and offers a new avenue to develop high-energy density batteries.

Strategies of Removing Residual Lithium Compounds on the Surface of Ni-Rich Cathode Materials

Ni-rich cathode materials have become one of the most promising cathode materials for advanced high-energy Li-ion batteries(LIBs)owing to their high specific capacity.However,Ni-rich cathode materials are sensitive to the trace H2O and CO2 in the air,and tend to react with them to generate LiOH and Li2COg at the particle surface region(named residual lithium compounds,labeled as RLCs).The RLCs will deteriorate the comprehensive performances of Ni-rich cathode materials and make trouble in the subsequent manufacturing process of electrode,including causing low initial coulombic efficiency and poor storage property,bringing about potential safety hazards,and gelatinizing the electrode slurry.Therefore,it is of considerable significance to remove the RLCs.Researchers have done a lot of work on the corresponding field,such as exploring the formation mechanism and elimination methods.This paper investigates the origin of the surface residual lithium compounds on Ni-rich cathode materials,analyzes their adverse effects on the per-formance and the subsequent electrode production process,and summarizes various kinds of feasible methods for removing the RLCS.Finally,we propose a new research direction of eliminating the lithium residuals after comparing and summing up the above.We hope this work can provide a reference for alleviating the adverse effects of residual lithium compounds for Ni-rich cathode materials'industrial production.

Advances and Prospects of Surface Modification on Nickel-Rich Materials for Lithium-Ion Batteries

Although layered Ni-rich cathode materials have attracted lots of attention for their high capacity and power density,several significant issues,such aspoor thermal stability and moderate oyclability lit their practical appications.Most of these undesired problems of Ni-rich materials are caused by theunstable surface or the parasic reactions at cathode-electrolyte interface.5urface coating is the most common method to suppress such interfacialproblems for Ni-rich materials.This review focuses on the surface engineering of the N-rich materials in recent years,including the species used in coat.ing synthetic strategies of uniform coating layer,and the positive effects of coating species on the active materials.Detailed discussions are also taken todescribe the formation mechanism of the surface coating layer with design philosophy.Finally,the prospects for further developments and challenges insurface coating are also summarized.

锂离子电池加速老化:连接电池老化机制分析与寿命预测的桥梁

储能行业和新能源汽车的爆发式增长要求对锂离子电池的老化行为尤其是电池的寿命行为有更加深入的了解.准确地预测电池在各种工作条件下的使用寿命有助于优化电池的实际运行条件和延长电池的使用寿命,最终达到降低电池生命周期内总成本的目的.加速老化是一种经济高效的产品寿命评价方法,可以在短时间内获得大量的电池老化信息,快速预测锂离子电池在各种工作应力下的寿命特征.然而,基于加速老化进行电池寿命预测的前提是电池老化机理的一致性.本文综述了锂离子电池内各部件的老化机理和应力加速条件下的电池衰退机制以及相应的老化模式,为评价电池老化机理的一致性提供了参考.此外,本文还介绍了一些基于加速老化的电池寿命经验预测模型并为今后锂离子电池的加速老化研究提供了一些建议.

高吡啶氮含量的氮掺杂蜂窝状碳促进对多硫化物的限制以实现高性能锂硫电池

提高碳材料中氮的掺杂含量,尤其是吡啶氮的含量,已被证明可以显著提升锂硫(Li-S)电池的性能.尽管在碳材料中氮掺杂具有积极作用,但在实际操作中要实现>5 at.%的高氮掺杂含量仍非易事.此外,无法调节碳材料中特定的氮种类也是研究中的一个难题.在本文中,我们通过在氩气气氛下煅烧预先经过磷化处理的泛酸钙,得到了一种三维蜂窝状的氮(N)掺杂介孔碳(PNMC),其N掺杂含量高达8.82 at.%(吡啶N含量为3.49 at.%).磷掺杂不仅有助于提高N掺杂量,还有助于提升对多硫化物的吸附能力.实验证明,在800℃下制备的PNMC组装的硫正极(S/PNMC-800)表现出优异的电化学性能,在1 C下经过300圈循环后仍有556.7 mA h g^(-1)放电比容量.本工作提出了一种调控碳材料中吡啶氮含量的简便方法,为用于锂硫电池的多功能硫载体材料的开发提供启发.

Removing the Intrinsic NiO Phase and Residual Lithium for High-Performance Nickel-Rich Materials

Layered Ni-rich materials for lithium-ion batteries exhibit high discharge capacities but degraded cyclability at the same time.The limited cycling stability originates from many aspects.One of the critical factors is the intrinsic insulating residual lithium compounds and the rock-salt(NiO)phase on the surface of particles.In this work,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) material is etched with a trace amount of boric acid and used as a model to demonstrate the influences of weak acid treatment on the surface phase regulations.After the etching process,the pH of the material is reduced from 12.08 to 11.82,along with a lower cation mixing degree and promoting electrochemical performances.Corresponding measurements demonstrate that weak acids such as H_(3)BO_(3) can also etch the NiO phase on the surface to adjust the surface of the particles to a pure layered structure.This process improves the lithium-ion diffusion and electron transport in the interface between material and electrolyte,consequently leading to better cycling performance and rate capability.This study provides a novel strategy and comprehensive understanding of acid modification and surface phase regulation process of Ni-rich cathode materials for lithium-ion batteries.

Building Better Batteries:Solid-State Batteries with Li-Rich Oxide Cathodes

High-capacity Li-rich oxide materials have received extensive attention due to their unique anion-cation charge compensation involvement.However,the high operating voltage,poor cycling performance,unsafe oxygen evolution,and voltage decay limit their industrial application.The emergence and development of solid-state batteries offer a great opportunity to solve these issues by replacing flammable and unstable liquid electrolytes with solid electrolytes.Meanwhile,utilization of high-capacity Li-rich oxide cathodes enables to establish high-energy-density solid-state batteries with wide voltage ranges,light weight,and high mechanical properties.This review summarizes the recent progress of Li-rich oxide materials and solid electrolytes,emphasizing their major advantages,interface challenges,and modification approaches in the development of Li-rich solid-state batteries.We also propose possible characterization strategies for effective interfacial observation and analyses.It is hoped that this review should inspire the rational design and development of better solid-state batteries for application in portable devices,electric vehicles,as well as power grids.