Research on Preparation and Electrochemical Performance of the High Compacted Density Ni-Co-Mn Ternary Cathode Materials

The high compacted density LiNi0.5-xCo0.2Mn0.3MgxO2 cathode material for lithium-ion batteries was synthesized by high temperature solid-state method, taking the Mg element as a doping element and the spherical Ni0.5Co0.2Mn0.3 (OH)2, Li2CO3 as raw materials. The effects of calcination temperature on the structure and properties of the products were investigated. The structure and morphology of cathode materials powder were analyzed by X-ray diffraction spectroscopy (XRD) and scanning electronmicroscopy (SEM). The electrochemical properties of the cathode materials were studied by charge-discharge test and cyclic properties test. The results show that LiNi0.4985Co0.2Mn0.3 Mg0.0015O2 cathode material prepared at calcination temperature 930°C has a good layered structure, and the compacted density of the electrode sheet is above 3.68 g/cm3. The discharge capacity retention rate is more than 97.5% after 100 cycles at a charge-discharge rate of 1C, displaying a good cyclic performance.

Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Stabilizing High-Nickel Cathodes via Interfacial Hydrogen Bonding Effects Using a Hydrofluoric Acid-Scavenging Separator

Nickel-rich layered Li transition metal oxides are the most promising cathode materials for high-energydensity Li-ion batteries.However,they exhibit rapid capacity degradation induced by transition metal dissolution and structural reconstruction,which are associated with hydrofluoric acid(HF)generation from lithium hexafluorophosphate decomposition.The potential for thermal runaway during the working process poses another challenge.Separators are promising components to alleviate the aforementioned obstacles.Herein,an ultrathin double-layered separator with a 10 lm polyimide(PI)basement and a 2 lm polyvinylidene difluoride(PVDF)coating layer is designed and fabricated by combining a nonsolvent induced phase inversion process and coating method.The PI skeleton provides good stability against potential thermal shrinkage,and the strong PI-PVDF bonding endows the composite separator with robust structural integrity;these characteristics jointly contribute to the extraordinary mechanical tolerance of the separator at elevated temperatures.Additionally,unique HF-scavenging effects are achieved with the formation of-CO…H-F hydrogen bonds for the abundant HF coordination sites provided by the imide ring;hence,the layered Ni-rich cathodes are protected from HF attack,which ultimately reduces transition metal dissolution and facilitates long-term cyclability of the Ni-rich cathodes.Li||NCM811 batteries(where“NCM”indicates LiNi_(x)Co_(y)Mn_(1-x-y)O_(2))with the proposed composite separator exhibit a 90.6%capacity retention after 400 cycles at room temperature and remain sustainable at 60℃with a 91.4%capacity retention after 200 cycles.By adopting a new perspective on separators,this study presents a feasible and promising strategy for suppressing capacity degradation and enabling the safe operation of Ni-rich cathode materials.

Early-stage latent thermal failure of single-crystal Ni-rich layered cathode

High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable guidance for material optimization on thermal stability and new opportunities in monitoring battery thermal runaway(TR).Herein,this work comprehensively investigates the thermal failure process of a single-crystal nickel-rich layered cathode and finds that the latent thermal failure starts at∼120℃far below the TR temperature(225℃).During this stage of heat accumulation,sequential structure transition is revealed by atomic resolution electron microscopy,which follows the layered→cation mixing layered→LiMn_(2)O_(4)-type spinel→disordered spinel→rock salt.This progression occurs as a result of the continuous migration and densification of transition metal cations.Phase transition generates gaseous oxygen,initially confined within the isolated closed pores,thereby not showing any thermal failure phenomena at the macro-level.Increasing temperature leads to pore growth and coalescence,and eventually to the formation of open pores,causing oxygen gas release and weight loss,which are the typical TR features.We highlight that latent thermal instability occurs before the macro-level TR,suggesting that suppressing phase transitions caused by early thermal instability is a crucial direction for material optimization.Our findings can also be used for early warning of battery thermal runaway.

Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells

Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.

Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.

Synergistic interphase modification with dual electrolyte additives to boost cycle stability of high nickel cathode for all-climate battery

B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)to facilitate the rapid Li+migration.Nevertheless,its wide-temperature application has been limited by the instability of B-derived CEI layer at high temperature.Herein,dual electrolyte additives,consisting of lithium tetraborate(Li_(2)TB)and 2,4-difluorobiphenyl(FBP),are proposed to boost the widetemperature performances of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)cathode.Theoretical calculation and electrochemical performances analyses indicate that Li_(2)TB and FBP undergo successive decomposition to form a unique dual-layer CEI.FBP acts as a synergistic filming additive to Li_(2)TB,enhancing the hightemperature performance of NCM cathode while preserving the excellent low-temperature cycle stability and the superior rate capability conferred by Li_(2)TB additive.Therefore,the capacity retention of NCM‖Li cells using optimal FBP-Li_(2)TB dual electrolyte additives increases to 100%after 200 cycles at-10℃,99%after 200 cycles at 25℃,and 83%after 100 cycles at 55℃,respectively,much superior to that of base electrolyte(63%/69%/45%).More surprisingly,galvanostatic c ha rge/discharge experiments at different temperatures reveal that NCM‖Li cells using FBP-Li_(2)TB additives can operate at temperatures ranging from-40℃to 60℃.This synergistic interphase modification utilizing dual electrolyte additives to construct a unique dual-layer CEI adaptive to a wide temperature range,provides valuable insights to the practical applications of NCM cathodes for all-climate batteries.

A review:Modification strategies of nickel-rich layer structure cathode(Ni≥0.8)materials for lithium ion power batteries

Lithium ion power batteries have undoubtedly become one of the most promising rechargeable batteries at present;nonetheless,they still suffer from the challenges such as requirement of even higher energy density and capacity retention.Nickel-rich layer oxides(Ni≥0.8)become ideal cathode materials to achieve the high specific capacity.Integration of optimization of synthesis process and modification of crystal structure to suppress the capacity fading can obviously improve the performance of the lithium ion batteries.This review presents the recent modification strategies of the nickel-rich layered oxide materials.Unlike in previous reviews and related papers,the specific mechanism about each type of the modification strategies is specially discussed in detail,which is mainly about inhibiting the anisotropic lattice strain and adjusting the cation mixing degree to maintain crystal structure.Based on the recent progress,the prospects and challenges of the modified nickel-rich layer cathodes to upgrade the property of lithium ion batteries are also comprehensively analyzed,and the potential applications in the field of plug-in hybrid vehicles and electric vehicles are further discussed.

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.

Spray pyrolysis synthesis of nickel-rich layered cathodes LiNi_(1-2x)Co_xMn_xO_2(x = 0.075, 0.05, 0.025) for lithium-ion batteries

In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.

Recent progress in synthesis and surface modification of nickel-rich layered oxide cathode materials for lithium-ion batteries

Nickel-rich layered oxides have been identified as the most promising commercial cathode materials for lithium-ion batteries(LIBs)for their high theoretical specific capacity.However,the poor cycling stability of nickel-rich cathode materials is one of the major barriers for the large-scale usage of LIBs.The existing obstructions that suppress the capacity degradation of nickel-rich cathode materials are as a result of phase transition,mechanical instability,intergranular cracks,side reaction,oxygen loss,and thermal instability during cycling.Core–shell structures,oxidating precursors,electrolyte additives,doping/coating and synthesizing single crystals have been identified as effective methods to improve cycling stability of nickel-rich cathode materials.Herein,recent progress of surface modification,e.g.coating and doping,in nickel-rich cathode materials are summarized based on Periodic table to provide a clear understanding.Electrochemical performances and mechanisms of modified structure are discussed in detail.It is hoped that an overview of synthesis and surface modification can be presented and a perspective of nickel-rich materials in LIBs can be given.

Functional copolymer binder for nickel-rich cathode with exceptional cycling stability at high temperature through coordination interaction

Nickel-rich layered oxide LiNi_(1-x-y)Co_(x)Al_yO_(2)(NCA) with high theoretical capacity is a promising cathode material for the next-generation high-energy batteries.However,it undergoes a rapid capacity fading when operating at high temperature due to the accelerated cathode/electrolyte interfacial reactions and adhesive efficacy loss of conventional polyvinylideneffuoride(PVdF) binder.Herein,poly(acrylonitrile-co-methyl acrylate) copolymer is designed with electron-rich-C≡N groups as a novel binder for LiNi_(0.8)Co_(0.1)Al_(0.1)O_(2) cathode at high temperature.The electron-rich-C≡N groups are able to coordinate with the active Ni^(3+) on the surface of NCA,alleviating electrolyte decomposition and cathode structure degradation.Moreover,the strong adhesive ability is conducive to maintain integrity of electrodes upon cycling at 55℃.In consequence,the NCA electrodes with this functional binder display improved cycling stability(81.5% capacity retention after 100 cycles) and rate performance at 55℃.

Recent progress on electrolyte functional additives for protection of nickel-rich layered oxide cathode materials

In advantages of their high capacity and high operating voltage,the nickel(Ni)-rich layered transition metal oxide cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2)(NCMxyz,x+y+z=1,x≥0.5)and LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA))have been arousing great interests to improve the energy density of LIBs.However,these Nirich cathodes always suffer from rapid capacity degradation induced by unstable cathode-electrolyte interphase(CEI)layer and destruction of bulk crystal structure.Therefore,varied electrode/electrolyte interface engineering strategies(such as electrolyte formulation,material coating or doping)have been developed for Ni-rich cathodes protection.Among them,developing electrolyte functional additives has been proven to be a simple,effective,and economic method to improve the cycling stability of Nirich cathodes.This is achieved by removing unfavorable species(such as HF,H_(2)O)or constructing a stable and protective CEI layer against unfavorable reactive species(such as HF,H_(2)O).Herein,this review mainly introduces the varied classes of electrolyte functional additives and their working mechanism for interfacial engineering of Ni-rich cathodes.Especially,key favorable species for stabilizing CEI layer are summarized.More importantly,we put forward perspectives for screening and customizing ideal functional additives for high performance Ni-rich cathodes based LIBs.

Surface-targeted functionalization of nickel-rich cathodes through synergistic slurry additive approach with multi-level impact using minimal quantity

LiNi0.8Co0.1Mn0.1O_(2)(NCM811),a Ni-rich layered oxide,is a promising cathode material for high-energy density lithium-ion batteries(LIBs).However,its structural instability,caused by adverse phase transitions and continuous oxygen release,as well as deteriorated interfacial stability due to excessive electrolyte oxidative decomposition,limits its widespread application.To address these issues,a new concept is proposed that surface targeted precise functionalization(STPF)of the NCM811 cathode using a synergistic slurry additive(SSA)approach.This approach involves coating the NCM811 particle surface with 3-aminopropyl dimethoxy methyl silane(3-ADMS),followed by the precise deposition of ascorbic acid via an acid-base interaction.The slurry additives induce the formation of an ultra-thin spinel surface layer and a stable cathode–electrolyte interface(CEI),which enhances the electrochemical kinetics and inhibits crack propagation.The STPF strategy implemented by the SSA approach significantly improves the cyclic stability and rate performance of the NCM811 cathode in both half-cell and full-cell configurations.This work establishes a promising strategy to enhance the structural stability and electrochemical performance of nickel-rich cathodes and provides a feasible route to promote practical applications of high-energy density lithium-ion battery technology.

Recovery of cathode copper and ternary precursors from CuS slag derived by waste lithium-ion batteries:Process analysis and evaluation

The efficient and environmentally friendly recycling technology of waste residue that including abundant heavy metal produced during the recovery of lithium batteries has become a research hotspot.Herein,a novelty process of acid leaching-selective electrodeposition-deep impurity removal-regeneration was proposed to recovery of the CuS slag,which has been efficient transferred to high purity cathode copper and commercially available ternary precursors.Copper cathode with a purity of 99.67%was prepared under electrochemical reaction conditions at-0.55 V for 2 h.A novel impurity remover-Mn powder,which was used to remove the residual impurities and as a feedstock for the ternary precursor.Finally,NCM523 was regenerated by co-precipitation.The process is superior to the traditional process in economy,energy consumption,CO_(2)emissions,product purity and process duration.This study provides a new approach for solid waste recovery and precious metal enrichment.

B-doped and La_(4)NiLiO_(8)-coated Ni-rich cathode with enhanced structural and interfacial stability for lithium-ion batteries

Ni-rich layered oxides are considered promising cathodes for advanced lithium-ion batteries(LIBs)in the future,owing to their high capacity and low cost.However,the issues on structural and interfacial stability of Ni-rich cathodes still pose substantial obstacles in the practical application of advanced LIBs.Here,we employ a one-step method to synthesize a B-doped and La_(4)NiLiO_(8)-coated LiNi_(0.82)5Co_(0.115)Mn_(0.06)O_(2)(BL-1)cathode with reliable structure and interface,for the first time.The La_(4)NiLiO_(8)coating layer can prevent cathodes from electrolyte assault and facilitate Li+diffusion kinetics.Moreover,B-doping can effectively restrain the pernicious H_(2)-H_(3) phase transition and adjust the orientation of primary particles to a radial alignment,which is obstructive to the arise of microcracks induced by the change of anisotropic volume.Specifically,when tested in pouch cells,the BL-1 cathode exhibits outstanding capacity retention of 93.49%after 500 cycles at 1 C.This dual-modification strategy dramatically enhances the stability of the structure and interface for Ni-rich cathode materials,consequently accelerating the commercialization process of high-energy–density LIBs.

Regeneration of Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material by simulated hydrometallurgy leachate of spent lithium-ion batteries

A uniform Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material was prepared using a coprecipitation method to take advantage of the positive effect of Al on regenerated NCM(Ni,Co,Mn)cathode materials and ameliorate cumbersome and high-cost impurity removal processes during lithium-ion battery recycling.When the Al^(3+) content in the leachate was 1 at.%with respect to the total amount of transition metals(Ni,Co,and Mn),the produced Al-doped NCM cathode material increased concentrations of lattice oxygen and Ni^(2+).The initial specific capacity at 0.1C was 167.4 mA·h/g,with a capacity retention of 79.1%after 400 cycles at 1C.Further,this Al-doped sample showed improved rate performance and a smaller electrochemical impedance.These findings provide a reference for developing industrial processes to resynthesize cathode materials with improved electrochemical performance by incorporating Al^(3+) impurities produced during lithium-ion battery recycling.

Suppressing irreversible phase transition and enhancing electrochemical performance of Ni-rich layered cathode LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) by fluorine substitution

Ni-rich layered oxide LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(x≥0.8)is the most promising cathodes for future high energy automotive lithium-ion batteries.However,its application is hindered by the undesirable cycle stability,mainly due to the irreversible structure change at high voltage.Herein,we demonstrate that F substitution with the appropriate amount(1 at%)is capable for improve the electrochemical performance of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cathode significantly.It is revealed that F substitution can reduce cation mixing,stabilize the crystal structure and improve Li transport kinetics.The resulted LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(1.99)F_(0.01)cathode can deliver a high capacity of 194.4 mAh g^(-1) with capacity retention of 95.5%after 100 cycles at 2 C and 165.2 mAh g^(-1) at 5 C.In-situ synchrotron X-ray technique proves that F ions in the cathode materials can suppress the irreversible phase transition from H2 phase to H3 phase in high voltage region by preventing oxygen gliding in a-b planes,ensuring a long-term cycle stability.

Enhancing Li NiO_(2) cathode materials by concentration-gradient yttrium modification for rechargeable lithium-ion batteries

Lithium nickel oxide(LiNiO_(2)) cathode materials are featured with high capacity and low cost for rechargeable lithium-ion batteries but suffer from severe interface and structure instability.Here we report that rationally designed LiNiO_(2) via concentration-gradient yttrium modification exhibits alleviative side reactions and improved electrochemical performance.The LiNiO_(2) cathode with LiYO_(2)-Y_(2) O_(3) coating layer delivers a discharge capacity of 225 mAh g^(-1) with a high initial Coulombic efficiency of 93.4%.These improvements can be attributed to the formation of in-situ modified hybrid LiYO_(2)-Y_(2 O3) coating layer,which suppresses phase transformation,electrolyte oxidation and salt dissociation due to the formation of protective cathode electrolyte interface.The results indicate promising application of concentration-gradient yttrium coating as a facile approach to stabilize nickel-rich cathode materials.

High-performance LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) cathode by nanoscale lithium sulfide coating via atomic layer deposition

The commercialization of nickel-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811) has been hindered by its continuous loss of practical capacity and reduction in average working voltage.To address these issues,surface modification has been well-recognized as an effective strategy.Different from the coatings reported in literature to date,in this work,we for the first time report a sulfide coating,amorphous Li_(2)S via atomic layer deposition (ALD).Our study revealed that the conformal nano-Li_(2)S coating shows exceptional protection over the NMC811 cathodes,accounting for the dramatically boosted capacity retention from~11.6%to~71%and the evidently mitigated voltage reduction from 0.39 to 0.18 V after 500 charge–discharge cycles.In addition,the Li_(2)S coating remarkably improved the rate capability of the NMC811 cathode.Our investigation further revealed that all these beneficial effects of the ALD-deposited nano-Li_(2)S coating lie in the following aspects:(i) maintain the mechanical integrity of the NMC811 electrode:(ii) stabilize the NMC electrode/electrolyte interface:and (iii) suppress the irreversible phase transition of NMC structure.Particularly,this study also has revealed that the nano-Li_(2)S coating has played some unique role not associated with traditional non-sulfide coatings such as oxides.In this regard,we disclosed that the Li_(2)S layer has reacted with the released O_(2) from the NMC lattices,and thereby has dramatically mitigated electrolyte oxidation and electrode corrosion.Thus,this study is significant and has demonstrated that sulfides may be an important class of coating materials to tackle the issues of NMCs and other layered cathodes in lithium batteries.