New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries

Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.

Interface-reinforced solid-state electrochromic Li-ion batteries enabled by in-situ liquid-solid transitional plastic glues

The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.

Two-dimensional MOF-based materials:Preparations and applications as electrodes in Li-ion batteries

Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.

Revealing the key role of non-solvating diluents for fast-charging and low temperature Li-ion batteries

Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics,narrow operating temperature and voltage range.Herein,an acetonitrile(AN)-based localized high-concentration electrolyte(LHCE)is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability.We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li^(+) solvates as temperature drops,maintaining the merits of fast Li transport and facile desolvation as at room temperature,which bestows the graphite electrode with remarkable low temperature performance(264 mA h g^(-1) at-20 C).Remarkably,an extremely high capacity retention of 97%is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at-20 C,and a high capacity of 110 mA h g^(-1)(71%of its room-temperature capacity)is retained at-30°C.The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.

A comprehensive review on the resynthesis of ternary cathode active materials from the leachate of Li-ion batteries

This review highlights the importance of recovering valuable metals from spent Li-ion battery(LIB)cathodes through the resynthesis of cathode active materials(CAMs).The resynthesis process of CAMs,a promising recycling method that directly produces CAM precursors from LIB leachate,is explored.This process encompasses six key steps,including pretreatment,leaching,purification,adjustment of metal concentrations,precursor synthesis,and sintering.The review also investigates the potential introduction of impurity elements during CAM resynthesis and provides tolerance levels for these impurities based on thorough reference analysis.Additionally,it addresses challenges related to the commercialization of the resynthesis process.Notably,this review represents the first comprehensive assessment of CAM resynthesis,including the systematic evaluation of 12 impurity elements(Fe,Li,Al,Cu,C,P,F,Na,Cl,S,Mg,and Zn).Overall,this comprehensive review is poised to support the commercial development of resynthesized CAMs by offering valuable guidelines for managing impurities and streamlining the purification process.

Atomistic understanding of capacity loss in LiNiO_(2)for high-nickel Li-ion batteries:First-principles study

Combining the first-principles calculations and structural enumeration with recognition,the delithiation process of LiNiO_(2)is investigated,where various supercell shapes are considered in order to obtain the formation energy of Li_(x)NiO_(2).Meanwhile,the voltage profile is simulated and the ordered phases of lithium vacancies corresponding to concentrations of 1/4,2/5,3/7,1/2,2/3,3/4,5/6,and 6/7 are predicted.To understand the capacity decay in the experiment during the charge/discharge cycles,deoxygenation and Li/Ni antisite defects are calculated,revealing that the chains of oxygen vacancies will be energetically preferrable.It can be inferred that in the absence of oxygen atom in high delithiate state,the diffusion of Ni atoms is facilitated and the formation of Li/Ni antisite is induced.

Direct recycling of Li-ion batteries from cell to pack level:Challenges and prospects on technology,scalability,sustainability,and economics

Direct recycling is a novel approach to overcoming the drawbacks of conventional lithium-ion battery(LIB)recycling processes and has gained considerable attention from the academic and industrial sectors in recent years.The primary objective of directly recycling LIBs is to efficiently recover and restore the active electrode materials and other components in the solid phase while retaining electrochemical performance.This technology's advantages over traditional pyrometallurgy and hydrometallurgy are costeffectiveness,energy efficiency,and sustainability,and it preserves the material structure and morphology and can shorten the overall recycling path.This review extensively discusses the advancements in the direct recycling of LIBs,including battery sorting,pretreatment processes,separation of cathode and anode materials,and regeneration and quality enhancement of electrode materials.It encompasses various approaches to successfully regenerate high-value electrode materials and streamlining the recovery process without compromising their electrochemical properties.Furthermore,we highlight key challenges in direct recycling when scaled from lab to industries in four perspectives:(1)battery design,(2)disassembling,(3)electrode delamination,and(4)commercialization and sustainability.Based on these challenges and changing market trends,a few strategies are discussed to aid direct recycling efforts,such as binders,electrolyte selection,and alternative battery designs;and recent transitions and technological advancements in the battery industry are presented.

Recent Advances in Nanoengineering of Electrode-Electrolyte Interfaces to Realize High-Performance Li-Ion Batteries

A suitable interface between the electrode and electrolyte is crucial in achieving highly stable electrochemical performance for Li-ion batteries,as facile ionic transport is required.Intriguing research and development have recently been conducted to form a stable interface between the electrode and electrolyte.Therefore,it is essential to investigate emerging knowledge and contextualize it.The nanoengineering of the electrode-electrolyte interface has been actively researched at the electrode/electrolyte and interphase levels.This review presents and summarizes some recent advances aimed at nanoengineering approaches to build a more stable electrode-electrolyte interface and assess the impact of each approach adopted.Furthermore,future perspectives on the feasibility and practicality of each approach will also be reviewed in detail.Finally,this review aids in projecting a more sustainable research pathway for a nanoengineered interphase design between electrode and electrolyte,which is pivotal for high-performance,thermally stable Li-ion batteries.

CoS Nanosheets Coated with Dopamine-Derived Carbon Standing on Carbon Fiber Cloth as Binder-Free Anode for Li-ion Batteries

Cobalt sulphides attract much attention as anode materials for Li-ion batteries(LIBs).However,its poor conductivity,low initial column efficiency and large volume changes during cycling have hindered its further development.Herein,novel interlaced CoS nanosheets were firstly prepared on Carbon Fiber Cloth(CFC)by two hydrothermal reactions followed with carbon coating via carbonizing dopamine(CoS NS@C/CFC).As a freestanding anode,the nanosheet structure of CoS not only accommodates the volume variation,but also provides a large interface area to proceed the charge transfer reaction.In addition,CFC works as both a three-dimensional skeleton and an active substance which can further improve the areal capacity of the resulting electrode.Furthermore,the coated carbon combined with the CFC work as a 3D conductive network to facilitate the electron conduction.The obtained CoS NS@C/CFC,and the contrast sample prepared with the same procedure but without carbon coating(CoS NS/CFC),are characterized with XRD,SEM,TEM,XPS and electrochemical measurements.The results show that the CoS NS@C/CFC possesses much improved electrochemical performance due to the synergistic effect of nanosheet CoS,the coated carbon and the CFC substrate,exhibiting high initial columbic efficiency(~87%),high areal capacity(2.5 at 0.15 mA cm−2),excellent rate performance(1.6 at 2.73 mA cm−2)and improved cycle stability(87.5%capacity retention after 300 cycles).This work may provide a new route to explore freestanding anodes with high areal specific capacity for LIBs.

Overview of multi-stage charging strategies for Li-ion batteries

To reduce the carbon footprint in the transportation sector and improve overall vehicle efficiency,a large number of electric vehicles are being manufactured.This is due to the fact that environmental concerns and the depletion of fossil fuels have become significant global problems.Lithium-ion batteries(LIBs)have been distinguished themselves from alternative energy storage technologies for electric vehicles(EVs) due to superior qualities like high energy and power density,extended cycle life,and low maintenance cost to a competitive price.However,there are still certain challenges to be solved,like EV fast charging,longer lifetime,and reduced weight.For fast charging,the multi-stage constant current(MSCC) charging technique is an emerging solution to improve charging efficiency,reduce temperature rise during charging,increase charging/discharging capacities,shorten charging time,and extend the cycle life.However,there are large variations in the implementation of the number of stages,stage transition criterion,and C-rate selection for each stage.This paper provides a review of these problems by compiling information from the literature.An overview of the impact of different design parameters(number of stages,stage transition,and C-rate) that the MSCC charging techniques have had on the LIB performance and cycle life is described in detail and analyzed.The impact of design parameters on lifetime,charging efficiency,charging and discharging capacity,charging speed,and rising temperature during charging is presented,and this review provides guidelines for designing advanced fast charging strategies and determining future research gaps.

Insight into the effect of thick graphite electrodes towards high-performance cylindrical Ni-rich NCA90 Li-ion batteries

This study explored the complex effect of graphite tortuosity on the electrochemical performance of Ni-rich NCA90 Li-ion batteries(LIBs).Different levels of graphite anode tortuosity were analyzed,revealing that low-tortuosity electrodes had better graphite utilization.The in-plane tortuosities of the graphite anode electrodes examined were 1.70,1.94,2.05,and 2.18,while their corresponding through-plane tortuosities were 4.74,6.94,8.19,and 9.80.In-operando X-ray diffraction and differential electrochemical mass spectrometry were employed to investigate the charge storage mechanism and gas evolution.The study revealed that while graphite electrode tortuosity impacted the amount of Li present in the lithiated graphite phase due to diffusion constraints,it did not affect gas generation.The Li-ion utilization in low-tortuosity electrodes was higher than that in high-tortuosity electrodes because of solid-diffusion limitations.Additionally,the galvanostatic intermittent titration technique(GITT) was employed to investigate a lithium-ion diffusion coefficient.Our results indicate that the lithium-ion diffusion coefficient exhibits a significant difference only during LiC_(6) phase transition.We also observed that the use of a lower tortuosity electrode leads to improved lithium-ion insertion.Consequently,graphite utilization is influenced by the porous electrode design.Safety tests adhering to UN38.3 guidelines verified battery safety.The study demonstrated the practical application of optimized NCA90 LIB cells with diverse graphite electrode tortuosities in a high-performance Lamborghini GoKart,paving the way for further advancements in Ni-rich LIB technology.

A class of Ga-Al-P-based compounds with disordered lattice as advanced anode materials for Li-ion batteries

Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries(LIBs).Through a facile mechanochemistry method, we prepare a novel ternary phosphide of Ga0.5Al0.5P whose crystalline structure is determined to be a cation-disordered cubic zinc sulfide structure according to XRD refinement. As an anode for LIBs, the Ga0.5Al0.5P delivers a reversible capacity of 1,352 mA h g^(-1)at100 mA g^(-1)with an initial Coulombic efficiency(ICE) up to 90.0% based on a reversible Li-storage mechanism integrating intercalation and subsequent conversion processes as confirmed by various characterizations techniques including in-situ XRD, ex-situ Raman, and XPS and electrochemical characterizations.Graphite-modified Ga0.5Al0.5P exhibits a long-lasting cycling stability of retaining 1,182 mA h g^(-1)after300 cycles at 100 m A g^(-1), and 625 mA h g^(-1)after 800 cycles at 2,000 mA g^(-1), and a high-rate performance of remaining 342 m A h g^(-1)at 20,000 mA g^(-1). The outstanding electrochemical performances can be attributed to enhanced reaction kinetics enabled by the capacitive behaviors and the faster Liion diffusion enabled by the cation-mixing. Importantly, by tuning the cationic ratio, we develop a novel series of cation-mixed compounds of Ga_(1/3)Al_(2/3)P, Ga_(1/4)Al_(3/4)P, Ga_(1/5)Al_(4/5)P, Ga_(2/3)Al_(1/3)P, Ga_(3/4)Al_(1/4)P, and Ga_(4/5)Al_(1/5)P, which demonstrate large capacity, high ICE, and suitable anode potentials. Broadly, these compounds with disordered lattices probably present novel physicochemical properties, and high electrochemical performances, thus providing a new perspective for new materials design.

KOH-assisted aqueous synthesis of ZIF-67 with high-yield and its derived cobalt selenide/carbon composites for high-performance Li-ion batteries

To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.

Seamlessly Merging the Capacity of P into Sb at Same Voltage with Maintained Superior Cycle Stability and Low-temperature Performance for Li-ion Batteries

Among the alloying-type anodes,elemental Sb possesses the suitable yet safe plateau,simple lithiation pathway,small voltage polarization,high conductivity,and superior cycle stability.However,challenge is that its intrinsic capacity is rather low(660 mAh g^(-1)),<1/6 of silicon.Herein,we propose a seamless integration strategy by merging the voltage and capacity of phosphorus and antimony into a solid solution alloy.Interestingly,the enlistment of P is found greatly enlarge the capacity from 660 to 993 mAh g^(-1) for such Sb_(30)P_(30) solid solution,while maintaining a single and stable discharge plateau(~0.79 V)similar to elemental Sb.Various experimental characterizations including XPS,PDF,Raman,and EDS mapping reveal that in such a material the P and Sb atoms have interacted with each other to form a homogenous solid solution alloy,rather than a simple mixing of the two substances.Thus,the Sb_(30)P_(30) exhibits superior rate performances(807 mAh g^(-1) at 5000 mA g^(-1))and cyclability(821 mAh g^(-1) remained after 300 cycles).Furthermore,such Sb_(60-x)P_(x) alloys can even deliver 621 mAh g^(-1) at
30℃,which can be served as the alternative anode materials for high-energy and low-temperature batteries.This unique seamless integration strategy based on solid solution chemistry can be easily leveraged to manipulate the capacity of other electrode materials at similar voltage.

Si-Based Anode Materials for Li-Ion Batteries:A Mini Review

Si has been considered as one of the most attractive anode materials for Li-ion batteries(LIBs) because of its high gravimetric and volumetric capacity. Importantly, it is also abundant, cheap, and environmentally benign. In this review, we summarized the recent progress in developments of Si anode materials. First, the electrochemical reaction and failure are outlined, and then, we summarized various methods for improving the battery performance, including those of nanostructuring, alloying, forming hierarchic structures, and using suitable binders. We hope that this review can be of benefit to more intensive investigation of Si-based anode materials.

Synthesis and electrochemical performances of LiCoO_2 recycled from the incisors bound of Li-ion batteries

A new LiCoO2 recovery technology for Li-ion batteries was studied in this paper. LiCoO2 was peeled from the Al foil with dimethyl acetamide （DMAC）, and then polyvinylidene fluoride （PVDF） and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li2CO3, LiOH-H20 and LiAc-2H2O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO2 was obtained by calcining the mixture at 850℃ for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO2 synthesized by adding Li2CO3 is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g^-1 between 3.0-4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g^-1.

Surface-engineering of layered LiNi_(0.815)Co_(0.15)Al_(0.035)O_2 cathode material for high-energy and stable Li-ion batteries

Surface engineering is an effective strategy to restrain the generation of rocksalt NiO phase on surface of layered LiNi0.815Co0.15Al0.035O2（NCA） primary nanoparticles, a representative Ni-rich layered oxides cathode materials. Herein, we demonstrate the kilogram-scale synthesis of few-layer reduced graphene oxide（rGO） conformably coated NCA primary nanoparticles cathode materials by a mechanical wet ball-milling strategy. The lightening rGO coating layer effectively avoids the direct contact of electrolyte and NCA with rapid electrons transfer. As a result, the as-obtained NCA@rGO hybrids with only 1.0 wt% rGO content can deliver a high specific capacity（196 mAh g-1 at 0.2 C） and fast charge/discharge capability（127 mAh g-1 at 5 C）, which is much higher than the corresponding NCA nanoparticles（95 mAh g-1 at 5 C）. Even after100 cycles at 1 C, 91.7% of initial reversible capacity is still maintained. Furthermore, a prismatic pouch cell（240 mAh） is also successfully assembled with the commercial graphite anode.

Nitrogen-doped carbon stabilized Li Fe0.5Mn0.5PO4/rGO cathode materials for high-power Li-ion batteries

Exploring high ion/electron conductive olivine-type transition metal phosphates is of vital significance to broaden their applicability in rapid-charging devices.Herein,we report an interface engineered Li Fe0.5Mn0.5PO4/rGO@C cathode material by the synergistic effects of r GO and polydopamine-derived N-doped carbon.The well-distributed Li Fe0.5Mn0.5PO4nanoparticles are tightly anchored on r GO nanosheet benefited by the coating of N-doped carbon layer.The design of such an architecture can effectively suppress the agglomeration of nanoparticles with a shortened Li+transfer path.Meantime,the high-speed conducting network has been constructed by r GO and N-doped carbon,which exhibits the face-to-face contact with Li Fe0.5Mn0.5PO4nanoparticles,guaranteeing the rapid electron transfer.These profits endow the Li Fe0.5Mn0.5PO4/rGO@C hybrids with a fast charge-discharge ability,e.g.a high reversible capacity of 105 m Ah·g^-1at 10 C,much higher than that of the Li Fe0.5Mn0.5PO4@C nanoparticles(46 mA·h·g^-1).Furthermore,a 90.8%capacity retention can be obtained even after cycling 500 times at 2 C.This work gives a new avenue to fabricate transition metal phosphate with superior electrochemical performance for high-power Li-ion batteries.

Oxygen redox chemistry in lithium-rich cathode materials for Li-ion batteries:Understanding from atomic structure to nano-engineering

Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries,owing to their high specific capacity.However,it remains a great challenge to achieve the fully reversible anionic redox reactions to realize high capacity,high stability,and low voltage hysteresis for lithiumrich cathode materials.Therefore,it is critically important to comprehensively understand and control the anionic redox chemistry of lithium-rich cathode materials,including atomic structure design,and nano-scale materials engineering technologies.Herein,we summarize the recent research progress of lithium-rich cathode materials with a focus on redox chemistry.Particularly,we highlight the oxygen-based redox reactions in lithium-rich metal oxides,with critical views of designing next generation oxygen redox lithium cathode materials.Furthermore,we purposed the most promising strategies for improving the performances of lithium-rich cathode materials with a technology-spectrum from the atomic scale to nano-scale.

Purification process of coal-based coke powder as anode for Li-ion batteries

A process of purification of coal-based coke powder as anode the treatment of coke powder with dilute hydrofluoric acid solution, for Li-ion batteries was attempted. The process started with followed by united-acid-leaching using sulfuric acid and hydrochloric acid. The effects of altering the hydrofluoric acid addition, hydrofluoric acid concentration, contact time, temperature and acid type were investigated. A minimum ash content of 0.35% was obtained when proper conditions were applied. The electrochemical performance of purified coke powder shows greatly improved electrochemical performance. The as-purified coke powder presented an initial reversible capacity of 257.4 mAh/g and a retention rate of 95% after 50 cycles. The proposed purification process paves a way to prepare a promising anode material with good performance with low cost of coke powder for Li-ion batteries.