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 recyclin...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.展开更多
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 uns...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.展开更多
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 t...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.展开更多
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 formati...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.展开更多
The recycling and reutilization of spent lithium-ion batteries(LIBs)have become an important measure to alleviate problems like resource scarcity and environmental pollution.Although some progress has been made,batter...The recycling and reutilization of spent lithium-ion batteries(LIBs)have become an important measure to alleviate problems like resource scarcity and environmental pollution.Although some progress has been made,battery recycling technology still faces challenges in terms of efficiency,effectiveness and environmental sustainability.This review aims to systematically review and analyze the current status of spent LIB recycling,and conduct a detailed comparison and evaluation of different recycling processes.In addition,this review introduces emerging recycling techniques,including deep eutectic solvents,molten salt roasting,and direct regeneration,with the intent of enhancing recycling efficiency and diminishing environmental repercussions.Furthermore,to increase the added value of recycled materials,this review proposes the concept of upgrading recycled materials into high value-added functional materials,such as catalysts,adsorbents,and graphene.Through life cycle assessment,the paper also explores the economic and environmental impacts of current battery recycling and highlights the importance that future recycling technologies should achieve a balance between recycling efficiency,economics and environmental benefits.Finally,this review outlines the opportunities and challenges of recycling key materials for next-generation batteries,and proposes relevant policy recommendations to promote the green and sustainable development of batteries,circular economy,and ecological civilization.展开更多
Safety issue is still a problem nowadays for the large-scale application of lithium-ion batteries(LIBs)in electric vehicles and energy storage stations.The unsafe behaviors of LIBs arise from the thermal run-away,whic...Safety issue is still a problem nowadays for the large-scale application of lithium-ion batteries(LIBs)in electric vehicles and energy storage stations.The unsafe behaviors of LIBs arise from the thermal run-away,which is intrinsically triggered by the overcharging and overheating.To improve the safety of LIBs,various protection strategies based on self-actuating reaction control mechanisms(SRCMs)have been proposed,including redox shuttle,polymerizable monomer additive,potential-sensitive separator,thermal shutdown separator,positive-temperature-coefficient electrode,thermally polymerizable addi-tive,and reversible thermal phase transition electrolyte.As build-in protection mechanisms,these meth-ods can sensitively detect either the temperature change inside battery or the potential change of the electrode,and spontaneously shut down the electrode reaction at risky conditions,thus preventing the battery from going into thermal runaway.Given their advantages in enhancing the intrinsic safety of LIBs,this paper overviews the research progresses of SRCMs after a brief introduction of thermal runaway mechanism and limitations of conventional thermal runaway mitigating measures.More importantly,the current states and issues,key challenges,and future developing trends of SRCTs are also discussed and outlined from the viewpoint of practical application,aiming at providing insights and guidance for developing more effective SRCMs for LIBs.展开更多
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 ...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.展开更多
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-t...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.展开更多
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...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.展开更多
Firstly, the definition, structure and working principles of storage batteries in automatic meteorological observation stations were stated simply, and then the daily maintenance of the storage batteries were introduc...Firstly, the definition, structure and working principles of storage batteries in automatic meteorological observation stations were stated simply, and then the daily maintenance of the storage batteries were introduced according to previous practical experience, finally typical faults of storage batteries were analyzed. Practical evidence shows that timely external maintenance and enough supply of electrolyte can greatly extend the lifespan of storage batteries.展开更多
Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacita...Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacitance,durability,and safety.However,such widespread use implies the generation of large amounts of electronic waste.It is estimated that more than 11 million ton of LIBs waste will have been generated by 2030.Battery recycling can contribute to minimizing environmental contamination and reducing production costs through the recovery of high-value raw materials such as lithium,cobalt,and nickel.The most common processes used to recycle spent LIBs are pyrometallurgical,biometallurgical,and hydrometallurgical.Given the current scenario,it is necessary to develop environmentally friendly methods to recycle batteries and synthesize materials with multiple technological applications.This study presents a review of industrial and laboratory processes for recycling spent LIBs and producing materials that can be used in new batteries,energy storage devices,electrochemical sensors,and photocatalytic reactions.展开更多
A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Amo...A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.展开更多
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 ben...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.展开更多
Li-ion batteries(LIBs)have demonstrated great promise in electric vehicles and hybrid electric vehicles.However,commercial graphite materials,the current predominant anodes in LIBs,have a low theoretical capacity of o...Li-ion batteries(LIBs)have demonstrated great promise in electric vehicles and hybrid electric vehicles.However,commercial graphite materials,the current predominant anodes in LIBs,have a low theoretical capacity of only 372 mAh·g?1,which cannot meet the everincreasing demand of LIBs for high energy density.Nanoscale Si is considered an ideal form of Si for the fabrication of LIB anodes as Si–C composites.Synthesis of nanoscale Si in a facile,cost-effective way,however,still poses a great challenge.In this work,nanoscale Si was prepared by a controlled magnesiothermic reaction using diatomite as the Si source.It was found that the nanoscale Si prepared under optimized conditions(800°C,10 h)can deliver a high initial specific capacity(3053 mAh·g?1 on discharge,2519 mAh·g?1 on charge)with a high first coulombic efficiency(82.5%).When using sand-milled diatomite as a precursor,the obtained nanoscale Si exhibited a well-dispersed morphology and had a higher first coulombic efficiency(85.6%).The Si–C(Si:graphite=1:7 in weight)composite using Si from the sand-milled diatomite demonstrated a high specific capacity(over 700 mAh·g?1 at 100 mA·g?1),good rate capability(587 mAh·g?1 at 500 mA·g?1),and a long cycle life(480 mAh·g?1 after 200 cycles at 500 mA·g?1).This work gives a facile method to synthesize nanoscale Si with both high capacity and high first coulombic efficiency.展开更多
One-dimensional(1-D) nanomaterials with superior specific capacity, higher rate capability, better cycling peroperties have demonstrated significant advantages for high-performance Li-ion batteries and supercapacito...One-dimensional(1-D) nanomaterials with superior specific capacity, higher rate capability, better cycling peroperties have demonstrated significant advantages for high-performance Li-ion batteries and supercapacitors. This review describes some recent developments on the rechargeable electrodes by using 1-D nanomaterials(such as Li Mn2O4 nanowires, carbon nanofibers, Ni Mo O4 · n H2O nanorods, V2O5 nanoribbons,carbon nanotubes, etc.). New preparation methods and superior electrochemical properties of the 1-D nanomaterials including carbon nanotube(CNT), some oxides, transition metal compounds and polymers, and their composites are emphatically introduced. The VGCF/Li Fe PO4/C triaxial nanowire cathodes for Li-ion battery present a positive cycling performance without any degradation in almost theoretical capacity(160 m Ah/g).The Si nanowire anodes for Li-ion battery show the highest known theoretical charge capacity(4277 m Ah/g),that is about 11 times lager than that of the commercial graphite(372 m Ah/g). The SWCNT/Ni foam electrodes for supercapacitor display small equivalent series resistance(ESR, 52 m?) and impressive high power density(20 k W/kg). The advantages and challenges associated with the application of these materials for energy conversion and storage devices are highlighted.展开更多
The demand for Li-ion batteries (LIBs) for vehicles is increasing. However, LIBs use valuable rare metals, such as Co and Li, aswell as environmentally toxic reagents. LIBs are also necessary to utilize for a long per...The demand for Li-ion batteries (LIBs) for vehicles is increasing. However, LIBs use valuable rare metals, such as Co and Li, aswell as environmentally toxic reagents. LIBs are also necessary to utilize for a long period and to recycle useful materials. The reduction, reuse,and recycle (3R) of spent LIBs is an important consideration in constructing a circular economy. In this paper, a flowsheet of the 3R of LIBs isproposed and methods to reduce the utilization of valuable rare metals and the amount of spent LIBs by remanufacturing used parts and designingnew batteries considering the concept of 3R are described. Next, several technological processes for the reuse and recycling of LIBs are introduced.These technologies include discharge, sorting, crushing, binder removal, physical separation, and pyrometallurgical and hydrometallurgicalprocessing. Each process, as well as the related physical, chemical, and biological treatments, are discussed. Finally, the problem of developedtechnologies and future subjects for 3R of LIBs are described.展开更多
Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and...Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and electrochemical performances of as-prepared LiFePO4 were evaluated by means of transmission electron microscopy (TEM), charge-discharge test, electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV). CNTs contribute to the interconnection of the isolated LiFePO4 or carbon particles. For the CNTs-modified LiFePO4, it exhibits excellent performance in terms of both specific capacity and cycle life. The initial discharge capacity is 147.9 mA·h/g at 0.2C rate and 134.2 mA·h/g at 1C rate, keeping a capacity retention ratio of 97% after 50 cycles. The results from EIS indicate that the impedance value of the solid electrolyte interface decreases. The cyclic voltammetric peak profiles is more symmetric and spiculate and there are fewer peaks. CNTs are promising conductive additives candidate for high-power Li-ion batteries.展开更多
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...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.展开更多
Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precu...Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g-1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g-1. The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(Ministry of Science and ICT(RS-2023-00254424)Ministry of Education(2020R1A6A1A03038540))。
文摘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.
基金supported by the National Natural Science Foundation of China(21975074,91834301)the Innovation Program of Shanghai Municipal Education Commissionthe Fundamental Research Funds for the Central Universities.
文摘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.
基金supported by the National Natural Science Foundation of China (No.92372123)the Natural Science Foundation of Guangdong Province (No.2022B1515020005)the Department of Science and Technology of Guangdong Province (No.2020B0101030005)
文摘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.
基金Project supported by the Science Fund of the Guangdong Major Project of Basic and Applied Basic Research,China(Grant No.2019B030302011)the Fund of the Science and Technology Program of Guangzhou,China(Grant No.202201010090)。
文摘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.
基金financially supported by the National Natural Science Foundation of China(NSFC)(52274295)the Natural Science Foundation of Hebei Province(E2020501001,E2021501029,A2021501007,E2022501028,E2022501029)+5 种基金the Natural Science Foundation-Steel,the Iron Foundation of Hebei Province(No.E2022501030)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(22567627H)the Science and Technology Project of Hebei Education Department(ZD2022158)the Central Guided Local Science and Technology Development Fund Project of Hebei province(226Z4401G)the China Scholarship Council(No.202206080061,202206050119)the 2023 Hebei Provincial Postgraduate Student Innovation Ability training funding project(CXZZSS2023195)。
文摘The recycling and reutilization of spent lithium-ion batteries(LIBs)have become an important measure to alleviate problems like resource scarcity and environmental pollution.Although some progress has been made,battery recycling technology still faces challenges in terms of efficiency,effectiveness and environmental sustainability.This review aims to systematically review and analyze the current status of spent LIB recycling,and conduct a detailed comparison and evaluation of different recycling processes.In addition,this review introduces emerging recycling techniques,including deep eutectic solvents,molten salt roasting,and direct regeneration,with the intent of enhancing recycling efficiency and diminishing environmental repercussions.Furthermore,to increase the added value of recycled materials,this review proposes the concept of upgrading recycled materials into high value-added functional materials,such as catalysts,adsorbents,and graphene.Through life cycle assessment,the paper also explores the economic and environmental impacts of current battery recycling and highlights the importance that future recycling technologies should achieve a balance between recycling efficiency,economics and environmental benefits.Finally,this review outlines the opportunities and challenges of recycling key materials for next-generation batteries,and proposes relevant policy recommendations to promote the green and sustainable development of batteries,circular economy,and ecological civilization.
基金financially supported by the National Natural Science Foundation of China(U22A20438)the National Key R&D Program of China(2022YFB2502100)the National Natural Science Foundation of China(22309138).
文摘Safety issue is still a problem nowadays for the large-scale application of lithium-ion batteries(LIBs)in electric vehicles and energy storage stations.The unsafe behaviors of LIBs arise from the thermal run-away,which is intrinsically triggered by the overcharging and overheating.To improve the safety of LIBs,various protection strategies based on self-actuating reaction control mechanisms(SRCMs)have been proposed,including redox shuttle,polymerizable monomer additive,potential-sensitive separator,thermal shutdown separator,positive-temperature-coefficient electrode,thermally polymerizable addi-tive,and reversible thermal phase transition electrolyte.As build-in protection mechanisms,these meth-ods can sensitively detect either the temperature change inside battery or the potential change of the electrode,and spontaneously shut down the electrode reaction at risky conditions,thus preventing the battery from going into thermal runaway.Given their advantages in enhancing the intrinsic safety of LIBs,this paper overviews the research progresses of SRCMs after a brief introduction of thermal runaway mechanism and limitations of conventional thermal runaway mitigating measures.More importantly,the current states and issues,key challenges,and future developing trends of SRCTs are also discussed and outlined from the viewpoint of practical application,aiming at providing insights and guidance for developing more effective SRCMs for LIBs.
基金supported by the National Natural Science Foundation of China (22178068)the Brain Pool program (2021H1D3A2A02045576) funded by National Research Foundation of Korea (NRF)。
文摘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.
基金financially supported under the Program Management Unit for National Competitiveness Enhancement (PMUC) by the Office of the National Higher Education Science Research and Innovation Policy Council (NXPO) PTT Public Company LimitedIRPC Public Company Limited, Thailand Science Research and Innovation (TSRI) under the Fundamental Fund by TSRI (FRB660004/0457)+2 种基金Vidyasirimedhi Institute of Science and Technology (VISTEC)Energy Policy and Planning Office (EPPO), Ministry of Energy, Thailandthe Frontier Research Centre (FRC) supported this work, VISTEC。
文摘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.
文摘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.
文摘Firstly, the definition, structure and working principles of storage batteries in automatic meteorological observation stations were stated simply, and then the daily maintenance of the storage batteries were introduced according to previous practical experience, finally typical faults of storage batteries were analyzed. Practical evidence shows that timely external maintenance and enough supply of electrolyte can greatly extend the lifespan of storage batteries.
基金the Brazilian Federal Agency for Support and Evaluation of Graduate Education(CAPES)the Brazilian National Council for Scientific and Technological Development(CNPq,306239/2019-1)for their financial support。
文摘Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacitance,durability,and safety.However,such widespread use implies the generation of large amounts of electronic waste.It is estimated that more than 11 million ton of LIBs waste will have been generated by 2030.Battery recycling can contribute to minimizing environmental contamination and reducing production costs through the recovery of high-value raw materials such as lithium,cobalt,and nickel.The most common processes used to recycle spent LIBs are pyrometallurgical,biometallurgical,and hydrometallurgical.Given the current scenario,it is necessary to develop environmentally friendly methods to recycle batteries and synthesize materials with multiple technological applications.This study presents a review of industrial and laboratory processes for recycling spent LIBs and producing materials that can be used in new batteries,energy storage devices,electrochemical sensors,and photocatalytic reactions.
基金National Natural Science Foundation of China,Grant/Award Number:52064049Key National Natural Science Foundation of Yunnan Province,Grant/Award Numbers:2018FA028,2019FY003023+1 种基金International Joint Research Center for Advanced Energy Materials of Yunnan Province,Grant/Award Number:202003AE140001Key Laboratory of Solid State Ions for Green Energy of Yunnan University,Grant/Award Number:2019。
文摘A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.
基金partially supported by Beijing High-level Oversea Talent Projectthe strategic research grant ‘‘Laser interference process of silver nanostructures for surface enhanced Raman spectroscopy and environment application’’ (KZ201410005001) of Beijing Nature Science Foundation, the P. R. China
文摘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.
基金the National Natural Science Foundation of China(No.51572238)Zhejiang Provincial Natural Science Foundation(No.LY19E020013)the Joint Research Project of Zhejiang University with Zotye Automobile Corporation Limited on Si-Based Anode Materials(No.P-ZH-2018-003).
文摘Li-ion batteries(LIBs)have demonstrated great promise in electric vehicles and hybrid electric vehicles.However,commercial graphite materials,the current predominant anodes in LIBs,have a low theoretical capacity of only 372 mAh·g?1,which cannot meet the everincreasing demand of LIBs for high energy density.Nanoscale Si is considered an ideal form of Si for the fabrication of LIB anodes as Si–C composites.Synthesis of nanoscale Si in a facile,cost-effective way,however,still poses a great challenge.In this work,nanoscale Si was prepared by a controlled magnesiothermic reaction using diatomite as the Si source.It was found that the nanoscale Si prepared under optimized conditions(800°C,10 h)can deliver a high initial specific capacity(3053 mAh·g?1 on discharge,2519 mAh·g?1 on charge)with a high first coulombic efficiency(82.5%).When using sand-milled diatomite as a precursor,the obtained nanoscale Si exhibited a well-dispersed morphology and had a higher first coulombic efficiency(85.6%).The Si–C(Si:graphite=1:7 in weight)composite using Si from the sand-milled diatomite demonstrated a high specific capacity(over 700 mAh·g?1 at 100 mA·g?1),good rate capability(587 mAh·g?1 at 500 mA·g?1),and a long cycle life(480 mAh·g?1 after 200 cycles at 500 mA·g?1).This work gives a facile method to synthesize nanoscale Si with both high capacity and high first coulombic efficiency.
基金supported by the National Natural Science Foundation of China(No.5073000809ZR1414800)+3 种基金Science and Technology Commission of Shanghai MunicipalityChina(No.1052nm02000 and 09JC1407400)Shanghai Research Fund for the Post-doctoral Program(No.10R21414700)China Postdoctoral Science Foundation funded project(No.20100470710)
文摘One-dimensional(1-D) nanomaterials with superior specific capacity, higher rate capability, better cycling peroperties have demonstrated significant advantages for high-performance Li-ion batteries and supercapacitors. This review describes some recent developments on the rechargeable electrodes by using 1-D nanomaterials(such as Li Mn2O4 nanowires, carbon nanofibers, Ni Mo O4 · n H2O nanorods, V2O5 nanoribbons,carbon nanotubes, etc.). New preparation methods and superior electrochemical properties of the 1-D nanomaterials including carbon nanotube(CNT), some oxides, transition metal compounds and polymers, and their composites are emphatically introduced. The VGCF/Li Fe PO4/C triaxial nanowire cathodes for Li-ion battery present a positive cycling performance without any degradation in almost theoretical capacity(160 m Ah/g).The Si nanowire anodes for Li-ion battery show the highest known theoretical charge capacity(4277 m Ah/g),that is about 11 times lager than that of the commercial graphite(372 m Ah/g). The SWCNT/Ni foam electrodes for supercapacitor display small equivalent series resistance(ESR, 52 m?) and impressive high power density(20 k W/kg). The advantages and challenges associated with the application of these materials for energy conversion and storage devices are highlighted.
文摘The demand for Li-ion batteries (LIBs) for vehicles is increasing. However, LIBs use valuable rare metals, such as Co and Li, aswell as environmentally toxic reagents. LIBs are also necessary to utilize for a long period and to recycle useful materials. The reduction, reuse,and recycle (3R) of spent LIBs is an important consideration in constructing a circular economy. In this paper, a flowsheet of the 3R of LIBs isproposed and methods to reduce the utilization of valuable rare metals and the amount of spent LIBs by remanufacturing used parts and designingnew batteries considering the concept of 3R are described. Next, several technological processes for the reuse and recycling of LIBs are introduced.These technologies include discharge, sorting, crushing, binder removal, physical separation, and pyrometallurgical and hydrometallurgicalprocessing. Each process, as well as the related physical, chemical, and biological treatments, are discussed. Finally, the problem of developedtechnologies and future subjects for 3R of LIBs are described.
基金Project(06B002)supported by Scientific Research Fund of Hunan Provincial Education Department of ChinaProject(09JJ3092)supported by Hunan Provincial Natural Science Foundation of ChinaProject(2008FJ3008)supported by the Planned Science and Technology Project of Hunan Province of China
文摘Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and electrochemical performances of as-prepared LiFePO4 were evaluated by means of transmission electron microscopy (TEM), charge-discharge test, electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV). CNTs contribute to the interconnection of the isolated LiFePO4 or carbon particles. For the CNTs-modified LiFePO4, it exhibits excellent performance in terms of both specific capacity and cycle life. The initial discharge capacity is 147.9 mA·h/g at 0.2C rate and 134.2 mA·h/g at 1C rate, keeping a capacity retention ratio of 97% after 50 cycles. The results from EIS indicate that the impedance value of the solid electrolyte interface decreases. The cyclic voltammetric peak profiles is more symmetric and spiculate and there are fewer peaks. CNTs are promising conductive additives candidate for high-power Li-ion batteries.
基金supported by the National Natural Science Foundation of China (Nos. 50762004 and 50864004)
文摘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.
基金This work was financially supported by the National Natural Science Foundation of China (No.50134020)
文摘Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g-1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g-1. The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.