The extensive application of lithium-ion batteries in electric vehicles has led to a torrential surge of endof-life batteries.As the dominant anode material,graphite's environmental and resource costs in productio...The extensive application of lithium-ion batteries in electric vehicles has led to a torrential surge of endof-life batteries.As the dominant anode material,graphite's environmental and resource costs in production highlight the necessity of recycling spent graphite(SG).However,SG recycling technologies remain markedly underdeveloped compared to the cathode recovery status,due to perceived lower economic value.This review provides an in-depth analysis of the current SG growth trend and highlights the cost accounting for graphite recycling and the significant importance of advanced recycling technologies.By examining the failure mechanisms of graphite,various recycling and upcycling technologies in both practical application and fundamental research are fully discussed,in terms of the regeneration principle,recycling effect,strengths,and limitations of each method.Furthermore,the multi-purpose applications of recycled graphite beyond LIB anodes are explored to enhance its high-value properties.Finally,the prospects of SG recycling and large-scale application challenges are presented,including economic feasibility,process optimization,and regulatory restrictions.This review provides a comprehensive overview of developments in SG recycling strategies,offering valuable insights for narrowing the gap between fundamental research and practical applications.展开更多
The recycling of spent batteries has become increasingly important owing to their wide applications,abundant raw material supply,and sustainable development.Compared with the degraded cathode,spent anode graphite ofte...The recycling of spent batteries has become increasingly important owing to their wide applications,abundant raw material supply,and sustainable development.Compared with the degraded cathode,spent anode graphite often has a relatively intact structure with few defects after long cycling.Yet,most spent graphite is simply burned or discarded due to its limited value and inferior performance on using conventional recycling methods that are complex,have low efficiency,and fail in performance restoration.Herein,we propose a fast,efficient,and“intelligent”strategy to regenerate and upcycle spent graphite based on defect‐driven targeted remediation.Using Sn as a nanoscale healant,we used rapid heating(~50 ms)to enable dynamic Sn droplets to automatically nucleate around the surface defects on the graphite upon cooling owing to strong binding to the defects(~5.84 eV/atom),thus simultaneously achieving Sn dispersion and graphite remediation.As a result,the regenerated graphite showed enhanced capacity and cycle stability(458.9 mAh g^(−1) at 0.2 A g^(−1) after 100 cycles),superior to those of commercial graphite.Benefiting from the self‐adaption of Sn dispersion,spent graphite with different degrees of defects can be regenerated to similar structures and performance.EverBatt analysis indicates that targeted regeneration and upcycling have significantly lower energy consumption(~99%reduction)and near‐zero CO_(2) emission,and yield much higher profit than hydrometallurgy,which opens a new avenue for direct upcycling of spend graphite in an efficient,green,and profitable manner for sustainable battery manufacture.展开更多
Spent battery recycling has received considerable attention because of its economic and environmental potential.A large amount of retired graphite has been produced as the main electrode material,accompanied by a deta...Spent battery recycling has received considerable attention because of its economic and environmental potential.A large amount of retired graphite has been produced as the main electrode material,accompanied by a detailed exploration of the repair mechanism.However,they still suffer from unclear repair mechanisms and physicochemical evolution.In this study,spent graphite was repaired employing three methodologies:pickling-sintering,pyrogenic-recovery,and high-temperature sintering.Owing to the catalytic effect of the metal-based impurities and temperature control,the as-obtained samples displayed an ordered transformation,including the interlayer distance,crystalline degree,and grain size.As anodes of lithium ions batteries,the capacity of repaired samples reached up to 310 mA h g^(-1)above after 300loops at 1.0 C,similar to that of commercial graphite.Meanwhile,benefitting from the effective assembly of carbon atoms in internal structure of graphite at>1400℃,their initial coulombic efficiency were>87%.Even at 2.0 C,the capacity of samples remained approximately 244 mA h g^(-1)after 500 cycles.Detailed electrochemical and kinetic analyses revealed that a low temperature enhanced the isotropy,thereby enhancing the rate properties.Further,economic and environmental analyses revealed that the revenue obtained through suitable pyrogenic-recovering manners was approximately the largest value(5500$t^(-1)).Thus,this study is expected to clarify the in-depth effect of different repair methods on the traits of graphite,while offering all-round evaluations of repaired graphite.展开更多
The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium st...The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium storage behavior.Herein,low-viscosity natural deep eutectic solvent(NDES)composed of citric acid(CA)and betaine hydrochloride was employed to remove the organic impurities in SG via a one-step benign process involving hydrogen bonds and electrostatic interactions at mild conditions of 80℃ for only 30 min.After NDES leaching under optimal conditions(molar ratio of CA to betaine hydrochloride=3:1,80℃,30 min),the as-obtained sample(denoted as BG-3)exhibited an extremely clean surface,moderately enlarged interlayer distance,and more structural defects at the edge of graphite lamellae.These features facilitated lithium-ion intercalation and withdrawal,bestowing BG-3 with remarkable activity in lithium-ion battery(LIB)recycling.For instance,BG-3 delivered a capacity of 438.6 mAh g^(-1) at a current density of 0.1 A g^(-1).Its capacity retention reached 97.9%,accompanied by a Coulombic efficiency of 99.1%,upon completing 100 cycles.A molecular dynamics simulation was employed to illuminate the regeneration mechanism for anode graphite from a theoretical perspective.It revealed that NDES exhibits lower binding energy with all contaminants compared to graphite,which is favorable for NDES to eliminate impurities from graphite surfaces.This study unveils a method of recycling SG from retired LIBs by a short eco-friendly process,providing a competitive blueprint to address the shortage of battery-grade anode graphite and to achieve carbon neutrality.展开更多
Regenerating spent graphite(SG)from retired lithium-ion batteries(LIBs)can effectively avoid resource waste.However,the technology is challenged by the impurity content and energy consumption.In this study,micro-expan...Regenerating spent graphite(SG)from retired lithium-ion batteries(LIBs)can effectively avoid resource waste.However,the technology is challenged by the impurity content and energy consumption.In this study,micro-expanded graphite(MEG)was synthesized by one-step oxidation method using waste LIBs anode graphite as material and perchloric acid as intercalation and oxidant agent.Then,its performance as a LIBs anode material were investigated as well as the greenhouse gas(GHG)emissions of the whole process were calculated.Perchloric acid was successfully embedded in the SG during the reaction,which effectively removed the impurities in the graphite.Defects introduced during intercalation and delamination,such as nanopores and intercrystalline cracks.Both provide additional space for Li ions during charging and discharging,thereby promoting capacity enhancement.The prepared MEG expresses a rate capability as high as 340.32 m Ah/g at a current density of 0.1 C and still retains 81.73%of the capacity after 100 cycles at a current density of 1 C.Additionally,the GHG emissions of the synthesis process of this article and other literatures are compared.The results demonstrated that perchloric acid treatment process provides a low-carbon,time-and energy-saving approach for regenerated SG as battery grade material.展开更多
Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and th...Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and the use of the purified SCC as an anode material for lithium-ion batteries is explored.The flotation and acid leaching processes were separately optimized through one-way experiments.The maximum SCC carbon content(93wt%)was achieved at a 90%proportion of−200-mesh flotation particle size,a slurry concentration of 10wt%,a rotation speed of 1600 r/min,and an inflatable capacity of 0.2 m^(3)/h(referred to as FSCC).In the subsequent acid leaching process,the SCC carbon content reached 99.58wt%at a leaching concentration of 5 mol/L,a leaching time of 100 min,a leaching temperature of 85°C,and an HCl/FSCC volume ratio of 5:1.The purified graphitized SCC(referred to as FSCC-CL)was utilized as an anode material,and it exhibited an initial capacity of 348.2 mAh/g at 0.1 C and a reversible capacity of 347.8 mAh/g after 100 cycles.Moreover,compared with commercial graphite,FSCC-CL exhibited better reversibility and cycle stability.Thus,purified SCC is an important candidate for anode material,and the flotation-acid leaching purification method is suitable for the resourceful recycling of SCC.展开更多
The recycling of anode graphite plays a crucial role in the overall recycling process of spent lithium-ion batteries(LIBs).In this study an environmentally friendly and cost-effective recycling method was proposed.The...The recycling of anode graphite plays a crucial role in the overall recycling process of spent lithium-ion batteries(LIBs).In this study an environmentally friendly and cost-effective recycling method was proposed.The spent graphite(SG)from LIBs was used to prepare graphene nanoplates(GNP)materials through a mechanochemical process without any additives.To figure out the mechanochemical mechanism within,we set the control group with pure graphite(PG).Characterization of SG and PG produced materials using XRD,Raman,XPS,IR,and BET analyses revealed the presence of oxygen-containing functional groups on the surface of SG-based GNP materials,along with a high specific surface area of 275.4 m^(2)/g and pore volume of 0.568 cm^(3)/g.Through an in-depth investigation of the electrochemical capacity of the GNP materials fabricated by SG,the specific capacitance per unit area of the graphite material is 10.10μF/cm^(2),revealing the intricate pore structure of GNP materials primarily contributes to the electrochemical capacity.展开更多
The potential for recycling graphitic carbon from lithium-ion battery(LIB)anodes has been overlooked due to its relatively low economic value in applications.This study proposed to use graphene nanoplates(GNPs),which ...The potential for recycling graphitic carbon from lithium-ion battery(LIB)anodes has been overlooked due to its relatively low economic value in applications.This study proposed to use graphene nanoplates(GNPs),which were obtained from spent lithium battery anode graphite,treated with ball-milling method,for hydrothermal synthesis of MnO_(2)-supported graphene nanoplates (MnO_(2)/GNPs)composites materials.The composites exhibited excellent electrochemical characterization curves,indicating ideal capacitance characteristics.The analysis of MG24-20 material showed the good impact resistance and capacity retention around 100%with capacitance of 124.6F/g at 10 mV/s,surpassed similar samples using precious metals and high-end materials,enabling the reuse of spent graphite in energy conversion and storage system for effective utility.展开更多
With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （...With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （12%-21%） of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°Cfor 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.展开更多
基金funded by the National Key Research and Development Program of China(grant no.2023YFB3809300)Longzhong Laboratory Research Project(grant no.2024KF-20)+4 种基金the National Science Foundation of China(grant no.52373306)the Key Research and Development Program Project of Hubei Province(grant no.2023BAB140,2024BAA013)the Natural Science Foundation of Hubei Province(grant no.2023AFA053)the Key Research and Development Program of Henan Province(grant no.251111240100)the Postdoctoral Fellowship Program of CPSF(grant no.GZB20230553)。
文摘The extensive application of lithium-ion batteries in electric vehicles has led to a torrential surge of endof-life batteries.As the dominant anode material,graphite's environmental and resource costs in production highlight the necessity of recycling spent graphite(SG).However,SG recycling technologies remain markedly underdeveloped compared to the cathode recovery status,due to perceived lower economic value.This review provides an in-depth analysis of the current SG growth trend and highlights the cost accounting for graphite recycling and the significant importance of advanced recycling technologies.By examining the failure mechanisms of graphite,various recycling and upcycling technologies in both practical application and fundamental research are fully discussed,in terms of the regeneration principle,recycling effect,strengths,and limitations of each method.Furthermore,the multi-purpose applications of recycled graphite beyond LIB anodes are explored to enhance its high-value properties.Finally,the prospects of SG recycling and large-scale application challenges are presented,including economic feasibility,process optimization,and regulatory restrictions.This review provides a comprehensive overview of developments in SG recycling strategies,offering valuable insights for narrowing the gap between fundamental research and practical applications.
基金The Fundamental Research Funds for the Central Universities,HUST,Grant/Award Number:2021GCRC046The Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies,Grant/Award Number:FZ2022005Natural Science Foundation of Hubei Province,China,Grant/Award Number:2022CFA031。
文摘The recycling of spent batteries has become increasingly important owing to their wide applications,abundant raw material supply,and sustainable development.Compared with the degraded cathode,spent anode graphite often has a relatively intact structure with few defects after long cycling.Yet,most spent graphite is simply burned or discarded due to its limited value and inferior performance on using conventional recycling methods that are complex,have low efficiency,and fail in performance restoration.Herein,we propose a fast,efficient,and“intelligent”strategy to regenerate and upcycle spent graphite based on defect‐driven targeted remediation.Using Sn as a nanoscale healant,we used rapid heating(~50 ms)to enable dynamic Sn droplets to automatically nucleate around the surface defects on the graphite upon cooling owing to strong binding to the defects(~5.84 eV/atom),thus simultaneously achieving Sn dispersion and graphite remediation.As a result,the regenerated graphite showed enhanced capacity and cycle stability(458.9 mAh g^(−1) at 0.2 A g^(−1) after 100 cycles),superior to those of commercial graphite.Benefiting from the self‐adaption of Sn dispersion,spent graphite with different degrees of defects can be regenerated to similar structures and performance.EverBatt analysis indicates that targeted regeneration and upcycling have significantly lower energy consumption(~99%reduction)and near‐zero CO_(2) emission,and yield much higher profit than hydrometallurgy,which opens a new avenue for direct upcycling of spend graphite in an efficient,green,and profitable manner for sustainable battery manufacture.
基金financially supported by National Natural Science Foundation of China(52374288,52204298)Young Elite Scientists Sponsorship Program by China Association for Science and Technology(2022QNRC001)+2 种基金National Key Research and Development Program of China(2022YFC3900805-4/7)Hunan Provincial Education Office Foundation of China(No.21B0147)Collaborative Innovation Centre for Clean and Efficient Utilization of Strategic Metal Mineral Resources,Found of State Key Laboratory of Mineral Processing(BGRIMM-KJSKL-2017-13)。
文摘Spent battery recycling has received considerable attention because of its economic and environmental potential.A large amount of retired graphite has been produced as the main electrode material,accompanied by a detailed exploration of the repair mechanism.However,they still suffer from unclear repair mechanisms and physicochemical evolution.In this study,spent graphite was repaired employing three methodologies:pickling-sintering,pyrogenic-recovery,and high-temperature sintering.Owing to the catalytic effect of the metal-based impurities and temperature control,the as-obtained samples displayed an ordered transformation,including the interlayer distance,crystalline degree,and grain size.As anodes of lithium ions batteries,the capacity of repaired samples reached up to 310 mA h g^(-1)above after 300loops at 1.0 C,similar to that of commercial graphite.Meanwhile,benefitting from the effective assembly of carbon atoms in internal structure of graphite at>1400℃,their initial coulombic efficiency were>87%.Even at 2.0 C,the capacity of samples remained approximately 244 mA h g^(-1)after 500 cycles.Detailed electrochemical and kinetic analyses revealed that a low temperature enhanced the isotropy,thereby enhancing the rate properties.Further,economic and environmental analyses revealed that the revenue obtained through suitable pyrogenic-recovering manners was approximately the largest value(5500$t^(-1)).Thus,this study is expected to clarify the in-depth effect of different repair methods on the traits of graphite,while offering all-round evaluations of repaired graphite.
基金supported by the National Natural Science Foundation of China(Project Nos.22372051 and 21406044)Australian Research Council/Discovery Early Career Researcher Award(DECRA)funding scheme(DE230100180).
文摘The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium storage behavior.Herein,low-viscosity natural deep eutectic solvent(NDES)composed of citric acid(CA)and betaine hydrochloride was employed to remove the organic impurities in SG via a one-step benign process involving hydrogen bonds and electrostatic interactions at mild conditions of 80℃ for only 30 min.After NDES leaching under optimal conditions(molar ratio of CA to betaine hydrochloride=3:1,80℃,30 min),the as-obtained sample(denoted as BG-3)exhibited an extremely clean surface,moderately enlarged interlayer distance,and more structural defects at the edge of graphite lamellae.These features facilitated lithium-ion intercalation and withdrawal,bestowing BG-3 with remarkable activity in lithium-ion battery(LIB)recycling.For instance,BG-3 delivered a capacity of 438.6 mAh g^(-1) at a current density of 0.1 A g^(-1).Its capacity retention reached 97.9%,accompanied by a Coulombic efficiency of 99.1%,upon completing 100 cycles.A molecular dynamics simulation was employed to illuminate the regeneration mechanism for anode graphite from a theoretical perspective.It revealed that NDES exhibits lower binding energy with all contaminants compared to graphite,which is favorable for NDES to eliminate impurities from graphite surfaces.This study unveils a method of recycling SG from retired LIBs by a short eco-friendly process,providing a competitive blueprint to address the shortage of battery-grade anode graphite and to achieve carbon neutrality.
基金financially supported by the National Key Research and Development Program of China(No.2019YFC1907900)the National Natural Science Foundation of China(Nos.52125002 and 52100043)the National Science Foundation of Jiangxi Province(No.20202BABL213037)。
文摘Regenerating spent graphite(SG)from retired lithium-ion batteries(LIBs)can effectively avoid resource waste.However,the technology is challenged by the impurity content and energy consumption.In this study,micro-expanded graphite(MEG)was synthesized by one-step oxidation method using waste LIBs anode graphite as material and perchloric acid as intercalation and oxidant agent.Then,its performance as a LIBs anode material were investigated as well as the greenhouse gas(GHG)emissions of the whole process were calculated.Perchloric acid was successfully embedded in the SG during the reaction,which effectively removed the impurities in the graphite.Defects introduced during intercalation and delamination,such as nanopores and intercrystalline cracks.Both provide additional space for Li ions during charging and discharging,thereby promoting capacity enhancement.The prepared MEG expresses a rate capability as high as 340.32 m Ah/g at a current density of 0.1 C and still retains 81.73%of the capacity after 100 cycles at a current density of 1 C.Additionally,the GHG emissions of the synthesis process of this article and other literatures are compared.The results demonstrated that perchloric acid treatment process provides a low-carbon,time-and energy-saving approach for regenerated SG as battery grade material.
基金supported by the National Natural Science Foundation of China(No.52274346).
文摘Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and the use of the purified SCC as an anode material for lithium-ion batteries is explored.The flotation and acid leaching processes were separately optimized through one-way experiments.The maximum SCC carbon content(93wt%)was achieved at a 90%proportion of−200-mesh flotation particle size,a slurry concentration of 10wt%,a rotation speed of 1600 r/min,and an inflatable capacity of 0.2 m^(3)/h(referred to as FSCC).In the subsequent acid leaching process,the SCC carbon content reached 99.58wt%at a leaching concentration of 5 mol/L,a leaching time of 100 min,a leaching temperature of 85°C,and an HCl/FSCC volume ratio of 5:1.The purified graphitized SCC(referred to as FSCC-CL)was utilized as an anode material,and it exhibited an initial capacity of 348.2 mAh/g at 0.1 C and a reversible capacity of 347.8 mAh/g after 100 cycles.Moreover,compared with commercial graphite,FSCC-CL exhibited better reversibility and cycle stability.Thus,purified SCC is an important candidate for anode material,and the flotation-acid leaching purification method is suitable for the resourceful recycling of SCC.
基金supported by the National Natural Science Foundation of China(52470154)China Environmental Protection Foundation.
文摘The recycling of anode graphite plays a crucial role in the overall recycling process of spent lithium-ion batteries(LIBs).In this study an environmentally friendly and cost-effective recycling method was proposed.The spent graphite(SG)from LIBs was used to prepare graphene nanoplates(GNP)materials through a mechanochemical process without any additives.To figure out the mechanochemical mechanism within,we set the control group with pure graphite(PG).Characterization of SG and PG produced materials using XRD,Raman,XPS,IR,and BET analyses revealed the presence of oxygen-containing functional groups on the surface of SG-based GNP materials,along with a high specific surface area of 275.4 m^(2)/g and pore volume of 0.568 cm^(3)/g.Through an in-depth investigation of the electrochemical capacity of the GNP materials fabricated by SG,the specific capacitance per unit area of the graphite material is 10.10μF/cm^(2),revealing the intricate pore structure of GNP materials primarily contributes to the electrochemical capacity.
基金supported by the National Natural Science Foundation of China(51534005,51278293and 51178262)China Environmental Protection Foundation.
文摘The potential for recycling graphitic carbon from lithium-ion battery(LIB)anodes has been overlooked due to its relatively low economic value in applications.This study proposed to use graphene nanoplates(GNPs),which were obtained from spent lithium battery anode graphite,treated with ball-milling method,for hydrothermal synthesis of MnO_(2)-supported graphene nanoplates (MnO_(2)/GNPs)composites materials.The composites exhibited excellent electrochemical characterization curves,indicating ideal capacitance characteristics.The analysis of MG24-20 material showed the good impact resistance and capacity retention around 100%with capacitance of 124.6F/g at 10 mV/s,surpassed similar samples using precious metals and high-end materials,enabling the reuse of spent graphite in energy conversion and storage system for effective utility.
文摘With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （12%-21%） of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°Cfor 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
