Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selectiv...Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.展开更多
Constructing robust surface and bulk structure is the prerequisite for realizing high performance high voltage LiCoO_(2)(LCO).Herein,we manage to synthesize a surface Mg-doping and bulk Al-doping coreshell structured ...Constructing robust surface and bulk structure is the prerequisite for realizing high performance high voltage LiCoO_(2)(LCO).Herein,we manage to synthesize a surface Mg-doping and bulk Al-doping coreshell structured LCO,which demonstrates excellent cycling performance.Half-cell shows 94.2%capacity retention after 100 cycles at 3.0-4.6 V(vs.Li/Li^(+))cycling,and no capacity decay after 300 cycles for fullcell test(3.0-4.55 V).Based on comprehensive microanalysis and theoretical calculations,the degradation mechanisms and doping effects are systematically revealed.For the undoped LCO,high voltage cycling induces severe interfacial and bulk degradations,where cracks,stripe defects,fatigue H2 phase,and spinel phase are identified in grain bulk.For the doped LCO,Mg-doped surface shell can suppress the interfacial degradations,which not only stabilizes the surface structure by forming a thin rock-salt layer but also significantly improves the electronic conductivity,thus enabling superior rate performance.Bulk Al-doping can suppress the lattice"breathing"effect and the detrimental H3 to H1-3 phase transition,which minimizes the internal strain and defects growth,maintaining the layered structure after prolonged cycling.Combining theoretical calculations,this work deepens our understanding of the doping effects of Mg and Al,which is valuable in guiding the future material design of high voltage LCO.展开更多
Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since ...Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.展开更多
To meet the demand for high-performance LiCoO_(2) batteries,it is necessary to overcome challenges such as interface degradation and rapid capacity degradation caused by changes in bulk structure,especially under deep...To meet the demand for high-performance LiCoO_(2) batteries,it is necessary to overcome challenges such as interface degradation and rapid capacity degradation caused by changes in bulk structure,especially under deep delithiation and high temperature conditions.The ion conductive coating layer of Li_(3)PO_(4) has been directly modified on the surface of LiCoO_(2) particles using magnetron sputtering method,significantly improving the lithium storage performance of LiCoO_(2)@Li_(3)PO_(4) composites.Compared to pure LiCoO_(2),the modified LiCoO_(2) sample exhibits obviously better cycle life and high-temperature performance.Especially,under the conditions of 2 and 1 C,the LiCoO_(2)@Li_(3)PO_(4) electrode delivers excellent cycling performance at high voltage of 4.5 V,with capacity retention rates of 89.7%and 75.7%at room temperature and high temperature of 45℃,being far greater than those of 12.3%and 29.1%for bare LiCoO_(2) electrodes.It is discovered that the Li_(3)PO_(4) coating layer not only effectively enhances interface compatibility and suppresses the irreversible phase transition of LiCoO_(2),but also further improves the Li^(+)transport kinetics and significantly reduces battery polarization,ultimately enabling the modified LiCoO_(2) electrode to exhibit excellent lithium storage performance and thermal safety characteristics under high voltage conditions.Thus,such effective modified strategy can undoubtedly provide an important academic inspiration for LiCoO_(2) implication.展开更多
High-voltage LiCoO_(2)(LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries(LIBs) in the 3 C markets.However,the sluggish lithium-ion diffusion at high voltage significantly hampers its ra...High-voltage LiCoO_(2)(LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries(LIBs) in the 3 C markets.However,the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability.Herein,combining experiments with density functional theory(DFT) calculations,we demonstrate that the kinetic limitations can be mitigated by a facial Mg^(2+)+Gd^(3+)co-doping method.The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage,making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process.The homogeneity enables the structural stability of LCO at a high-rate current density,inhibiting stress accumulation and irreversible phase transition.When used in combination with a Li metal anode,the doped LCO shows an extreme fast charging(XFC) capability,with a superior high capacity of 193.1 mAh g^(-1)even at the current density of 20 C and high-rate capacity retention of 91.3% after 100 cycles at 5 C.This work provides a new insight to prepare XFC high-voltage LCO cathode materials.展开更多
The overcharge behaviors of 1000 m Ah LiCoO_(2)/graphite pouch cells are systematically investigated through the analysis of morphology,structural and thermal stability of LiCoO_(2) under different state of charge(SOC...The overcharge behaviors of 1000 m Ah LiCoO_(2)/graphite pouch cells are systematically investigated through the analysis of morphology,structural and thermal stability of LiCoO_(2) under different state of charge(SOC)of 120%,150%,174%,190%and 220%.The LiCoO_(2) experiences the phase transition from O3 to H1-3 and then O1 together with the grain breakage and boundary slip as evidenced by XRD and SEM analysis respectively,which results in the pronounced Co dissolution after the SOC of 174%.The impedance analysis of the pouch cells and coin cells demonstrates that the main contribution of impedance increase originates from the LiCoO_(2) electrode.Under the combined effect of structural collapse,Co dissolution,and electrolyte oxidization,the thermal stability of Li CoO_(2) cathode materials reduces with the progressing of overcharge as revealed by differential scanning calorimetry(DSC)results.We hope that this comprehensive understanding can provide meaningful guidance for advancing the overcharge performance of LiCoO_(2)/graphite pouch cells.展开更多
基金the Science and Technology Key Project of Anhui Province,China(No.2022e03020004).
文摘Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.
基金the National Natural Science Foundation of China(12174015)the Natural Science Foundation of Beijing,China(2212003)+1 种基金the China National Petroleum Corporation Innovation Found(2021DQ02-1004)the National Natural Science Foundation of China(12102053)。
文摘Constructing robust surface and bulk structure is the prerequisite for realizing high performance high voltage LiCoO_(2)(LCO).Herein,we manage to synthesize a surface Mg-doping and bulk Al-doping coreshell structured LCO,which demonstrates excellent cycling performance.Half-cell shows 94.2%capacity retention after 100 cycles at 3.0-4.6 V(vs.Li/Li^(+))cycling,and no capacity decay after 300 cycles for fullcell test(3.0-4.55 V).Based on comprehensive microanalysis and theoretical calculations,the degradation mechanisms and doping effects are systematically revealed.For the undoped LCO,high voltage cycling induces severe interfacial and bulk degradations,where cracks,stripe defects,fatigue H2 phase,and spinel phase are identified in grain bulk.For the doped LCO,Mg-doped surface shell can suppress the interfacial degradations,which not only stabilizes the surface structure by forming a thin rock-salt layer but also significantly improves the electronic conductivity,thus enabling superior rate performance.Bulk Al-doping can suppress the lattice"breathing"effect and the detrimental H3 to H1-3 phase transition,which minimizes the internal strain and defects growth,maintaining the layered structure after prolonged cycling.Combining theoretical calculations,this work deepens our understanding of the doping effects of Mg and Al,which is valuable in guiding the future material design of high voltage LCO.
基金the Hong Kong Polytechnic University(Q-CDBG),the Science and Technology Program of Guangdong Province of China(2020A0505090001)the Research Grants Council of the Hong Kong Special Administrative Region,China(Project No.PolyU152178/20E)+2 种基金the National Natural Science Foundation of China(22379052)the Natural Science Foundation of Guangdong(No.2022A1515011667)China Postdoctoral Science Foundation(2021T140268).
文摘Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.
基金jointly supported by the Natural Science Foundations of China(No.22179020,12174057)Fujian Province’s“Young Eagle Program”Youth Top Talents Program。
文摘To meet the demand for high-performance LiCoO_(2) batteries,it is necessary to overcome challenges such as interface degradation and rapid capacity degradation caused by changes in bulk structure,especially under deep delithiation and high temperature conditions.The ion conductive coating layer of Li_(3)PO_(4) has been directly modified on the surface of LiCoO_(2) particles using magnetron sputtering method,significantly improving the lithium storage performance of LiCoO_(2)@Li_(3)PO_(4) composites.Compared to pure LiCoO_(2),the modified LiCoO_(2) sample exhibits obviously better cycle life and high-temperature performance.Especially,under the conditions of 2 and 1 C,the LiCoO_(2)@Li_(3)PO_(4) electrode delivers excellent cycling performance at high voltage of 4.5 V,with capacity retention rates of 89.7%and 75.7%at room temperature and high temperature of 45℃,being far greater than those of 12.3%and 29.1%for bare LiCoO_(2) electrodes.It is discovered that the Li_(3)PO_(4) coating layer not only effectively enhances interface compatibility and suppresses the irreversible phase transition of LiCoO_(2),but also further improves the Li^(+)transport kinetics and significantly reduces battery polarization,ultimately enabling the modified LiCoO_(2) electrode to exhibit excellent lithium storage performance and thermal safety characteristics under high voltage conditions.Thus,such effective modified strategy can undoubtedly provide an important academic inspiration for LiCoO_(2) implication.
基金financially supported by the National Natural Science Foundation of China (No. 52102201, No. 52102200)the Basic and Applied Basic Research Foundation of Guangdong Province (No. 2021B1515130002)。
基金supported by the National Key R&D Program of China(2020YFA0406203)the Shenzhen Science and Technology Innovation Commission(JCYJ20180507181806316,JCYJ20200109105618137)+1 种基金the ECS Scheme(City U 21307019,City U7020043,City U7005500,City U7005612)the Shenzhen Research Institute,City University of Hong Kong。
文摘High-voltage LiCoO_(2)(LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries(LIBs) in the 3 C markets.However,the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability.Herein,combining experiments with density functional theory(DFT) calculations,we demonstrate that the kinetic limitations can be mitigated by a facial Mg^(2+)+Gd^(3+)co-doping method.The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage,making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process.The homogeneity enables the structural stability of LCO at a high-rate current density,inhibiting stress accumulation and irreversible phase transition.When used in combination with a Li metal anode,the doped LCO shows an extreme fast charging(XFC) capability,with a superior high capacity of 193.1 mAh g^(-1)even at the current density of 20 C and high-rate capacity retention of 91.3% after 100 cycles at 5 C.This work provides a new insight to prepare XFC high-voltage LCO cathode materials.
基金supported by the National Natural Science Foundation of China(51974370)the Program of Huxiang Young Talents(2019RS2002)the Innovation and Entrepreneurship Project of Hunan Province,China(Grant No.2018GK5026)。
文摘The overcharge behaviors of 1000 m Ah LiCoO_(2)/graphite pouch cells are systematically investigated through the analysis of morphology,structural and thermal stability of LiCoO_(2) under different state of charge(SOC)of 120%,150%,174%,190%and 220%.The LiCoO_(2) experiences the phase transition from O3 to H1-3 and then O1 together with the grain breakage and boundary slip as evidenced by XRD and SEM analysis respectively,which results in the pronounced Co dissolution after the SOC of 174%.The impedance analysis of the pouch cells and coin cells demonstrates that the main contribution of impedance increase originates from the LiCoO_(2) electrode.Under the combined effect of structural collapse,Co dissolution,and electrolyte oxidization,the thermal stability of Li CoO_(2) cathode materials reduces with the progressing of overcharge as revealed by differential scanning calorimetry(DSC)results.We hope that this comprehensive understanding can provide meaningful guidance for advancing the overcharge performance of LiCoO_(2)/graphite pouch cells.
