The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructur...The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).展开更多
Owing to the further requirement for electric vehicle market, it is appropriate to lower the cost and improve the energy density of lithium-ion batteries by adopting the Co-free and Ni-rich layered cathodes.However, t...Owing to the further requirement for electric vehicle market, it is appropriate to lower the cost and improve the energy density of lithium-ion batteries by adopting the Co-free and Ni-rich layered cathodes.However, their practical application is severely limited by structural instability and slow kinetics. Herein,ultrahigh-nickel cobalt-free LiNi_(0.9)Mn_(0.1)O_(2) cathode is elaborate designed via in-situ trace substitution of tungsten by a wet co-precipitation method following by high-temperature sintering. It is revealed that the in-situ doping strategy of high valence W^(6+) can effectively improve the structure stability by reducing irreversible phase transition and suppressing the formation of microcracks. Moreover, the transformed fine particles determined by W-doping can facilitate the kinetic characteristics by shortening Li^(+) diffusion paths. As expected, 0.3 mol% W-doped LiNi_(0.9)Mn_(0.1)O_(2) cathode exhibits a high specific capacity of 143.5 mAh/g after 200 cycles at high rate of 5 C in the wide potential range of 2.8-4.5 V, representing a potential next-generation cathode with low-cost, high energy-density and fast-charging capabilities.展开更多
Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion ba...Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.展开更多
The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gel...The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gelation,leading to the capacity decay of batteries with these cathodes and complicating their manufacturing.Traditional approaches for addressing this issue,including direct removal,coverage,and utilization,are complex and require surface regeneration.Herein,we propose neutralizing residual alkaline compounds with 3-thiopheneboronic acid(3-TBA)to improve the performance of LiNi_(0.9)5Co_(0.04)Mn_(0.01)O_(2)(NCM)cathode material,a facile strategy that does not require any post-treatment.The suggested reaction yields a uniform and thin organic-modified layer on the surface of the NCM cathode,improving its chemical stability toward the electrolyte,as demonstrated by multiple characterization methods.The modified NCM cathode exhibited impressive cyclic and rate performances,achieving a capacity retention of 83.34%after 200 cycles at 1.0 C and a specific capacity of 162.00 mAh·g^(−1) at 10.0 C.Most importantly,the proposed approach can efficiently suppress unfavorable phase transitions,severe electrolyte degradation,and CO_(2) gas evolution,improving the application potential of ultrahigh-nickel layered oxide cathode materials.展开更多
The rapid expansion of the automotive sector has significantly increased the demand for highperformance lithium-ion batteries,positioning Ni-rich layered cathodes as a promising solution due to their high energy densi...The rapid expansion of the automotive sector has significantly increased the demand for highperformance lithium-ion batteries,positioning Ni-rich layered cathodes as a promising solution due to their high energy density and cost-efficiency.However,these cathodes face critical challenges,including thermal instability and structural degradation at an elevated temperature,which hinder their practical application.This study introduces an advanced surface reconstruction strategy combining a LiScF_(4)coating,Sc/F surface co-doping,and a cation-mixing layer to address these issues.The LiScF_(4)coating serves as a durable protective barrier,reducing electrolyte decomposition,minimizing transition metal dissolution,and enhancing lithium-ion transport.Sc/F surface co-doping stabilizes lattice oxygen by increasing the energy barrier for oxygen vacancy formation and minimizing oxygen release,thereby suppressing phase transitions and interfacial side reactions.Additionally,the cation-mixing layer improves interfacial stability by alleviating lattice strain and supporting reversible cation migration,ensuring prolonged durability during cycling and under high-temperature conditions.These integrated modifications work synergistically to mitigate various degradation mechanisms,significantly improving the thermal stability,structural integrity,and electrochemical performance of Ni-rich cathodes.This approach offers a viable pathway for incorporating Ni-rich cathodes into advanced lithium-ion batteries,making them well-suited for applications requiring high thermal stability.Moreover,this research provides valuable guidance for the development of a multi-component modification strategy,paving the way for future innovations in energy storage materials and advancing high-performance battery technology.展开更多
基金supported by the National Key R&D Program of China(2022YFB3803501)the National Natural Science Foundation of China(22179008,22209156)+5 种基金support from the Beijing Nova Program(20230484241)support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)support from beamline BL08U1A of Shanghai Synchrotron Radiation Facility(2024-SSRF-PT-506950)beamline 1W1B of the Beijing Synchrotron Radiation Facility(2021-BEPC-PT-006276)support from Initial Energy Science&Technology Co.,Ltd(IEST)。
文摘The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).
基金financial support from the National Natural Science Foundation of China (Nos. 51908555, 52070194)。
文摘Owing to the further requirement for electric vehicle market, it is appropriate to lower the cost and improve the energy density of lithium-ion batteries by adopting the Co-free and Ni-rich layered cathodes.However, their practical application is severely limited by structural instability and slow kinetics. Herein,ultrahigh-nickel cobalt-free LiNi_(0.9)Mn_(0.1)O_(2) cathode is elaborate designed via in-situ trace substitution of tungsten by a wet co-precipitation method following by high-temperature sintering. It is revealed that the in-situ doping strategy of high valence W^(6+) can effectively improve the structure stability by reducing irreversible phase transition and suppressing the formation of microcracks. Moreover, the transformed fine particles determined by W-doping can facilitate the kinetic characteristics by shortening Li^(+) diffusion paths. As expected, 0.3 mol% W-doped LiNi_(0.9)Mn_(0.1)O_(2) cathode exhibits a high specific capacity of 143.5 mAh/g after 200 cycles at high rate of 5 C in the wide potential range of 2.8-4.5 V, representing a potential next-generation cathode with low-cost, high energy-density and fast-charging capabilities.
基金supported by the Natural Science Foundation of Jiangsu Province (BK20210887)the Jiangsu Provincial Double Innovation Program (JSSCB20210984)+1 种基金the Natural Science Fund for Colleges and Universities of Jiangsu Province (21KJB450003)the Jiangsu University of Science and Technology Doctoral Research Start-up Fund (120200012)。
文摘Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.
基金the Yunnan Fundamental Research Projects(Grant Nos.202501AT070298,202401AU070163,and 202401AT070368)the National Natural Science Foundation of China(Grant No.52162030)+5 种基金the Yunnan Major Scientific and Technological Projects(Grant No.202202AG050003)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Yunnan Thousand Talents Program for Young Talents(Grant No.KKS2202052001)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Testing Foundation of Kunming University of Science and Technology(Grant No.2023T20220122).
文摘The presence of residual alkaline compounds in the ultrahigh-nickel layered oxide cathodes(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x≥_(0.9))aggravates structural degradation,increases surface reactivity,and promotes slurry gelation,leading to the capacity decay of batteries with these cathodes and complicating their manufacturing.Traditional approaches for addressing this issue,including direct removal,coverage,and utilization,are complex and require surface regeneration.Herein,we propose neutralizing residual alkaline compounds with 3-thiopheneboronic acid(3-TBA)to improve the performance of LiNi_(0.9)5Co_(0.04)Mn_(0.01)O_(2)(NCM)cathode material,a facile strategy that does not require any post-treatment.The suggested reaction yields a uniform and thin organic-modified layer on the surface of the NCM cathode,improving its chemical stability toward the electrolyte,as demonstrated by multiple characterization methods.The modified NCM cathode exhibited impressive cyclic and rate performances,achieving a capacity retention of 83.34%after 200 cycles at 1.0 C and a specific capacity of 162.00 mAh·g^(−1) at 10.0 C.Most importantly,the proposed approach can efficiently suppress unfavorable phase transitions,severe electrolyte degradation,and CO_(2) gas evolution,improving the application potential of ultrahigh-nickel layered oxide cathode materials.
基金supported by the National Natural Science Foundation of China(22179008)support from the Beijing Nova Program(20230484241)+1 种基金support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)。
文摘The rapid expansion of the automotive sector has significantly increased the demand for highperformance lithium-ion batteries,positioning Ni-rich layered cathodes as a promising solution due to their high energy density and cost-efficiency.However,these cathodes face critical challenges,including thermal instability and structural degradation at an elevated temperature,which hinder their practical application.This study introduces an advanced surface reconstruction strategy combining a LiScF_(4)coating,Sc/F surface co-doping,and a cation-mixing layer to address these issues.The LiScF_(4)coating serves as a durable protective barrier,reducing electrolyte decomposition,minimizing transition metal dissolution,and enhancing lithium-ion transport.Sc/F surface co-doping stabilizes lattice oxygen by increasing the energy barrier for oxygen vacancy formation and minimizing oxygen release,thereby suppressing phase transitions and interfacial side reactions.Additionally,the cation-mixing layer improves interfacial stability by alleviating lattice strain and supporting reversible cation migration,ensuring prolonged durability during cycling and under high-temperature conditions.These integrated modifications work synergistically to mitigate various degradation mechanisms,significantly improving the thermal stability,structural integrity,and electrochemical performance of Ni-rich cathodes.This approach offers a viable pathway for incorporating Ni-rich cathodes into advanced lithium-ion batteries,making them well-suited for applications requiring high thermal stability.Moreover,this research provides valuable guidance for the development of a multi-component modification strategy,paving the way for future innovations in energy storage materials and advancing high-performance battery technology.
