We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs)...We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs).SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries,owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes.However,the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges.Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity.By optimizing binder molecular weights,we effectively shield the active materials from degradation and mechanical stress,significantly boosting the functionality and longevity of SSBs.These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.展开更多
Single crystallization is an important strategy to resolve intergranular cracks and unnecessary side reactions with electrolytes in layered transition metal oxide cathodes LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811).Due t...Single crystallization is an important strategy to resolve intergranular cracks and unnecessary side reactions with electrolytes in layered transition metal oxide cathodes LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811).Due to the limitations of high-temperature sintering and multi-step calcination,single crystal NMC811 generally shows irregular particles with a size of 2-3μm.However,the prolonged Li-ion diffusion pathway and the stress generated by the uneven de-/intercalation sluggish Li-ion diffusion kinetics,what is more,cause structural damage such as intragranular cracks.A slow Li extraction rate or particle size reduction will ameliorate the structural damage and improve the cycling stability.As the most promising cathodes for next-generation power batteries,NMC811 required fast charge performance and cycle stability.Particle size reduction appears to be the displacement option.Nanonization is an effective strategy to mitigate intragranular cracks of single crystal NMC811.However,the serious aggregation and increased specific surface area become new challenges.In this article,we synthesized monodisperse nanoscale single crystal NMC811 by molten salt method and modified the surface by LiNbO3 coating.The electrochemical performance shows that nanoscale single crystal NMC811 has faster kinetic and higher capacity retention,so the strategy of combining nanonization and surface coating is an alternative way to prepare high specific capacity and cycle stable single crystal NMC811.展开更多
Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with ...Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.展开更多
Surface modification offers an alternative strategy to improve both ageing resistance and electrochemical performance of cathode materials for lithium-ion batteries.From the viewpoint of real application,surface modif...Surface modification offers an alternative strategy to improve both ageing resistance and electrochemical performance of cathode materials for lithium-ion batteries.From the viewpoint of real application,surface modification of the cathode materials should be designed with scientificity,effectiveness,low cost,less Li+leaching,and remained tap density.In this contribution,a selective adsorption-involved in-situ growth of polyaniline(PANI)nanoparticles on LiNi_(0.5)Mn_(0.3)Co_(0.2)O_(2)(NMC532)has been designed through a room-temperature-and-pressure chemical vapor deposition technique.The selective growth of PANTI on NMC532 is based on theoretical computation results that multivalent Ni,Mn,and Co are capable of specifically conjugating and activating aniline molecules and,hence,initiating in-situ oxidation polymerization.With only trace amount of aniline monomer,the resulting PANI nanoparticles-inlaid NMC532 microparticles can endure four-month ageing in ambient atmosphere and exhibit improved electrochemical performance at both room temperature and 55℃ compared with pristine NMC532.The improved electrochemical performance of NMC532/PANI is attributed to the enhanced structural stability of NMC532 and inhibited side reactions related to Li_(2)CO_(3) formation,PVDF degradation,electrolyte decomposition,and transition-metal dissolution,owing to PANI modification.展开更多
基金partially sponsored by the Office of Energy Efficiency and Renewable Energy(EERE)in the Vehicle Technologies Office(VTO)through the Advanced Battery Materials Research(BMR)Program,managed by DrsThe Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan(http://energy.gov/downloads/doe-public-access-plan).
文摘We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs).SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries,owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes.However,the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges.Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity.By optimizing binder molecular weights,we effectively shield the active materials from degradation and mechanical stress,significantly boosting the functionality and longevity of SSBs.These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.52022088,51971245,51772262,U20A20336,21935009)Natural Science Foundation of Hebei Province(Nos.F2021203097,B2020203037)China Postdoctoral Science Foundation(No.2021M702756)。
文摘Single crystallization is an important strategy to resolve intergranular cracks and unnecessary side reactions with electrolytes in layered transition metal oxide cathodes LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811).Due to the limitations of high-temperature sintering and multi-step calcination,single crystal NMC811 generally shows irregular particles with a size of 2-3μm.However,the prolonged Li-ion diffusion pathway and the stress generated by the uneven de-/intercalation sluggish Li-ion diffusion kinetics,what is more,cause structural damage such as intragranular cracks.A slow Li extraction rate or particle size reduction will ameliorate the structural damage and improve the cycling stability.As the most promising cathodes for next-generation power batteries,NMC811 required fast charge performance and cycle stability.Particle size reduction appears to be the displacement option.Nanonization is an effective strategy to mitigate intragranular cracks of single crystal NMC811.However,the serious aggregation and increased specific surface area become new challenges.In this article,we synthesized monodisperse nanoscale single crystal NMC811 by molten salt method and modified the surface by LiNbO3 coating.The electrochemical performance shows that nanoscale single crystal NMC811 has faster kinetic and higher capacity retention,so the strategy of combining nanonization and surface coating is an alternative way to prepare high specific capacity and cycle stable single crystal NMC811.
基金supported by the National Natural Science Foundation of China (No.21972049)the Guangdong-Hong KongMacao Greater Bay Area Exchange Programs of SCNU (2022)。
文摘Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2019MEM015 and ZR2017QB003)Young Taishan Scholar Program of Shandong Province(No.tsqn201909139)the Introduction and Cultivation Plan of Young Innovative Talents in Colleges and Universities of Shandong Province。
文摘Surface modification offers an alternative strategy to improve both ageing resistance and electrochemical performance of cathode materials for lithium-ion batteries.From the viewpoint of real application,surface modification of the cathode materials should be designed with scientificity,effectiveness,low cost,less Li+leaching,and remained tap density.In this contribution,a selective adsorption-involved in-situ growth of polyaniline(PANI)nanoparticles on LiNi_(0.5)Mn_(0.3)Co_(0.2)O_(2)(NMC532)has been designed through a room-temperature-and-pressure chemical vapor deposition technique.The selective growth of PANTI on NMC532 is based on theoretical computation results that multivalent Ni,Mn,and Co are capable of specifically conjugating and activating aniline molecules and,hence,initiating in-situ oxidation polymerization.With only trace amount of aniline monomer,the resulting PANI nanoparticles-inlaid NMC532 microparticles can endure four-month ageing in ambient atmosphere and exhibit improved electrochemical performance at both room temperature and 55℃ compared with pristine NMC532.The improved electrochemical performance of NMC532/PANI is attributed to the enhanced structural stability of NMC532 and inhibited side reactions related to Li_(2)CO_(3) formation,PVDF degradation,electrolyte decomposition,and transition-metal dissolution,owing to PANI modification.
