Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferio...Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.展开更多
The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficie...The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficiency(ICE)and poor rate performance,which is one of the main bottlenecks that limits the practical application of HCs.Ether electrolyte(diglyme)was reported to improve the rate performance of HCs.Nevertheless,the underlying mechanism for the excellent rate capability is still lack of in-depth study.In this work,the differences of sodium-ion diffusion between ether and carbonate-base electrolytes in HCs are analyzed layer by layer.Firstly,when sodium-ions are diffused in electrolyte,the diffusion coefficient of sodium-ion in ether electrolyte is about 2.5 times higher than that in ester electrolytes by molecular dynamics(MD)simulation and experimental characterization.Furthermore,when the solvated sodium-ions are diffused into the solid electrolyte interphase(SEI)interface and the HCs material,the enhanced charge transfer kinetics(thin SEI layer(4.6 vs.12 nm)and low RSEI(1.5 vs.24Ω))at the SEI combined with low desolvation energy(0.248 eV)are responsible for high-rate performance and good cycling stability of HC in ether electrolyte.Therefore,high diffusion coefficient,low desolvation energy,and good interface are the intrinsic reasons for enhanced rate performance in ether electrolyte,which also has guiding significance for the design of other high-rate electrolytes.展开更多
Stibium(Sb)metal with high theoretic capacity,suitable negative working window and inexpensive nature are promising anode material for advanced aqueous alkaline batteries(AABs).However,the further development of Sb an...Stibium(Sb)metal with high theoretic capacity,suitable negative working window and inexpensive nature are promising anode material for advanced aqueous alkaline batteries(AABs).However,the further development of Sb anode is severely hindered by the low capacity and poor rate capability which is originated from deficient adsorption of[Sb(OH)_(4)]^(-)and its sluggish desolvation kinetics.Herein,a nitrogen doped carbon cages(NCCs)substrate is constructed as high capacity and rate capability anode by promoting the adsorption and following desolvation process of[Sb(OH)_(4)]^(-)via the enhanced attraction toward(OH)-in the solvated[Sb(OH)_(4)]^(-).Consequently,the designed Sb/NCCs anode delivers a high capacity of 627 m Ah g^(-1)with an average 95%Sb utilization,an outstanding coulombic efficiency(CE)of 95%and an impressive lifespan(>110 h).Meanwhile,the Ni_(3)Se_(2)//Sb/NCCs batteries show great capacity retention of 86.7%after 2000 cycles with an areal capacity of 0.52 m Ah cm^(-2).Implementation of the designed anode allows for the construction of Sb-based AABs with enhanced rate capability,energy density and cycling performance.展开更多
Aqueous zinc ion batteries(AZIBs)are an advanced secondary battery technology to supplement lithiumion batteries.It has been widely concerned and developed recently based on the element abundance and safety advantages...Aqueous zinc ion batteries(AZIBs)are an advanced secondary battery technology to supplement lithiumion batteries.It has been widely concerned and developed recently based on the element abundance and safety advantages.However,AZIBs still suffer from serious problems such as dendrites Zn,hydrogen evolution corrosion,and surface passivation,which hinder the further commercial application of AZIBs.Herein,an in-situ ZnCr_(2)O_(4)(ZCO)interface endows AZIBs with dendrite-free and ultra-low polarization by realizing Zn^(2+)pre-desolvation,constraining H2O-induced corrosio n,and boosting Zn^(2+)transport/deposition kinetics.The ZCO@Zn anode harvests an ultrahigh cumulative capacity of~20000 mA h cm^(-2)(cycle time:over 4000 h)at a high current density of 10 mA cm^(-2),indicating excellent reversibility of Zn deposition,Such superior performance is among the best cyclability in AZIBs.Moreover,the multifunctional ZCO interface improves the Coulombic efficiency(CE)to 99.7%for more than 2600 cycles.The outstanding electrochemical performance is also verified by the long-term cycle stability of ZCO@Zn//α-MnO_(2) full cells.Notably,the as-proposed method is efficient and low-cost enough to enable mass production.This work provides new insights into the uniform Zn electrodeposition at the scale of interfacial Zn^(2+)predesolvation and kinetics improvement.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21975087,22008082)。
文摘Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.
基金supported by the National Natural Science Foundation of China(Nos.22179077,51774251,and 21908142)Shanghai Science and Technology Commission’s“2020 Science and Technology In-novation Action Plan”(No.20511104003)Natural Science Foundation in Shanghai(No.21ZR1424200).
文摘The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficiency(ICE)and poor rate performance,which is one of the main bottlenecks that limits the practical application of HCs.Ether electrolyte(diglyme)was reported to improve the rate performance of HCs.Nevertheless,the underlying mechanism for the excellent rate capability is still lack of in-depth study.In this work,the differences of sodium-ion diffusion between ether and carbonate-base electrolytes in HCs are analyzed layer by layer.Firstly,when sodium-ions are diffused in electrolyte,the diffusion coefficient of sodium-ion in ether electrolyte is about 2.5 times higher than that in ester electrolytes by molecular dynamics(MD)simulation and experimental characterization.Furthermore,when the solvated sodium-ions are diffused into the solid electrolyte interphase(SEI)interface and the HCs material,the enhanced charge transfer kinetics(thin SEI layer(4.6 vs.12 nm)and low RSEI(1.5 vs.24Ω))at the SEI combined with low desolvation energy(0.248 eV)are responsible for high-rate performance and good cycling stability of HC in ether electrolyte.Therefore,high diffusion coefficient,low desolvation energy,and good interface are the intrinsic reasons for enhanced rate performance in ether electrolyte,which also has guiding significance for the design of other high-rate electrolytes.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(No.2019A1515110538)Dongguan Science and Technology of Social Development Program(No.20211800904642)+2 种基金the open research fund of Guangdong Provincial Key Laboratory of Distributed Energy Systems(No.2020DES2)Joint Science Foundation of Wuyi University and HK and Macao(2019WGALH14)Guangdong province innovation and strong school project(2020ZDZX2004)。
文摘Stibium(Sb)metal with high theoretic capacity,suitable negative working window and inexpensive nature are promising anode material for advanced aqueous alkaline batteries(AABs).However,the further development of Sb anode is severely hindered by the low capacity and poor rate capability which is originated from deficient adsorption of[Sb(OH)_(4)]^(-)and its sluggish desolvation kinetics.Herein,a nitrogen doped carbon cages(NCCs)substrate is constructed as high capacity and rate capability anode by promoting the adsorption and following desolvation process of[Sb(OH)_(4)]^(-)via the enhanced attraction toward(OH)-in the solvated[Sb(OH)_(4)]^(-).Consequently,the designed Sb/NCCs anode delivers a high capacity of 627 m Ah g^(-1)with an average 95%Sb utilization,an outstanding coulombic efficiency(CE)of 95%and an impressive lifespan(>110 h).Meanwhile,the Ni_(3)Se_(2)//Sb/NCCs batteries show great capacity retention of 86.7%after 2000 cycles with an areal capacity of 0.52 m Ah cm^(-2).Implementation of the designed anode allows for the construction of Sb-based AABs with enhanced rate capability,energy density and cycling performance.
基金supported by the National Natural Science Foundation of China(52172159)the Provincial key R&D Program of Zhejiang Province(2021C01030)the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SZ-TD006)。
文摘Aqueous zinc ion batteries(AZIBs)are an advanced secondary battery technology to supplement lithiumion batteries.It has been widely concerned and developed recently based on the element abundance and safety advantages.However,AZIBs still suffer from serious problems such as dendrites Zn,hydrogen evolution corrosion,and surface passivation,which hinder the further commercial application of AZIBs.Herein,an in-situ ZnCr_(2)O_(4)(ZCO)interface endows AZIBs with dendrite-free and ultra-low polarization by realizing Zn^(2+)pre-desolvation,constraining H2O-induced corrosio n,and boosting Zn^(2+)transport/deposition kinetics.The ZCO@Zn anode harvests an ultrahigh cumulative capacity of~20000 mA h cm^(-2)(cycle time:over 4000 h)at a high current density of 10 mA cm^(-2),indicating excellent reversibility of Zn deposition,Such superior performance is among the best cyclability in AZIBs.Moreover,the multifunctional ZCO interface improves the Coulombic efficiency(CE)to 99.7%for more than 2600 cycles.The outstanding electrochemical performance is also verified by the long-term cycle stability of ZCO@Zn//α-MnO_(2) full cells.Notably,the as-proposed method is efficient and low-cost enough to enable mass production.This work provides new insights into the uniform Zn electrodeposition at the scale of interfacial Zn^(2+)predesolvation and kinetics improvement.
