KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause...KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability.Here,a high-energy and low-strain KVPO_(4)F composite cathode assisted by multifunctional K_(2)C_(4)O_(4)electrode stabilizer is exquisitely designed.Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg^(-1)with 142.7 mAh g^(-1)of reversible capacity at 25 mA g^(-1),outstanding rate capability of 70.6 mAh g^(-1)at 1000 mA g^(-1),and decent cycling stability.Furthermore,slight volume change(~5%)and increased interfacial stability with thin and even cathode-electrolyte interphase can be observed through in situ and ex situ characterizations,which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K_(2)C_(4)O_(4)additive.Moreover,potassium-ion full cells manifest significant improvement in energy density and cycling stability.This work demonstrates a positive impact of K_(2)C_(4)O_(4)additive on the comprehensive electrochemical enhancement,especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.展开更多
The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercializ...The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercialization.The regular concentration(1_(M))electrolytes with suitable properties(viscosity,ionic conductivity,etc.)are cost-guaranteed,but undesired reactions would always occur and lead to battery degradation during long cycles.To promote the long-term cycle stability in a cost-effective way,this work constructs bidirectional fluorine-rich electrode/electrolyte interphase(EEI)by redistribution of solvents and electrochemical induction.The fluorinated effect with reasonable zoning planning restricts morphological disintegration,meanwhile,forms spatial confinement on cathode.In particular,the obtained cathode electrolyte interphase(CEI)gets the ample ability of Na^(+)transport,which benefits from the fluorinated organics arranged in the epitaxy and the hemi-carbonate content acting on the thickness.Thus,the electrochemical long cycling performance of F-NVPOFⅡF-CC full cells is significantly enhanced(the decay rate at 1 C per cycle is as low as 0.01%).Such a fluorine-rich EEI engineering is expected to take transitional layers against the degradation of cells and make ultra-long cycle batteries possible.展开更多
Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodi...Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodium metal batteries.Here,we overturn this conclusion by incorporating fluoroethylene carbonate(FEC)as cosolvent that renders a Na plating/stripping fficiency of>95%with conventional NaPF。salt at a regular concentration(1.0M).The peculiar role of FEC is firstly.unraveled via its involvement into the solvation structure,where a threshold FEC concentration with a coordination number>1.2 is needed in guaranteeing high Na reversibility over the long-term.Specifially,by incorporating an average number of 1.2 FEC molecules into the primary Na*solvation sheath,lowest unoccupied molecular orbital(LUMO)levels of such Nat-FEC solvates undergo further decrease,with spin electrons residing either on the O=C 0(O)moiety of FEC or sharing between Na*and its C=:O bond,which ensures a prior FEC decomposition in passivating the Na surface against other carbonate molecules.Further,by adopting cryogenic tranmission electron microscopy(cryo-TEM),we found that the Na filaments grow into substantially larger diameter from-400nm to>1 pum with addition of FEC upon the threshold value.A.highly crstalline and much thiner(-40 nm)slid-electrolyte interphase(SED)is consequently observed to uniformly wrap the Na surface,in contrast to the severely corroded Na as retrieved from the blank electrolyte.The potence of FEC is further demonstrated in a series of"corrosive solvents"such as ethy!l acetate(EA)。trimethyl phosphate(TMP),and actonitrile(AN)enabling highly reversible SMAs in the otherwise unusable solvent systems.展开更多
This highlight is based on a recent work by Prof.Cheng,Prof.Zhou,Prof.Liang and coworkers published in Nature Sustainability[1].This work blazes a new trail to recycle spent lithium-ion batteries(LIBs)by upcycling the...This highlight is based on a recent work by Prof.Cheng,Prof.Zhou,Prof.Liang and coworkers published in Nature Sustainability[1].This work blazes a new trail to recycle spent lithium-ion batteries(LIBs)by upcycling the exhausted cathode to a more advantageous and functional highvoltage cathode.展开更多
基金the financial support from the National Key R&D Program of China(Grant No.2023YFE0202000)the National Natural Science Foundation of China(Grant No.52102213)+1 种基金Natural Science Foundation of Jilin Province(Grant No.20230101128JC)Double-Thousand Talents Plan of Jiangxi Province(jxsq2023102005)
文摘KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability.Here,a high-energy and low-strain KVPO_(4)F composite cathode assisted by multifunctional K_(2)C_(4)O_(4)electrode stabilizer is exquisitely designed.Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg^(-1)with 142.7 mAh g^(-1)of reversible capacity at 25 mA g^(-1),outstanding rate capability of 70.6 mAh g^(-1)at 1000 mA g^(-1),and decent cycling stability.Furthermore,slight volume change(~5%)and increased interfacial stability with thin and even cathode-electrolyte interphase can be observed through in situ and ex situ characterizations,which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K_(2)C_(4)O_(4)additive.Moreover,potassium-ion full cells manifest significant improvement in energy density and cycling stability.This work demonstrates a positive impact of K_(2)C_(4)O_(4)additive on the comprehensive electrochemical enhancement,especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.
基金supported by the National Natural Science Foundation of China(No.91963118 and 52102213)Science Technology Program of Jilin Province(No.20200201066JC)the 111 Project(No.B13013).
文摘The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercialization.The regular concentration(1_(M))electrolytes with suitable properties(viscosity,ionic conductivity,etc.)are cost-guaranteed,but undesired reactions would always occur and lead to battery degradation during long cycles.To promote the long-term cycle stability in a cost-effective way,this work constructs bidirectional fluorine-rich electrode/electrolyte interphase(EEI)by redistribution of solvents and electrochemical induction.The fluorinated effect with reasonable zoning planning restricts morphological disintegration,meanwhile,forms spatial confinement on cathode.In particular,the obtained cathode electrolyte interphase(CEI)gets the ample ability of Na^(+)transport,which benefits from the fluorinated organics arranged in the epitaxy and the hemi-carbonate content acting on the thickness.Thus,the electrochemical long cycling performance of F-NVPOFⅡF-CC full cells is significantly enhanced(the decay rate at 1 C per cycle is as low as 0.01%).Such a fluorine-rich EEI engineering is expected to take transitional layers against the degradation of cells and make ultra-long cycle batteries possible.
基金sponsored by the National Natural Science Foundation of China(NSFC Nos.21975186,51632001,and 22005334)supports from Natural Science Foundation of Beijing(grant No.Z200013).
文摘Sodium metal anodes(SMAs)sufer from extremely low reversibility(<20%)in carbonate based clectrolytes-this piece of knowledge gained from previous studics has ruled out the application of carbonate solvents for sodium metal batteries.Here,we overturn this conclusion by incorporating fluoroethylene carbonate(FEC)as cosolvent that renders a Na plating/stripping fficiency of>95%with conventional NaPF。salt at a regular concentration(1.0M).The peculiar role of FEC is firstly.unraveled via its involvement into the solvation structure,where a threshold FEC concentration with a coordination number>1.2 is needed in guaranteeing high Na reversibility over the long-term.Specifially,by incorporating an average number of 1.2 FEC molecules into the primary Na*solvation sheath,lowest unoccupied molecular orbital(LUMO)levels of such Nat-FEC solvates undergo further decrease,with spin electrons residing either on the O=C 0(O)moiety of FEC or sharing between Na*and its C=:O bond,which ensures a prior FEC decomposition in passivating the Na surface against other carbonate molecules.Further,by adopting cryogenic tranmission electron microscopy(cryo-TEM),we found that the Na filaments grow into substantially larger diameter from-400nm to>1 pum with addition of FEC upon the threshold value.A.highly crstalline and much thiner(-40 nm)slid-electrolyte interphase(SED)is consequently observed to uniformly wrap the Na surface,in contrast to the severely corroded Na as retrieved from the blank electrolyte.The potence of FEC is further demonstrated in a series of"corrosive solvents"such as ethy!l acetate(EA)。trimethyl phosphate(TMP),and actonitrile(AN)enabling highly reversible SMAs in the otherwise unusable solvent systems.
文摘This highlight is based on a recent work by Prof.Cheng,Prof.Zhou,Prof.Liang and coworkers published in Nature Sustainability[1].This work blazes a new trail to recycle spent lithium-ion batteries(LIBs)by upcycling the exhausted cathode to a more advantageous and functional highvoltage cathode.
