Rational design of solid-state electrolytes(SSEs)with high ionic conductivity and low activation energy(Ea)is vital for all solid-state batteries.Machine learning(ML)techniques have recently been successful in predict...Rational design of solid-state electrolytes(SSEs)with high ionic conductivity and low activation energy(Ea)is vital for all solid-state batteries.Machine learning(ML)techniques have recently been successful in predicting Li^(+) conduction property in SSEs with various descriptors and accelerating the development of SSEs.In this work,we extend the previous efforts and introduce a framework of ML prediction for E_(a) in SSEs with hierarchically encoding crystal structure-based(HECS)descriptors.Taking cubic Li-argyrodites as an example,an Ea prediction model is developed to the coefficient of determination(R^(2))and rootmean-square error(RMSE)values of 0.887 and 0.02 eV for training dataset,and 0.820 and 0.02 eV for test dataset,respectively by partial least squares(PLS)analysis,proving the prediction power of HECSdescriptors.The variable importance in projection(VIP)scores demonstrate the combined effects of the global and local Li^(+) conduction environments,especially the anion size and the resultant structural changes associated with anion site disorder.The developed E_(a) prediction model directs us to optimize and design new Li-argyrodites with lower Ea,such as Li_(6–x)PS_(5–x)Cl_(1+x)(<0.322 eV),Li_(6+x)PS_(5+x)Br_(1–x)(<0.273 eV),Li_(6+x)PS_(5+x)Br_(0.25)I_(0.75–x)(<0.352 eV),Li_(6+(5–n)y)P_(1–y)N_(y)S_(5)I(<0.420 eV),Li_(6+(5–n)y)As_(1–y)N_(y)S_(5)I(<0.371 eV),Li_(6+(5–n)y)As_(1–y)NySe_(5)I(<0.450 eV),by broadening bottleneck size,invoking site disorder and activating concerted Li+conduction.This analysis shows great potential in promoting rational design of advanced SSEs and the same approach can be applied to other types of materials.展开更多
Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electr...Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.展开更多
Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn m...Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn metal anode seriously hinders the application of ZIBs.Herein,we use the zinc-ion intercalatable V_(2)O_(5)nH_(2)O(VO)as the interface modification material,for the first time,to on-site build a Zn^(2+)-conductive ZnxV_(2)O_(5)nH_(2)O(ZnVO)interfacial layer via the spontaneous short-circuit reaction between the pre-fabricated VO film and Zn metal foil.Compared with the bare Zn,the ZnVO-coated Zn anode exhibits better electrochemical performances with dendrite-free Zn deposits,lower polarization,higher coulombic efficiency over 99%after long cycles and 10 times higher cycle life,which is confirmed by constructing Zn symmetrical cell and Zn|ZnSO_(4)+Li_(2)SO_(4)|LiFePO_(4) full cell.展开更多
Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reaction...Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.展开更多
A three-state hopping model is established ac-cording to experiments to study permeation of an open-state potassium channel from Streptomyces Lividans (KcsA po-tassium channel). The master equations are used to charac...A three-state hopping model is established ac-cording to experiments to study permeation of an open-state potassium channel from Streptomyces Lividans (KcsA po-tassium channel). The master equations are used to charac-terize the dynamics of the system. In this model, ion conduc-tion involves transitions of three states, with one three-ion state and two two-ion states in the selectivity filter respec-tively. In equilibrium, the well-known Nernst equation is deduced. It is further shown that the current follows Micha-elis-Menten kinetics in steady state. According to the pa-rameters provided by Nelson, the current-voltage relation-ship is proved to be ohmic and the current-concentration relationship is also obtained reasonably. Additional valida-tion of the model in the characteristic time to reach the steady state for the potassium channel is also discussed. This model lays a possible physical basis for the permeation of ion channel, and opens an avenue for further research.展开更多
基金the National Key Research and Development Program of China(2017YFB0701600)the National Natural Science Foundation of China(11874254,51622207,and U1630134)。
文摘Rational design of solid-state electrolytes(SSEs)with high ionic conductivity and low activation energy(Ea)is vital for all solid-state batteries.Machine learning(ML)techniques have recently been successful in predicting Li^(+) conduction property in SSEs with various descriptors and accelerating the development of SSEs.In this work,we extend the previous efforts and introduce a framework of ML prediction for E_(a) in SSEs with hierarchically encoding crystal structure-based(HECS)descriptors.Taking cubic Li-argyrodites as an example,an Ea prediction model is developed to the coefficient of determination(R^(2))and rootmean-square error(RMSE)values of 0.887 and 0.02 eV for training dataset,and 0.820 and 0.02 eV for test dataset,respectively by partial least squares(PLS)analysis,proving the prediction power of HECSdescriptors.The variable importance in projection(VIP)scores demonstrate the combined effects of the global and local Li^(+) conduction environments,especially the anion size and the resultant structural changes associated with anion site disorder.The developed E_(a) prediction model directs us to optimize and design new Li-argyrodites with lower Ea,such as Li_(6–x)PS_(5–x)Cl_(1+x)(<0.322 eV),Li_(6+x)PS_(5+x)Br_(1–x)(<0.273 eV),Li_(6+x)PS_(5+x)Br_(0.25)I_(0.75–x)(<0.352 eV),Li_(6+(5–n)y)P_(1–y)N_(y)S_(5)I(<0.420 eV),Li_(6+(5–n)y)As_(1–y)N_(y)S_(5)I(<0.371 eV),Li_(6+(5–n)y)As_(1–y)NySe_(5)I(<0.450 eV),by broadening bottleneck size,invoking site disorder and activating concerted Li+conduction.This analysis shows great potential in promoting rational design of advanced SSEs and the same approach can be applied to other types of materials.
基金Supported by the National Science Fund for Distinguished Young Scholars of China(Grant No.21125628)the Major National Scienti fic Instrument Development Project(Grant No.21527812)+3 种基金the National Natural Science Foundation of China(Grant Nos.21406031 and 21476044)the State Key Laboratory of Fine Chemicals(KF1507)the Fundamental Research Funds for the Central Universities(Grant Nos.DUTPJ14RC(3)003)State Key Laboratory of fine chemicals(Panjin)project(Grant No.JH2014009)
文摘Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.
基金supported by the National Natural Science Foundation(51772115)the National Key Research and Development Program of China(2018YFE0206900)the Hubei Provincial Natural Science Foundation(2019CFA002)。
文摘Aqueous zinc ion batteries(ZIBs)show great potential in large-scale energy storage systems for their advantages of high safety,low cost,high capacity,and environmental friendliness.However,the poor performance of Zn metal anode seriously hinders the application of ZIBs.Herein,we use the zinc-ion intercalatable V_(2)O_(5)nH_(2)O(VO)as the interface modification material,for the first time,to on-site build a Zn^(2+)-conductive ZnxV_(2)O_(5)nH_(2)O(ZnVO)interfacial layer via the spontaneous short-circuit reaction between the pre-fabricated VO film and Zn metal foil.Compared with the bare Zn,the ZnVO-coated Zn anode exhibits better electrochemical performances with dendrite-free Zn deposits,lower polarization,higher coulombic efficiency over 99%after long cycles and 10 times higher cycle life,which is confirmed by constructing Zn symmetrical cell and Zn|ZnSO_(4)+Li_(2)SO_(4)|LiFePO_(4) full cell.
基金supported by the National Natural Science Foundation of China(91963118 and 52173246)Science Technology Program of Jilin Province(20200201066JC)the 111 Project(B13013)。
文摘Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.
文摘A three-state hopping model is established ac-cording to experiments to study permeation of an open-state potassium channel from Streptomyces Lividans (KcsA po-tassium channel). The master equations are used to charac-terize the dynamics of the system. In this model, ion conduc-tion involves transitions of three states, with one three-ion state and two two-ion states in the selectivity filter respec-tively. In equilibrium, the well-known Nernst equation is deduced. It is further shown that the current follows Micha-elis-Menten kinetics in steady state. According to the pa-rameters provided by Nelson, the current-voltage relation-ship is proved to be ohmic and the current-concentration relationship is also obtained reasonably. Additional valida-tion of the model in the characteristic time to reach the steady state for the potassium channel is also discussed. This model lays a possible physical basis for the permeation of ion channel, and opens an avenue for further research.
