Silicon is the most promising anode material for the next generation high- performance lithium ion batteries. However, its commercial application is hindered by its poor performance due to the huge volume change durin...Silicon is the most promising anode material for the next generation high- performance lithium ion batteries. However, its commercial application is hindered by its poor performance due to the huge volume change during cycling. Although two-dimensional silicon-based materials show significantly improved performance, flexible synthesis of such materials is still a challenge. In this work, silicon-based nanosheets with a multilayer structure are synthesized for the first time by a topochemical reaction. The morphology and oxidation state of these nanosheets can be controlled by appropriate choice of reaction media and oxidants. Benefiting from the hierarchical structure and ultrathin size, when the silicon-based nanosheets are employed as anodes they exhibit a charge （delithiation） capacity of 800 mAh/g after 50 cycles with a maximum coulombic efficiency of 99.4% and good rate performance （647 mAh/g at 1 A/g）. This work demonstrates a novel method for preparing nanosheets not only for lithium ion batteries but also having various potential applications in other fields, such as catalysts, electronics and photonics.展开更多
The development of promising zinc anodes mainly suffers from their low plating/stripping coulombic efficiencies when using aqueous electrolyte,which are mainly associated with the interfacial formation of irreversible...The development of promising zinc anodes mainly suffers from their low plating/stripping coulombic efficiencies when using aqueous electrolyte,which are mainly associated with the interfacial formation of irreversible by-products.It is urgent to develop technologies that can solve this issue fundamentally.Herein,we report an artificial Sc_(2)O_(3) protective film to construct a new class of interface for Zn anode.The density functional theory simulation and experimental results have proven that the interfacial side reaction was inhibited via a stratified adsorption effect between this artificial layer and Zn anode.Benefiting from this novel structure,the Sc_(2)O_(3)-coated Zn anode can run for more than 100 cycles without short circuit and exhibit low voltage hysteresis,and the coulombic efficiency increases by 1.2%.Importantly,it shows a good application prospect when matched with two of popular manganese-based and vanadium-based cathodes.The excellent electrochemical performance of the Sc_(2)O_(3)-coated Zn anode highlights the importance of rational design of anode materials and demonstrates a good way for developing high-performance Zn anodes with long lifespan and high efficiency.展开更多
Aqueous rechargeable zinc metal batteries display high theoretical capacity along with economical effectiveness,environmental benignity and high safety.However,dendritic growth and chemical corrosion at the Zn anodes ...Aqueous rechargeable zinc metal batteries display high theoretical capacity along with economical effectiveness,environmental benignity and high safety.However,dendritic growth and chemical corrosion at the Zn anodes limit their widespread applications.Here,we construct a Zn/Bi electrode via in-situ growth of a Bi-based energizer upon Zn metal surface using a replacement reaction.Experimental and theoretical calculations reveal that the Bi-based energizer composed of metallic Bi and ZnBi alloy contributes to Zn plating/stripping due to strong adsorption energy and fast ion transport rates.The resultant Zn/Bi electrode not only circumvents Zn dendrite growth but also improves Zn anode anti-corrosion performance.Specifically,the corrosion current of the Zn/Bi electrode is reduced by 90%compared to bare Zn.Impressively,an ultra-low overpotential of 12mV and stable cycling for 4000h are achieved in a Zn/Bi symmetric cell.A Zn–Cu/Bi asymmetric cell displays a cycle life of 1000 cycles,with an average Coulombic efficiency as high as 99.6%.In addition,an assembled Zn/Bi-activated carbon hybrid capacitor exhibits a stable life of more than 50,000 cycles,an energy density of 64Wh kg−1,and a power density of 7kWkg−1.The capacity retention rate of a Zn/Bi–MnO_(2)full cell is improved by over 150%compared to a Zn–MnO_(2)cell without the Bi-based energizer.Our findings open a new arena for the industrialization of Zn metal batteries for large-scale energy storage applications.展开更多
A soil remediation method combining in situ reduction of Cr（VI） with approaching anodes electroki- netic （AAs-EK） remediation is proposed. EK experiments were conducted to compare the effect of approaching anodes ...A soil remediation method combining in situ reduction of Cr（VI） with approaching anodes electroki- netic （AAs-EK） remediation is proposed. EK experiments were conducted to compare the effect of approaching anodes （AAs） and fixed electrodes （FEs） with and without sodium bisulfite （NaHSO3） as a reducing agent. When NaHSO3 was added to the soil before EK treatment, 90.3% of the Cr（VI） was reduced to Cr（III）. EK experiments showed that the adverse effect of contrasting migration of Cr（III） and Cr（VI） species, which limits the practical application of this technique, was eliminated in the presence of the reducing agent. Furthermore, Tessier fractionation analysis indicated that the reducing agent changed the distribution of the chemical forms of Cr. The AAs-EK method was shown to acidize the soil as the anode moved toward the cathode and this acid front pushed the ＂focusing＂ region toward the cathode. After remedia- tion, the pH of the soil was between 1.8 and 5.0 in AAs-EK experiments. The total Cr removal efficiency was 64.4% （except in the ＂focusing＂ region） when the reduction reaction was combined with AAs-EK method. We conclude that AAs-EK remediation in the presence of NaHSO3 is an appropriate method for Cr-contaminated soil.展开更多
Aqueous zinc-ion batteries(AZIBs)have been regarded as prospective rechargeable energy storage devices because of the high theoretical capacity and low redox potential of Zn metal.However,the uncontrollable formation ...Aqueous zinc-ion batteries(AZIBs)have been regarded as prospective rechargeable energy storage devices because of the high theoretical capacity and low redox potential of Zn metal.However,the uncontrollable formation of dendrites and the water-induced side reactions at the Zn/electrolyte interface,and the poor reversibility under a high current density(>2 mA·cm^(-2))and large area capacity(>2 mAh·cm^(-2))still limit the practical applications of AZIBs.Therefore,a strategy that can overcome these difficulties is urgently needed.Here,we introduce an environmentally friendly and low-cost additive,namely urea,to the electrolyte of AZIBs to induce uniform Zn deposition and suppress the side reactions.Measurements of the adsorption behavior,electrochemical characterization,and observations of the morphology revealed the interfacial modification induced by urea on the Zn/electrolyte interface,demonstrating its huge potential in AZIBs.Consequently,the long-term cycling stability(over2100 h)of a Zn/Zn symmetric cell under a high current density of 5 mA·cm^(-2)and a capacity of 5 mAh·cm^(-2)was achieved with a 1 mol·L^(-1)ZnSO_(4)electrolyte with the urea additive.Additionally,the assembled Zn/NH_4V_4O_(10)full cell with urea exhibited excellent cycling performance and an outstanding average Coulombic efficiency of 99.98%.These results indicate that this is a low-cost and effective additive strategy for realizing highly reversible AZIBs.展开更多
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv...Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.展开更多
Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechan...Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.展开更多
All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significa...All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.展开更多
Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted...Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted to addressing drastic volume change and severe pulverization issues of such anodes,the underlying mechanisms involving dynamic phase evolutions and reaction kinetics have not yet been fully comprehended.Herein,taking antimony(Sb)anode as a representative paradigm,its microscopic operating mechanisms down to the atomic scale during live(de)potassiation cycling are systematically unraveled using in situ transmission electron microscopy.Highly reversible phase transformations at single-particle level,that are Sb←→KSb_(2)←→KSb←→K_5Sb_(4)←→K_(3)Sb,were revealed during cycling.Meanwhile,multiple phase interfaces associated with different reaction kinetics coexisted and this phenomenon was properly elucidated in the context of density functional theory calculations.Impressively,previously unexplored unidirectional circulation of reaction interfaces within individual Sb particle is confirmed for both potassiation and depotassiation.Based on the empirical results,the surface diffusion-mediated potassiation-depotassiation pathways at single-particle level are suggested.This work affords new insights into energy storage mechanisms of Sb anode and valuable guidance for targeted optimization of alloy-typed anodes(not limited to Sb)toward advanced potassium-ion batteries.展开更多
The electrochemical performances of lithium-ion batteries(LIBs)are closely related to the interphase between the electrode materials and electrolytes.However,the development of lithium-ion batteries is hampered by the...The electrochemical performances of lithium-ion batteries(LIBs)are closely related to the interphase between the electrode materials and electrolytes.However,the development of lithium-ion batteries is hampered by the formation of uncontrollable solid electrolyte interphase(SEI)and subsequent potential safety issues associated with dendritic formation and cell short-circuits during cycling.Fabricating artificial SEI layer can be one promising approach to solve the above issues.This review summarizes the principles and methods of fabricating artificial SEI for three types of main anodes:deposition-type(e.g.,Li),intercalation-type(e.g.,graphite)and alloy-type(e.g.,Si,Al).The review elucidates recent progress and discusses possible methods for constructing stable artificial SEIs composed of salts,polymers,oxides,and nanomaterials that simultaneously passivate anode against side reactions with electrolytes and regulate Li^+ions transport at interfaces.Moreover,the reaction mechanism of artificial SEIs was briefly analyzed,and the research prospect was also discussed.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
SnO2-based anode materials have attracted much attention due to high capacity and relatively mild voltage platforms.However,limited by low initial Coulombic efficiency(ICE)and poor stability,its practical application ...SnO2-based anode materials have attracted much attention due to high capacity and relatively mild voltage platforms.However,limited by low initial Coulombic efficiency(ICE)and poor stability,its practical application is still challenging.Recently,it has been found that compositing carbon or metal particles with SnO2 is an effective strategy to achieve high alkaline-ion storages.Although this strategy may improve the kinetics and ICE of the electrochemical reaction,the specific mechanism has not been clearly elucidated.In this work,we found that the invalidation SnO2 may go through two steps:1)the conversion process from SnO2 to Sn and Li2O;2)the collapse of the electrode material resulted from huge volume changes during the alloyed Sn with alkaline ions.To address these issues,a unique robust Co-NC shell derived from ZIF-67 is introduced,in which the transited metallic Co nanoparticles could accelerate the decomposition of Sn-O and Li-O bonds,thus expedite the kinetics of conversion reaction.As a result,the SnO2@Co-NC electrode achieves a more complete and efficient transfer between SnO2 and Sn phases,possessing a potential to achieve high alkaline-ion(Li+/Na+/K+)storages.展开更多
Anodic bonding of glass to Kovar alloy coated with Al film (Glass Al film/Kovar) was performed in the temperature range of 513 ～ 713?K under the static electric voltage of 500?V in order to investigate the interfacia...Anodic bonding of glass to Kovar alloy coated with Al film (Glass Al film/Kovar) was performed in the temperature range of 513 ～ 713?K under the static electric voltage of 500?V in order to investigate the interfacial phenomena of Al glass joint. The results reveal that Na and K ions within the glass are displaced by the applied field from the anode side surface of the glass to form depletion layers of them. The K ion depletion layer is narrow and followed by a K pile up layer, and both the two layers are formed within the Na depletion layer. The width of the Na and K depletion layers is increased with increasing bonding temperature and time. The activation energies for the growth of both depletion layers were close to that for Na diffusion in the glass. TEM observations reveal that Al film coated at the surface of Kovar alloy is oxidized to amorphous Al 2O 3 containing a few of Fe, Ni and Co by oxygen ions from the glass drifted by high electric field during bonding. The amount of Fe ions diffusing into the glass adjacent to the anode is significantly low due to the presence of Al film between Kovar alloy and the glass. As a result, the amorphous reaction layer of Fe Si O in the glass near the interface is avoided which is formed in Kovar glass joints.展开更多
文摘Silicon is the most promising anode material for the next generation high- performance lithium ion batteries. However, its commercial application is hindered by its poor performance due to the huge volume change during cycling. Although two-dimensional silicon-based materials show significantly improved performance, flexible synthesis of such materials is still a challenge. In this work, silicon-based nanosheets with a multilayer structure are synthesized for the first time by a topochemical reaction. The morphology and oxidation state of these nanosheets can be controlled by appropriate choice of reaction media and oxidants. Benefiting from the hierarchical structure and ultrathin size, when the silicon-based nanosheets are employed as anodes they exhibit a charge （delithiation） capacity of 800 mAh/g after 50 cycles with a maximum coulombic efficiency of 99.4% and good rate performance （647 mAh/g at 1 A/g）. This work demonstrates a novel method for preparing nanosheets not only for lithium ion batteries but also having various potential applications in other fields, such as catalysts, electronics and photonics.
基金supported by the National Natural Science Foundation of China(Grant no.51932011)。
文摘The development of promising zinc anodes mainly suffers from their low plating/stripping coulombic efficiencies when using aqueous electrolyte,which are mainly associated with the interfacial formation of irreversible by-products.It is urgent to develop technologies that can solve this issue fundamentally.Herein,we report an artificial Sc_(2)O_(3) protective film to construct a new class of interface for Zn anode.The density functional theory simulation and experimental results have proven that the interfacial side reaction was inhibited via a stratified adsorption effect between this artificial layer and Zn anode.Benefiting from this novel structure,the Sc_(2)O_(3)-coated Zn anode can run for more than 100 cycles without short circuit and exhibit low voltage hysteresis,and the coulombic efficiency increases by 1.2%.Importantly,it shows a good application prospect when matched with two of popular manganese-based and vanadium-based cathodes.The excellent electrochemical performance of the Sc_(2)O_(3)-coated Zn anode highlights the importance of rational design of anode materials and demonstrates a good way for developing high-performance Zn anodes with long lifespan and high efficiency.
基金the startup funding support from the Fundamental Research Funds for the Central Universities(Grant KY2060000150,WK2060000040)the support from USTC Center for Micro and Nanoscale Research and Fabrication and NEWAREThe authors also acknowledge the advanced computing resources provided by the Supercomputing Center of the USTC.
文摘Aqueous rechargeable zinc metal batteries display high theoretical capacity along with economical effectiveness,environmental benignity and high safety.However,dendritic growth and chemical corrosion at the Zn anodes limit their widespread applications.Here,we construct a Zn/Bi electrode via in-situ growth of a Bi-based energizer upon Zn metal surface using a replacement reaction.Experimental and theoretical calculations reveal that the Bi-based energizer composed of metallic Bi and ZnBi alloy contributes to Zn plating/stripping due to strong adsorption energy and fast ion transport rates.The resultant Zn/Bi electrode not only circumvents Zn dendrite growth but also improves Zn anode anti-corrosion performance.Specifically,the corrosion current of the Zn/Bi electrode is reduced by 90%compared to bare Zn.Impressively,an ultra-low overpotential of 12mV and stable cycling for 4000h are achieved in a Zn/Bi symmetric cell.A Zn–Cu/Bi asymmetric cell displays a cycle life of 1000 cycles,with an average Coulombic efficiency as high as 99.6%.In addition,an assembled Zn/Bi-activated carbon hybrid capacitor exhibits a stable life of more than 50,000 cycles,an energy density of 64Wh kg−1,and a power density of 7kWkg−1.The capacity retention rate of a Zn/Bi–MnO_(2)full cell is improved by over 150%compared to a Zn–MnO_(2)cell without the Bi-based energizer.Our findings open a new arena for the industrialization of Zn metal batteries for large-scale energy storage applications.
文摘A soil remediation method combining in situ reduction of Cr（VI） with approaching anodes electroki- netic （AAs-EK） remediation is proposed. EK experiments were conducted to compare the effect of approaching anodes （AAs） and fixed electrodes （FEs） with and without sodium bisulfite （NaHSO3） as a reducing agent. When NaHSO3 was added to the soil before EK treatment, 90.3% of the Cr（VI） was reduced to Cr（III）. EK experiments showed that the adverse effect of contrasting migration of Cr（III） and Cr（VI） species, which limits the practical application of this technique, was eliminated in the presence of the reducing agent. Furthermore, Tessier fractionation analysis indicated that the reducing agent changed the distribution of the chemical forms of Cr. The AAs-EK method was shown to acidize the soil as the anode moved toward the cathode and this acid front pushed the ＂focusing＂ region toward the cathode. After remedia- tion, the pH of the soil was between 1.8 and 5.0 in AAs-EK experiments. The total Cr removal efficiency was 64.4% （except in the ＂focusing＂ region） when the reduction reaction was combined with AAs-EK method. We conclude that AAs-EK remediation in the presence of NaHSO3 is an appropriate method for Cr-contaminated soil.
基金financially supported by the Key Science and Technology Program of Henan Province(Nos.212102210219 and 232102241020)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001)。
文摘Aqueous zinc-ion batteries(AZIBs)have been regarded as prospective rechargeable energy storage devices because of the high theoretical capacity and low redox potential of Zn metal.However,the uncontrollable formation of dendrites and the water-induced side reactions at the Zn/electrolyte interface,and the poor reversibility under a high current density(>2 mA·cm^(-2))and large area capacity(>2 mAh·cm^(-2))still limit the practical applications of AZIBs.Therefore,a strategy that can overcome these difficulties is urgently needed.Here,we introduce an environmentally friendly and low-cost additive,namely urea,to the electrolyte of AZIBs to induce uniform Zn deposition and suppress the side reactions.Measurements of the adsorption behavior,electrochemical characterization,and observations of the morphology revealed the interfacial modification induced by urea on the Zn/electrolyte interface,demonstrating its huge potential in AZIBs.Consequently,the long-term cycling stability(over2100 h)of a Zn/Zn symmetric cell under a high current density of 5 mA·cm^(-2)and a capacity of 5 mAh·cm^(-2)was achieved with a 1 mol·L^(-1)ZnSO_(4)electrolyte with the urea additive.Additionally,the assembled Zn/NH_4V_4O_(10)full cell with urea exhibited excellent cycling performance and an outstanding average Coulombic efficiency of 99.98%.These results indicate that this is a low-cost and effective additive strategy for realizing highly reversible AZIBs.
基金supported by the National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22379013 and 22209010)the Beijing Institute of Technology“Xiaomi Young Scholars”program。
文摘Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.
基金This work was financially supported by the National Natural Science Foundation of China(22075171)Natural Science Foundation of Shanghai(23ZR1423400)The firstprinciples calculations were supported by the High Performance Computing Center of Shanghai University.
文摘Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.
基金supported by the Outstanding Youth Fund Project by the Department of Science and Technology of Jiangsu Province(Grant No.BK20220045)the Key R&D Project funded by the Department of Science and Technology of Jiangsu Province(Grant No.BE2020003)+6 种基金Key Program-Automobile Joint Fund of National Natural Science Foundation of China(Grant No.U1964205)General Program of National Natural Science Foundation of China(Grant No.51972334)General Program of National Natural Science Foundation of Beijing(Grant No.2202058)Cultivation project of leading innovative experts in Changzhou City(CQ20210003)National Overseas High-level Expert recruitment Program(Grant No.E1JF021E11)Talent Program of Chinese Academy of Sciences,“Scientist Studio Program Funding”from Yangtze River Delta Physics Research Center,and Tianmu Lake Institute of Advanced Energy Storage Technologies(Grant No.TIESSS0001)Science and Technology Research Institute of China Three Gorges Corporation(Grant No.202103402)
文摘All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.
基金supported by the National Natural Science Foundation of China(Grant Nos.12174049,51972058)the Big Data Computing Center of Southeast University。
文摘Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted to addressing drastic volume change and severe pulverization issues of such anodes,the underlying mechanisms involving dynamic phase evolutions and reaction kinetics have not yet been fully comprehended.Herein,taking antimony(Sb)anode as a representative paradigm,its microscopic operating mechanisms down to the atomic scale during live(de)potassiation cycling are systematically unraveled using in situ transmission electron microscopy.Highly reversible phase transformations at single-particle level,that are Sb←→KSb_(2)←→KSb←→K_5Sb_(4)←→K_(3)Sb,were revealed during cycling.Meanwhile,multiple phase interfaces associated with different reaction kinetics coexisted and this phenomenon was properly elucidated in the context of density functional theory calculations.Impressively,previously unexplored unidirectional circulation of reaction interfaces within individual Sb particle is confirmed for both potassiation and depotassiation.Based on the empirical results,the surface diffusion-mediated potassiation-depotassiation pathways at single-particle level are suggested.This work affords new insights into energy storage mechanisms of Sb anode and valuable guidance for targeted optimization of alloy-typed anodes(not limited to Sb)toward advanced potassium-ion batteries.
基金the Key-Area Research and Development Program of Guangdong Province,China(No.2019B090914003)the National Natural Science Foundation of China(Nos.51822210,51972329)+2 种基金the Shenzhen Science and Technology Planning Project,China(No.JCYJ20190807172001755)the China Postdoctoral Science Foundation(No.2018M643235)the Science and Technology Planning Project of Guangdong Province,China(No.2019A1515011902)。
文摘The electrochemical performances of lithium-ion batteries(LIBs)are closely related to the interphase between the electrode materials and electrolytes.However,the development of lithium-ion batteries is hampered by the formation of uncontrollable solid electrolyte interphase(SEI)and subsequent potential safety issues associated with dendritic formation and cell short-circuits during cycling.Fabricating artificial SEI layer can be one promising approach to solve the above issues.This review summarizes the principles and methods of fabricating artificial SEI for three types of main anodes:deposition-type(e.g.,Li),intercalation-type(e.g.,graphite)and alloy-type(e.g.,Si,Al).The review elucidates recent progress and discusses possible methods for constructing stable artificial SEIs composed of salts,polymers,oxides,and nanomaterials that simultaneously passivate anode against side reactions with electrolytes and regulate Li^+ions transport at interfaces.Moreover,the reaction mechanism of artificial SEIs was briefly analyzed,and the research prospect was also discussed.
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.
基金This work is financially supported by the National Key R&D Program of China(No.2017YFE0198100)the National Natural Science Foundation of China(Nos.21975250 and 52072145)+2 种基金Science and Technology Development Program of Jilin Province(No.YDZJ202101ZYTS185)the Open Pogram of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,China(Nos.2020005 and 2021007)the Open Pogram of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University),China(No.202110).
文摘SnO2-based anode materials have attracted much attention due to high capacity and relatively mild voltage platforms.However,limited by low initial Coulombic efficiency(ICE)and poor stability,its practical application is still challenging.Recently,it has been found that compositing carbon or metal particles with SnO2 is an effective strategy to achieve high alkaline-ion storages.Although this strategy may improve the kinetics and ICE of the electrochemical reaction,the specific mechanism has not been clearly elucidated.In this work,we found that the invalidation SnO2 may go through two steps:1)the conversion process from SnO2 to Sn and Li2O;2)the collapse of the electrode material resulted from huge volume changes during the alloyed Sn with alkaline ions.To address these issues,a unique robust Co-NC shell derived from ZIF-67 is introduced,in which the transited metallic Co nanoparticles could accelerate the decomposition of Sn-O and Li-O bonds,thus expedite the kinetics of conversion reaction.As a result,the SnO2@Co-NC electrode achieves a more complete and efficient transfer between SnO2 and Sn phases,possessing a potential to achieve high alkaline-ion(Li+/Na+/K+)storages.
文摘Anodic bonding of glass to Kovar alloy coated with Al film (Glass Al film/Kovar) was performed in the temperature range of 513 ～ 713?K under the static electric voltage of 500?V in order to investigate the interfacial phenomena of Al glass joint. The results reveal that Na and K ions within the glass are displaced by the applied field from the anode side surface of the glass to form depletion layers of them. The K ion depletion layer is narrow and followed by a K pile up layer, and both the two layers are formed within the Na depletion layer. The width of the Na and K depletion layers is increased with increasing bonding temperature and time. The activation energies for the growth of both depletion layers were close to that for Na diffusion in the glass. TEM observations reveal that Al film coated at the surface of Kovar alloy is oxidized to amorphous Al 2O 3 containing a few of Fe, Ni and Co by oxygen ions from the glass drifted by high electric field during bonding. The amount of Fe ions diffusing into the glass adjacent to the anode is significantly low due to the presence of Al film between Kovar alloy and the glass. As a result, the amorphous reaction layer of Fe Si O in the glass near the interface is avoided which is formed in Kovar glass joints.
