H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an elec...H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.展开更多
Hydrogen evolution reaction(HER),zinc corrosion,and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries.Herein,an in-situ physical/chemical cross-linked ...Hydrogen evolution reaction(HER),zinc corrosion,and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries.Herein,an in-situ physical/chemical cross-linked hydrogel electrolyte(carrageenan/polyacrylamide/ZnSO_(4),denoted as CPZ)has been developed to stabilize the zinc anode-electrolyte interface,which can eliminate side reactions and prevent dendrites growth.The in-situ CPZ hydrogel electrolyte improves the reversibility of zinc anode due to eliminating side reactions caused by active water molecules.Furthermore,the electrostatic interaction between the SO_(4)^(-)groups in CPZ and Zn^(2+)can encourage the preferential deposition of zinc atoms on(002)crystal plane,which achieve dendrite-free and homogeneous zinc deposition.The in-situ hydrogel electrolyte offers a streamlined approach to battery manufacturing by allowing for direct integration into the battery.Subsequently,the Zn//Zn half battery with CPZ hydrogel electrolyte can enable an ultra-long cycle over 5500 h at a current density of 0.5 mA cm^(-2),and the Zn//Cu half battery reach an average coulombic efficiency of 99.37%.The Zn//V_(2)O_5-GO full battery with CPZ hydrogel electrolyte demonstrates94.5%of capacity retention after 2100 cycles.This study is expected to open new thought for the development of commercial hydrogel electrolytes for low-cost and long-life zinc-ion batteries.展开更多
The interest for solid-state lithium metal(Li◦)batteries(SSLMBs)has been growing exponentially in recent years in view of their higher energy density and eliminated safety concerns.Solid polymer electrolytes(SPEs)are ...The interest for solid-state lithium metal(Li◦)batteries(SSLMBs)has been growing exponentially in recent years in view of their higher energy density and eliminated safety concerns.Solid polymer electrolytes(SPEs)are soft ionic conductors which can be easily processed into thin films at industrial level;these unique features confer solid-state Li◦polymer batteries(SSLMPBs,i.e.,SSLMBs utilizing SPEs as electrolytes)distinct advantages compared to SSLMBs containing other electrolytes.In this article,we briefly review recent progresses and achievements in SSLMPBs including the improvement of ionic conductivity of SPEs and their interfacial stability with Li◦anode.Moreover,we outline several advanced in-situ and ex-situ characterizing techniques which could assist in-depth understanding of the anode-electrolyte interphases in SSLMPBs.This article is hoped not only to update the state-of-the-art in the research on SSLMPBs but also to bring intriguing insights that could improve the fundamental properties(e.g.,transport,dendrite formation,and growth,etc.)and electrochemical performance of SSLMPBs.展开更多
A robust electrode-electrolyte interface is the cornerstone for every battery system,as demonstrated in the meandering history of the development of Li-ion batteries(LIBs).In the thrust to replace the graphite anode w...A robust electrode-electrolyte interface is the cornerstone for every battery system,as demonstrated in the meandering history of the development of Li-ion batteries(LIBs).In the thrust to replace the graphite anode with more energetic ones in LIBs,the effectual strategy for stabilizing the original graphite-electrolyte interface becomes obsolete and a new anode-electrolyte interface needs reconfiguration.Unfortunately,this interface has become the Achilles'heel for those anodes,such as Li-metal anode(LMA)and Si-based anode owing to their excessive reductivity,enormous volume change,and so forth.Encouragingly,in the last decade,impressive progress has been made on taming these extremely unstable interfaces and on the solid-state batteries(SSBs)that are reported to be less susceptible to parasitic reactions.One of the distinguished strategies is the application of artificial Li-alloying intermetallic interphases onto the surface of LMA,via the direct introduction of foreign metals to the Li anode or indirect hetero-cations doping in the electrolyte,to regulate the Li deposition/stripping behavior,which has markedly improved the stability of the LMA-electrolyte interface.In parallel,the intermetallic interphases are also witnessed to profoundly enhance the anode-solid electrolyte contact and the corresponding charge transfer kinetics in various SSBs.This review will provide a panoramic overview of the application of the intermetallic interphases at the anode-electrolyte interfaces in the lithium metal batteries(LMBs),SSBs,and also derivative works in the conventional LIBs,which will focus on different concepts,methodologies,and understandings from the encircled studies.展开更多
基金supported by the National Natural Science Foundation of China(22479031,22162004)the Natural Science Foundation of Guangxi(2022JJD120011).
文摘H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.
基金supported by the Key Program of Natural Science Foundation of Gansu Province (23JRRA789)the Major Science and Technology Project of Gansu Province (22ZD6GA008)。
文摘Hydrogen evolution reaction(HER),zinc corrosion,and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries.Herein,an in-situ physical/chemical cross-linked hydrogel electrolyte(carrageenan/polyacrylamide/ZnSO_(4),denoted as CPZ)has been developed to stabilize the zinc anode-electrolyte interface,which can eliminate side reactions and prevent dendrites growth.The in-situ CPZ hydrogel electrolyte improves the reversibility of zinc anode due to eliminating side reactions caused by active water molecules.Furthermore,the electrostatic interaction between the SO_(4)^(-)groups in CPZ and Zn^(2+)can encourage the preferential deposition of zinc atoms on(002)crystal plane,which achieve dendrite-free and homogeneous zinc deposition.The in-situ hydrogel electrolyte offers a streamlined approach to battery manufacturing by allowing for direct integration into the battery.Subsequently,the Zn//Zn half battery with CPZ hydrogel electrolyte can enable an ultra-long cycle over 5500 h at a current density of 0.5 mA cm^(-2),and the Zn//Cu half battery reach an average coulombic efficiency of 99.37%.The Zn//V_(2)O_5-GO full battery with CPZ hydrogel electrolyte demonstrates94.5%of capacity retention after 2100 cycles.This study is expected to open new thought for the development of commercial hydrogel electrolytes for low-cost and long-life zinc-ion batteries.
基金NationalNatural Science Foundation of China,Grant/Award Numbers:51773092,21975124Research Foundation of Material-orientedChemicalEngineering StateKey Lab,Grant/Award Number:ZK201717+1 种基金FundamentalResearch Funds for the CentralUniversities,Grant/Award Number:2020kfyXJJS095Spanish Government,Grant/Award Number:MINECO RETOS/RTI2018-098301-B-I00。
文摘The interest for solid-state lithium metal(Li◦)batteries(SSLMBs)has been growing exponentially in recent years in view of their higher energy density and eliminated safety concerns.Solid polymer electrolytes(SPEs)are soft ionic conductors which can be easily processed into thin films at industrial level;these unique features confer solid-state Li◦polymer batteries(SSLMPBs,i.e.,SSLMBs utilizing SPEs as electrolytes)distinct advantages compared to SSLMBs containing other electrolytes.In this article,we briefly review recent progresses and achievements in SSLMPBs including the improvement of ionic conductivity of SPEs and their interfacial stability with Li◦anode.Moreover,we outline several advanced in-situ and ex-situ characterizing techniques which could assist in-depth understanding of the anode-electrolyte interphases in SSLMPBs.This article is hoped not only to update the state-of-the-art in the research on SSLMPBs but also to bring intriguing insights that could improve the fundamental properties(e.g.,transport,dendrite formation,and growth,etc.)and electrochemical performance of SSLMPBs.
基金National Key R&D Program of China,Grant/Award Numbers:2016YFB0100100,2018YFB0104400National Natural Science Foundation of China,Grant/Award Numbers:92045302,21972055,21825202,21733012,21972133+1 种基金Newton Advanced Fellowships,Grant/Award Number:NAF/R2/180603Scientist Studio Funding。
文摘A robust electrode-electrolyte interface is the cornerstone for every battery system,as demonstrated in the meandering history of the development of Li-ion batteries(LIBs).In the thrust to replace the graphite anode with more energetic ones in LIBs,the effectual strategy for stabilizing the original graphite-electrolyte interface becomes obsolete and a new anode-electrolyte interface needs reconfiguration.Unfortunately,this interface has become the Achilles'heel for those anodes,such as Li-metal anode(LMA)and Si-based anode owing to their excessive reductivity,enormous volume change,and so forth.Encouragingly,in the last decade,impressive progress has been made on taming these extremely unstable interfaces and on the solid-state batteries(SSBs)that are reported to be less susceptible to parasitic reactions.One of the distinguished strategies is the application of artificial Li-alloying intermetallic interphases onto the surface of LMA,via the direct introduction of foreign metals to the Li anode or indirect hetero-cations doping in the electrolyte,to regulate the Li deposition/stripping behavior,which has markedly improved the stability of the LMA-electrolyte interface.In parallel,the intermetallic interphases are also witnessed to profoundly enhance the anode-solid electrolyte contact and the corresponding charge transfer kinetics in various SSBs.This review will provide a panoramic overview of the application of the intermetallic interphases at the anode-electrolyte interfaces in the lithium metal batteries(LMBs),SSBs,and also derivative works in the conventional LIBs,which will focus on different concepts,methodologies,and understandings from the encircled studies.
