Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic ...Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic engineering strategy is proposed to regulate the Na^(+)coordinated structure by employing a fluorinated metal–organic framework as an electron-rich model.Theoretical and experimental results revealed that the abundant electron-rich F sites can accelerate the disassociation of Na-salt through electrostatic attraction to release free Na^(+),while forcing anions into a Na^(+)coordination structure though electrostatic repulsion to weaken the Na^(+)coordination with polymer,thus promoting rapid Na^(+)transport.The optimized anion-rich weak solvation structure fosters a stable inorganic-dominated solid–electrolyte interphase,significantly enhancing the interfacial stability toward Na anode.Consequently,the Na/Na symmetric cell delivered stable Na plating/stripping over 2500 h at 0.1 mA cm^(−2).Impressively,the assembled ASSMBs demonstrated stable performance of over 2000 cycles even under high rate of 2 C with capacity retention nearly 100%,surpassing most reported ASSMBs using various solid-state electrolytes.This work provides a new avenue for regulating the Na^(+)coordination structure of SPEs by exploration of electrostatic effect engineering to achieve high-performance all-solid-state alkali metal batteries.展开更多
Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic co...Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic conductivity and interfacial stability remains a challenge.Here,a donor-acceptor(D-A)like solid plasticizer,tris(pentafluorophenyl)borane(TPFPB),containing electron-rich F atoms and electrondeficient B sites,was introduced to regulate the ion transport behavior and interfacial chemistry of polyethylene oxide(PEO)-based SPEs.Owing to the multiple ion-dipole interactions(F Li^(+)TFSI^(-)and B TFSI^(-)Li^(+))between the TPFPB molecule and Li salts,a multimodal electrolyte environment featuring more free Li^(+)and trapped TFSI^(-)anions was generated,which cooperates with the reduced crystallinity of PEO,significantly facilitating the rapid migration of Li^(+).More importantly,TPFPB tends to be preferentially reduced to form a stable inorganic-rich solid electrolyte interphase on the Li-metal anode,ensuring uniform Li plating/stripping behavior.Thus,the TPFPB-modulated SPEs system achieves a high Li^(+)conductivity of 0.74 m S cm^(-1)and effectively suppresses dendrite growth,which enables a long-cycle dendrite-free Li/Li symmetric cell for over 5000 h,and remarkable electrochemical performance has been further validated in operational ASSLMBs.The findings in this work would inspire efforts to develop highperformance SPEs for all-solid-state alkali-metal batteries.展开更多
Flame-retardant gel polymer electrolyte(FRGPE)with high ionic conductivity and practical safety is essential for the next generation of high energy density sodium metal batteries(SMBs).However,they suffer from serious...Flame-retardant gel polymer electrolyte(FRGPE)with high ionic conductivity and practical safety is essential for the next generation of high energy density sodium metal batteries(SMBs).However,they suffer from serious side reactions and insufficient interfacial stability against sodium metal anode,causing severe performance degradation and even safety issues.Herein,to address these challenges,a fluoroethylene carbonate(FEC)additive confined metal-organic framework(MOF)-based composite gel(AC-MCG)interlayer was constructed upon sodium anode through a facile in-situ UV-induced photopolymerization.The FEC confined in AC-MCG induces the formation of NaF-rich inorganic solid-electrolyte interphase,effectively eliminating the side reactions between the FRGPE and sodium metal anode.Moreover,the MOF with ordered nanochannels can homogenize Na^(+)flux during the plating process and also endow the AC-MCG interlayer with high mechanical strength,thus sufficiently suppressing the growth of sodium dendrites.Benefitting from these merits of the AC-MCG interlayer,a high critical current density of 2.0 mA cm^(-2)and a long-term cycling life for over 4200 h at 0.1 mA cm^(-2)are achieved for the Na/Na symmetric cells.Besides,the solid-state SMBs paired with the constructed AC-MCG interlayer also demonstrated considerable electrochemical performance and practical safety.展开更多
Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF d...Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.展开更多
The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)...The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.展开更多
Because sodium-ion batteries are relatively inexpensive,they have gained significant traction as large-scale energy storage devices instead of lithium-ion batteries in recent years.However,sodium-ion batteries have a ...Because sodium-ion batteries are relatively inexpensive,they have gained significant traction as large-scale energy storage devices instead of lithium-ion batteries in recent years.However,sodium-ion batteries have a lower energy density than lithium-ion batteries because sodium-ion batteries have not been as well developed as lithium-ion batteries.Solid-state batteries using solid electrolytes have a higher energy density than liquid batteries in regard to applications with sodium-ion batteries,making them more suitable for energy storage systems than liquid batteries.Due to their low ionic conductivity,solid electrolytes are currently unable to achieve comparable performance to liquid electrolytes at room temperature.In this review,we discuss the advancements in SSEs applied to sodium-ion batteries in recent years,including inorganic solid electrolytes,such as Na-β-Al_(2)O_(3),NASICON and Na_(3)PS_(4),polymer solid electrolytes based on PEO,PVDF-HFP and PAN,and plastic crystal solid electrolytes mainly composed of succinonitrile.Additionally,appropriate solutions for low ionic conductivity,a narrow electrochemical stability window and poor contact with electrodes,which are the significant flaws in current SSEs,are discussed in this review.展开更多
Gel polymer electrolytes (GPEs) with flexibility, easy processability, and low cost have been regarded as promising alternatives for conventional liquid electrolytes in next-generation sodium metal batteries (SMBs). H...Gel polymer electrolytes (GPEs) with flexibility, easy processability, and low cost have been regarded as promising alternatives for conventional liquid electrolytes in next-generation sodium metal batteries (SMBs). However, GPEs often suffer from combustion risk and inferior interfacial compatibility toward Na metal anode, which severely limit their wide commercial applications. Here, a rational design of asymmetric fireproof GPE (AFGPE) modified with a boron-contained covalent organic framework (BCOF) on one side is developed through in-situ crosslinking polymerization process. Benefiting from the unique structure and composition, the resulting AFGPE exhibits high Na+ transference number, wide electrochemical window, excellent mechanical properties and high safety. Especially, the nanoscale BCOF layer with uniform nanochannels works as ion sieve that homogenizes Na+ flux during Na plating process, while the abundant Lewis-acid B sites can strongly capture counter anions and decrease space charge layer at anode side, thus promoting the uniform Na deposition to effectively suppress dendrite growth. Consequently, the Na/AFGPE/Na symmetric cells demonstrate remarkable cycling stability for over 1200 h at 0.1 mA·cm^(-2), and the solid-state SMBs exhibit outstanding cycling properties and rate capability, delivering a high capacity retention of 96.4% under current density of 1 C for over 1000 cycles.展开更多
Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and opera...Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.展开更多
基金supported by the National Natural Science Foundation of China(No.52473213 and No.52203261)。
文摘Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic engineering strategy is proposed to regulate the Na^(+)coordinated structure by employing a fluorinated metal–organic framework as an electron-rich model.Theoretical and experimental results revealed that the abundant electron-rich F sites can accelerate the disassociation of Na-salt through electrostatic attraction to release free Na^(+),while forcing anions into a Na^(+)coordination structure though electrostatic repulsion to weaken the Na^(+)coordination with polymer,thus promoting rapid Na^(+)transport.The optimized anion-rich weak solvation structure fosters a stable inorganic-dominated solid–electrolyte interphase,significantly enhancing the interfacial stability toward Na anode.Consequently,the Na/Na symmetric cell delivered stable Na plating/stripping over 2500 h at 0.1 mA cm^(−2).Impressively,the assembled ASSMBs demonstrated stable performance of over 2000 cycles even under high rate of 2 C with capacity retention nearly 100%,surpassing most reported ASSMBs using various solid-state electrolytes.This work provides a new avenue for regulating the Na^(+)coordination structure of SPEs by exploration of electrostatic effect engineering to achieve high-performance all-solid-state alkali metal batteries.
基金supported by the National Natural Science Foundation of China(No.52203261,No.52473213)。
文摘Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic conductivity and interfacial stability remains a challenge.Here,a donor-acceptor(D-A)like solid plasticizer,tris(pentafluorophenyl)borane(TPFPB),containing electron-rich F atoms and electrondeficient B sites,was introduced to regulate the ion transport behavior and interfacial chemistry of polyethylene oxide(PEO)-based SPEs.Owing to the multiple ion-dipole interactions(F Li^(+)TFSI^(-)and B TFSI^(-)Li^(+))between the TPFPB molecule and Li salts,a multimodal electrolyte environment featuring more free Li^(+)and trapped TFSI^(-)anions was generated,which cooperates with the reduced crystallinity of PEO,significantly facilitating the rapid migration of Li^(+).More importantly,TPFPB tends to be preferentially reduced to form a stable inorganic-rich solid electrolyte interphase on the Li-metal anode,ensuring uniform Li plating/stripping behavior.Thus,the TPFPB-modulated SPEs system achieves a high Li^(+)conductivity of 0.74 m S cm^(-1)and effectively suppresses dendrite growth,which enables a long-cycle dendrite-free Li/Li symmetric cell for over 5000 h,and remarkable electrochemical performance has been further validated in operational ASSLMBs.The findings in this work would inspire efforts to develop highperformance SPEs for all-solid-state alkali-metal batteries.
基金supported by the National Natural Science Foundation of China(No.52203261,No.52473213)the China Postdoctoral Science Foundation(2023731330)the Central Laboratory,School of Chemical and Material Engineering,Jiangnan University。
文摘Flame-retardant gel polymer electrolyte(FRGPE)with high ionic conductivity and practical safety is essential for the next generation of high energy density sodium metal batteries(SMBs).However,they suffer from serious side reactions and insufficient interfacial stability against sodium metal anode,causing severe performance degradation and even safety issues.Herein,to address these challenges,a fluoroethylene carbonate(FEC)additive confined metal-organic framework(MOF)-based composite gel(AC-MCG)interlayer was constructed upon sodium anode through a facile in-situ UV-induced photopolymerization.The FEC confined in AC-MCG induces the formation of NaF-rich inorganic solid-electrolyte interphase,effectively eliminating the side reactions between the FRGPE and sodium metal anode.Moreover,the MOF with ordered nanochannels can homogenize Na^(+)flux during the plating process and also endow the AC-MCG interlayer with high mechanical strength,thus sufficiently suppressing the growth of sodium dendrites.Benefitting from these merits of the AC-MCG interlayer,a high critical current density of 2.0 mA cm^(-2)and a long-term cycling life for over 4200 h at 0.1 mA cm^(-2)are achieved for the Na/Na symmetric cells.Besides,the solid-state SMBs paired with the constructed AC-MCG interlayer also demonstrated considerable electrochemical performance and practical safety.
基金supported by the Natural Science Foundation of Jiangsu Province (No.BK20210474)the National Natural Science Foundation of China (No.21938005)the Fundamental Research Funds for the Central Universities (No.JUSRP122013).
文摘Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.
基金financially supported by the National Natural Science Foundation of China(NSFC)(52203261)Natural Science Foundation of Jiangsu Province(BK20210474)the project of research on the industrial application of"controllable synthesis of nanocarbon-based polymer composites and their application in new energy”(N0.CJGJZD20210408092400002).
文摘The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.
基金supported by the Natural Science Foundation of China(22005190,21938005)the Science&Technology Commission of Shanghai Municipality(20QB1405700,19DZ1205500)the Zhejiang Key Research and Development Program(2020C01128).
文摘Because sodium-ion batteries are relatively inexpensive,they have gained significant traction as large-scale energy storage devices instead of lithium-ion batteries in recent years.However,sodium-ion batteries have a lower energy density than lithium-ion batteries because sodium-ion batteries have not been as well developed as lithium-ion batteries.Solid-state batteries using solid electrolytes have a higher energy density than liquid batteries in regard to applications with sodium-ion batteries,making them more suitable for energy storage systems than liquid batteries.Due to their low ionic conductivity,solid electrolytes are currently unable to achieve comparable performance to liquid electrolytes at room temperature.In this review,we discuss the advancements in SSEs applied to sodium-ion batteries in recent years,including inorganic solid electrolytes,such as Na-β-Al_(2)O_(3),NASICON and Na_(3)PS_(4),polymer solid electrolytes based on PEO,PVDF-HFP and PAN,and plastic crystal solid electrolytes mainly composed of succinonitrile.Additionally,appropriate solutions for low ionic conductivity,a narrow electrochemical stability window and poor contact with electrodes,which are the significant flaws in current SSEs,are discussed in this review.
基金financially supported by the Natural Science Foundation of Jiangsu Province(No.BK20210474)the National Natural Science Foundation of China(NSFC,No.52203261)the project of research on the industrial application of “controllable synthesis of nanocarbon-based polymer composites and their application in new energy”(No.CJGJZD20210408092400002)。
文摘Gel polymer electrolytes (GPEs) with flexibility, easy processability, and low cost have been regarded as promising alternatives for conventional liquid electrolytes in next-generation sodium metal batteries (SMBs). However, GPEs often suffer from combustion risk and inferior interfacial compatibility toward Na metal anode, which severely limit their wide commercial applications. Here, a rational design of asymmetric fireproof GPE (AFGPE) modified with a boron-contained covalent organic framework (BCOF) on one side is developed through in-situ crosslinking polymerization process. Benefiting from the unique structure and composition, the resulting AFGPE exhibits high Na+ transference number, wide electrochemical window, excellent mechanical properties and high safety. Especially, the nanoscale BCOF layer with uniform nanochannels works as ion sieve that homogenizes Na+ flux during Na plating process, while the abundant Lewis-acid B sites can strongly capture counter anions and decrease space charge layer at anode side, thus promoting the uniform Na deposition to effectively suppress dendrite growth. Consequently, the Na/AFGPE/Na symmetric cells demonstrate remarkable cycling stability for over 1200 h at 0.1 mA·cm^(-2), and the solid-state SMBs exhibit outstanding cycling properties and rate capability, delivering a high capacity retention of 96.4% under current density of 1 C for over 1000 cycles.
基金supported by the Singapore National Research Foundation Central Gap Fund(grant no.NRF2020NRF-CG001-010)Competitive Research Programme,Singapore(grant no.NRF-CRP26-2021-0002)+6 种基金National Research Foundation Investigatorship,Singapore(grant no.NRF-NRFI08-2022-0011)the Agency for Science,Technology,and Research in Advanced Manufacturing and Engineering(A*STAR AME)Individual Research Grant,Singapore(grant no.A20E5c0082)Institute for Digital Institute for Digital Molecular Analytics and Science,Singapore(IDMxS)J.R.T.C.acknowledges scholarship support from Nanyang Technological University,Singaporethe funding support from the Jiangsu Specially-Appointed Professor project(grant no.1046010241230830)the National Natural Science Foundation of China(NSFC,grant no.22108030)the Natural Science Foundation of Shanghai,China(grant no.22ZR1401500).
文摘Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.
