Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy densit...Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.展开更多
Ceramic electrolytes are important in ceramic-liquid hybrid electrolytes(CLHEs),which can effectively solve the interfacial issues between the electrolyte and electrodes in solid-state batteries and provide a highly e...Ceramic electrolytes are important in ceramic-liquid hybrid electrolytes(CLHEs),which can effectively solve the interfacial issues between the electrolyte and electrodes in solid-state batteries and provide a highly efficient Li-ion transfer for solid–liquid Li metal batteries.Understanding the ionic transport mechanisms in CLHEs and the corresponding role of ceramic electrolytes is crucial for a rational design strategy.Herein,the Li-ion transfer in the ceramic electrolytes of CLHEs was confirmed by tracking the 6Li and 7Li substitution behavior through solid-state nuclear magnetic resonance spectroscopy.The ceramic and liquid electrolytes simultaneously participate in Li-ion transport to achieve highly efficient Li-ion transfer in CLHEs.A spontaneous Li-ion exchange was also observed between ceramic and liquid electrolytes,which serves as a bridge that connects the ceramic and liquid electrolytes,thereby greatly strengthening the continuity of Li-ion pathways in CLHEs and improving the kinetics of Li-ion transfer.The importance of an abundant solid–liquid interface for CLHEs was further verified by the enhanced electrochemical performance in LiFePO4/Li and LiNi0.8Co0.1Mn0.1O2/Li batteries from the generated interface.This work provides a clear understanding of the Li-ion transport pathway in CLHEs that serves as a basis to build a universal Li-ion transport model of CLHEs.展开更多
Polyethylene oxide(PEO)-based electrolytes are considered as one of the most promising solid-state electrolytes for next-generation lithium batteries with high safety and energy density;however,the drawbacks such as i...Polyethylene oxide(PEO)-based electrolytes are considered as one of the most promising solid-state electrolytes for next-generation lithium batteries with high safety and energy density;however,the drawbacks such as insufficient ion conductance,mechanical strength and electrochemical stability hinder their applications in metallic lithium batteries.To enhance their overall properties,flexible and thin composite polymer electrolyte(CPE)membranes with 3D continuous aramid nanofiber(ANF)–Li_(1.4)Al_(0.4)Ti_(1.6)(PO_(4))_(3)(LATP)nanoparticle hybrid frameworks are facilely prepared by filling PEO–Li TFSI in the 3D nanohybrid scaffolds via a solution infusion way.The construction of the 3D continuous nanohybrid networks can effectively inhibit the PEO crystallization,facilitate the lithium salt dissociation and meanwhile increase the fast-ion transport in the continuous LATP electrolyte phase,and thus greatly improving the ionic conductivity(~3 times that of the pristine one).With the integration of the 3D continuity and flexibility of the 3D ANF networks and the thermostability of the LATP phase,the CPE membranes also show a wider electrochemical window(~5.0 V vs.4.3 V),higher tensile strength(~4–10times that of the pristine one)and thermostability,and better lithium dendrite resistance capability.Furthermore,the CPE-based Li FePO_(4)/Li cells exhibit superior cycling stability(133 m Ah/g after 100 cycles at 0.3 C)and rate performance(100 m Ah/g at 1 C)than the pristine electrolyte-based cell(79 and 29m Ah/g,respectively).This work offers an important CPE design criteria to achieve comprehensivelyupgraded solid-state electrolytes for safe and high-energy metal battery applications.展开更多
A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li_(4)Ti_(5)O_(12) to provide the outstanding electrochemical stability and better normal interface contact.Scanning Electron Microscope(SEM...A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li_(4)Ti_(5)O_(12) to provide the outstanding electrochemical stability and better normal interface contact.Scanning Electron Microscope(SEM),Scanning Transmission Electron Microscopy(STEM),Transmission Electron Microscopy(TEM),and Energy Dispersive Spectrometer(EDS)were used to analyze the structural evolution and performance of plasma sprayed amorphous LTO electrode and ceramic/polymer composite electrolyte before and after electrochemical experiments.By comparing the electrochemical performance of the amorphous LTO electrode and the traditional LTO electrode,the electrochemical behavior of different electrodes is studied.The results show that plasma spraying can prepare an amorphous LTO electrode coating of about 8μm.After 200 electrochemical cycles,the structure of the electrode evolved,and the inside of the electrode fractured and cracks expanded,because of recrystallization at the interface between the rich fluorine compounds and the amorphous LTO electrode.Similarly,the ceramic/polymer composite electrolyte has undergone structural evolution after 200 test cycles.The electrochemical cycle results show that the cycle stability,capacity retention rate,coulomb efficiency,and internal impedance of amorphous LTO electrode are better than traditional LTO electrode.This innovative and facile quasi-solid-state strategy is aimed to promote the intrinsic safety and stability of working lithium battery,shedding light on the development of next-generation high-performance solid-state lithium batteries.展开更多
Protonic ceramic energy devices represent a promising frontier for sustainable energy conversion and storage,operating efficiently at intermediate temperatures(350-650℃)and facilitating integration with renewable ene...Protonic ceramic energy devices represent a promising frontier for sustainable energy conversion and storage,operating efficiently at intermediate temperatures(350-650℃)and facilitating integration with renewable energy sources.Among protonic ceramic materials,yttrium-doped barium zirconate(BaZr_(1-x)Y_(x)O_(3-δ),BZY)stands out for its competitive proton conductivity,chemical resilience,and compatibility with diverse fuels and environments.This review critically examines the fundamentals and multiscale design strategies for BZY-based ceramic cells.We discuss atomic-level composition-structure relationships,innovative synthesis routes,and advanced processing methods to overcome manufacturing and scalability challenges.We then highlight microstructure engineering and interface design approaches that minimize resistance and elevate device performance,supported by state-of-the-art characterization and predictive modeling techniques,including density functional theory and machine learning.Recent advances,such as hybrid architectures and AI-driven defect optimization,demonstrate significant improvements in conductivity,stability,and Faradaic efficiency,confirming BZY's pivotal role in green hydrogen production and power-to-chemicals applications.By integrating insights across materials chemistry,electrochemistry,and engineering,this review provides a comprehensive roadmap for researchers aiming to translate laboratory breakthroughs into robust,scalable protonic ceramic technologies for decarbonized energy systems.展开更多
Solid-state sodium metal batteries(SSMBs)have garnered significant attention for their high energy density and intrinsic safety,however,the sluggish kinetic and dendrite growth caused by solid-solid interfacial failur...Solid-state sodium metal batteries(SSMBs)have garnered significant attention for their high energy density and intrinsic safety,however,the sluggish kinetic and dendrite growth caused by solid-solid interfacial failure have severely constrained their practical applications.Understanding the structure-function relationships underlying the interfacial failure is therefore critical for guiding the design and modification of solid electrolytes.This work systematically investigates the electrochemical-mechanical synergistic failure mechanisms of NASICON-type Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)ceramic electrolyte at its interfaces with anode and cathode.The analysis reveals that the sodium-rich interfacial phase,formed from the reaction between NZSP and sodium metal,accelerates the pore formation and dendrite growth at the interface.Simultaneously,the decomposition products layer of the liquid electrolyte at the cathode/ceramic electrolyte interface significantly increases the resistance for sodium-ion transportation.Together,these factors contribute to the degradation of battery performance.The above findings not only make up for the lack of knowledge on the mechano-electrochemical correlation of interface failure in existing studies,but also provide a principle of cross-scale regulation for the design of long-life and high-performance NZSP-based SSMBs.展开更多
基金supported by the University of Wollongong,Wollongong,Australiafinancial support from the National Natural Science Foundation of China(22272086)Natural Science Foundation of Sichuan Province(2023NSFSC0009).
文摘Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.
基金supported by the National Natural Science Foundation of China(U2001220)Key-Area Research and Development Program of Guangdong Province(2020B090919001)+2 种基金Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center(XMHT20200203006)Shenzhen Technical Plan Project(RCJC20200714114436091,JCYJ20180508152210821JCYJ20180508152135822)。
文摘Ceramic electrolytes are important in ceramic-liquid hybrid electrolytes(CLHEs),which can effectively solve the interfacial issues between the electrolyte and electrodes in solid-state batteries and provide a highly efficient Li-ion transfer for solid–liquid Li metal batteries.Understanding the ionic transport mechanisms in CLHEs and the corresponding role of ceramic electrolytes is crucial for a rational design strategy.Herein,the Li-ion transfer in the ceramic electrolytes of CLHEs was confirmed by tracking the 6Li and 7Li substitution behavior through solid-state nuclear magnetic resonance spectroscopy.The ceramic and liquid electrolytes simultaneously participate in Li-ion transport to achieve highly efficient Li-ion transfer in CLHEs.A spontaneous Li-ion exchange was also observed between ceramic and liquid electrolytes,which serves as a bridge that connects the ceramic and liquid electrolytes,thereby greatly strengthening the continuity of Li-ion pathways in CLHEs and improving the kinetics of Li-ion transfer.The importance of an abundant solid–liquid interface for CLHEs was further verified by the enhanced electrochemical performance in LiFePO4/Li and LiNi0.8Co0.1Mn0.1O2/Li batteries from the generated interface.This work provides a clear understanding of the Li-ion transport pathway in CLHEs that serves as a basis to build a universal Li-ion transport model of CLHEs.
基金supported partially by the project of State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(LAPS21004)the National Natural Science Foundation of China(51972110,52102245,52072121)+5 种基金the Beijing Science and Technology Project(Z211100004621010)the Beijing Natural Science Foundation(2222076,2222077)the Huaneng Group Headquarters Science and Technology Project(HNKJ20-H88)the Hebei Natural Science Foundation(E2022502022)the Fundamental Research Funds for the Central Universities(2021MS028,2020MS023,2020MS028)the NCEPU“Double First-Class”Program。
文摘Polyethylene oxide(PEO)-based electrolytes are considered as one of the most promising solid-state electrolytes for next-generation lithium batteries with high safety and energy density;however,the drawbacks such as insufficient ion conductance,mechanical strength and electrochemical stability hinder their applications in metallic lithium batteries.To enhance their overall properties,flexible and thin composite polymer electrolyte(CPE)membranes with 3D continuous aramid nanofiber(ANF)–Li_(1.4)Al_(0.4)Ti_(1.6)(PO_(4))_(3)(LATP)nanoparticle hybrid frameworks are facilely prepared by filling PEO–Li TFSI in the 3D nanohybrid scaffolds via a solution infusion way.The construction of the 3D continuous nanohybrid networks can effectively inhibit the PEO crystallization,facilitate the lithium salt dissociation and meanwhile increase the fast-ion transport in the continuous LATP electrolyte phase,and thus greatly improving the ionic conductivity(~3 times that of the pristine one).With the integration of the 3D continuity and flexibility of the 3D ANF networks and the thermostability of the LATP phase,the CPE membranes also show a wider electrochemical window(~5.0 V vs.4.3 V),higher tensile strength(~4–10times that of the pristine one)and thermostability,and better lithium dendrite resistance capability.Furthermore,the CPE-based Li FePO_(4)/Li cells exhibit superior cycling stability(133 m Ah/g after 100 cycles at 0.3 C)and rate performance(100 m Ah/g at 1 C)than the pristine electrolyte-based cell(79 and 29m Ah/g,respectively).This work offers an important CPE design criteria to achieve comprehensivelyupgraded solid-state electrolytes for safe and high-energy metal battery applications.
基金supported by the Fund Project of the GDAS Special Project of Science and Technology Development,Guangdong Academy of Sciences Program(No.2020GDASYL-20200104030)the Innovation Project of Guangxi University of Science and Technology Graduate Education(No.YCSW2020217)+2 种基金Guangxi Innovation Driven Development Project(No.AA18242036-2)Innovation Team Project of Guangxi University of Science and Technology(No.3)the Fund Project of the Key Lab of Guangdong for Modern Surface Engineering Technology(No.2018KFKT01)。
文摘A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li_(4)Ti_(5)O_(12) to provide the outstanding electrochemical stability and better normal interface contact.Scanning Electron Microscope(SEM),Scanning Transmission Electron Microscopy(STEM),Transmission Electron Microscopy(TEM),and Energy Dispersive Spectrometer(EDS)were used to analyze the structural evolution and performance of plasma sprayed amorphous LTO electrode and ceramic/polymer composite electrolyte before and after electrochemical experiments.By comparing the electrochemical performance of the amorphous LTO electrode and the traditional LTO electrode,the electrochemical behavior of different electrodes is studied.The results show that plasma spraying can prepare an amorphous LTO electrode coating of about 8μm.After 200 electrochemical cycles,the structure of the electrode evolved,and the inside of the electrode fractured and cracks expanded,because of recrystallization at the interface between the rich fluorine compounds and the amorphous LTO electrode.Similarly,the ceramic/polymer composite electrolyte has undergone structural evolution after 200 test cycles.The electrochemical cycle results show that the cycle stability,capacity retention rate,coulomb efficiency,and internal impedance of amorphous LTO electrode are better than traditional LTO electrode.This innovative and facile quasi-solid-state strategy is aimed to promote the intrinsic safety and stability of working lithium battery,shedding light on the development of next-generation high-performance solid-state lithium batteries.
基金supported by the U.S.Department of Energy(USDOE),Office of Energy Efficiency and Renewable Energy(EERE),Hydrogen and Fuel Cell Technologies Office(FCTO)under contract DEEE0011336H.D.would like to thank the startup research grant from the University of OklahomaW.B.thanks the support from the INL Laboratory Directed Research and Development(LDRD)Program 24A1081-098FP under DOE Idaho Operations Office Contract DE-AC07-05ID14517.
文摘Protonic ceramic energy devices represent a promising frontier for sustainable energy conversion and storage,operating efficiently at intermediate temperatures(350-650℃)and facilitating integration with renewable energy sources.Among protonic ceramic materials,yttrium-doped barium zirconate(BaZr_(1-x)Y_(x)O_(3-δ),BZY)stands out for its competitive proton conductivity,chemical resilience,and compatibility with diverse fuels and environments.This review critically examines the fundamentals and multiscale design strategies for BZY-based ceramic cells.We discuss atomic-level composition-structure relationships,innovative synthesis routes,and advanced processing methods to overcome manufacturing and scalability challenges.We then highlight microstructure engineering and interface design approaches that minimize resistance and elevate device performance,supported by state-of-the-art characterization and predictive modeling techniques,including density functional theory and machine learning.Recent advances,such as hybrid architectures and AI-driven defect optimization,demonstrate significant improvements in conductivity,stability,and Faradaic efficiency,confirming BZY's pivotal role in green hydrogen production and power-to-chemicals applications.By integrating insights across materials chemistry,electrochemistry,and engineering,this review provides a comprehensive roadmap for researchers aiming to translate laboratory breakthroughs into robust,scalable protonic ceramic technologies for decarbonized energy systems.
基金support from the Beijing Natural Science Foundation(No.2252055)National Natural Science Foundation of China(Nos.52072033 and 52271234)+1 种基金the State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2024010)BIT Research and Innovation Promoting Project(Grant Nos.2024YCXY040,GIIP2023-34).
文摘Solid-state sodium metal batteries(SSMBs)have garnered significant attention for their high energy density and intrinsic safety,however,the sluggish kinetic and dendrite growth caused by solid-solid interfacial failure have severely constrained their practical applications.Understanding the structure-function relationships underlying the interfacial failure is therefore critical for guiding the design and modification of solid electrolytes.This work systematically investigates the electrochemical-mechanical synergistic failure mechanisms of NASICON-type Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)ceramic electrolyte at its interfaces with anode and cathode.The analysis reveals that the sodium-rich interfacial phase,formed from the reaction between NZSP and sodium metal,accelerates the pore formation and dendrite growth at the interface.Simultaneously,the decomposition products layer of the liquid electrolyte at the cathode/ceramic electrolyte interface significantly increases the resistance for sodium-ion transportation.Together,these factors contribute to the degradation of battery performance.The above findings not only make up for the lack of knowledge on the mechano-electrochemical correlation of interface failure in existing studies,but also provide a principle of cross-scale regulation for the design of long-life and high-performance NZSP-based SSMBs.
