High-voltage lithium(Li)metal batteries(LMBs)face substantial challenges,including Li dendrite growth and instability in high-voltage cathodes such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811),which impede their practic...High-voltage lithium(Li)metal batteries(LMBs)face substantial challenges,including Li dendrite growth and instability in high-voltage cathodes such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811),which impede their practical applications and long-term stability.To address these challenges,tris(pentafluorophenyl)borane additive as an electron acceptor is introduced into an ethyl methyl carbonate/fluoroethylene carbonate-based electrolyte.This approach effectively engineers robust dual interfaces on the Li metal anode and the NCM811 cathode,thereby mitigating dendritic growth of Li and enhancing the stability of the cathode.This additive-driven strategy enables LMBs to operate at ultra-high voltages up to 4.7 V.Consequently,Li||Cu cells achieve a coulombic efficiency of 98.96%,and Li||Li symmetric cells extend their cycle life to an impressive 4000 h.Li||NCM811 full cells maintain a high capacity retention of 87.8%after 100 cycles at 4.7 V.Additionally,Li||LNMO full cells exhibit exceptional rate capability,delivering 132.2 mAh g^(-1)at 10 C and retaining 95.0%capacity after 250 cycles at 1 C and 5 V.As a result,NCM811||graphite pouch cells maintain a 93.4%capacity retention after 1100 cycles at 1 C.These findings underscore the efficacy of additive engineering in addressing Li dendrite formation and instability of cathode under high voltage,thereby paving the road for durable,high-performance LMBs.展开更多
Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact l...Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.展开更多
Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nano...Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable batteries.展开更多
基金financially supported by the Guangdong Major Project of Basic and Applied Basic Research(No.2023B0303000002)the Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)the High level of special funds(G03034K001)。
文摘High-voltage lithium(Li)metal batteries(LMBs)face substantial challenges,including Li dendrite growth and instability in high-voltage cathodes such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811),which impede their practical applications and long-term stability.To address these challenges,tris(pentafluorophenyl)borane additive as an electron acceptor is introduced into an ethyl methyl carbonate/fluoroethylene carbonate-based electrolyte.This approach effectively engineers robust dual interfaces on the Li metal anode and the NCM811 cathode,thereby mitigating dendritic growth of Li and enhancing the stability of the cathode.This additive-driven strategy enables LMBs to operate at ultra-high voltages up to 4.7 V.Consequently,Li||Cu cells achieve a coulombic efficiency of 98.96%,and Li||Li symmetric cells extend their cycle life to an impressive 4000 h.Li||NCM811 full cells maintain a high capacity retention of 87.8%after 100 cycles at 4.7 V.Additionally,Li||LNMO full cells exhibit exceptional rate capability,delivering 132.2 mAh g^(-1)at 10 C and retaining 95.0%capacity after 250 cycles at 1 C and 5 V.As a result,NCM811||graphite pouch cells maintain a 93.4%capacity retention after 1100 cycles at 1 C.These findings underscore the efficacy of additive engineering in addressing Li dendrite formation and instability of cathode under high voltage,thereby paving the road for durable,high-performance LMBs.
基金This work was financially supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)+1 种基金This work was also financially supported by the Shenzhen Science and Technology Innovation Commission(GJHZ20200731095606021,20200925155544005)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083)。
文摘Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
基金supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001).
文摘Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable batteries.
