Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditio...Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.展开更多
Coal-derived hard carbon(HC)represents a promising anode material for sodium-ion batteries owing to its cost-effectiveness and high carbon yield.However,conventional carbonization induces excessive graphitization,yiel...Coal-derived hard carbon(HC)represents a promising anode material for sodium-ion batteries owing to its cost-effectiveness and high carbon yield.However,conventional carbonization induces excessive graphitization,yielding insufficient interlayer spacing(d_(002)<0.37 nm)and underdeveloped closed pores.Herein,we propose a dynamic crystallization control strategy through carbothermal shock treatment(1300°C,30 s)that decouples thermodynamic and kinetic constraints.This method precisely modulates graphite domain ordering kinetics,producing short-range ordered structures with expanded interlayer spacing(d_(002)=0.385 nm)and homogeneously distributed closed nanopores.Through combined in situ characterization and first-principles calculations,we elucidate a three-stage crystallization mechanism:(i)amorphous carbon transformation,(ii)open-pore collapse,and(iii)pseudo-graphitic ordering.The optimized HC achieves record performance with 88.6%initial Coulombic efficiency and 204 mA h g^(−1)plateau capacity,while its optimal interlayer spacing lowers Na+diffusion barriers to enable exceptional rate capability(221 mA h g^(−1)at 0.5C after 300 cycles).Practical pouch cells maintain 85%capacity retention after 100 cycles at−20°C and deliver 284 Wh kg^(−1)energy density.This work establishes a kinetic regulation paradigm for graphitization-prone precursors,advancing the rational design of high-performance HC anodes.展开更多
The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate elect...The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.展开更多
Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application,which leads to poor stability.In this work,we propose c-CoSe_(2...Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application,which leads to poor stability.In this work,we propose c-CoSe_(2)/o-CoSe_(2)as the oxygen electrode of lithium-oxygen batteries(LOBs)to improve its cycle stability.The heterogeneous interface inside c-CoSe_(2)/o-CoSe_(2)leads to an increase in the covalence bonds between Co and Se ions,which greatly enhances the robustness of the crystal lattice,thereby improving the stability of the catalyst.In addition,the strong interaction between the mixed phases is favorable for adjusting the electron density around the active sites and boosting oxygen electrode kinetics.Moreover,the epitaxial growth of o-CoSe_(2)on c-CoSe_(2)will cause abundant heterogeneous interfaces and slight lattice distortion along the interfaces,thereby providing sufficient catalytic reaction sites.The DFT calculation results show that the optimized adsorption of intermediates at the heterogeneous interface plays an important role in boosting oxygen electrode reactions and improving the electrochemical performance of LOBs.The experimental results show that LOBs with the c-CoSe_(2)/o-CoSe_(2)electrodes exhibit outstanding performance,including large specific capacity of about 23,878 m A h g^(-1),high coulombic efficiency of up to 93.66%,and excellent stability of over 176 cycles(1410 h).展开更多
Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes h...Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ZAB.Herein,the N-doped carbon cloth(NC)prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite growth.Results show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn^(2+)by boosting the desolvation process of Zn^(2+),eventually reducing the nucleation overpotential.Besides,theoretical calculation results confirm the zincophilicity of N-containing functional group(such as pyridine N and pyrrole N),which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn^(2+) in the vicinity of the surface and enhancing its interaction with zinc atoms.As a result,the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8%and long-term stability of over 500 cycles at 0.2 mA cm^(-2).And the Coulombic efficiency reached about 99.5%at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm^(-2).The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 mV.In addition,the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh g_(Zn)^(-1) and a long life of over 430 cycles.The effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn^(2+) presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.展开更多
Tin dioxide(SnO_(2))holds promise as an anode material for high-capacity sodium-ion storage.However,its practical use is hindered by low conductivity,sluggish Na^(+)kinetics,and drastic volume changes,leading to inade...Tin dioxide(SnO_(2))holds promise as an anode material for high-capacity sodium-ion storage.However,its practical use is hindered by low conductivity,sluggish Na^(+)kinetics,and drastic volume changes,leading to inadequate rate capability and cycling stability.Herein,we report the SnO_(2)/Zn_(2)SnO_(4)nanoparticles uniformly anchored on N-doped graphene nanosheets(SnO_(2)/ZTO@NGr)anode for sodium-ion batteries/hybrid capacitors(SIBs/SIHCs).A dynamic phase reconstruction during cycling where sodiation-generated Na_(15)Sn_(4)and NaZn_(13)alloys reversibly convert into amorphous SnO_(2)and crystalline ZTO upon desodiation,enabling isotropic Na^(+)diffusion through amorphous SnO_(2)while leveraging ZTO's low-energy diffusion pathways(0.37 eV barrier).Density functional theory confirms strong Na^(+)adsorption on SnO_(2),synergizing with fast ion mobility on ZTO to boost storage kinetics.The conductive NGr network can prevent nanoparticle aggregation and ensure rapid electron transport,thus contributing to excellent electrochemical performance.The SnO_(2)/ZTO@NGr anode yields exceptional cycling stability(279 mA h g^(-1)after 700 cycles at 2 A g^(-1))and high-rate capability(363 mA h g^(-1)at 5 A g^(-1))in SIBs.The assembled SnO_(2)/ZTO@NGr//AC(activated carbon)SIHCs deliver a high energy density of 122 Wh kg^(-1)at 200 W kg^(-1),establishing a new phase-complementary design paradigm coupled with conductive hybridization for advanced energy storage.展开更多
Silicon dioxide(SiO)is regarded as a promising anode candidate for high-energy-density lithium-ion batteries(LIBs)owing to its superior theoretical specific capacity.However,SiO anodes encounter substantial challenges...Silicon dioxide(SiO)is regarded as a promising anode candidate for high-energy-density lithium-ion batteries(LIBs)owing to its superior theoretical specific capacity.However,SiO anodes encounter substantial challenges,including substantial volume expansion and persistent growth of a thick solid electrolyte interphase(SEI).In this work,a composite conductive network with dual pinning and piezoelectric effects is proposed,which is cleverly designed to improve the electrochemical reaction kinetics of the electrode.Within the proposed network architecture,single-walled carbon nanotubes(CNTs)serve as fast electronic conductors and structural protective layers,forming a three-dimensional(3D)coating network on the surface of SiO particles.Barium titanate(BTO)nanoparticles are anchored at the nodes of the CNT network through the formation of rigid anchor points,dispersing stress throughout the network.Concurrently,mechanical stress induced by electrochemical reactions prompts BTO to generate a local electric field,facilitating Li^(+)transport.Consequently,the developed anode(SiO@PCB)demonstrates remarkable electrochemical performance in LIBs,exhibiting a capacity retention rate of 94%even after 500 cycles at 1 A g^(-1).Furthermore,a capacity retention of 71.6%is demonstrated by SiO@PCB anode after 1000 cycles at 5 C in sulfide-based all-solid-state LIBs using an NCM83 cathode.This composite conductive network structure provides an effective guidance plan for achieving interface stability and long-term lithium storage of Si-based anodes.展开更多
Lithium metal batteries(LMBs)are widely recognized as one of the most promising candidates for next-generation energy storage systems.However,their practical deployment is severely constrained by critical challenges s...Lithium metal batteries(LMBs)are widely recognized as one of the most promising candidates for next-generation energy storage systems.However,their practical deployment is severely constrained by critical challenges such as lithium dendrite formation and interfacial instability.Herein,we propose a lithiophobic dilution-induced solvation reconstruction(LDSR)strategy to address these issues.By incorporating a weakly coordinating and electrochemically stable diluent,pentafluorobenzyl ether(FBEN),into a conventional carbonate-based electrolyte,the interaction between lithium ions and solvent molecules is significantly weakened.This facilitates the incorporation of hexafluorophosphate anions into the primary solvation shell of Li^(+),resulting in the formation of an anion-dominated solvation structure consisting of contact ion pairs and ionic aggregates.Such a solvation environment promotes the in situ formation of a LiF-rich inorganic solid electrolyte interphase layer,thereby improving interfacial stability and enhancing ionic transport kinetics.Li||Li symmetric cells demonstrate over 650 h of stable cycling at 1 mA cm^(-2)with low overpotential.Furthermore,Li||NCM811 full cells retain 80%of their capacity after 400 cycles at 1C,and maintain 67%of their initial capacity after 300 cycles at 5C.The LDSR strategy offers a viable pathway toward stable Li metal anodes,advancing the development of next-generation LMBs.展开更多
Metallic lithium is deemed as the“Holy Grail”anode in high-energy-density secondary batteries.Uncontrollable lithium dendrite growth and related issues originated from uneven concentration distribution of Li+in the ...Metallic lithium is deemed as the“Holy Grail”anode in high-energy-density secondary batteries.Uncontrollable lithium dendrite growth and related issues originated from uneven concentration distribution of Li+in the vicinity of the anode,however,induce severe safety concerns and poor cycling efficiency,dragging lithium metal anode out of practical application.Herein we address these issues by using cross-linked lithiophilic amino phosphonic acid resin as the effective host with the ion-transportenhancement feature.Based on theoretical calculations and multiphysics simulation,it is found that this ion-transportenhancement feature is capable of facilitating the self-concentration kinetics of Li+and accelerating Li^(+)transfer at the electrolyte/electrode interface,leading to uniform bulk lithium deposition.Experimental results show that the proposed lithiumhosting resin decreases the irreversible lithium capacity and improves lithium utilization(with the Coulombic efficiency(CE)of 98.8%over 130 cycles).Our work demonstrates that inducing the self-concentrating distribution of Li+at the interface can be an effective strategy for improving the interfacial ion concentration gradient and optimizing lithium deposition,which opens a new avenue for the practical development of next-generation lithium metal batteries.展开更多
The implementation of a robust artificial solid electrolyte interphase(ASEI)to replace the unstable natural SEI can regulate lithium deposition behaviors and avoid the safety hazards caused by dendrites permeation in ...The implementation of a robust artificial solid electrolyte interphase(ASEI)to replace the unstable natural SEI can regulate lithium deposition behaviors and avoid the safety hazards caused by dendrites permeation in lithium metal batteries.Despite of devoted efforts in tailoring components of ASEI,the intrinsic mechanism of interfacial synergy within the heterogeneous interphases has not been well elucidated yet.Herein,we show that the lithium plating/striping behaviors can be substantially enhanced(over 900 h with an overpotential of less than 20 mV at 1 mA·cm^(−2)in Li|Li symmetric cells and 146 cycles in anode-free cells)by regulating the heterogeneous interphases.This favorable ASEI composed of LiF and Li_(3)N components can be in-situ generated during cycling by large-scale fabricated fluorinated boron nitride coatings.Further,the synergy of each heterogeneous component within ASEI was explored theoretically and experimentally.Li_(3)N has high adsorption energy and low ion diffusion barrier,which facilitates the transport of lithium ions and avoids its local accumulation to evolve into dendrites.Both the substrate and LiF are interfacially stable with high electron tunneling barriers,preventing the electrolyte decomposition and parasitic reactions.Finally,the high stiffness of the boron nitride also ensures lithium dendrites are suppressed once they grow,providing a stable environment for long-term cycling of lithium metal batteries.展开更多
Lithium-sulfur(Li-S)batteries have demonstrated the potential to conquer the energy storage related market due to the extremely high energy density.However,their performances at low temperature are still needed to be ...Lithium-sulfur(Li-S)batteries have demonstrated the potential to conquer the energy storage related market due to the extremely high energy density.However,their performances at low temperature are still needed to be improved to broaden their applications.Therefore,in this review,the basic failure mechanisms and major challenges of Li-S battery at low temperature are categorized as the high desolvation barrier of Li^(+),uncontrolled nucleation and deposition of lithium,polysulfides clustering,and passivation of cathode by film like Li_(2)S.Targeting these major issues,strategies,and advances concerning the design of optimized electrolyte,composite cathode and functional separator are highlighted and discussed.Finally,the suggestions are proposed for the future development of practical Li-S battery working at low temperature scenarios,hoping to accelerate the commercialization process and bring revolution to the energy storage market.展开更多
Recently,aqueous zinc ion batteries(AZIBs)have emerged as novel energy storage devices for their low cost,favorable safety and high theoretical capacity.However,layered ammonium vanadates,as promising cathode material...Recently,aqueous zinc ion batteries(AZIBs)have emerged as novel energy storage devices for their low cost,favorable safety and high theoretical capacity.However,layered ammonium vanadates,as promising cathode materials,suffer from slow Zn^(2+)diffusion kinetics due to the strong electrostatic interactions between Zn^(2+)and the[VOn]layer,irreversible deammoniation and poor conductivity.In this work,Ag^(+)intercalated NH_(4)V_(4)O_(10)(ANVO)was synthesized as a high-performance cathode for AZIBs.The pre-intercalated Ag^(+)interacts with the lattice oxygen to form strong Ag-O bonds,acting as“pillars”to stabilize the layered structure in electrochemical reactions.Moreover,the Ag0 generated in situ during the discharge process favors enhancement of the electronic conductivity of the material.The dual effects of Ag^(+)intercalation endow AVNO with high structural stability and fast electron/Zn^(2+)diffusion kinetics,leading to superior electrochemical performance.In particular,it exhibits an ultralong cycling life(with 95%capacity retention after 1000 cycles at 5 A g^(-1))as well as competitive rate performance(473.6 mA h g^(-1) at 0.2 A g^(-1) and 286.6 mA h g^(-1) at 10 A g^(-1)).This research provides valuable insights for designing high-capacity and long-life cathode materials.展开更多
基金supported by the Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology(LRMKF202405)the National Natural Science Foundation of China(52402226)the Sichuan Provincial Natural Science Foundation (2024NSFSC1016)
文摘Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.
基金supported by the Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology(LRMKF202405)the National Natural Science Foundation of China(52402226)the Natural Science Foundation of Sichuan Province(2024NSFSC1016).
文摘Coal-derived hard carbon(HC)represents a promising anode material for sodium-ion batteries owing to its cost-effectiveness and high carbon yield.However,conventional carbonization induces excessive graphitization,yielding insufficient interlayer spacing(d_(002)<0.37 nm)and underdeveloped closed pores.Herein,we propose a dynamic crystallization control strategy through carbothermal shock treatment(1300°C,30 s)that decouples thermodynamic and kinetic constraints.This method precisely modulates graphite domain ordering kinetics,producing short-range ordered structures with expanded interlayer spacing(d_(002)=0.385 nm)and homogeneously distributed closed nanopores.Through combined in situ characterization and first-principles calculations,we elucidate a three-stage crystallization mechanism:(i)amorphous carbon transformation,(ii)open-pore collapse,and(iii)pseudo-graphitic ordering.The optimized HC achieves record performance with 88.6%initial Coulombic efficiency and 204 mA h g^(−1)plateau capacity,while its optimal interlayer spacing lowers Na+diffusion barriers to enable exceptional rate capability(221 mA h g^(−1)at 0.5C after 300 cycles).Practical pouch cells maintain 85%capacity retention after 100 cycles at−20°C and deliver 284 Wh kg^(−1)energy density.This work establishes a kinetic regulation paradigm for graphitization-prone precursors,advancing the rational design of high-performance HC anodes.
基金supported by the Lithium Resources and Lithium Materials Key Laboratory of Sichuan Province(LRMKF202405)the National Natural Science Foundation of China(52402226)+3 种基金the Natural Science Foundation of Sichuan Province(2024NSFSC1016)the Scientific Research Startup Foundation of Chengdu University of Technology(10912-KYQD2023-10240)the opening funding from Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology)(KFM202507,Ministry of Education)the funding provided by the Alexander von Humboldt Foundation。
文摘The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.
基金financially supported by the National Natural Science Foundation of China(No.21905033)Department of Science and Technology of Sichuan Province(No.2019YJ0503)State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(No.2020P4FZG02A)。
文摘Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application,which leads to poor stability.In this work,we propose c-CoSe_(2)/o-CoSe_(2)as the oxygen electrode of lithium-oxygen batteries(LOBs)to improve its cycle stability.The heterogeneous interface inside c-CoSe_(2)/o-CoSe_(2)leads to an increase in the covalence bonds between Co and Se ions,which greatly enhances the robustness of the crystal lattice,thereby improving the stability of the catalyst.In addition,the strong interaction between the mixed phases is favorable for adjusting the electron density around the active sites and boosting oxygen electrode kinetics.Moreover,the epitaxial growth of o-CoSe_(2)on c-CoSe_(2)will cause abundant heterogeneous interfaces and slight lattice distortion along the interfaces,thereby providing sufficient catalytic reaction sites.The DFT calculation results show that the optimized adsorption of intermediates at the heterogeneous interface plays an important role in boosting oxygen electrode reactions and improving the electrochemical performance of LOBs.The experimental results show that LOBs with the c-CoSe_(2)/o-CoSe_(2)electrodes exhibit outstanding performance,including large specific capacity of about 23,878 m A h g^(-1),high coulombic efficiency of up to 93.66%,and excellent stability of over 176 cycles(1410 h).
基金supported by the National Natural Science Foundation of China(Grant No.21905033)the Science and Technology Department of Sichuan Province(Grant No.2019YJ0503)State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2020P4FZG02A).
文摘Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ZAB.Herein,the N-doped carbon cloth(NC)prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite growth.Results show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn^(2+)by boosting the desolvation process of Zn^(2+),eventually reducing the nucleation overpotential.Besides,theoretical calculation results confirm the zincophilicity of N-containing functional group(such as pyridine N and pyrrole N),which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn^(2+) in the vicinity of the surface and enhancing its interaction with zinc atoms.As a result,the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8%and long-term stability of over 500 cycles at 0.2 mA cm^(-2).And the Coulombic efficiency reached about 99.5%at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm^(-2).The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 mV.In addition,the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh g_(Zn)^(-1) and a long life of over 430 cycles.The effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn^(2+) presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.
基金National Natural Science Foundation of China(21903051,52402226)Key Research and Development Projects of Shaanxi Province(2023-YBGY-383)+2 种基金Three Qin Talents Special Support Program for Science and Technology Innovation Leading Talents(Z20240889)National Fund Cultivation Project of Xi'an University of Architecture and Technology(X20230034)Sichuan Provincial Natural Science Foundation(2024NSFSC1016)。
文摘Tin dioxide(SnO_(2))holds promise as an anode material for high-capacity sodium-ion storage.However,its practical use is hindered by low conductivity,sluggish Na^(+)kinetics,and drastic volume changes,leading to inadequate rate capability and cycling stability.Herein,we report the SnO_(2)/Zn_(2)SnO_(4)nanoparticles uniformly anchored on N-doped graphene nanosheets(SnO_(2)/ZTO@NGr)anode for sodium-ion batteries/hybrid capacitors(SIBs/SIHCs).A dynamic phase reconstruction during cycling where sodiation-generated Na_(15)Sn_(4)and NaZn_(13)alloys reversibly convert into amorphous SnO_(2)and crystalline ZTO upon desodiation,enabling isotropic Na^(+)diffusion through amorphous SnO_(2)while leveraging ZTO's low-energy diffusion pathways(0.37 eV barrier).Density functional theory confirms strong Na^(+)adsorption on SnO_(2),synergizing with fast ion mobility on ZTO to boost storage kinetics.The conductive NGr network can prevent nanoparticle aggregation and ensure rapid electron transport,thus contributing to excellent electrochemical performance.The SnO_(2)/ZTO@NGr anode yields exceptional cycling stability(279 mA h g^(-1)after 700 cycles at 2 A g^(-1))and high-rate capability(363 mA h g^(-1)at 5 A g^(-1))in SIBs.The assembled SnO_(2)/ZTO@NGr//AC(activated carbon)SIHCs deliver a high energy density of 122 Wh kg^(-1)at 200 W kg^(-1),establishing a new phase-complementary design paradigm coupled with conductive hybridization for advanced energy storage.
文摘Silicon dioxide(SiO)is regarded as a promising anode candidate for high-energy-density lithium-ion batteries(LIBs)owing to its superior theoretical specific capacity.However,SiO anodes encounter substantial challenges,including substantial volume expansion and persistent growth of a thick solid electrolyte interphase(SEI).In this work,a composite conductive network with dual pinning and piezoelectric effects is proposed,which is cleverly designed to improve the electrochemical reaction kinetics of the electrode.Within the proposed network architecture,single-walled carbon nanotubes(CNTs)serve as fast electronic conductors and structural protective layers,forming a three-dimensional(3D)coating network on the surface of SiO particles.Barium titanate(BTO)nanoparticles are anchored at the nodes of the CNT network through the formation of rigid anchor points,dispersing stress throughout the network.Concurrently,mechanical stress induced by electrochemical reactions prompts BTO to generate a local electric field,facilitating Li^(+)transport.Consequently,the developed anode(SiO@PCB)demonstrates remarkable electrochemical performance in LIBs,exhibiting a capacity retention rate of 94%even after 500 cycles at 1 A g^(-1).Furthermore,a capacity retention of 71.6%is demonstrated by SiO@PCB anode after 1000 cycles at 5 C in sulfide-based all-solid-state LIBs using an NCM83 cathode.This composite conductive network structure provides an effective guidance plan for achieving interface stability and long-term lithium storage of Si-based anodes.
基金the support from Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology (LRMKF202405), Chinathe National Natural Science Foundation of China (52402226), Chinathe Sichuan Provincial Natural Science Foundation (2024NSFSC1016), China
文摘Lithium metal batteries(LMBs)are widely recognized as one of the most promising candidates for next-generation energy storage systems.However,their practical deployment is severely constrained by critical challenges such as lithium dendrite formation and interfacial instability.Herein,we propose a lithiophobic dilution-induced solvation reconstruction(LDSR)strategy to address these issues.By incorporating a weakly coordinating and electrochemically stable diluent,pentafluorobenzyl ether(FBEN),into a conventional carbonate-based electrolyte,the interaction between lithium ions and solvent molecules is significantly weakened.This facilitates the incorporation of hexafluorophosphate anions into the primary solvation shell of Li^(+),resulting in the formation of an anion-dominated solvation structure consisting of contact ion pairs and ionic aggregates.Such a solvation environment promotes the in situ formation of a LiF-rich inorganic solid electrolyte interphase layer,thereby improving interfacial stability and enhancing ionic transport kinetics.Li||Li symmetric cells demonstrate over 650 h of stable cycling at 1 mA cm^(-2)with low overpotential.Furthermore,Li||NCM811 full cells retain 80%of their capacity after 400 cycles at 1C,and maintain 67%of their initial capacity after 300 cycles at 5C.The LDSR strategy offers a viable pathway toward stable Li metal anodes,advancing the development of next-generation LMBs.
基金This work was financially supported by the National Natural Science Foundation of China(No.21905033)the Science and Technology Department of Sichuan Province(No.2019YJ0503)The support from the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(No.2020P4FZG02A)is also appreciated.
文摘Metallic lithium is deemed as the“Holy Grail”anode in high-energy-density secondary batteries.Uncontrollable lithium dendrite growth and related issues originated from uneven concentration distribution of Li+in the vicinity of the anode,however,induce severe safety concerns and poor cycling efficiency,dragging lithium metal anode out of practical application.Herein we address these issues by using cross-linked lithiophilic amino phosphonic acid resin as the effective host with the ion-transportenhancement feature.Based on theoretical calculations and multiphysics simulation,it is found that this ion-transportenhancement feature is capable of facilitating the self-concentration kinetics of Li+and accelerating Li^(+)transfer at the electrolyte/electrode interface,leading to uniform bulk lithium deposition.Experimental results show that the proposed lithiumhosting resin decreases the irreversible lithium capacity and improves lithium utilization(with the Coulombic efficiency(CE)of 98.8%over 130 cycles).Our work demonstrates that inducing the self-concentrating distribution of Li+at the interface can be an effective strategy for improving the interfacial ion concentration gradient and optimizing lithium deposition,which opens a new avenue for the practical development of next-generation lithium metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.52003038 and 52192610)Startup funds of Yangtze Delta Region Institute(Huzhou),University of Electronic Science and Technology of China(No.U03210019).
文摘The implementation of a robust artificial solid electrolyte interphase(ASEI)to replace the unstable natural SEI can regulate lithium deposition behaviors and avoid the safety hazards caused by dendrites permeation in lithium metal batteries.Despite of devoted efforts in tailoring components of ASEI,the intrinsic mechanism of interfacial synergy within the heterogeneous interphases has not been well elucidated yet.Herein,we show that the lithium plating/striping behaviors can be substantially enhanced(over 900 h with an overpotential of less than 20 mV at 1 mA·cm^(−2)in Li|Li symmetric cells and 146 cycles in anode-free cells)by regulating the heterogeneous interphases.This favorable ASEI composed of LiF and Li_(3)N components can be in-situ generated during cycling by large-scale fabricated fluorinated boron nitride coatings.Further,the synergy of each heterogeneous component within ASEI was explored theoretically and experimentally.Li_(3)N has high adsorption energy and low ion diffusion barrier,which facilitates the transport of lithium ions and avoids its local accumulation to evolve into dendrites.Both the substrate and LiF are interfacially stable with high electron tunneling barriers,preventing the electrolyte decomposition and parasitic reactions.Finally,the high stiffness of the boron nitride also ensures lithium dendrites are suppressed once they grow,providing a stable environment for long-term cycling of lithium metal batteries.
基金the support from the National Natural Science Foundation of China(No.52003038)China Postdoctoral Science Foundation funded project(No.2022M710600)+1 种基金the China National Postdoctoral Program for Innovative Talents(No.BX20220053)the Doctoral Project of Xichang University(No.YBZ202221)。
文摘Lithium-sulfur(Li-S)batteries have demonstrated the potential to conquer the energy storage related market due to the extremely high energy density.However,their performances at low temperature are still needed to be improved to broaden their applications.Therefore,in this review,the basic failure mechanisms and major challenges of Li-S battery at low temperature are categorized as the high desolvation barrier of Li^(+),uncontrolled nucleation and deposition of lithium,polysulfides clustering,and passivation of cathode by film like Li_(2)S.Targeting these major issues,strategies,and advances concerning the design of optimized electrolyte,composite cathode and functional separator are highlighted and discussed.Finally,the suggestions are proposed for the future development of practical Li-S battery working at low temperature scenarios,hoping to accelerate the commercialization process and bring revolution to the energy storage market.
基金supported by the Natural Science Foundation of Sichuan Province(2022NSFSC1212).
文摘Recently,aqueous zinc ion batteries(AZIBs)have emerged as novel energy storage devices for their low cost,favorable safety and high theoretical capacity.However,layered ammonium vanadates,as promising cathode materials,suffer from slow Zn^(2+)diffusion kinetics due to the strong electrostatic interactions between Zn^(2+)and the[VOn]layer,irreversible deammoniation and poor conductivity.In this work,Ag^(+)intercalated NH_(4)V_(4)O_(10)(ANVO)was synthesized as a high-performance cathode for AZIBs.The pre-intercalated Ag^(+)interacts with the lattice oxygen to form strong Ag-O bonds,acting as“pillars”to stabilize the layered structure in electrochemical reactions.Moreover,the Ag0 generated in situ during the discharge process favors enhancement of the electronic conductivity of the material.The dual effects of Ag^(+)intercalation endow AVNO with high structural stability and fast electron/Zn^(2+)diffusion kinetics,leading to superior electrochemical performance.In particular,it exhibits an ultralong cycling life(with 95%capacity retention after 1000 cycles at 5 A g^(-1))as well as competitive rate performance(473.6 mA h g^(-1) at 0.2 A g^(-1) and 286.6 mA h g^(-1) at 10 A g^(-1)).This research provides valuable insights for designing high-capacity and long-life cathode materials.
