High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.He...Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.Herein,a separator with multifunctional layers composed of N-doped mesoporous hollow carbon spheres(HCS)as the inner layer and sodium fluoride(NaF)as the outer layer on commercial polypropylene separator(PP)is proposed(PP@HCS-NaF)to achieve stable cycling in SMB.At the molecular level,the inner HCS layer with a high content of pyrrolic-N induces the uniform Na^(+)flux as a potential Na^(+)redistributor for homogenous deposition,whereas its hollow mesoporous structure offers nanoporous buffers and ion channels to regulate Na^(+)ion distribution and uniform deposition.The outer layer(NaF)constructs the NaF-enriched robust solid electrolyte interphase layer,significantly lowering the Na^(+)ions diffusion barrier.Benefiting from these merits,higher electrochemical performances are achieved with multifunctional double-layered PP@HCS-NaF separators compared with single-layered separators(i.e.PP@HCS or PP@NaF)in SMBs.The Na‖Cu half-cell with PP@HCS-NaF offers stable cycling(280 cycles)with a high CE(99.6%),and Na‖Na symmetric cells demonstrate extended lifespans for over 6000 h at 1 mA cm^(-2)with a progressively stable overpotential of 9 mV.Remarkably,in Na‖NVP full-cells,the PP@HCS-NaF separator grants a stable capacity of~81 mA h g^(-1)after 3500 cycles at 1 C and an impressive rate capability performance(~70 mA h g^(-1)at 15 C).展开更多
Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is ...Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.展开更多
Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the un...Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the uneven zinc deposition at the anode side caused by localized reaction activity from the passivation layer presents challenges that significantly impact the battery's stability and lifespan.In this study,we have proposed an expandable and maneuverable gel sustained-release(GSR)treatment to polish the Zn metal,which in situ converts its native passivation layer into a composite interphase layer with nanocrystal zinc phosphate and flexible polyvinyl alcohol.Such a thin and uniform interface contributes to fast and homogeneous Zn ion transport and improved anti-corrosion ability,enabling uniform zinc deposition without dendrite growth and thereby improving the battery performance with high-rate ability and long cycle life.This GSR treatment method,characterized by its simplicity,low cost,and universality,facilitates the widespread application of aqueous zinc batteries.展开更多
Rechargeable zinc-ion batteries have emerged as one of the most promising candidates for large-scale energy storage applications due to their high safety and low cost.However,the use of Zn metal in batteries suffers f...Rechargeable zinc-ion batteries have emerged as one of the most promising candidates for large-scale energy storage applications due to their high safety and low cost.However,the use of Zn metal in batteries suffers from many severe issues,including dendrite growth and parasitic reactions,which often lead to short cycle lives.Herein,we propose the construction of functional organic interfacial layers(OIL)on the Zn metal anodes to address these challenges.Through a well-designed organic-assist pre-construction process,a densely packed artificial layer featuring the immobilized zwitterionic molecular brush can be constructed,which can not only efficiently facilitate the smooth Zn plating and stripping,but also introduce a stable environment for battery reactions.Through density functional theory calculations and experimental characterizations,we verify that the immobilized organic propane sulfonate on Zn anodes can significantly lower the energy barrier and increase the kinetics of Zn^(2+)transport.Thus,the Zn metal anode with the functional OIL can significantly improve the cycle life of the symmetric cell to over 3500 h stable operation.When paired with the H_(2)V_(3)O_(8)cathode,the aqueous Zn-ion full cells can be continuously cycled over 7000 cycles,marking an important milestone for Zn anode development for potential industrial applications.展开更多
Gel polymer electrolytes(GPEs)with high flame‐retardant concentration can remarkably reduce the thermal runaway risk of lithium metal batteries(LMBs).However,higher flame‐retardant content in GPEs always leads to in...Gel polymer electrolytes(GPEs)with high flame‐retardant concentration can remarkably reduce the thermal runaway risk of lithium metal batteries(LMBs).However,higher flame‐retardant content in GPEs always leads to increased leakage of active component and severe lithium corrosion,which greatly hinders the service life of LMBs.Herein,GPEs with high‐loading triphenyl phosphate(TPP)are originally fabricated by coaxial electrospinning and stabilized by dual confinement effects,including chemisorption of polyvinylidene fluoride‐hexafluoropropylene(PVDF‐HFP),and physical encapsulation of polyacrylonitrile(PAN)/PVDF‐HFP.These effects arise from the strong polar interactions between the−CF3 group in PVDF‐HFP and P=O group in TPP,as well as the superior anti‐swelling property of PAN.To mitigate TPP‐induced corrosion during cycling,the optimized Li anode is armored with LiF‐rich solid electrolyte interphase(SEI)layer through immersing it in fluoroethylene carbonate‐containing electrolyte.As expected,the corresponding Li||Li symmetric cells deliver long‐term stable cycling behavior over 2400 h at 0.5 mA cm−2,and the LiFePO4||Li batteries hold a high‐capacity retention ratio of 81.7%after 6000 cycles at 10 C with excellent flame retardancy.These findings offer new insight into designing the SEI layer for lithium metal in flame‐retardant electrolytes,thus promoting the development and application of high‐security LMBs.展开更多
Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature ...Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.展开更多
Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dend...Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid ...Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.展开更多
Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the L...Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the Li-S battery has been plagued by the rapid failure of the Li anode due to the Li dendrite growth and severe parasitic reactions between Li and lithium polysulfides.The physicochemical properties of the solid-electrolyte interphase have a profound impact on the performance of the Li anode.Herein,a lithium polyacrylic acid/lithium nitrate(LPL)-protective layer is developed to inhibit the dendrite Li growth and parasitic reactions by tailoring the spatial distribution and content of LiN_(x)O_(y) and Li_(3)N at the SEI.The modified SEI is thoroughly investigated for compositions,ion transport properties,and Li plating/stripping kinetics.Consequently,the Li-S cell with a high S loading cathode(5.0 mg cm^(−2)),LPL layer-protected thin Li anode(50μm),and 40μL electrolyte shows a long life span of 120 cycles.This work evokes the avenue for regulating the spatial distribution of inorganic nitride at the SEI to suppress the formation of Li dendrites and parasitic reactions in Li-S batteries and perhaps guiding the design of analogous battery systems.展开更多
Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tr...Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tris(2,2,2-trifluoroethyl)phosphite(TTFP),which can control parasitic reactions such as the pulverization of SiO_(x)anode materials and electrolyte decomposition,has been proposed to improve the lifespan of the cell.The electrochemical reduction of TTFP results in solid-electrolyte interphase(SEI)layers that are mainly composed of LiF,which occur at a higher potential than the working potential of the SiO_(x)anode and carbonate-based solvents.The electrolyte with TTFP exhibited a substantial improvement in cycling retention after 100 cycles,whereas the standard electrolyte showed acutely decreased retention.The thickness of the SiO_(x)anode with TTFP also changed only slightly without any considerable delamination spots,whereas the SiO_(x)anode without TTFP was prominently deformed by an enormous volume expansion with several internal cracks.The cycled SiO_(x)anode with TTFP exhibited less increase in resistance after cycling than that in the absence of TTFP,in addition to fewer decomposition adducts in corresponding X-ray photoelectron spectroscopy(XPS)analyses between the cycled SiO_(x)anodes.These results demonstrate that TTFP formed SEI layers at the SiO_(x)interface,which substantially reduced the pulverization of the SiO_(x)anode materials;in addition,electrolyte decomposition at the interface decreased,which led to improved cycling retention.展开更多
Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and...Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.展开更多
The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electro...The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).展开更多
The lithium-ion batteries are recognized as the most promising energy storage system,but it still does not meet the power requirements of electric vehicle batteries owing to low volumetric energy density with the trad...The lithium-ion batteries are recognized as the most promising energy storage system,but it still does not meet the power requirements of electric vehicle batteries owing to low volumetric energy density with the traditional graphite electrode system.In this study,we report the development of a novel electrode system fabricated by implantation of a solid electrolyte interphase(SEI)layer on the graphite surface.The SEI-implanted graphite electrode is made using a lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)-based electrolyte and cycled with a lithium tetrafluoroborate LiBF4-based electrolyte.This new electrode system shows significantly enhanced electrochemical properties owing to the rapid and efficient diffusion of Li ions through the SEI layer between the electrolyte and electrode.This graphite electrode with its pre-formed SEI layer achieves a reversible capacity of 357 mAh g^-1 at 0.5 C after 50 cycles,which is significantly higher than that of commercial lithium-ion battery systems constructed with LiPF6(312mAh g^-1).The resulting unique electrode system could present a new avenue in SEI research for highperformance lithium-ion batteries.展开更多
Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs ...Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs suffer from an inherently finite Li reservoir and exhibit poor cycle stability,low Coulombic efficiency(CE)and severe dendrite growth.In this work,polydiallyl lithium disulfide(PDS-Li)was successfully synthesized and coated on Cu current collector by electrochemical polymerization.The PDS-Li acts as an additional lithium resource to compensate for the irreversible loss of lithium during cycling.In addition,the special structure and lithiophilicity of PDS-Li contribute to lower nucleation overpotential and uniform lithium deposition.When coupled with Li-rich manganese-based(LRM)cathode of Li1.2Mn0.54Ni0.13Co0.13O2,the anode-free full cell exhibits significantly improved cycle stability over 100 cycles and capacity retention of 63.3%and 57%after 80 and 100 cycles,respectively.We believe that PDS-Li can be used to ensure stable cycling performance and high-energy-density in AFLMBs.展开更多
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the National Natural Science Foundation of China(Grant Number 22350410379)Zhejiang Provincial Natural Science Foundation of China(LZ23B030003)+1 种基金the Fundamental Research Funds for the Central Universities(226-202400075)Ten Thousand Talent Program of Zhejiang Province.
文摘Separator modification is an effective approach to suppress dendrite growth to realize high-energy sodium metal batteries(SMBs)in practical applications,however,its success is mainly subject to surface modification.Herein,a separator with multifunctional layers composed of N-doped mesoporous hollow carbon spheres(HCS)as the inner layer and sodium fluoride(NaF)as the outer layer on commercial polypropylene separator(PP)is proposed(PP@HCS-NaF)to achieve stable cycling in SMB.At the molecular level,the inner HCS layer with a high content of pyrrolic-N induces the uniform Na^(+)flux as a potential Na^(+)redistributor for homogenous deposition,whereas its hollow mesoporous structure offers nanoporous buffers and ion channels to regulate Na^(+)ion distribution and uniform deposition.The outer layer(NaF)constructs the NaF-enriched robust solid electrolyte interphase layer,significantly lowering the Na^(+)ions diffusion barrier.Benefiting from these merits,higher electrochemical performances are achieved with multifunctional double-layered PP@HCS-NaF separators compared with single-layered separators(i.e.PP@HCS or PP@NaF)in SMBs.The Na‖Cu half-cell with PP@HCS-NaF offers stable cycling(280 cycles)with a high CE(99.6%),and Na‖Na symmetric cells demonstrate extended lifespans for over 6000 h at 1 mA cm^(-2)with a progressively stable overpotential of 9 mV.Remarkably,in Na‖NVP full-cells,the PP@HCS-NaF separator grants a stable capacity of~81 mA h g^(-1)after 3500 cycles at 1 C and an impressive rate capability performance(~70 mA h g^(-1)at 15 C).
基金financial support from National Natural Science Foundation of China(22271178,U2032131,21972103)International Cooperation Key Project of Science and Technology Department of Shaanxi,China(2022KWZ-06)+3 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(20210602)Research Project of Xi’an Science and Technology Bureau(2022GXFW0011)Science and Technology New Star in Shaanxi Province(2023KJXX-045)Shaanxi Provincial Department of Education Service Local Special Project,Industrialization Cultivation Project(23JC007)。
文摘Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.
基金supported by the National Key R&D Program of China(Grant 2022YFB2402200)National Natural Science Foundation of China(Grant 92372206,52271140,52171194)+2 种基金Jilin Province Science and Technology Development Plan Funding Project(Grant YDZJ202301-ZYTS545)National Natural Science Foundation of China Excellent Young Scientists(Overseas)Youth Innovation Promotion Association CAS(Grant 2020230)。
文摘Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the uneven zinc deposition at the anode side caused by localized reaction activity from the passivation layer presents challenges that significantly impact the battery's stability and lifespan.In this study,we have proposed an expandable and maneuverable gel sustained-release(GSR)treatment to polish the Zn metal,which in situ converts its native passivation layer into a composite interphase layer with nanocrystal zinc phosphate and flexible polyvinyl alcohol.Such a thin and uniform interface contributes to fast and homogeneous Zn ion transport and improved anti-corrosion ability,enabling uniform zinc deposition without dendrite growth and thereby improving the battery performance with high-rate ability and long cycle life.This GSR treatment method,characterized by its simplicity,low cost,and universality,facilitates the widespread application of aqueous zinc batteries.
基金supported by the Australian Research Council (FT180100705, DP230101579, DE240100868)CSIRO “International Hydrogen Research Collaboration ProgramRESEARCH FELLOWSHIPS”+2 种基金the National Natural Science Foundation of China (22209103)support from the “Joint International Laboratory on Environmental and Energy Frontier Materials”the “Innovation Research Team of High-Level Local Universities in Shanghai”
文摘Rechargeable zinc-ion batteries have emerged as one of the most promising candidates for large-scale energy storage applications due to their high safety and low cost.However,the use of Zn metal in batteries suffers from many severe issues,including dendrite growth and parasitic reactions,which often lead to short cycle lives.Herein,we propose the construction of functional organic interfacial layers(OIL)on the Zn metal anodes to address these challenges.Through a well-designed organic-assist pre-construction process,a densely packed artificial layer featuring the immobilized zwitterionic molecular brush can be constructed,which can not only efficiently facilitate the smooth Zn plating and stripping,but also introduce a stable environment for battery reactions.Through density functional theory calculations and experimental characterizations,we verify that the immobilized organic propane sulfonate on Zn anodes can significantly lower the energy barrier and increase the kinetics of Zn^(2+)transport.Thus,the Zn metal anode with the functional OIL can significantly improve the cycle life of the symmetric cell to over 3500 h stable operation.When paired with the H_(2)V_(3)O_(8)cathode,the aqueous Zn-ion full cells can be continuously cycled over 7000 cycles,marking an important milestone for Zn anode development for potential industrial applications.
基金supported by the National Natural Science Foundation of China (52404316, 52474325)the S&T program of Hebei Province(225A4404D)+3 种基金the Natural Science Foundation of Hainan Province (524RC475)the Collaborative Innovation Center of Marine Science and Technology of Hainan University (XTCX2022HYC14)the Xingtai City Natural Science Foundation (2023ZZ027)The Pico Electron Microscopy Center of Hainan University partially supported this study
文摘Gel polymer electrolytes(GPEs)with high flame‐retardant concentration can remarkably reduce the thermal runaway risk of lithium metal batteries(LMBs).However,higher flame‐retardant content in GPEs always leads to increased leakage of active component and severe lithium corrosion,which greatly hinders the service life of LMBs.Herein,GPEs with high‐loading triphenyl phosphate(TPP)are originally fabricated by coaxial electrospinning and stabilized by dual confinement effects,including chemisorption of polyvinylidene fluoride‐hexafluoropropylene(PVDF‐HFP),and physical encapsulation of polyacrylonitrile(PAN)/PVDF‐HFP.These effects arise from the strong polar interactions between the−CF3 group in PVDF‐HFP and P=O group in TPP,as well as the superior anti‐swelling property of PAN.To mitigate TPP‐induced corrosion during cycling,the optimized Li anode is armored with LiF‐rich solid electrolyte interphase(SEI)layer through immersing it in fluoroethylene carbonate‐containing electrolyte.As expected,the corresponding Li||Li symmetric cells deliver long‐term stable cycling behavior over 2400 h at 0.5 mA cm−2,and the LiFePO4||Li batteries hold a high‐capacity retention ratio of 81.7%after 6000 cycles at 10 C with excellent flame retardancy.These findings offer new insight into designing the SEI layer for lithium metal in flame‐retardant electrolytes,thus promoting the development and application of high‐security LMBs.
基金supported by National Key Research and Development Program(2016YFA0202500)the National Natural Science Foundation of China(21776019)Beijing Natural Science Foundation(L182021)。
文摘Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.
基金supported by the National Natural Science Foundation of China (No. 51861165101)。
文摘Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.51972198 and 62133007)the Natural Science Foundation of Shandong Province(ZR2020JQ19)the Taishan Scholars Program of Shandong Province(Nos.tsqn201812002 and ts20190908)。
文摘Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.
基金partially supported by grants from the National Natural Science Foundation of China(51772069 and 52072099).
文摘Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the Li-S battery has been plagued by the rapid failure of the Li anode due to the Li dendrite growth and severe parasitic reactions between Li and lithium polysulfides.The physicochemical properties of the solid-electrolyte interphase have a profound impact on the performance of the Li anode.Herein,a lithium polyacrylic acid/lithium nitrate(LPL)-protective layer is developed to inhibit the dendrite Li growth and parasitic reactions by tailoring the spatial distribution and content of LiN_(x)O_(y) and Li_(3)N at the SEI.The modified SEI is thoroughly investigated for compositions,ion transport properties,and Li plating/stripping kinetics.Consequently,the Li-S cell with a high S loading cathode(5.0 mg cm^(−2)),LPL layer-protected thin Li anode(50μm),and 40μL electrolyte shows a long life span of 120 cycles.This work evokes the avenue for regulating the spatial distribution of inorganic nitride at the SEI to suppress the formation of Li dendrites and parasitic reactions in Li-S batteries and perhaps guiding the design of analogous battery systems.
基金This work was financially supported by the National Research Foundation of Korea financially(NRF)(No.NRF-2022R1F1A1069039)the Core Research Institute(CRI)Program,the Basic Science Research Program through the National Research Foundation of Korea(NRF),Ministry of Education(No.NRF-2017R1A6A1A06015181)the Technology Innovation Program(No.20011905)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tris(2,2,2-trifluoroethyl)phosphite(TTFP),which can control parasitic reactions such as the pulverization of SiO_(x)anode materials and electrolyte decomposition,has been proposed to improve the lifespan of the cell.The electrochemical reduction of TTFP results in solid-electrolyte interphase(SEI)layers that are mainly composed of LiF,which occur at a higher potential than the working potential of the SiO_(x)anode and carbonate-based solvents.The electrolyte with TTFP exhibited a substantial improvement in cycling retention after 100 cycles,whereas the standard electrolyte showed acutely decreased retention.The thickness of the SiO_(x)anode with TTFP also changed only slightly without any considerable delamination spots,whereas the SiO_(x)anode without TTFP was prominently deformed by an enormous volume expansion with several internal cracks.The cycled SiO_(x)anode with TTFP exhibited less increase in resistance after cycling than that in the absence of TTFP,in addition to fewer decomposition adducts in corresponding X-ray photoelectron spectroscopy(XPS)analyses between the cycled SiO_(x)anodes.These results demonstrate that TTFP formed SEI layers at the SiO_(x)interface,which substantially reduced the pulverization of the SiO_(x)anode materials;in addition,electrolyte decomposition at the interface decreased,which led to improved cycling retention.
基金supported by the Jilin Province Science and Technology Department Program(YDZJ202201ZYTS304)the Science and Technology Project of Jilin Provincial Education Department(JJKH20220428KJ)+3 种基金the Jilin Province Science and Technology Department Program(YDZJ202101ZYTS047)the National Natural Science Foundation of China(21905110,21905041,22279045,22102020)the Special foundation of Jilin Province Industrial Technology Research and Development(2019C042)the Fundamental Research Funds for the Central Universities(2412020FZ008)。
文摘Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.
基金financially supported by the Natural Sciences and Engineering Research Council of Canada (NSERC),through the Discovery Grant Program (RGPIN-2018-06725)the Discovery Accelerator Supplement Grant program (RGPAS-2018-522651)+2 种基金the New Frontiers in Research Fund-Exploration program (NFRFE-2019-00488)supported by funding from the Canada First Research Excellence Fund as part of the University of Alberta’s Future Energy Systems research initiative (FES-T06-Q03)supported by the Chinese Scholarship Council (CSC)(Grant No. 202006450027).
文摘The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(NRF-2019R1A2C2088174)。
文摘The lithium-ion batteries are recognized as the most promising energy storage system,but it still does not meet the power requirements of electric vehicle batteries owing to low volumetric energy density with the traditional graphite electrode system.In this study,we report the development of a novel electrode system fabricated by implantation of a solid electrolyte interphase(SEI)layer on the graphite surface.The SEI-implanted graphite electrode is made using a lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)-based electrolyte and cycled with a lithium tetrafluoroborate LiBF4-based electrolyte.This new electrode system shows significantly enhanced electrochemical properties owing to the rapid and efficient diffusion of Li ions through the SEI layer between the electrolyte and electrode.This graphite electrode with its pre-formed SEI layer achieves a reversible capacity of 357 mAh g^-1 at 0.5 C after 50 cycles,which is significantly higher than that of commercial lithium-ion battery systems constructed with LiPF6(312mAh g^-1).The resulting unique electrode system could present a new avenue in SEI research for highperformance lithium-ion batteries.
基金financially supported by the National Natural Science Foundations of China(Nos.52071226,51872193 and U21A20332)the Natural Science Foundations of Jiangsu Province(Nos.BK20181168,BK20201171 and BK20220061)+2 种基金the Key R&D Project funded by Department of Science and Technology of Jiangsu Province(No.BE2020003-3)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.19KJA210004)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs suffer from an inherently finite Li reservoir and exhibit poor cycle stability,low Coulombic efficiency(CE)and severe dendrite growth.In this work,polydiallyl lithium disulfide(PDS-Li)was successfully synthesized and coated on Cu current collector by electrochemical polymerization.The PDS-Li acts as an additional lithium resource to compensate for the irreversible loss of lithium during cycling.In addition,the special structure and lithiophilicity of PDS-Li contribute to lower nucleation overpotential and uniform lithium deposition.When coupled with Li-rich manganese-based(LRM)cathode of Li1.2Mn0.54Ni0.13Co0.13O2,the anode-free full cell exhibits significantly improved cycle stability over 100 cycles and capacity retention of 63.3%and 57%after 80 and 100 cycles,respectively.We believe that PDS-Li can be used to ensure stable cycling performance and high-energy-density in AFLMBs.
