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
Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conv...Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.展开更多
Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synth...Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.展开更多
Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the de...Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.展开更多
Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid e...Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.展开更多
Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stabil...Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.展开更多
The realization of a stable lithium-metal free(LiMF)sulfur battery based on amorphous carbon anode and lithium sulfide(Li_(2)S)cathode is here reported.In particular,a biomass waste originating full-cell combining a c...The realization of a stable lithium-metal free(LiMF)sulfur battery based on amorphous carbon anode and lithium sulfide(Li_(2)S)cathode is here reported.In particular,a biomass waste originating full-cell combining a carbonized brewer's spent grain(CBSG)biochar anode with a Li_(2)S-graphene composite cathode(Li_(2)S70Gr30)is proposed.This design is particularly attractive for applying a cost-effective,high performance,environment friendly,and safe anode material,as an alternative to standard graphite and metallic lithium in emerging battery technologies.The anodic and cathodic materials are characterized in terms of structure,morphology and composition through X-ray diffraction,scanning and transmission electron microscopy,X-ray photoelectron and Raman spectroscopies.Furthermore,an electrochemical characterization comprising galvanostatic cycling,rate capability and cyclic voltammetry tests were carried out both in half-cell and full-cell configurations.The systematic investigation reveals that unlike graphite,the biochar electrode displays good compatibility with the electrolyte typically employed in sulfur batteries.The CBSG/Li_(2)S70Gr30 full-cell demonstrates an initial charge and discharge capacities of 726 and 537 mAh g^(-1),respectively,at 0.05C with a coulombic efficiency of 74%.Moreover,it discloses a reversible capacity of 330 mAh g^(-1)(0.1 C)after over 300 cycles.Based on these achievements,the CBSG/Li_(2)S70Gr30 battery system can be considered as a promising energy storage solution for electric vehicles(EVs),especially when taking into account its easy scalability to an industrial level.展开更多
Heterostructure engineering combined with carbonaceous materials shows great promise toward promoting sluggish kinetics,improving electronic conductivity,and mitigating the huge expansion of transition metal sulfide e...Heterostructure engineering combined with carbonaceous materials shows great promise toward promoting sluggish kinetics,improving electronic conductivity,and mitigating the huge expansion of transition metal sulfide electrodes for high-performance sodium storage.Herein,the iron sulfide-based heterostructures in situ hybridized with nitrogen-doped carbon nanotubes(Fe_(7)S_(8)/FeS_(2)/NCNT)have been prepared through a successive pyrolysis and sulfidation approach.The Fe_(7)S_(8)/FeS_(2)/NCNT heterostructure delivered a high reversible capacity of 403.2 mAh g^(−1) up to 100 cycles at 1.0 A g^(−1) and superior rate capability(273.4 mAh g^(−1) at 20.0 A g^(−1))in ester-based electrolyte.Meanwhile,the electrodes also demonstrated long-term cycling stability(466.7 mAh g^(−1) after 1,000 cycles at 5.0 A g^(−1))and outstanding rate capability(536.5 mAh g^(−1) at 20.0 A g^(−1))in ether-based electrolyte.This outstanding performance could be mainly attributed to the fast sodium-ion diffusion kinetics,high capacitive contribution,and convenient interfacial dynamics in ether-based electrolyte.展开更多
As one of the promising anode materials,iron selenide has received much attention for potassium-ion batteries(KIBs).Nevertheless,volume expansion and sluggish kinetics of iron selenide result in the poor reversibility...As one of the promising anode materials,iron selenide has received much attention for potassium-ion batteries(KIBs).Nevertheless,volume expansion and sluggish kinetics of iron selenide result in the poor reversibility and stability during potassiation–depotassiation process.In this work,we develop iron selenide composite matching ether-based electrolyte for KIBs,which presents a reversible specific capacity of 356 mAh g^(−1) at 200 mA g^(−1) after 75 cycles.According to the measurement of mechanical properties,it is found that iron selenide composite also exhibits robust and elastic solid electrolyte interphase layer in ether-based electrolyte,contributing to the improvement in reversibility and stability for KIBs.To further investigate the electrochemical enhancement mechanism of ether-based electrolyte in KIBs,we also utilize in situ visualization technique to monitor the potassiation–depotassiation process.For comparison,iron selenide composite matching carbonate-based electrolyte presents vast morphology change during potassiation–depotassiation process.When changing to ether-based electrolyte,a few minor morphology changes can be observed.This phenomenon indicates an occurrence of homogeneous electrochemical reaction in ether-based electrolyte,which results in a stable performance for potassium-ion(K-ion)storage.We believe that our work will provide a new perspective to visually monitor the potassium-ion storage process and guide the improvement in electrode material performance.展开更多
Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especial...Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especially with limited anode excess required in a working full cell.In this contribution,a mixed diisopropyl ether-based(mixed-DIPE) electrolyte was proposed to effectively protect lithium metal anode in Li-S batteries with sulfurized polyacrylonitrile(SPAN) cathodes.The mixed-DIPE electrolyte improves the compatibility to lithium metal and suppresses the dissolution of lithium polysulfides,rendering significantly improved cycling stability.Concretely,Li | Cu half-cells with the mixed-DIPE electrolyte cycled stably for 120 cycles,which is nearly five times longer than that with routine carbonate-based electrolyte.Moreover,the mixedDIPE electrolyte contributed to a doubled life span of 156 cycles at 0.5 C in Li | SPAN full cells with ultrathin 50 μm Li metal anodes compared with the routine electrolyte.This contribution affords an effective electrolyte formula for Li metal anode protection and is expected to propel the practical applications of high-energy-density Li-S batteries.展开更多
Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porou...Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porous evolution of microsized Bi during the charge/discharge process is still mysterious.Herein,various electrolytes are employed to disclose the origin of porous evolution of microsized Bi in PIBs.Experimentally and theoretically,the 3D porous network originates from the uniform interfacial charge distribution on the Bi surface in the linear ether-based electrolyte.In addition,the universality of the interfacial charge distribution mechanism was verified by microsized Sn and Sb.The in-situ constructed 3D porous network of Bi enables a superior potassium storage performance in a wide temperature range from-40 to 40℃.More importantly,the K_(0.9)Mn_(0.7)Ni_(0.3)O_(2)||Bi full cell delivers excellent cycling stability(a high capacity retention of 88.44%even after 2,000 cycles)and good temperature tolerance.This work gives a distinct clarification of the origin of the porous evolution of microsized Bi during cycling,which is critical for developing high-performance PIBs.展开更多
A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-...A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-tion so far has been largely constrained to primary batteries.Here,we demonstrate that one of the major limiting factors preventing the stable cycling of Li-MnO_(2)batteries,Mn dissolution,can be effectively mitigated by employing a common ether electrolyte,1 mol/L lithium bis(trifluorometha-nesulfonyl)imide(LiTFSI)in 1,3-dioxane(DOL)/1,2-dimethoxyethane(DME).We discover that the suppression of this dissolution enables highly reversible cycling of the MnO_(2)cathode regardless of the synthesized phase and morphology.Moreover,we find that both the LiPF_(6)salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges.The ether electrolyte,paired with MnO_(2)cathodes is able to demonstrate stable cycling performance at various rates,even at elevated temperature such as 60℃.Our discovery not only represents a defining step in Li-MnO_(2)batteries with extended life but provides design criteria of electrolytes for vast manganese-based cathodes in rechargeable batteries.展开更多
Sodium-ion batteries(SIBs) have been considered as promising candidates for large-scale energy storage, owing to the high abundance and low cost of sodium(Na) resources. However, the development of full SIB has been h...Sodium-ion batteries(SIBs) have been considered as promising candidates for large-scale energy storage, owing to the high abundance and low cost of sodium(Na) resources. However, the development of full SIB has been hindered by low energy density because of the sluggish kinetics of large Na^+. Here, we report a full SIB with commercial tin(Sn) anode, cross-linked Na_3V_2(PO_4)_3/carbon nanotubes composites(NVP-CNT) cathode, and ether-based electrolyte. Sn is capable of delivering high reversible capacity via formation of Na15 Sn4 and stable solid-electrolyte interface(SEI) in initial cycles. Meanwhile, the NASICON-type NVP enables ultrafast and stable Na^+intercalation/extraction, and the incorporation of CNT can improve its electrical conductivity. The assembled full SIB delivers high output voltage of ～3.2 V, high energy density of 253.4 W h kg^(-1) at1600 W kg^(-1) based on total mass of both cathode and anode, and remarkable capacity retention of 96.1% after 180 cycles. These merit construction of high-energy full SIBs and will promote the development of SIBs.展开更多
Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage ...Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage solely relies on the disordered region of the carbon materials in a carbonate-based electrolyte. The solvent co-intercalation mechanism for Na ions has been recently reported in natural graphite anodes for Na-ion batteries with ether-based electrolytes, but their capacities are still unsatisfactory. We show here for the first time that by combining regular Na ion storage in the disordered carbon layer and solvent co-intercalation mechanism in the graphitized layer of a commercial N330 carbon black as an anode material for Na-ion batteries in ether-based electrolyte, the reversible capacity could be fully realized and doubled in magnitude. This unique sodium intercalation process resulted in a significantly improved electrochemical performance for the N330 electrode with an initial reversible capacity of 234 mAh.g-1 at 50 mA.g-1 and a superior rate capability of 105 mAh.g-1 at 3,200 mA-g-1. When cycled at 3,200 mA.g-1 over 2,000 cycles, the electrode still exhibited a highly reversible capacity of 72 mAh.g-1 with a negligible capacity loss per cycle （0.0167%）. Additionally, surface-sensitive C K-edge X-ray absorption spectroscopy, with the assistance of electrochemical and physicochemical characterizations, helped in identifying the controlled formation and evolution of a thin and robust solid electrolyte interphase film. This film not only reduced the resistance for sodium ion diffusion, but also maintained the structural stability of the electrode for extended cycle reversibility. The superior electrochemical performance of N330 carbon black strongly demonstrated the potential of applying ether-based electrolytes for a wide range of carbon anodes apart from natural graphite.展开更多
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supported by the National Natural Science Foundation of China(No.21972049)。
文摘Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金supported by funding from the National Key Technologies R&D Program (2016YFB0901500)the NSFC (11234013 and 51421002)the One Hundred Talent Project of the Chinese Academy of Sciences
文摘Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.
基金the National Natural Science Foundation of China (21773055, U1604122, 22005085)。
文摘Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.
基金support from the National Key Research and Development Program of China(No.2022YFB2402200)National Natural Science Foundation of China(No.22109028)+1 种基金Natural Science Foundation of Shanghai(No.22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.19CG01).
文摘Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
基金financial support from the Natural Science Foundation of Hunan Province,China (No.2023JJ40759)the State Key Laboratory of Powder Metallurgy in Central South University,China。
文摘Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.
基金the Natural Science Foundation of China,grant no.32071317
文摘The realization of a stable lithium-metal free(LiMF)sulfur battery based on amorphous carbon anode and lithium sulfide(Li_(2)S)cathode is here reported.In particular,a biomass waste originating full-cell combining a carbonized brewer's spent grain(CBSG)biochar anode with a Li_(2)S-graphene composite cathode(Li_(2)S70Gr30)is proposed.This design is particularly attractive for applying a cost-effective,high performance,environment friendly,and safe anode material,as an alternative to standard graphite and metallic lithium in emerging battery technologies.The anodic and cathodic materials are characterized in terms of structure,morphology and composition through X-ray diffraction,scanning and transmission electron microscopy,X-ray photoelectron and Raman spectroscopies.Furthermore,an electrochemical characterization comprising galvanostatic cycling,rate capability and cyclic voltammetry tests were carried out both in half-cell and full-cell configurations.The systematic investigation reveals that unlike graphite,the biochar electrode displays good compatibility with the electrolyte typically employed in sulfur batteries.The CBSG/Li_(2)S70Gr30 full-cell demonstrates an initial charge and discharge capacities of 726 and 537 mAh g^(-1),respectively,at 0.05C with a coulombic efficiency of 74%.Moreover,it discloses a reversible capacity of 330 mAh g^(-1)(0.1 C)after over 300 cycles.Based on these achievements,the CBSG/Li_(2)S70Gr30 battery system can be considered as a promising energy storage solution for electric vehicles(EVs),especially when taking into account its easy scalability to an industrial level.
基金support by the National Natural Science Foundation of China(G.No.22102141).
文摘Heterostructure engineering combined with carbonaceous materials shows great promise toward promoting sluggish kinetics,improving electronic conductivity,and mitigating the huge expansion of transition metal sulfide electrodes for high-performance sodium storage.Herein,the iron sulfide-based heterostructures in situ hybridized with nitrogen-doped carbon nanotubes(Fe_(7)S_(8)/FeS_(2)/NCNT)have been prepared through a successive pyrolysis and sulfidation approach.The Fe_(7)S_(8)/FeS_(2)/NCNT heterostructure delivered a high reversible capacity of 403.2 mAh g^(−1) up to 100 cycles at 1.0 A g^(−1) and superior rate capability(273.4 mAh g^(−1) at 20.0 A g^(−1))in ester-based electrolyte.Meanwhile,the electrodes also demonstrated long-term cycling stability(466.7 mAh g^(−1) after 1,000 cycles at 5.0 A g^(−1))and outstanding rate capability(536.5 mAh g^(−1) at 20.0 A g^(−1))in ether-based electrolyte.This outstanding performance could be mainly attributed to the fast sodium-ion diffusion kinetics,high capacitive contribution,and convenient interfacial dynamics in ether-based electrolyte.
基金The authors thank the financial supports from the National Natural Science Foundation of China(51772135)the Fundamental Research Funds for the Central Universities(11619103,21621406)+1 种基金the Science and Technology Program of Guangzhou,China(202102020737,201605030008)the Shenzhen Science and Technology Program(JCYJ20200109113606007).We also thank Prof.Weiguang Xie and Dr.Haojie Lai for the measurement of AFM.
文摘As one of the promising anode materials,iron selenide has received much attention for potassium-ion batteries(KIBs).Nevertheless,volume expansion and sluggish kinetics of iron selenide result in the poor reversibility and stability during potassiation–depotassiation process.In this work,we develop iron selenide composite matching ether-based electrolyte for KIBs,which presents a reversible specific capacity of 356 mAh g^(−1) at 200 mA g^(−1) after 75 cycles.According to the measurement of mechanical properties,it is found that iron selenide composite also exhibits robust and elastic solid electrolyte interphase layer in ether-based electrolyte,contributing to the improvement in reversibility and stability for KIBs.To further investigate the electrochemical enhancement mechanism of ether-based electrolyte in KIBs,we also utilize in situ visualization technique to monitor the potassiation–depotassiation process.For comparison,iron selenide composite matching carbonate-based electrolyte presents vast morphology change during potassiation–depotassiation process.When changing to ether-based electrolyte,a few minor morphology changes can be observed.This phenomenon indicates an occurrence of homogeneous electrochemical reaction in ether-based electrolyte,which results in a stable performance for potassium-ion(K-ion)storage.We believe that our work will provide a new perspective to visually monitor the potassium-ion storage process and guide the improvement in electrode material performance.
基金supported by National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)National Natural Science Foundation of China(21776019,21825501,and U1801257)the Tsinghua University Initiative Scientific Research Program
文摘Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especially with limited anode excess required in a working full cell.In this contribution,a mixed diisopropyl ether-based(mixed-DIPE) electrolyte was proposed to effectively protect lithium metal anode in Li-S batteries with sulfurized polyacrylonitrile(SPAN) cathodes.The mixed-DIPE electrolyte improves the compatibility to lithium metal and suppresses the dissolution of lithium polysulfides,rendering significantly improved cycling stability.Concretely,Li | Cu half-cells with the mixed-DIPE electrolyte cycled stably for 120 cycles,which is nearly five times longer than that with routine carbonate-based electrolyte.Moreover,the mixedDIPE electrolyte contributed to a doubled life span of 156 cycles at 0.5 C in Li | SPAN full cells with ultrathin 50 μm Li metal anodes compared with the routine electrolyte.This contribution affords an effective electrolyte formula for Li metal anode protection and is expected to propel the practical applications of high-energy-density Li-S batteries.
基金supported by the National Natural Science Foundation of China(No.22005082,52202286)Natural Science Foundation of Hebei Province(No.B2020202065)+2 种基金the Special Project of Local Science and Technology Development Guided by the Central Government of China(226Z4402G)Science Research Project of Hebei Education Department(No.QN2020209,CXY2024036)Basic Research Project of Wenzhou City(G20220016)。
文摘Microsized bismuth(Bi)with in-situ constructed three-dimensional(3D)porous network has been considered as a promising anode for high-performance potassium-ion batteries(PIBs).However,the mechanism of the in-situ porous evolution of microsized Bi during the charge/discharge process is still mysterious.Herein,various electrolytes are employed to disclose the origin of porous evolution of microsized Bi in PIBs.Experimentally and theoretically,the 3D porous network originates from the uniform interfacial charge distribution on the Bi surface in the linear ether-based electrolyte.In addition,the universality of the interfacial charge distribution mechanism was verified by microsized Sn and Sb.The in-situ constructed 3D porous network of Bi enables a superior potassium storage performance in a wide temperature range from-40 to 40℃.More importantly,the K_(0.9)Mn_(0.7)Ni_(0.3)O_(2)||Bi full cell delivers excellent cycling stability(a high capacity retention of 88.44%even after 2,000 cycles)and good temperature tolerance.This work gives a distinct clarification of the origin of the porous evolution of microsized Bi during cycling,which is critical for developing high-performance PIBs.
基金supported by NSF through the UC San Diego Materials Research Science and Engineering Center(UCSD MRSEC)DMR-2011924Part of the work used the UCSD-MTI Battery Fabrication Facility and the UCSDArbin Battery Testing Facility.Electron microscopic characterization was performed at the San Diego Nanotechnology Infrastructure(SDNI)of UCSD,a member of the National Nanotechnology Coordinated Infrastructure,which is supported by the National Science Foundation(Grant No.ECCS-1542148)Use of the Stanford Synchrotron Radiation Light source,SLAC National Accelerator Laboratory,is supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under Contract No.DE-AC02-76SF00515.
文摘A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-tion so far has been largely constrained to primary batteries.Here,we demonstrate that one of the major limiting factors preventing the stable cycling of Li-MnO_(2)batteries,Mn dissolution,can be effectively mitigated by employing a common ether electrolyte,1 mol/L lithium bis(trifluorometha-nesulfonyl)imide(LiTFSI)in 1,3-dioxane(DOL)/1,2-dimethoxyethane(DME).We discover that the suppression of this dissolution enables highly reversible cycling of the MnO_(2)cathode regardless of the synthesized phase and morphology.Moreover,we find that both the LiPF_(6)salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges.The ether electrolyte,paired with MnO_(2)cathodes is able to demonstrate stable cycling performance at various rates,even at elevated temperature such as 60℃.Our discovery not only represents a defining step in Li-MnO_(2)batteries with extended life but provides design criteria of electrolytes for vast manganese-based cathodes in rechargeable batteries.
基金supported by the Ministry of Science and Technology of China(2017YFA0206700)the National Natural Science Foundation of China(21822506,51671107)
文摘Sodium-ion batteries(SIBs) have been considered as promising candidates for large-scale energy storage, owing to the high abundance and low cost of sodium(Na) resources. However, the development of full SIB has been hindered by low energy density because of the sluggish kinetics of large Na^+. Here, we report a full SIB with commercial tin(Sn) anode, cross-linked Na_3V_2(PO_4)_3/carbon nanotubes composites(NVP-CNT) cathode, and ether-based electrolyte. Sn is capable of delivering high reversible capacity via formation of Na15 Sn4 and stable solid-electrolyte interface(SEI) in initial cycles. Meanwhile, the NASICON-type NVP enables ultrafast and stable Na^+intercalation/extraction, and the incorporation of CNT can improve its electrical conductivity. The assembled full SIB delivers high output voltage of ～3.2 V, high energy density of 253.4 W h kg^(-1) at1600 W kg^(-1) based on total mass of both cathode and anode, and remarkable capacity retention of 96.1% after 180 cycles. These merit construction of high-energy full SIBs and will promote the development of SIBs.
文摘Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage solely relies on the disordered region of the carbon materials in a carbonate-based electrolyte. The solvent co-intercalation mechanism for Na ions has been recently reported in natural graphite anodes for Na-ion batteries with ether-based electrolytes, but their capacities are still unsatisfactory. We show here for the first time that by combining regular Na ion storage in the disordered carbon layer and solvent co-intercalation mechanism in the graphitized layer of a commercial N330 carbon black as an anode material for Na-ion batteries in ether-based electrolyte, the reversible capacity could be fully realized and doubled in magnitude. This unique sodium intercalation process resulted in a significantly improved electrochemical performance for the N330 electrode with an initial reversible capacity of 234 mAh.g-1 at 50 mA.g-1 and a superior rate capability of 105 mAh.g-1 at 3,200 mA-g-1. When cycled at 3,200 mA.g-1 over 2,000 cycles, the electrode still exhibited a highly reversible capacity of 72 mAh.g-1 with a negligible capacity loss per cycle （0.0167%）. Additionally, surface-sensitive C K-edge X-ray absorption spectroscopy, with the assistance of electrochemical and physicochemical characterizations, helped in identifying the controlled formation and evolution of a thin and robust solid electrolyte interphase film. This film not only reduced the resistance for sodium ion diffusion, but also maintained the structural stability of the electrode for extended cycle reversibility. The superior electrochemical performance of N330 carbon black strongly demonstrated the potential of applying ether-based electrolytes for a wide range of carbon anodes apart from natural graphite.
