In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely us...In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.展开更多
High-voltage(>4.0 V)lithium metal battery(LBM)is considered to be one of the most promising candidates for next-generation high-energy batteries.However,the commercial carbonate electrolyte delivers a poor compatib...High-voltage(>4.0 V)lithium metal battery(LBM)is considered to be one of the most promising candidates for next-generation high-energy batteries.However,the commercial carbonate electrolyte delivers a poor compatibility with Li metal anode,and its organic dominated solid electrolyte interphase(SEI)shows a low interfacial energy and a slow Li^(+)diffusion ability.In this work,an inorganic LiF-Li_(3)N rich SEI is designed to enable high-voltage LBM by introducing nano-cubic LiF and LiNO_(3)into1 M LiPF_(6)ethylene carbonate(EC)/dimethyl carbonate(DMC)(v:v=1:1)electrolyte.Specifically,the unique nano-cubic structure of as-synthetized LiF particles achieves its high concentration dissolution in carbonate electrolyte to enhance the interfacial energy of SEI.In addition,tetramethylene sulfolane(TMS)is used as a carrier solvent to dissolve LiNO_(3)in the carbonate electrolyte,thereby deriving a Li_(3)N-rich SEI.As a result,the as-designed electrolyte shows a high average Li plating/striping CE of 98.3%after 100 cycles at 0.5 m A cm^(-2)/0.5 mA h cm^(-2).Furthermore,it also enables the ultrathin Li(~50μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM,4.4 mA h cm^(-2))full cell to deliver a high-capacity retention of 80.4%after 100 cycles with an outstanding average CE of 99.7%.Notably,the practical application prospect of the modified electrolyte is also estimated in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)‖Li pouch cell with an energy density of 261.2 W h kg^(-1).This work sheds light on the internal mechanism of Li^(+)transport within the inorganic dominated SEI and provides a simple approach to stabilize the high-voltage LMBs.展开更多
Lithium(Li)metal is considered as the candidate for the next generation of Li metal battery(LMB)anodes due to its high capacity and the lowest potential,which is expected to meet the requirements of energy storage dev...Lithium(Li)metal is considered as the candidate for the next generation of Li metal battery(LMB)anodes due to its high capacity and the lowest potential,which is expected to meet the requirements of energy storage devices.Unfortunately,the uncontrollable growth of Li dendrites during the charge/discharge process,as well as the resulting problems of poor cycling stability,low coulomb efficiency and safety risk,has restricted the commercialization of Li anode.Herein,an in-situ interfacial film containing three-dimensional(3D)rod-like micron-structure silver(Ag)is constructed on the surface of the Li metal.Due to the 3D rod-like micron-structure used to homogenize the distribution of current density,achieving uniform nucleation and growth of electrodeposited Li,the produced Li-Ag alloy was employed to restrain the formation of“dead”Li and the in-situ formed LiNO_(3) was utilized to facilitate the stability of solid-electrolyte interface(SEI)film,so the growth of dendritic Li is suppressed via the synergistic effect of structure and surface chemistry regulation.The obtained Li anode can achieve cycling stability at a high current density of 10 mA/cm^(2).This work considers multiaspect factors inducing uniform Li electrodeposition,and provides new insights for the commercialization of LMB.展开更多
Ni-rich layered oxides in lithium-ion batteries have problems with gas generation and electrochemical performance reduction due to residual lithium's reaction on the surface with the electrolyte.To address this is...Ni-rich layered oxides in lithium-ion batteries have problems with gas generation and electrochemical performance reduction due to residual lithium's reaction on the surface with the electrolyte.To address this issue,in this study,the Acid solvent evaporation(AsE)method has been proposed as a potential method to remove residual lithium while promoting the formation of a new LiNO_(3)-derived coating layer on the cathode surface.The reduction of residual lithium using the ASE method and the construction of a LiNO_(3)-derived coating layer suppresses gas evolution caused by the side effects of the electrolyte,improves electrochemical performance,and improves thermal stability by facilitating the smooth movement of lithium ions.Furthermore,the structural stability and resistance change due to the LiNO_(3)-derived coating layer effects is guaranteed through cycling and DCIR of the pouch cell.As a result,compared to Pristine,the capacity retention of coin cells increased by 8%after 100 cycles,and pouch cells increased by 25%after 160 cycles.In addition,after cycling the pouch cell,CO_(2) gas has significantly reduced by about 30%compared to Pristine using gas chromatography.The ASE method effectively forms a robust LiNO_(3)-derived coating layer on the cathode active material,which helps minimize electrolyte reactivity,suppress ,CO_(2) emissions,enhance surface structure stability,improve thermal stability,and improveoverallbatteryperformance.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
Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n（LiClO4）∶n（LiNO3）∶n（LiBr）=1.6∶3.8∶1.0 was prepared. The poly（lithium acrylate-acrylonitrile）/LiClO4-...Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n（LiClO4）∶n（LiNO3）∶n（LiBr）=1.6∶3.8∶1.0 was prepared. The poly（lithium acrylate-acrylonitrile）/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly（lithium acrylate-acrylonitrile） and （LiClO4-LiNO3-LiBr） eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly（lithium acrylate-acrylonitrile）/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly（lithium acrylate-acrylonitrile） of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly（lithium acrylate-acrylonitrile） can suppress the crystallization of eutectic salts in this system.展开更多
The α-Al_2O_3 platelets were prepared via solid-state reactions and the effect of the amount of lithium nitrate additive on the property of the platelets was investigated. The ICP results indicated that the high temp...The α-Al_2O_3 platelets were prepared via solid-state reactions and the effect of the amount of lithium nitrate additive on the property of the platelets was investigated. The ICP results indicated that the high temperature calcination process resulted in a large loss of lithium species because of volatilization, but there was still a small amount of residual lithium species in the α-Al_2O_3 platelets. The SEM micrographs showed that lithium nitrate led to decrease in the thickness of α-Al_2O_3 platelets and irregular morphology of aggregates. Pore structures results exhibited that addition of lithium nitrate led to decrease in the pore size and increase in the specific surface area of aggregates of α-Al_2O_3 platelets. The XRD and IR patterns suggested that the residual lithium and aluminum oxide formed LiAl_5O_8. The existence of LiAl_5O_8 was the basic reason for the changed performance of α-Al_2O_3 platelets.展开更多
基金partially supported by grants from the National Natural Science Foundation of China (52072099, 52102228)Team program of the Natural Science Foundation of Heilongjiang Province, China (TD2021E005)+1 种基金The National general entrepreneurial practice program (202210231088S)The National general innovation training program (202210231076)。
文摘In practical lithium-sulfur batteries(LSBs),the shuttle effect and Li cycling coulombic efficiency(CE) are strongly affected by the physicochemical properties of solid electrolyte interphase(SEI).LiNO_(3) is widely used as an additive in electrolytes to build a high-quality SEI,but its self-sacrificial nature limits the ability to mitigate the shuttle effect and stabilize Li anode during long-term cycling.To counteract LiNO_(3) consumption during long-term cycling without using a high initial concentration,inspired by sustainedrelease drugs,we encapsulated LiNO_(3) in lithiated Nafion polymer and added an electrolyte co-solvent(1,1,2,2-tetrafluoroethylene 2,2,2-trifluoromethyl ether) with poor LiNO_(3) solubility to construct highquality and durable F-and N-rich SEI.Theoretical calculations,experiments,multiphysics simulations,and in-situ observations confirmed that the F-and N-rich SEI can modulate lithium deposition behavior and allow persistent repair of SEI during prolonged cycling.Hence,the F-and N-rich SEI improves the Li anode cycling CE to 99.63% and alleviates the shuttle effect during long-term cycling.The lithium anode with sustainable F-and N-rich SEI shows a stable Li plating/stripping over 2000 h at 1 mA cm^(-2).As expected,Li‖S full cells with this SEI achieved a long lifespan of 250 cycles,far exceeding cells with a routine SEI.The Li‖S pouch cell based on F-and N-rich SEI also can achieve a high energy density of about300 Wh kg^(-1) at initial cycles.This strategy provides a novel design for high-quality and durable SEls in LSBs and may also be extendable to other alkali metal batteries.
基金supported by the Natural Science Foundation of Henan Province(No.202300410163)the Innovative Research Team(in Science and Technology)in University of Henan Province(No.20IRTSTHN016)+1 种基金the Outstanding Talent Introduction Project of University of Electronic Science and Technology of China(No.08JC00303)the Innovative Research Team of Sichuan Fuhua New Energy High-Tech Co.,Ltd.(No.621006)。
文摘High-voltage(>4.0 V)lithium metal battery(LBM)is considered to be one of the most promising candidates for next-generation high-energy batteries.However,the commercial carbonate electrolyte delivers a poor compatibility with Li metal anode,and its organic dominated solid electrolyte interphase(SEI)shows a low interfacial energy and a slow Li^(+)diffusion ability.In this work,an inorganic LiF-Li_(3)N rich SEI is designed to enable high-voltage LBM by introducing nano-cubic LiF and LiNO_(3)into1 M LiPF_(6)ethylene carbonate(EC)/dimethyl carbonate(DMC)(v:v=1:1)electrolyte.Specifically,the unique nano-cubic structure of as-synthetized LiF particles achieves its high concentration dissolution in carbonate electrolyte to enhance the interfacial energy of SEI.In addition,tetramethylene sulfolane(TMS)is used as a carrier solvent to dissolve LiNO_(3)in the carbonate electrolyte,thereby deriving a Li_(3)N-rich SEI.As a result,the as-designed electrolyte shows a high average Li plating/striping CE of 98.3%after 100 cycles at 0.5 m A cm^(-2)/0.5 mA h cm^(-2).Furthermore,it also enables the ultrathin Li(~50μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM,4.4 mA h cm^(-2))full cell to deliver a high-capacity retention of 80.4%after 100 cycles with an outstanding average CE of 99.7%.Notably,the practical application prospect of the modified electrolyte is also estimated in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)‖Li pouch cell with an energy density of 261.2 W h kg^(-1).This work sheds light on the internal mechanism of Li^(+)transport within the inorganic dominated SEI and provides a simple approach to stabilize the high-voltage LMBs.
基金Projects(51974256,51804259)supported by the National Natural Science Foundation of ChinaProject(2019ZDLGY04-05)supported by the Key R&D Program of Shaanxi,China+6 种基金Projects(2019JLZ-01,2019JLM-29,2020JQ-189)supported by the Natural Science Foundation of Shaanxi,ChinaProject(2019JC-12)supported by the Outstanding Young Scholars of Shaanxi,ChinaProject(2019-TS-06)supported by the Research Fund of the State Key Laboratory of Solidification Processing(NPU),ChinaProjects(19GH020302,3102019JC005)supported by the Fundamental Research Funds for the Central Universities,ChinaProject(2018M641015)supported by the China Postdoctoral Science FoundationProject(BK20180191)supported by the Natural Science Foundation of Jiangsu,ChinaProject(CX202026)supported by the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University,China。
文摘Lithium(Li)metal is considered as the candidate for the next generation of Li metal battery(LMB)anodes due to its high capacity and the lowest potential,which is expected to meet the requirements of energy storage devices.Unfortunately,the uncontrollable growth of Li dendrites during the charge/discharge process,as well as the resulting problems of poor cycling stability,low coulomb efficiency and safety risk,has restricted the commercialization of Li anode.Herein,an in-situ interfacial film containing three-dimensional(3D)rod-like micron-structure silver(Ag)is constructed on the surface of the Li metal.Due to the 3D rod-like micron-structure used to homogenize the distribution of current density,achieving uniform nucleation and growth of electrodeposited Li,the produced Li-Ag alloy was employed to restrain the formation of“dead”Li and the in-situ formed LiNO_(3) was utilized to facilitate the stability of solid-electrolyte interface(SEI)film,so the growth of dendritic Li is suppressed via the synergistic effect of structure and surface chemistry regulation.The obtained Li anode can achieve cycling stability at a high current density of 10 mA/cm^(2).This work considers multiaspect factors inducing uniform Li electrodeposition,and provides new insights for the commercialization of LMB.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIP)(2021R1F1A1055946)SolarEdge Technologies Korea(GCU-202203070002)。
文摘Ni-rich layered oxides in lithium-ion batteries have problems with gas generation and electrochemical performance reduction due to residual lithium's reaction on the surface with the electrolyte.To address this issue,in this study,the Acid solvent evaporation(AsE)method has been proposed as a potential method to remove residual lithium while promoting the formation of a new LiNO_(3)-derived coating layer on the cathode surface.The reduction of residual lithium using the ASE method and the construction of a LiNO_(3)-derived coating layer suppresses gas evolution caused by the side effects of the electrolyte,improves electrochemical performance,and improves thermal stability by facilitating the smooth movement of lithium ions.Furthermore,the structural stability and resistance change due to the LiNO_(3)-derived coating layer effects is guaranteed through cycling and DCIR of the pouch cell.As a result,compared to Pristine,the capacity retention of coin cells increased by 8%after 100 cycles,and pouch cells increased by 25%after 160 cycles.In addition,after cycling the pouch cell,CO_(2) gas has significantly reduced by about 30%compared to Pristine using gas chromatography.The ASE method effectively forms a robust LiNO_(3)-derived coating layer on the cathode active material,which helps minimize electrolyte reactivity,suppress ,CO_(2) emissions,enhance surface structure stability,improve thermal stability,and improveoverallbatteryperformance.
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.
文摘Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n（LiClO4）∶n（LiNO3）∶n（LiBr）=1.6∶3.8∶1.0 was prepared. The poly（lithium acrylate-acrylonitrile）/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly（lithium acrylate-acrylonitrile） and （LiClO4-LiNO3-LiBr） eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly（lithium acrylate-acrylonitrile）/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly（lithium acrylate-acrylonitrile） of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly（lithium acrylate-acrylonitrile） can suppress the crystallization of eutectic salts in this system.
基金supported by the Technology Development (Commission) Project of SINOPEC Catalyst Co. Ltd. (Grant No. 14-05-01)
文摘The α-Al_2O_3 platelets were prepared via solid-state reactions and the effect of the amount of lithium nitrate additive on the property of the platelets was investigated. The ICP results indicated that the high temperature calcination process resulted in a large loss of lithium species because of volatilization, but there was still a small amount of residual lithium species in the α-Al_2O_3 platelets. The SEM micrographs showed that lithium nitrate led to decrease in the thickness of α-Al_2O_3 platelets and irregular morphology of aggregates. Pore structures results exhibited that addition of lithium nitrate led to decrease in the pore size and increase in the specific surface area of aggregates of α-Al_2O_3 platelets. The XRD and IR patterns suggested that the residual lithium and aluminum oxide formed LiAl_5O_8. The existence of LiAl_5O_8 was the basic reason for the changed performance of α-Al_2O_3 platelets.
