The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes h...The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes has become a stumbling block for achieving stable cycling in LMBs.In this work,a Li-containing polyethylene oxide(LPEO)was introduced between LAGP and electrodes as a buffer layer to regulate the interfacial compatibility and reduce interfacial impedance,inhibiting the side reactions.Moreover,ether-oxygen bond on LPEO chain can coordinate with Li+and guide the transportation of Li+,achieving fast Li+diffusion between Li1+xAlxGe2-x(PO4)3(LAGP)and electrodes.Specifically,the growth of lithium dendrites is effectively suppressed in LAGP with LPEO modification,which would lead to remarkable cycling stability and rate capability.Therefore,the Li|LPEO-LAGP|Li battery can cycle stably for more than 600 h at 0.1 mA cm−2.In addition,long-term performance of Li|LPEO-LAGP|LiFePO4(LFP)battery was achieved at a rate of 0.4 C,and capacity retention is more than 74%after 200 cycles.The Li|LPEO-LAGP|LiNi0.8Co0.1Mn0.1O2 also realized the steady operation in the voltage range of 2.8-4.3 V.展开更多
As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculati...As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.展开更多
实现水溶液锂电池的关键技术是如何保护金属锂电极不与水反应。提出了一种保护金属锂电极,其不仅在有机电解液体系稳定而且在水溶液中也可稳定工作,这种锂电极可以用于水体系锂电池。该研究制备了双层锂离子电解质保护的金属锂电极,其...实现水溶液锂电池的关键技术是如何保护金属锂电极不与水反应。提出了一种保护金属锂电极,其不仅在有机电解液体系稳定而且在水溶液中也可稳定工作,这种锂电极可以用于水体系锂电池。该研究制备了双层锂离子电解质保护的金属锂电极,其外层采用的LAGP(Li1+x+yAlxGe2-x SiyP3-yO12)玻璃陶瓷电解质相对于包括水溶液等电解液是稳定的,该玻璃陶瓷电解质的电导率达到0.57 mS cm-1。通过交流阻抗评估发现不同电解质间的界面阻抗是水体系锂电池内阻的主要来源。最终采用双层保护金属锂电极制备的水体系锂空气电池和锂水电池可以稳定工作。展开更多
Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composit...Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composite with the optimum concentration of 45 wt% LiTFSI and 75 wt% Li1.5Al0.5Ge1.5(PO4)3(LAGP,NASICON-type structure) exhibits a high ionic conductivity(σi=0.17 mS cm-1) at 30℃,a transference number of 0.30,and is stable up to 5.0 V.The composite electrolyte is a flexible and self-standing membrane.Solid-state LiFePO4//Li batteries with this composite electrolyte demonstrate excellent cycling stability with high discharge capacity of 157 mA h g-1,high capacity retention of 96% and coulombic efficiency of 98.5% after 130 cycles at 30℃ and 0.1 C rate.These electrochemical properties are better than other PCL-based allsolid-lithium batteries,and validate the concept of "polymer-in-ceramic" by avoiding the drawback of lower conductivity in prior "polymer-in-ceramic" electrolyte at high concentration of the ceramic.展开更多
A solid electrolyte of LAGP[Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)]contained 0.5 wt%Li F was prepared by using low-volatile raw materials.The effects of different heat treatment conditions(750–900°C,4–10 h)and ad...A solid electrolyte of LAGP[Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)]contained 0.5 wt%Li F was prepared by using low-volatile raw materials.The effects of different heat treatment conditions(750–900°C,4–10 h)and additive(Li F)on the ionic conductivity,structural morphology,and crystal transformation process were investigated in detail.EIS(electrochemical impedance spectroscopies)showed that the ionic conductivity of LAGP contained 0.5 wt%Li F had a highest value of 3.17×10^(-4)S cm^(-1)with low activation energy(0.31 e V)after treating 825°C for 6 h,more than LAGP of 2.45×10^(-4)S cm^(-1).DSC analysis and SEM images indicated that adding a small amount of Li F to LAGP not only can lower the glass transition temperature(from 513°C to507°C)and crystallization temperature(from 622°C to 605°C),but also can modify the grain boundary and increase the relative density of LAGP(from 95.8%to 97.7%).展开更多
Li1.5Al0.5Ge1.5(PO4)3(LAGP)is a solid-state electrolyte with high ionic conductivity and air stability but poor chemical stability and high interfacial impedance when directly contacted with Li metal.In this work,we d...Li1.5Al0.5Ge1.5(PO4)3(LAGP)is a solid-state electrolyte with high ionic conductivity and air stability but poor chemical stability and high interfacial impedance when directly contacted with Li metal.In this work,we develop an inorganic/polymer hybrid interlayer composed of Li bis(trifluoromethylsulfonyl)imide/poly(vinylene carbonate)polymer electrolyte and SiO2 submicrospheres to stabilize the Li/LAGP interface.The polymeric component renders high ionic conductance and low interfacial resistance,whereas the inorganic component imparts flame retardancy and a physical barrier to the known Li-LAGP side reaction,together enabling stable Li stripping/plating for more than 1,500 h at room temperature.With this interlayer at both electrodes,all-solid-state Li∥LiFePO4 full cells with stable cycling performance are also demonstrated.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52372188,51902090)Henan Key Research Project Plan for Higher Education Institutions(No.24A150019,23A150038)+5 种基金2023 Introduction of studying abroad talent program,“111 Project”(No.D17007)Henan Provincial Key Scientific Research Project of Colleges and Universities(No.23A150038)Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National Students,Platform for Innovation and Entrepreneurship Training Program(No.201910476010)the China Postdoctoral Science Foundation(No.2019 M652546)the Henan Province Postdoctoral Start-Up Foundation(No.1901017).
文摘The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes has become a stumbling block for achieving stable cycling in LMBs.In this work,a Li-containing polyethylene oxide(LPEO)was introduced between LAGP and electrodes as a buffer layer to regulate the interfacial compatibility and reduce interfacial impedance,inhibiting the side reactions.Moreover,ether-oxygen bond on LPEO chain can coordinate with Li+and guide the transportation of Li+,achieving fast Li+diffusion between Li1+xAlxGe2-x(PO4)3(LAGP)and electrodes.Specifically,the growth of lithium dendrites is effectively suppressed in LAGP with LPEO modification,which would lead to remarkable cycling stability and rate capability.Therefore,the Li|LPEO-LAGP|Li battery can cycle stably for more than 600 h at 0.1 mA cm−2.In addition,long-term performance of Li|LPEO-LAGP|LiFePO4(LFP)battery was achieved at a rate of 0.4 C,and capacity retention is more than 74%after 200 cycles.The Li|LPEO-LAGP|LiNi0.8Co0.1Mn0.1O2 also realized the steady operation in the voltage range of 2.8-4.3 V.
基金supported by the National Key Research and Development Program of China (Grant No. 2019YFA0705700)National Natural Science Foundation of China (Grant No. 11704019)+1 种基金the Hundreds of Talents Program of Sun Yat-sen Universitythe Fundamental Research Funds for the Central Universities。
文摘As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.
文摘实现水溶液锂电池的关键技术是如何保护金属锂电极不与水反应。提出了一种保护金属锂电极,其不仅在有机电解液体系稳定而且在水溶液中也可稳定工作,这种锂电极可以用于水体系锂电池。该研究制备了双层锂离子电解质保护的金属锂电极,其外层采用的LAGP(Li1+x+yAlxGe2-x SiyP3-yO12)玻璃陶瓷电解质相对于包括水溶液等电解液是稳定的,该玻璃陶瓷电解质的电导率达到0.57 mS cm-1。通过交流阻抗评估发现不同电解质间的界面阻抗是水体系锂电池内阻的主要来源。最终采用双层保护金属锂电极制备的水体系锂空气电池和锂水电池可以稳定工作。
基金supported by the National Key R&D Program of China (2016YFB0100500)Special fund of key technology research and development projects (20180201097GX) (20180201099GX) (20180201096GX) (20190302130GX)+1 种基金Jilin province science and technology department. The R&D Program of power batteries with low temperature and high energy, Science and Technology Bureau of Changchun (19SS013)Key Subject Construction of Physical Chemistry of Northeast Normal University。
文摘Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composite with the optimum concentration of 45 wt% LiTFSI and 75 wt% Li1.5Al0.5Ge1.5(PO4)3(LAGP,NASICON-type structure) exhibits a high ionic conductivity(σi=0.17 mS cm-1) at 30℃,a transference number of 0.30,and is stable up to 5.0 V.The composite electrolyte is a flexible and self-standing membrane.Solid-state LiFePO4//Li batteries with this composite electrolyte demonstrate excellent cycling stability with high discharge capacity of 157 mA h g-1,high capacity retention of 96% and coulombic efficiency of 98.5% after 130 cycles at 30℃ and 0.1 C rate.These electrochemical properties are better than other PCL-based allsolid-lithium batteries,and validate the concept of "polymer-in-ceramic" by avoiding the drawback of lower conductivity in prior "polymer-in-ceramic" electrolyte at high concentration of the ceramic.
基金financially supported by the National Natural Science Foundation of China(Grant Nos 51503102)
文摘A solid electrolyte of LAGP[Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)]contained 0.5 wt%Li F was prepared by using low-volatile raw materials.The effects of different heat treatment conditions(750–900°C,4–10 h)and additive(Li F)on the ionic conductivity,structural morphology,and crystal transformation process were investigated in detail.EIS(electrochemical impedance spectroscopies)showed that the ionic conductivity of LAGP contained 0.5 wt%Li F had a highest value of 3.17×10^(-4)S cm^(-1)with low activation energy(0.31 e V)after treating 825°C for 6 h,more than LAGP of 2.45×10^(-4)S cm^(-1).DSC analysis and SEM images indicated that adding a small amount of Li F to LAGP not only can lower the glass transition temperature(from 513°C to507°C)and crystallization temperature(from 622°C to 605°C),but also can modify the grain boundary and increase the relative density of LAGP(from 95.8%to 97.7%).
基金This work was supported by the US National Science Foundation(No.CBET-1903342)Y.R.H.acknowledges the exchange graduate student scholarship from the China Scholarship Council.Y.R.Z.acknowledges the Link Foundation Energy Fellowship.L.M.Q.acknowledges support from the Ministry of Science and Technology of China(No.2018YFA0703502)H.L.W.acknowledges the Sloan Research Fellowship.
文摘Li1.5Al0.5Ge1.5(PO4)3(LAGP)is a solid-state electrolyte with high ionic conductivity and air stability but poor chemical stability and high interfacial impedance when directly contacted with Li metal.In this work,we develop an inorganic/polymer hybrid interlayer composed of Li bis(trifluoromethylsulfonyl)imide/poly(vinylene carbonate)polymer electrolyte and SiO2 submicrospheres to stabilize the Li/LAGP interface.The polymeric component renders high ionic conductance and low interfacial resistance,whereas the inorganic component imparts flame retardancy and a physical barrier to the known Li-LAGP side reaction,together enabling stable Li stripping/plating for more than 1,500 h at room temperature.With this interlayer at both electrodes,all-solid-state Li∥LiFePO4 full cells with stable cycling performance are also demonstrated.
