固态锂离子电池以其高的理论比容量与宽的电化学窗口成为替代传统液态锂离子电池的主要研究方向。NASICON型的LATP作为固态电解质中研究较为广泛的种类,其与锂金属电极间的副反应问题制约着LATP未来的发展。本文通过掺杂LiTFSI的环氧树...固态锂离子电池以其高的理论比容量与宽的电化学窗口成为替代传统液态锂离子电池的主要研究方向。NASICON型的LATP作为固态电解质中研究较为广泛的种类,其与锂金属电极间的副反应问题制约着LATP未来的发展。本文通过掺杂LiTFSI的环氧树脂粘结剂表面渗透修复LATP固态电解质表面孔隙,环氧树脂的填充有效减少了Li|LATP界面间的接触面积,延缓了Li|LATP界面间的副反应,LiTFSI的掺杂使环氧树脂粘结剂具有一定的离子导电性,增强了电池的长循环性能。改性后的对称电池在0.1 mA cm−2电流密度下循环超过130 h。在Li|LATP界面间加入PEO凝胶缓冲层后,在0.1 mA cm−2电流密度下稳定循环超过1800 h,全电池稳定循环200次,容量保持率为89%,库伦效率约为100%。展开更多
Solid polymer electrolytes(SPEs) have been considered as the spotlight in recent years due to their high safety, non-flammability and good flexibility. Nonetheless, high crystallinity of polymer matrix leads to low io...Solid polymer electrolytes(SPEs) have been considered as the spotlight in recent years due to their high safety, non-flammability and good flexibility. Nonetheless, high crystallinity of polymer matrix leads to low ionic conductivity at ambient conditions and retards the practical applications of SPEs. Herein, we report hybrid solid electrolytes(HSE) containing bulky LATP in poly(ethylene oxide)(PEO) matrix, which significantly enhances the electrochemical properties. LATP has been easily obtained by an accessible solid-state method. The solid electrolyte based on 20 wt% LATP in PEO polymer matrix(abbreviated as PEO-20) exhibits an ionic conductivity of 2.1 ×10-5 S·cm-1 at 30 ℃, an order of magnitude higher than 2.9 × 10-6 S·cm-1 of the pristine PEO solid electrolyte(abbreviated as PEO-0), mainly resulting from the decline of crystallinity in polymer matrix. The electrochemical window of PEO-20 can reach 4.84 V at room temperature, compared with 4.40 V for PEO-0, which could be compatible with high-voltage cathode materials.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side st...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.展开更多
Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion...Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion O^(2-).In this work,the modified LATP with a series of LiCl(LATPClx,x=0.1,0.2,0.3,0.4)additives is prepared to enhance ionic conductivity.The successful introduction of Cl-makes the length of the c axis decrease from 20.822(2)to 20.792(1)Å,and the bulk conductivity of 2.13×10^(-3) S·cm^(-1) is achieved in LATPCl_(0.3).Moreover,the Al/Ti-O1/Cl1 and Al/Ti-O_(2)/Cl_(2) distance decrease,while the Li1-O_(2)/Cl_(2) distance increases.Lithium ions migrate more easily in the nanochannel of M3-M1-M3.In addition,the LiCl additive increases the relative density and the grain boundary conductivity of LATPClx compounds.Naturally,a higher ionic conductivity of 2.12×10^(–4) S·cm^(-1) and a low activation energy of 0.30 eV are obtained in LATPCl_(0.3).Correspondingly,the symmetric cell exhibits a low overpotential of±50 mV for over 200 h in LATPCl_(0.3).The solid-state Li|LATPCl_(0.3)|NCM811(NCM811=LiNi0.8Co0.1Mn0.1O_(2))battery exhibits high initial capacity 185.1 mAh·g^(-1) with a capacity retention rate of 95.4%after 100 cycles at 0.5 C.This result suggests that LiCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.展开更多
Lithium aluminum titanium phosphate(LATP)is one of the materials under consideration as an electrolyte in future all-solid-state lithium-ion batteries.In ceramic processing,the presence of secondary phases and porosit...Lithium aluminum titanium phosphate(LATP)is one of the materials under consideration as an electrolyte in future all-solid-state lithium-ion batteries.In ceramic processing,the presence of secondary phases and porosity play an important role.In a presence of more than one secondary phase and pores,image analysis must tackle the difficulties about distinguishing between these microstructural features.In this study,we study the phase evolution of LATP ceramics sintered at temperatures between 950 and 1100℃by image segmentation based on energy-dispersive X-ray spectroscopy(EDS)elemental maps combined with quantitative analysis of LATP grains.We found aluminum phosphate(AlPO4)and another phosphate phase((Lix)PyOz).The amount of these phases changes with sintering temperature.First,since the grains act as an aluminum source for AlPO4 formation,the aluminum content in the LATP grains decreases.Second,the amount of secondary phase changes from more(Lix)PyOz at 950℃to mainly AlPO4 at 1100℃sintering temperature.We also used scanning electron microscopy(SEM)and confocal laser scanning microscopy(CLSM)to study the evolution of the LATP grains and AlPO4,and LATP grain size increases with sintering temperature.In addition,transmission electron microscopy(TEM)was used for the determination of grain boundary width and to identify the amorphous structure of AlPO4.展开更多
文摘固态锂离子电池以其高的理论比容量与宽的电化学窗口成为替代传统液态锂离子电池的主要研究方向。NASICON型的LATP作为固态电解质中研究较为广泛的种类,其与锂金属电极间的副反应问题制约着LATP未来的发展。本文通过掺杂LiTFSI的环氧树脂粘结剂表面渗透修复LATP固态电解质表面孔隙,环氧树脂的填充有效减少了Li|LATP界面间的接触面积,延缓了Li|LATP界面间的副反应,LiTFSI的掺杂使环氧树脂粘结剂具有一定的离子导电性,增强了电池的长循环性能。改性后的对称电池在0.1 mA cm−2电流密度下循环超过130 h。在Li|LATP界面间加入PEO凝胶缓冲层后,在0.1 mA cm−2电流密度下稳定循环超过1800 h,全电池稳定循环200次,容量保持率为89%,库伦效率约为100%。
基金the Fujian Provincial Science and Technology Program (No. 2018H0042,2019T3017)Putian Municipal Science and Technology Program (2019HJSTS009)the DNL Cooperation Fund,CAS (DNL180308)。
文摘Solid polymer electrolytes(SPEs) have been considered as the spotlight in recent years due to their high safety, non-flammability and good flexibility. Nonetheless, high crystallinity of polymer matrix leads to low ionic conductivity at ambient conditions and retards the practical applications of SPEs. Herein, we report hybrid solid electrolytes(HSE) containing bulky LATP in poly(ethylene oxide)(PEO) matrix, which significantly enhances the electrochemical properties. LATP has been easily obtained by an accessible solid-state method. The solid electrolyte based on 20 wt% LATP in PEO polymer matrix(abbreviated as PEO-20) exhibits an ionic conductivity of 2.1 ×10-5 S·cm-1 at 30 ℃, an order of magnitude higher than 2.9 × 10-6 S·cm-1 of the pristine PEO solid electrolyte(abbreviated as PEO-0), mainly resulting from the decline of crystallinity in polymer matrix. The electrochemical window of PEO-20 can reach 4.84 V at room temperature, compared with 4.40 V for PEO-0, which could be compatible with high-voltage cathode materials.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20200800)the National Natural Science Foundation of China(22209075,51902165,12004145)+1 种基金the Natural Science Foundation of Jiangxi Province(20212BAB214032,20192ACBL20048)the Key Science and Technology Plan Project of Ji’an City(20211-015311)。
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.51772239,51972262 and 22005186)the 111 Project(No.B14040).
文摘Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion O^(2-).In this work,the modified LATP with a series of LiCl(LATPClx,x=0.1,0.2,0.3,0.4)additives is prepared to enhance ionic conductivity.The successful introduction of Cl-makes the length of the c axis decrease from 20.822(2)to 20.792(1)Å,and the bulk conductivity of 2.13×10^(-3) S·cm^(-1) is achieved in LATPCl_(0.3).Moreover,the Al/Ti-O1/Cl1 and Al/Ti-O_(2)/Cl_(2) distance decrease,while the Li1-O_(2)/Cl_(2) distance increases.Lithium ions migrate more easily in the nanochannel of M3-M1-M3.In addition,the LiCl additive increases the relative density and the grain boundary conductivity of LATPClx compounds.Naturally,a higher ionic conductivity of 2.12×10^(–4) S·cm^(-1) and a low activation energy of 0.30 eV are obtained in LATPCl_(0.3).Correspondingly,the symmetric cell exhibits a low overpotential of±50 mV for over 200 h in LATPCl_(0.3).The solid-state Li|LATPCl_(0.3)|NCM811(NCM811=LiNi0.8Co0.1Mn0.1O_(2))battery exhibits high initial capacity 185.1 mAh·g^(-1) with a capacity retention rate of 95.4%after 100 cycles at 0.5 C.This result suggests that LiCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.
文摘Lithium aluminum titanium phosphate(LATP)is one of the materials under consideration as an electrolyte in future all-solid-state lithium-ion batteries.In ceramic processing,the presence of secondary phases and porosity play an important role.In a presence of more than one secondary phase and pores,image analysis must tackle the difficulties about distinguishing between these microstructural features.In this study,we study the phase evolution of LATP ceramics sintered at temperatures between 950 and 1100℃by image segmentation based on energy-dispersive X-ray spectroscopy(EDS)elemental maps combined with quantitative analysis of LATP grains.We found aluminum phosphate(AlPO4)and another phosphate phase((Lix)PyOz).The amount of these phases changes with sintering temperature.First,since the grains act as an aluminum source for AlPO4 formation,the aluminum content in the LATP grains decreases.Second,the amount of secondary phase changes from more(Lix)PyOz at 950℃to mainly AlPO4 at 1100℃sintering temperature.We also used scanning electron microscopy(SEM)and confocal laser scanning microscopy(CLSM)to study the evolution of the LATP grains and AlPO4,and LATP grain size increases with sintering temperature.In addition,transmission electron microscopy(TEM)was used for the determination of grain boundary width and to identify the amorphous structure of AlPO4.
