钠超离子导体(NASICON)型Li1.3Al0.3Ti1.7(PO4)3 (LATP)由于其高的锂离子电导率、优异的空气稳定性和低成本而备受关注,被认为是下一代固态锂电池最有前途的固态电解质之一。然而,由于其与锂金属会发生强烈的副反应,存在着严重的界面问...钠超离子导体(NASICON)型Li1.3Al0.3Ti1.7(PO4)3 (LATP)由于其高的锂离子电导率、优异的空气稳定性和低成本而备受关注,被认为是下一代固态锂电池最有前途的固态电解质之一。然而,由于其与锂金属会发生强烈的副反应,存在着严重的界面问题。在此,提出了一种简单且方便的滴筑方法,通过构建PEO-ZnO梯度缓冲层,在LATP和锂金属阳极之间形成紧密而稳定的界面。缓冲层除了能够减缓副反应,减缓LATP的消耗分解之外,该缓冲层还能够抑制锂枝晶的生长和提高界面稳定性。与未引入氧化锌相比,引入1%和5%梯度缓冲层的扣式电池,在0.1 mA·cm−2单位面积电流稳定长时间循环(1000小时),而纯PEO基对称电池在0.1 mA·cm−2电流密度下仅循环500小时。以LiFePO4构建的全电池在0.1 C倍率下首次放电比容量为154.99 mAh·g−1,循环150圈后容量下降至129.76%。同时具有较高的化学稳定性窗口(5 V vs. Li/Li+)以及抑制锂枝晶的能力。在动态电流测试模式下仍维持优异的循环特性。这种策略有效提高了LATP与电极界面的相容性,减缓了副反应的发生,为开发低成本、高稳定性固态锂金属电池铺平了新的道路。Sodium superionic conductor (NASICON) type Li1.3Al0.3Ti1.7(PO4)3 (LATP) has attracted much attention due to its high lithium-ion conductivity, excellent air stability, and low cost, and is considered to be one of the most promising solid-state electrolytes for next-generation solid-state lithium batteries. However, due to the strong side reaction with lithium metal, there are serious interface problems. Here, a simple and convenient drip construction method is proposed to form a tight and stable interface between LATP and lithium metal anode by constructing a PEO-ZnO gradient buffer layer. In addition to slowing down the side reaction and the dissipation decomposition of LATP, the buffer layer can also inhibit the growth of lithium dendrites and improve the interfacial stability. Compared with the non-introduction of zinc oxide, the button battery with 1% and 5% gradient buffer layer was stable for a long time cycle (1000 hours) at 0.1 mA·cm−2 unit area current, while the pure PEO-based symmetric battery was only cycled for 500 hours at 0.1 mA·cm−2 current density. The full battery built with LiFePO4 has a specific capacity of 154.99 mAh·g−1 at 0.1 C, and the capacity drops to 129.76% after 150 cycles. It also has a high chemical stability window (5 V vs. Li/Li+) and the ability to inhibit lithium dendrites. Excellent cycling characteristics are maintained in dynamic current test mode. This strategy effectively improves the compatibility between LATP and electrode interface, slows down the occurrence of side reactions, and paves a new way for the development of low-cost, high-stability solid-state lithium metal batteries.展开更多
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
This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Proces...This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.展开更多
Solid electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)has attracted significant attention due to its high ionic conductivity,good air stability,and low cost.However,the practical application of LATP is limited b...Solid electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)has attracted significant attention due to its high ionic conductivity,good air stability,and low cost.However,the practical application of LATP is limited by its instability with Li metal,poor interfacial contact,and sluggish ion transport.Herein,a multifunctional layer composed of LiN_(x)O_(y)and LiGa is designed via an in situ conversion reaction between Li metal and Ga(NO_(3))_(3).LiN_(x)O_(y)(LiNO_(3)phase)with low interface energy and high affinity can improve interfacial contact,while LiN_(x)O_(y)(Li_(3)N phase)can provide rapid Li^(+)transport with its low migration barrier.The insulating LiN_(x)O_(y)prevents side reactions,and the conductive LiGa alloy homogenizes electric fields,enabling uniform Li deposition.Therefore,the preference layer ensures stable and tight contact at the interface throughout the cycle.The initial interfacial resistance of the symmetric battery is reduced from1677.2 to 152.2 X cm^(-2),and the critical current density is increased to 1.6 mA cm^(-2).Long-term stable cycling at 0.1 mA cm^(-2)/0.1 m A h cm^(-2)for 3000 h and 0.2 mA cm^(-2)/0.2 mA h cm^(-2)for 2500 h can be achieved.Full cells with LiFePO_(4)retain 89.3% capacity after 300 cycles at 0.5C,while Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)-based cells also exhibit high capacity and cycling stability.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
Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing wi...Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing with lithium metal,hindering practical applications.Herein,we introduce a flexible metal-organic framework(MOF:NUS-6)-incorporated polymeric layer,denoted as NP,designed to protect the sodium superionic conductor(NASICON)-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)electrolyte from Li metal anodes.The NP matrix establishes a soft interface with the LATP surface,effectively reducing voids and gaps that may arise between the LATP electrolyte and Li metal.Moreover,the MOF component in NP enhances ionic conductivity,offers abundant Li^(+)transport sites,and provides hierarchical ion channels,ensuring a homogeneous Li^(+)flow and thus effectively inhibiting Li dendrite formation.Utilizing NP,we fabricate Li symmetrical cells cycled for over 1600 h at 0.2 mA cm^(-2)and all-solid-state LiINP-LATPI LiFePO_(4)batteries,achieving a remarkable 99.3%capacity retention after 200 cycles at 0.2 C.This work outlines a general strategy for designing long-lasting and stable solid-state Li metal batteries.展开更多
文摘钠超离子导体(NASICON)型Li1.3Al0.3Ti1.7(PO4)3 (LATP)由于其高的锂离子电导率、优异的空气稳定性和低成本而备受关注,被认为是下一代固态锂电池最有前途的固态电解质之一。然而,由于其与锂金属会发生强烈的副反应,存在着严重的界面问题。在此,提出了一种简单且方便的滴筑方法,通过构建PEO-ZnO梯度缓冲层,在LATP和锂金属阳极之间形成紧密而稳定的界面。缓冲层除了能够减缓副反应,减缓LATP的消耗分解之外,该缓冲层还能够抑制锂枝晶的生长和提高界面稳定性。与未引入氧化锌相比,引入1%和5%梯度缓冲层的扣式电池,在0.1 mA·cm−2单位面积电流稳定长时间循环(1000小时),而纯PEO基对称电池在0.1 mA·cm−2电流密度下仅循环500小时。以LiFePO4构建的全电池在0.1 C倍率下首次放电比容量为154.99 mAh·g−1,循环150圈后容量下降至129.76%。同时具有较高的化学稳定性窗口(5 V vs. Li/Li+)以及抑制锂枝晶的能力。在动态电流测试模式下仍维持优异的循环特性。这种策略有效提高了LATP与电极界面的相容性,减缓了副反应的发生,为开发低成本、高稳定性固态锂金属电池铺平了新的道路。Sodium superionic conductor (NASICON) type Li1.3Al0.3Ti1.7(PO4)3 (LATP) has attracted much attention due to its high lithium-ion conductivity, excellent air stability, and low cost, and is considered to be one of the most promising solid-state electrolytes for next-generation solid-state lithium batteries. However, due to the strong side reaction with lithium metal, there are serious interface problems. Here, a simple and convenient drip construction method is proposed to form a tight and stable interface between LATP and lithium metal anode by constructing a PEO-ZnO gradient buffer layer. In addition to slowing down the side reaction and the dissipation decomposition of LATP, the buffer layer can also inhibit the growth of lithium dendrites and improve the interfacial stability. Compared with the non-introduction of zinc oxide, the button battery with 1% and 5% gradient buffer layer was stable for a long time cycle (1000 hours) at 0.1 mA·cm−2 unit area current, while the pure PEO-based symmetric battery was only cycled for 500 hours at 0.1 mA·cm−2 current density. The full battery built with LiFePO4 has a specific capacity of 154.99 mAh·g−1 at 0.1 C, and the capacity drops to 129.76% after 150 cycles. It also has a high chemical stability window (5 V vs. Li/Li+) and the ability to inhibit lithium dendrites. Excellent cycling characteristics are maintained in dynamic current test mode. This strategy effectively improves the compatibility between LATP and electrode interface, slows down the occurrence of side reactions, and paves a new way for the development of low-cost, high-stability solid-state lithium metal batteries.
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support from Generalitat Valenciana under Pla Complementari“Programa de Materials Avanc¸ats”,2022(grant number MFA/2022/030)Ministerio de Ciencia,Innovaci´on y Universidades(Spain)(grant number MCIN/AEI/10.13039/501100011033)+1 种基金support from UJI(UJI-2023-16 and GACUJIMC/2023/08)Generalitat Valenciana through FPI Fellowship Program(grant numbers ACIF/2020/294 and CIACIF/2021/050).
文摘This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.
基金the support from the National Key R&D Program of China(2022YFB3807700)National Natural Science Foundation of China(22179071)+3 种基金the Hubei Natural Science Foundation for Distinguished Young Scholars(2023AFA089)the Hubei Natural Science Foundation,Hubei(2024AFB993)the Hubei Natural Science Foundation Innovation Group Project(2022CFA020)the Joint Funds of the Hubei Natural Science Foundation Innovation and Development(2022CFD034)。
文摘Solid electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)has attracted significant attention due to its high ionic conductivity,good air stability,and low cost.However,the practical application of LATP is limited by its instability with Li metal,poor interfacial contact,and sluggish ion transport.Herein,a multifunctional layer composed of LiN_(x)O_(y)and LiGa is designed via an in situ conversion reaction between Li metal and Ga(NO_(3))_(3).LiN_(x)O_(y)(LiNO_(3)phase)with low interface energy and high affinity can improve interfacial contact,while LiN_(x)O_(y)(Li_(3)N phase)can provide rapid Li^(+)transport with its low migration barrier.The insulating LiN_(x)O_(y)prevents side reactions,and the conductive LiGa alloy homogenizes electric fields,enabling uniform Li deposition.Therefore,the preference layer ensures stable and tight contact at the interface throughout the cycle.The initial interfacial resistance of the symmetric battery is reduced from1677.2 to 152.2 X cm^(-2),and the critical current density is increased to 1.6 mA cm^(-2).Long-term stable cycling at 0.1 mA cm^(-2)/0.1 m A h cm^(-2)for 3000 h and 0.2 mA cm^(-2)/0.2 mA h cm^(-2)for 2500 h can be achieved.Full cells with LiFePO_(4)retain 89.3% capacity after 300 cycles at 0.5C,while Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)-based cells also exhibit high capacity and cycling stability.
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 National Key R&D Program of China(2022YFB2404700)the Natural Science Foundation of China(22109186)+1 种基金the Guangdong Innovative and Entrepreneurial Research Team Program(2021ZT09L227)supported by the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(22hytd01)。
文摘Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing with lithium metal,hindering practical applications.Herein,we introduce a flexible metal-organic framework(MOF:NUS-6)-incorporated polymeric layer,denoted as NP,designed to protect the sodium superionic conductor(NASICON)-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)electrolyte from Li metal anodes.The NP matrix establishes a soft interface with the LATP surface,effectively reducing voids and gaps that may arise between the LATP electrolyte and Li metal.Moreover,the MOF component in NP enhances ionic conductivity,offers abundant Li^(+)transport sites,and provides hierarchical ion channels,ensuring a homogeneous Li^(+)flow and thus effectively inhibiting Li dendrite formation.Utilizing NP,we fabricate Li symmetrical cells cycled for over 1600 h at 0.2 mA cm^(-2)and all-solid-state LiINP-LATPI LiFePO_(4)batteries,achieving a remarkable 99.3%capacity retention after 200 cycles at 0.2 C.This work outlines a general strategy for designing long-lasting and stable solid-state Li metal batteries.
