相对于传统商用锂离子电池,使用不易燃无机固体电解质的全固态锂电池可在实现高电压和大容量的同时确保电池的安全性。为实现全固态锂电池在室温条件下的稳定循环,开发具有良好电极相容性的超离子导体作为无机固体电解质材料显得至关重...相对于传统商用锂离子电池,使用不易燃无机固体电解质的全固态锂电池可在实现高电压和大容量的同时确保电池的安全性。为实现全固态锂电池在室温条件下的稳定循环,开发具有良好电极相容性的超离子导体作为无机固体电解质材料显得至关重要。2018年,采用Li_(3)YCl_(6)快离子导体作为电解质的In Li/Li Co O_(2)全固态锂电池在无需任何额外界面修饰情况下即可实现室温下的稳定循环,这使得氯化物基固体电解质材料重新引起关注,并在近几年得到飞速发展。本文首先强调了良好的正极相容性是氯化物基超离子导体最具吸引力的优势,同时指出传统氯化物基电解质在负极侧的界面不稳定性来源于易被还原的中心金属元素,并提出了通过非密堆积型阴离子亚晶格实现氯化物基超离子导体更快、更低势垒的离子传导设计思路。最后,总结了近几年氯化物基固体电解质材料的研究进展,并讨论了在其大规模应用之前仍需解决的问题。展开更多
用硅溶胶和聚乙烯醇缩聚反应生成的溶胶、凝胶制备了固体电解质钠快离子导体(natrium super ionic conductor,Nasicon)。用热重-差热、X射线衍射、透射电镜等现代分析方法表征锻烧温度为800～1000℃,锻烧时间为2～8h Nasicon粉体的相结...用硅溶胶和聚乙烯醇缩聚反应生成的溶胶、凝胶制备了固体电解质钠快离子导体(natrium super ionic conductor,Nasicon)。用热重-差热、X射线衍射、透射电镜等现代分析方法表征锻烧温度为800～1000℃,锻烧时间为2～8h Nasicon粉体的相结构和形貌。与传统的由正硅酸乙酯水解、缩聚反应生成的溶胶、凝胶制得的Nasicon粉体的对比,发现:用硅溶胶和聚乙烯醇反应制得的Nasicon粉体相的纯度更高,粉体颗粒粒径在80～100nm,并且颗粒分散均匀、大致成球形,为今后制备性能良好的传感器创造了条件。展开更多
Poly(vinylidene fluoride)(PVDF)-based solid polymer electrolytes(SPEs)with“lithium salt in polymer”configurations typically exhibit poor lithium salt dissociation and mechanical strength.In this study,we proposed a ...Poly(vinylidene fluoride)(PVDF)-based solid polymer electrolytes(SPEs)with“lithium salt in polymer”configurations typically exhibit poor lithium salt dissociation and mechanical strength.In this study,we proposed a composite polymer electrolyte(CPE)for solid-state lithium-ion batteries(LIBs)as a novel approach to address the challenges.The CPE incorporates a high dielectric polymer poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene)(P(VDF-TrFE-CTFE))as the polymer matrix,and sodium super ionic conductor(NASICON)-type ceramic Li_(1.5)Al_(0.5)Ti_(1.5)(PO_(4))_(3)(LATP)as fillers.The optimized CPE demonstrates enhanced dissociation of lithium salts,leading to high ionic conductivity tLi+(1.1 mS·cm^(-1))and improved lithium transference numbers(=0.51).Meanwhile,the interaction between LATP inorganic filler and P(VDF-TrFE-CTFE)enhances the elasticity and tensile strength(1.09 MPa)of the CPE.The graphite|CPE|NCM811(NCM stands for lithium nickel manganese cobalt oxide.Chemical formula of NCM811 is“LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)”)cell achieves a high specific capacity of 160 mAh·g^(-1) with excellent cycles stably for 300 cycles at 1 C.In addition,the flexible graphite|CPE|NCM811 pouch cell demonstrates exceptional capacity stability under dynamic bending for 10,000 times.Furthermore,the CPE can fulfil the fabrication process needs of flexible stacking-type and winding-type cells,highlighting its versatility and suitability for various LIB configurations in real applications.展开更多
Na_(3)MnTi(PO_(4))_(3)(NMTP)shows significant potential as a cathode for sodium-ion batteries(SIBs)owing to its multi-electron transfer capability and high theoretical capacity.Nevertheless,its practical application i...Na_(3)MnTi(PO_(4))_(3)(NMTP)shows significant potential as a cathode for sodium-ion batteries(SIBs)owing to its multi-electron transfer capability and high theoretical capacity.Nevertheless,its practical application is significantly limited by sluggish ion diffusion and rapid capacity decay,which stem from structural evolution during the sodiation/desodiation process.Herein,an Fe-doping strategy is proposed to reinforce the structural framework and enhance the electrochemical performance of NMTP.Trace Fe doping is found to shorten the M-O(M=Ti and Mn)bond while extending the Na-O bond,effectively minimizing structural fluctuations in NMTP during charge/discharge cycles and enhancing sodium-ion diffusion kinetics.Consequently,the Na_(3)Mn_(0.99)Fe_(0.02)Ti_(0.99)(PO_(4))_(3)(NMTP-Fe_(0.02))cathode demonstrates exceptional rate capability and long-term stability,delivering a high reversible capacity of 153.2 mAh·g^(-1)at 0.1 C and retaining 99.3 mAh·g^(-1)after 800 cycles at 5 C,exhibiting a capacity preservation rate of 81.5%.Moreover,its outstanding performance in full-cell configurations highlights the significant potential of NMTP-Fe0.02 for practical applications.展开更多
All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,...All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,the issue of lithium resource availability is selectively overlooked.Considering that the amount of lithium required for all-solidstate LIBs is not sustainable with current lithium resources,another system that also offers the dual advantages of high energy density and safetydall-solid-state sodium-ion batteries(SIBs)dholds significant sustainable advantages and is likely to be the strong contender in the competition for developing next-generation high-energy-density batteries.This article briefly introduces the research status of all-solid-state SIBs,explains the sources of their advantages,and discusses potential approaches to the development of solid sodium-ion conductors,aiming to spark the interest of researchers and attract more attention to the field of all-solid-state SIBs.展开更多
Sodium ion batteries (SIBs) are alternatives to lithium ion batteries (LIBs), and offer some significant benefits such as cost reduction and a lower environmental impact;however, to compete with LIBs, further research...Sodium ion batteries (SIBs) are alternatives to lithium ion batteries (LIBs), and offer some significant benefits such as cost reduction and a lower environmental impact;however, to compete with LIBs, further research is required to improve the performance of SIBs. In this study, an orthorhombic Na super ionic conductor structural Fe_(2)(MoO_(4))_(3) nanosheet with amorphous-crystalline core-shell alignment was synthesized using a facile low-temperature water-vapor-assisted solid-state reaction and applied as a cathode material for SIBs. The obtained material has a well-defined three-dimensional stacking structure, and exhibits a high specific capacity of 87.8 mAh·g^(−1) at a current density of 1 C = 91 mA·g^(−1) after 1,000 cycles, which is due to the considerable contribution of extra surface-related reaction such as the pseudo-capacitive process. This material shows significantly improved cycling and rated behavior as well as enhanced performance under high- and low-temperature conditions, as compared to the same materials prepared by the conventional high-temperature solid-state reaction. This enhancement is explained by the unique morphology in combination with the improved kinetics of the electrochemical reaction due to its lower charge transfer resistance and higher sodium ion conductivity.展开更多
The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom...The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom doping in a von-Alpen-type Na super ionic conductor(NASICON)was investigated by substituting Zr^(4+)with Mg^(2+),Zn^(2+),and La^(3+)to enhance its material properties and evaluate its potential for solid-state sodium battery applications.Computational chemistry was employed to predict the thermodynamic stability influenced by dopant introduction and the changes in ionic conductivity arising from crystal structure distortion,with the predictions validated by experiments.The optimized Zn^(2+)-doped NASICON(Zn-NZSP0.07)exhibited the highest total ionic conductivity of 2.74×10^(−3)S∙cm^(−1),representing a 4.5-fold increase compared with undoped NASICON(6.00×10−4 S∙cm^(−1)).The material also showed a high relative density of 99.1%,indicating a compact and well-sintered microstructure,as confirmed by a three-point bending test.Furthermore,a high critical current density of 1.4 mA∙cm^(−2)was achieved in symmetric cell testing.Additionally,a Na_(3)V_(2)(PO_(4))_(3)||Zn-NZSP0.07||Na cell delivered an initial capacity of 103.9 mAh∙g^(−1)at 0.1 A∙g^(−1)and retained 73.4%of its capacity after 200 cycles.These results demonstrate that optimal heteroatom doping is crucial for enhancing the performance of NASICON.展开更多
文摘相对于传统商用锂离子电池,使用不易燃无机固体电解质的全固态锂电池可在实现高电压和大容量的同时确保电池的安全性。为实现全固态锂电池在室温条件下的稳定循环,开发具有良好电极相容性的超离子导体作为无机固体电解质材料显得至关重要。2018年,采用Li_(3)YCl_(6)快离子导体作为电解质的In Li/Li Co O_(2)全固态锂电池在无需任何额外界面修饰情况下即可实现室温下的稳定循环,这使得氯化物基固体电解质材料重新引起关注,并在近几年得到飞速发展。本文首先强调了良好的正极相容性是氯化物基超离子导体最具吸引力的优势,同时指出传统氯化物基电解质在负极侧的界面不稳定性来源于易被还原的中心金属元素,并提出了通过非密堆积型阴离子亚晶格实现氯化物基超离子导体更快、更低势垒的离子传导设计思路。最后,总结了近几年氯化物基固体电解质材料的研究进展,并讨论了在其大规模应用之前仍需解决的问题。
文摘用硅溶胶和聚乙烯醇缩聚反应生成的溶胶、凝胶制备了固体电解质钠快离子导体(natrium super ionic conductor,Nasicon)。用热重-差热、X射线衍射、透射电镜等现代分析方法表征锻烧温度为800～1000℃,锻烧时间为2～8h Nasicon粉体的相结构和形貌。与传统的由正硅酸乙酯水解、缩聚反应生成的溶胶、凝胶制得的Nasicon粉体的对比,发现:用硅溶胶和聚乙烯醇反应制得的Nasicon粉体相的纯度更高,粉体颗粒粒径在80～100nm,并且颗粒分散均匀、大致成球形,为今后制备性能良好的传感器创造了条件。
文摘Poly(vinylidene fluoride)(PVDF)-based solid polymer electrolytes(SPEs)with“lithium salt in polymer”configurations typically exhibit poor lithium salt dissociation and mechanical strength.In this study,we proposed a composite polymer electrolyte(CPE)for solid-state lithium-ion batteries(LIBs)as a novel approach to address the challenges.The CPE incorporates a high dielectric polymer poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene)(P(VDF-TrFE-CTFE))as the polymer matrix,and sodium super ionic conductor(NASICON)-type ceramic Li_(1.5)Al_(0.5)Ti_(1.5)(PO_(4))_(3)(LATP)as fillers.The optimized CPE demonstrates enhanced dissociation of lithium salts,leading to high ionic conductivity tLi+(1.1 mS·cm^(-1))and improved lithium transference numbers(=0.51).Meanwhile,the interaction between LATP inorganic filler and P(VDF-TrFE-CTFE)enhances the elasticity and tensile strength(1.09 MPa)of the CPE.The graphite|CPE|NCM811(NCM stands for lithium nickel manganese cobalt oxide.Chemical formula of NCM811 is“LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)”)cell achieves a high specific capacity of 160 mAh·g^(-1) with excellent cycles stably for 300 cycles at 1 C.In addition,the flexible graphite|CPE|NCM811 pouch cell demonstrates exceptional capacity stability under dynamic bending for 10,000 times.Furthermore,the CPE can fulfil the fabrication process needs of flexible stacking-type and winding-type cells,highlighting its versatility and suitability for various LIB configurations in real applications.
基金supported by the National Natural Science Foundation of China(Nos.52102239,52072112,and 51672069)the Foundation of Henan Educational Committee(No.22A140003)+6 种基金the Zhong yuan Thousand Talents Program of Henan Province(No.ZYQR201912155)the Natural Science Foundation of Henan Province Youth Foundation(No.242300420315)the Henan Overseas Expertise Introduction Center for Discipline Innovation(No.CXJD2021003)the Program for Innovative Research Team in Science and Technology in the University of Henan Province(No.20IRTSTHN012)Science and Technology Development Project of Henan Province(No.202102210105)the Major Science and Technology Projects in Henan Province,China(No.241100240200)the Natural Science Foundation of Henan Province in China(No.242300421011).
文摘Na_(3)MnTi(PO_(4))_(3)(NMTP)shows significant potential as a cathode for sodium-ion batteries(SIBs)owing to its multi-electron transfer capability and high theoretical capacity.Nevertheless,its practical application is significantly limited by sluggish ion diffusion and rapid capacity decay,which stem from structural evolution during the sodiation/desodiation process.Herein,an Fe-doping strategy is proposed to reinforce the structural framework and enhance the electrochemical performance of NMTP.Trace Fe doping is found to shorten the M-O(M=Ti and Mn)bond while extending the Na-O bond,effectively minimizing structural fluctuations in NMTP during charge/discharge cycles and enhancing sodium-ion diffusion kinetics.Consequently,the Na_(3)Mn_(0.99)Fe_(0.02)Ti_(0.99)(PO_(4))_(3)(NMTP-Fe_(0.02))cathode demonstrates exceptional rate capability and long-term stability,delivering a high reversible capacity of 153.2 mAh·g^(-1)at 0.1 C and retaining 99.3 mAh·g^(-1)after 800 cycles at 5 C,exhibiting a capacity preservation rate of 81.5%.Moreover,its outstanding performance in full-cell configurations highlights the significant potential of NMTP-Fe0.02 for practical applications.
基金the support of the Grant-in-Aid for JSPS Research Fellow.
文摘All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,the issue of lithium resource availability is selectively overlooked.Considering that the amount of lithium required for all-solidstate LIBs is not sustainable with current lithium resources,another system that also offers the dual advantages of high energy density and safetydall-solid-state sodium-ion batteries(SIBs)dholds significant sustainable advantages and is likely to be the strong contender in the competition for developing next-generation high-energy-density batteries.This article briefly introduces the research status of all-solid-state SIBs,explains the sources of their advantages,and discusses potential approaches to the development of solid sodium-ion conductors,aiming to spark the interest of researchers and attract more attention to the field of all-solid-state SIBs.
基金This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science, ICT and Future Planning (NRF-2017R1A2B3011967)This work was supported by the Engineering Research Center through National Research Foundation of Korea (NRF)funded by the Korean Government (MSIT) (NRF-2018R1A5A1025224).
文摘Sodium ion batteries (SIBs) are alternatives to lithium ion batteries (LIBs), and offer some significant benefits such as cost reduction and a lower environmental impact;however, to compete with LIBs, further research is required to improve the performance of SIBs. In this study, an orthorhombic Na super ionic conductor structural Fe_(2)(MoO_(4))_(3) nanosheet with amorphous-crystalline core-shell alignment was synthesized using a facile low-temperature water-vapor-assisted solid-state reaction and applied as a cathode material for SIBs. The obtained material has a well-defined three-dimensional stacking structure, and exhibits a high specific capacity of 87.8 mAh·g^(−1) at a current density of 1 C = 91 mA·g^(−1) after 1,000 cycles, which is due to the considerable contribution of extra surface-related reaction such as the pseudo-capacitive process. This material shows significantly improved cycling and rated behavior as well as enhanced performance under high- and low-temperature conditions, as compared to the same materials prepared by the conventional high-temperature solid-state reaction. This enhancement is explained by the unique morphology in combination with the improved kinetics of the electrochemical reaction due to its lower charge transfer resistance and higher sodium ion conductivity.
基金supported by Korea Research Institute for defense Technology planning and advancement(KRIT)grant funded by the Korea government(Defense Acquisition Program Administration(DAPA))(No.21-107-D00-009,Design and development of core materials and unit cells for seawater secondary batteries,2025).
文摘The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom doping in a von-Alpen-type Na super ionic conductor(NASICON)was investigated by substituting Zr^(4+)with Mg^(2+),Zn^(2+),and La^(3+)to enhance its material properties and evaluate its potential for solid-state sodium battery applications.Computational chemistry was employed to predict the thermodynamic stability influenced by dopant introduction and the changes in ionic conductivity arising from crystal structure distortion,with the predictions validated by experiments.The optimized Zn^(2+)-doped NASICON(Zn-NZSP0.07)exhibited the highest total ionic conductivity of 2.74×10^(−3)S∙cm^(−1),representing a 4.5-fold increase compared with undoped NASICON(6.00×10−4 S∙cm^(−1)).The material also showed a high relative density of 99.1%,indicating a compact and well-sintered microstructure,as confirmed by a three-point bending test.Furthermore,a high critical current density of 1.4 mA∙cm^(−2)was achieved in symmetric cell testing.Additionally,a Na_(3)V_(2)(PO_(4))_(3)||Zn-NZSP0.07||Na cell delivered an initial capacity of 103.9 mAh∙g^(−1)at 0.1 A∙g^(−1)and retained 73.4%of its capacity after 200 cycles.These results demonstrate that optimal heteroatom doping is crucial for enhancing the performance of NASICON.
