Mechanical degradation, especially fractures in active particles in an electrode, is a major reason why the capacity of lithiumion batteries fades. This paper proposes a model that couples Li-ion diffusion, stress evo...Mechanical degradation, especially fractures in active particles in an electrode, is a major reason why the capacity of lithiumion batteries fades. This paper proposes a model that couples Li-ion diffusion, stress evolution, and damage mechanics to simulate the growth of central cracks in cathode particles（Li Mn_2 O_4） by an extended finite element method by considering the influence of multiple factors. The simulation shows that particles are likely to crack at a high discharge rate, when the particle radius is large, or when the initial central crack is longer. It also shows that the maximum principal tensile stress decreases and cracking becomes more difficult when the influence of crack surface diffusion is considered. The fracturing process occurs according to the following stages： no crack growth, stable crack growth, and unstable crack growth. Changing the charge/discharge strategy before unstable crack growth sets in is beneficial to prevent further capacity fading during electrochemical cycling.展开更多
Based on the unified Hauser–Feshbach and exciton model,which can describe the particle emission processes between discrete energy levels with energy,angular momentum,and parity conservations,a statistical theory of l...Based on the unified Hauser–Feshbach and exciton model,which can describe the particle emission processes between discrete energy levels with energy,angular momentum,and parity conservations,a statistical theory of light nucleus reaction(STLN)is developed to calculate the double-differential cross-sections of the outgoing neutron and light charged particles for the proton-induced^(6) Li reaction.A significant difference is observed between the p+^(6) Li and p+^(7) Li reactions owing to the discrepancies in the energy-level structures of the targets.The reaction channels,including sequential and simultaneous emission processes,are analyzed in detail.Taking the double-differential cross-sections of the outgoing proton as an example,the influence of contaminations(such as^(1) H,^(7)Li,^(12)C,and^(16)O)on the target is identified in terms of the kinetic energy of the first emitted particles.The optical potential parameters of the proton are obtained by fitting the elastic scattering differential cross-sections.The calculated total double-differential cross-sections of the outgoing proton and deuteron at E_(p)=14 MeV agree well with the experimental data for different outgoing angles.Simultaneously,the mixed double differential cross-sections of^(3) He andαare in good agreement with the measurements.The agreement between the measured data and calculated results indicates that the two-body and three-body breakup reactions need to be considered,and the pre-equilibrium reaction mechanism dominates the reaction processes.Based on the STLN model,a PLUNF code for the p+^(6) Li reaction is developed to obtain an ENDF-6-formatted file of the double-differential cross-sections of the nucleon and light composite charged particles.展开更多
利用超细旋转盘式砂磨机细化颗粒固相烧结法,合成锂离子电池正极材料Li Ni0.80Co0.15Al0.05O2。原料经过砂磨后,混合均匀,粒径达到纳米级。根据塔曼定理,混合均匀的微小粒径可以在相同的烧结温度下,提高烧结的强度。SEM、XRD分别表征NC...利用超细旋转盘式砂磨机细化颗粒固相烧结法,合成锂离子电池正极材料Li Ni0.80Co0.15Al0.05O2。原料经过砂磨后,混合均匀,粒径达到纳米级。根据塔曼定理,混合均匀的微小粒径可以在相同的烧结温度下,提高烧结的强度。SEM、XRD分别表征NCA材料的颗粒形貌和晶形结构。结果显示,通过细化颗粒烧结后的样品具有良好的形貌和层状结构。CV法测试样品的氧化还原性能,电池测试系统测试样品的电化学性能。测试结果显示,经过细化颗粒,在720℃合成的NCA材料具有良好的层状结构,018/110峰分裂明显。样品的电化学性能优良,0.2C下,首次放电容量达到182 m Ah?g?1,30次循环后容量保持率99.9%。1C下,首次放电容量153 m Ah?g?1,100次循环后容量保持率92.6%。展开更多
采用碳酸盐共沉淀的方法成功制备了不同二次颗粒粒径的富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2。并运用X射线衍射(XRD)、场发射扫描电镜(FESEM)、激光粒度测试和电化学测试等手段对所得材料的结构、形貌、粒度分布及电化学性能进行...采用碳酸盐共沉淀的方法成功制备了不同二次颗粒粒径的富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2。并运用X射线衍射(XRD)、场发射扫描电镜(FESEM)、激光粒度测试和电化学测试等手段对所得材料的结构、形貌、粒度分布及电化学性能进行表征。结果显示,不同二次颗粒粒径的Li1.2Mn0.54Ni0.13Co0.13O2在材料结构上没有明显的差别,且首次放电比容量接近,均达到了281m Ah·g-1。但是,二次颗粒粒径越小,富锂层状材料的表现出的倍率性能越优异,当二次颗粒的D50为4.59μm,其在3C倍率下的放电容量达到了199 m Ah·g-1。这是因为二次颗粒粒径越小,富锂层状材料可更好的与导电剂和电解液接触,且锂离子的扩散路径更短,从而表现出更好的倍率特性。展开更多
将热处理后的电解二氧化锰(EMD)进行10 h球磨,粉碎为200目、250目及300目等不同粒径,作为正极活性材料制备CR123A型锂/二氧化锰电池。使用200目、250目及300目EMD制备的电池,在60℃高温下存储7 d后的平均内阻分别为305.4 mΩ、296.1 mΩ...将热处理后的电解二氧化锰(EMD)进行10 h球磨,粉碎为200目、250目及300目等不同粒径,作为正极活性材料制备CR123A型锂/二氧化锰电池。使用200目、250目及300目EMD制备的电池,在60℃高温下存储7 d后的平均内阻分别为305.4 mΩ、296.1 mΩ和272.4 mΩ,30 m A恒流放电容量均约为1 300 m Ah,1.8 A恒流放电容量分别为748 m Ah、927 m Ah和998 m Ah。展开更多
通常需要将电活性材料与导电剂、粘接剂等辅助物质混合后,制成复合电极来评测材料的电化学性能,但辅助物质和复合电极结构可能影响评测结果的准确性.由于单颗粒微电极可选取单一颗粒进行测试,无需加入添加剂材料,因此,采用单颗粒微电极...通常需要将电活性材料与导电剂、粘接剂等辅助物质混合后,制成复合电极来评测材料的电化学性能,但辅助物质和复合电极结构可能影响评测结果的准确性.由于单颗粒微电极可选取单一颗粒进行测试,无需加入添加剂材料,因此,采用单颗粒微电极评测材料性能可以得到材料的本征性能.同时,单颗粒微电极还可以实现对材料的快速、精确评测.本文利用单颗粒微电极方法测试了球形LiFePO_4颗粒的循环伏安特性、循环稳定性和动力学性能.结果表明,单颗粒微电极可以20 m V·s^(-1)的速率快速扫描、精确测试,测得锂离子在该颗粒中的扩散系数约为2.4~3.2×10^(-11)cm^2·s^(-1),电化学反应的控制步骤为锂离子的固相扩散控制.另外,LiFePO_4颗粒在该单颗粒微电极构成的电池中表现出良好的循环稳定性.这些显示了单颗粒微电极在电极材料特性研究中的可行性.展开更多
基金support of the National Natural Science Foundation of China (11472165 and 11332005)
文摘Mechanical degradation, especially fractures in active particles in an electrode, is a major reason why the capacity of lithiumion batteries fades. This paper proposes a model that couples Li-ion diffusion, stress evolution, and damage mechanics to simulate the growth of central cracks in cathode particles（Li Mn_2 O_4） by an extended finite element method by considering the influence of multiple factors. The simulation shows that particles are likely to crack at a high discharge rate, when the particle radius is large, or when the initial central crack is longer. It also shows that the maximum principal tensile stress decreases and cracking becomes more difficult when the influence of crack surface diffusion is considered. The fracturing process occurs according to the following stages： no crack growth, stable crack growth, and unstable crack growth. Changing the charge/discharge strategy before unstable crack growth sets in is beneficial to prevent further capacity fading during electrochemical cycling.
基金supported by the Open Fund of State Key Laboratory of Advanced Forming Technology and Equipment (No. SKL202005)the Major Scientific and Technological Innovation Project of Luoyang,China(No. 2201029A)+1 种基金the National Natural Science Foundation of China (Nos. 51771115, 51775334)the Research Program of SAST-SJTU Joint Research Center of Advanced Spaceflight Technologies,China (No. USCAST2020-14)。
基金supported by the National Natural Science Foundation of China(No.12065003)the Guangxi Key R&D Project(2023AB07029)+1 种基金the Scientific Research and Technology Development Project of Guilin(20210104-2)the Central Government Guides Local Scientific and Technological Development Funds of China(Guike ZY22096024)。
文摘Based on the unified Hauser–Feshbach and exciton model,which can describe the particle emission processes between discrete energy levels with energy,angular momentum,and parity conservations,a statistical theory of light nucleus reaction(STLN)is developed to calculate the double-differential cross-sections of the outgoing neutron and light charged particles for the proton-induced^(6) Li reaction.A significant difference is observed between the p+^(6) Li and p+^(7) Li reactions owing to the discrepancies in the energy-level structures of the targets.The reaction channels,including sequential and simultaneous emission processes,are analyzed in detail.Taking the double-differential cross-sections of the outgoing proton as an example,the influence of contaminations(such as^(1) H,^(7)Li,^(12)C,and^(16)O)on the target is identified in terms of the kinetic energy of the first emitted particles.The optical potential parameters of the proton are obtained by fitting the elastic scattering differential cross-sections.The calculated total double-differential cross-sections of the outgoing proton and deuteron at E_(p)=14 MeV agree well with the experimental data for different outgoing angles.Simultaneously,the mixed double differential cross-sections of^(3) He andαare in good agreement with the measurements.The agreement between the measured data and calculated results indicates that the two-body and three-body breakup reactions need to be considered,and the pre-equilibrium reaction mechanism dominates the reaction processes.Based on the STLN model,a PLUNF code for the p+^(6) Li reaction is developed to obtain an ENDF-6-formatted file of the double-differential cross-sections of the nucleon and light composite charged particles.
文摘利用超细旋转盘式砂磨机细化颗粒固相烧结法,合成锂离子电池正极材料Li Ni0.80Co0.15Al0.05O2。原料经过砂磨后,混合均匀,粒径达到纳米级。根据塔曼定理,混合均匀的微小粒径可以在相同的烧结温度下,提高烧结的强度。SEM、XRD分别表征NCA材料的颗粒形貌和晶形结构。结果显示,通过细化颗粒烧结后的样品具有良好的形貌和层状结构。CV法测试样品的氧化还原性能,电池测试系统测试样品的电化学性能。测试结果显示,经过细化颗粒,在720℃合成的NCA材料具有良好的层状结构,018/110峰分裂明显。样品的电化学性能优良,0.2C下,首次放电容量达到182 m Ah?g?1,30次循环后容量保持率99.9%。1C下,首次放电容量153 m Ah?g?1,100次循环后容量保持率92.6%。
文摘采用碳酸盐共沉淀的方法成功制备了不同二次颗粒粒径的富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2。并运用X射线衍射(XRD)、场发射扫描电镜(FESEM)、激光粒度测试和电化学测试等手段对所得材料的结构、形貌、粒度分布及电化学性能进行表征。结果显示,不同二次颗粒粒径的Li1.2Mn0.54Ni0.13Co0.13O2在材料结构上没有明显的差别,且首次放电比容量接近,均达到了281m Ah·g-1。但是,二次颗粒粒径越小,富锂层状材料的表现出的倍率性能越优异,当二次颗粒的D50为4.59μm,其在3C倍率下的放电容量达到了199 m Ah·g-1。这是因为二次颗粒粒径越小,富锂层状材料可更好的与导电剂和电解液接触,且锂离子的扩散路径更短,从而表现出更好的倍率特性。
文摘将热处理后的电解二氧化锰(EMD)进行10 h球磨,粉碎为200目、250目及300目等不同粒径,作为正极活性材料制备CR123A型锂/二氧化锰电池。使用200目、250目及300目EMD制备的电池,在60℃高温下存储7 d后的平均内阻分别为305.4 mΩ、296.1 mΩ和272.4 mΩ,30 m A恒流放电容量均约为1 300 m Ah,1.8 A恒流放电容量分别为748 m Ah、927 m Ah和998 m Ah。
文摘通常需要将电活性材料与导电剂、粘接剂等辅助物质混合后,制成复合电极来评测材料的电化学性能,但辅助物质和复合电极结构可能影响评测结果的准确性.由于单颗粒微电极可选取单一颗粒进行测试,无需加入添加剂材料,因此,采用单颗粒微电极评测材料性能可以得到材料的本征性能.同时,单颗粒微电极还可以实现对材料的快速、精确评测.本文利用单颗粒微电极方法测试了球形LiFePO_4颗粒的循环伏安特性、循环稳定性和动力学性能.结果表明,单颗粒微电极可以20 m V·s^(-1)的速率快速扫描、精确测试,测得锂离子在该颗粒中的扩散系数约为2.4~3.2×10^(-11)cm^2·s^(-1),电化学反应的控制步骤为锂离子的固相扩散控制.另外,LiFePO_4颗粒在该单颗粒微电极构成的电池中表现出良好的循环稳定性.这些显示了单颗粒微电极在电极材料特性研究中的可行性.
