Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs fur...Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs further understanding of the structural complexity and dynamic evolution of monoclinic and rhombohedral phases, in order to overcome the issues including voltage decay, poor rate capability, initial irreversible capacity loss and etc. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, have fueled rapid progress in the understanding of the mechanism of such issues. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, migration of transition metal, and the activation of oxygen of LrLOs are then explored in detail, with a particular focus on the mechanism of voltage decay.展开更多
Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO ...Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.展开更多
Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but...Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but also inhibits the structural strain during cycling processes.Herein,we report the hierarchical flower-like pure spinel manganese-based oxide nanosheets synthesized via a template-orientated strategy.The oriented template is fabricated by decomposition of carbonate obtained from"bubble reaction",via an alcoholassisted hydrothermal process.The resultant spinel manganese-based oxide nanosheets simultaneously possess excellent rate capability and cycling stability.The high-voltage LiNi0.5Mn1.5O4(LNMO-HF)has a uniform phase distribution without the common impurity phase LixNi1-xO2 and NixO.Besides,the LNMO-HF delivers high discharge capacity of142.6 mA h g-with specific energy density of 660.7 W h kg 1 at 1 C under 55℃.More importantly,the template-orientated strategy can be extended to the synthesis of LiMn2 O4(LMO),which can achieve 88.12%capacity retention after 1000 cycles.展开更多
Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batt...Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batteries because of their ultrahigh specific capacity. However, redox reaction mechanisms, especially for the anionic redox reaction of these materials, are still not very clear. Meanwhile, several pivotal challenges associated with the redox reactions mechanisms, such as structural instability and limited cycle life, hinder the practical applications of these high-capacity lithium-rich cathode oxides. Herein, we review the lithium-rich oxides with various crystal structures. The multivalent cationic/anionic redox reaction mechanisms of several representative high capacity lithium-rich cathode oxides are discussed, attempting to understand the origins of the high lithium storage capacities of these materials. In addition, we provide perspectives for the further development of these lithium-rich cathode oxides based on multivalent cationic and anionic redox reactions, focusing on addressing the fundamental problems and promoting their practical applications.展开更多
Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capaci...Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capacity fading,which is focused in this review.First,an overview of crystal structure,band structure and electrochemical performances of LLOs is provided.After that,current understanding on oxygen loss,capacity fading and voltage fading is summarized.Finally,five strategies to mitigate capacity and voltage fading are reviewed.It is believed that these understandings can help solve the fading problems of LLOs.展开更多
应用共沉淀结合固相烧结合成了富锂层状氧化物(Li-rich layered oxide,LLO)Li1.2Ni0.13Co0.13Mn0.54O2.对制备的富锂材料用氧化石墨烯(Graphene Oxide,GO)包覆后,再经300oC空气中煅烧,制备了石墨烯(Graphene,Gra)卷绕包覆的复合材料(LLO...应用共沉淀结合固相烧结合成了富锂层状氧化物(Li-rich layered oxide,LLO)Li1.2Ni0.13Co0.13Mn0.54O2.对制备的富锂材料用氧化石墨烯(Graphene Oxide,GO)包覆后,再经300oC空气中煅烧,制备了石墨烯(Graphene,Gra)卷绕包覆的复合材料(LLO/Gra).使用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)及电化学方法表征所得样品.结果表明,富锂层状氧化物均匀地卷绕在石墨烯中.与原始富锂材料相比,石墨烯包覆后的复合材料表现出更加优异的电化学性能.尤其是石墨烯卷绕可以改善富锂材料的导电性,提高材料的放电倍率性能,在2.0至4.8 V电压范围内,0.1C(20 m A·g-1)电流充放电下,容量达270 m Ah·g-1,1C倍率下复合物的放电容量接近200 m Ah·g-1,比原始LLO材料170 m Ah·g-1提高了15%.展开更多
为了提高球形Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2正极材料的电化学性能,通过非均匀成核法在材料颗粒表面包覆一层纳米CuO;采用XRD、SEM、TEM和充放电测试仪对所包覆材料进行测试与表征。结果表明：适量的CuO包覆可有效地提...为了提高球形Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2正极材料的电化学性能,通过非均匀成核法在材料颗粒表面包覆一层纳米CuO;采用XRD、SEM、TEM和充放电测试仪对所包覆材料进行测试与表征。结果表明：适量的CuO包覆可有效地提高Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2正极材料的电化学性能;当CuO包覆量为2%（质量分数）时,材料的电化学性能最佳。在0.1C、2.0~4.6 V充放电条件下,其首次放电容量为213.7 m A·h/g,首次库仑效率可达86.9%。此外,该材料在0.5C倍率下循环100次后其放电比容量仍为169.5 mA·h/g,容量保持率为79.3%;而未经包覆的Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2在相同循环条件下,容量保持率仅为65.5%。展开更多
采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li_(1/3)Mn_(2/3)]O2·0.4LiNi_(5/12)Mn_(5/12)Co_(1/6)O_2(简称LNMCO),并使用Zr(CH3COO)4进行ZrO_2的包覆改性。TEM测试结果显示纳米级的ZrO_2颗粒附着在LNMCO的表面。包覆质量...采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li_(1/3)Mn_(2/3)]O2·0.4LiNi_(5/12)Mn_(5/12)Co_(1/6)O_2(简称LNMCO),并使用Zr(CH3COO)4进行ZrO_2的包覆改性。TEM测试结果显示纳米级的ZrO_2颗粒附着在LNMCO的表面。包覆质量分数为1.5%的ZrO_2包覆样品的首圈库伦效率和放电比容量有着显著提升,在室温下其首圈库伦效率和放电比容量(电流密度:20 m A·g-1,电压:2.0~4.8 V)分别为87.2%,279.3 m Ah·g-1,而原样则为75.1%,224.1 m Ah·g-1,循环100圈之后,1.5%ZrO_2包覆样品的放电比容量为248.3 m Ah·g-1,容量保持率为88.9%,高于原样的195.9 m Ah·g-1和87.4%。展开更多
基金finically supported by the National Key Research and Development Program of China (Grant No. 2016YFB0100100)Strategic Priority Research Program of Chinese Academy of Sciences (CAS, Grant No. XDA09010101)Ningbo Key Science and Technology Projects "Industrial Application Development of Graphene" (Grant No. 2014S10008)
文摘Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs further understanding of the structural complexity and dynamic evolution of monoclinic and rhombohedral phases, in order to overcome the issues including voltage decay, poor rate capability, initial irreversible capacity loss and etc. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, have fueled rapid progress in the understanding of the mechanism of such issues. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, migration of transition metal, and the activation of oxygen of LrLOs are then explored in detail, with a particular focus on the mechanism of voltage decay.
基金This work was financially supported by the High‐level Talents'Discipline Construction Fund of Shandong University(31370089963078)the Shandong Provincial Science and Technology Major Project(2018JM RH0211 and 2017CXGC1010)+3 种基金the Research Funds of Shandong University(10000089395121)the Natural Science Foundation of Shandong Province(ZR2019MEM052 and ZR2017MEM002)The National Natural Science Foundation of China(grant no.52002287)the Start‐up Funding of Wenzhou University are acknowledged.
文摘Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.
基金financially supported by the National Natural Science Foundation of China(21371023)
文摘Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but also inhibits the structural strain during cycling processes.Herein,we report the hierarchical flower-like pure spinel manganese-based oxide nanosheets synthesized via a template-orientated strategy.The oriented template is fabricated by decomposition of carbonate obtained from"bubble reaction",via an alcoholassisted hydrothermal process.The resultant spinel manganese-based oxide nanosheets simultaneously possess excellent rate capability and cycling stability.The high-voltage LiNi0.5Mn1.5O4(LNMO-HF)has a uniform phase distribution without the common impurity phase LixNi1-xO2 and NixO.Besides,the LNMO-HF delivers high discharge capacity of142.6 mA h g-with specific energy density of 660.7 W h kg 1 at 1 C under 55℃.More importantly,the template-orientated strategy can be extended to the synthesis of LiMn2 O4(LMO),which can achieve 88.12%capacity retention after 1000 cycles.
基金supported by the National Key Research and Development Program of China (2016YFA202500)the “One Hundred Talent Project” of the Chinese Academy of Sciencesthe National Natural Science Foundation of China (11675255)
文摘Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batteries because of their ultrahigh specific capacity. However, redox reaction mechanisms, especially for the anionic redox reaction of these materials, are still not very clear. Meanwhile, several pivotal challenges associated with the redox reactions mechanisms, such as structural instability and limited cycle life, hinder the practical applications of these high-capacity lithium-rich cathode oxides. Herein, we review the lithium-rich oxides with various crystal structures. The multivalent cationic/anionic redox reaction mechanisms of several representative high capacity lithium-rich cathode oxides are discussed, attempting to understand the origins of the high lithium storage capacities of these materials. In addition, we provide perspectives for the further development of these lithium-rich cathode oxides based on multivalent cationic and anionic redox reactions, focusing on addressing the fundamental problems and promoting their practical applications.
基金supported by China-Japanese Research Cooperative Program founded by the Ministry of Science and Technology of the People’s Republic of China(2017YFE0127600)the National Natural Science Foundation of China(No.21978153,51774191).
文摘Lithium rich layered oxides(LLOs)are attractive cathode materials for Li-ion batteries owing to their high capacity(>250 mA h g^(-1))and suitable voltage(∼3.6 V).However,they suffer from serious voltage and capacity fading,which is focused in this review.First,an overview of crystal structure,band structure and electrochemical performances of LLOs is provided.After that,current understanding on oxygen loss,capacity fading and voltage fading is summarized.Finally,five strategies to mitigate capacity and voltage fading are reviewed.It is believed that these understandings can help solve the fading problems of LLOs.
文摘应用共沉淀结合固相烧结合成了富锂层状氧化物(Li-rich layered oxide,LLO)Li1.2Ni0.13Co0.13Mn0.54O2.对制备的富锂材料用氧化石墨烯(Graphene Oxide,GO)包覆后,再经300oC空气中煅烧,制备了石墨烯(Graphene,Gra)卷绕包覆的复合材料(LLO/Gra).使用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)及电化学方法表征所得样品.结果表明,富锂层状氧化物均匀地卷绕在石墨烯中.与原始富锂材料相比,石墨烯包覆后的复合材料表现出更加优异的电化学性能.尤其是石墨烯卷绕可以改善富锂材料的导电性,提高材料的放电倍率性能,在2.0至4.8 V电压范围内,0.1C(20 m A·g-1)电流充放电下,容量达270 m Ah·g-1,1C倍率下复合物的放电容量接近200 m Ah·g-1,比原始LLO材料170 m Ah·g-1提高了15%.
文摘为了提高球形Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2正极材料的电化学性能,通过非均匀成核法在材料颗粒表面包覆一层纳米CuO;采用XRD、SEM、TEM和充放电测试仪对所包覆材料进行测试与表征。结果表明：适量的CuO包覆可有效地提高Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2正极材料的电化学性能;当CuO包覆量为2%（质量分数）时,材料的电化学性能最佳。在0.1C、2.0~4.6 V充放电条件下,其首次放电容量为213.7 m A·h/g,首次库仑效率可达86.9%。此外,该材料在0.5C倍率下循环100次后其放电比容量仍为169.5 mA·h/g,容量保持率为79.3%;而未经包覆的Li_（1.13）[Ni_（0.5）Mn_（0.5）]_（0.87）O_2在相同循环条件下,容量保持率仅为65.5%。
文摘采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li_(1/3)Mn_(2/3)]O2·0.4LiNi_(5/12)Mn_(5/12)Co_(1/6)O_2(简称LNMCO),并使用Zr(CH3COO)4进行ZrO_2的包覆改性。TEM测试结果显示纳米级的ZrO_2颗粒附着在LNMCO的表面。包覆质量分数为1.5%的ZrO_2包覆样品的首圈库伦效率和放电比容量有着显著提升,在室温下其首圈库伦效率和放电比容量(电流密度:20 m A·g-1,电压:2.0~4.8 V)分别为87.2%,279.3 m Ah·g-1,而原样则为75.1%,224.1 m Ah·g-1,循环100圈之后,1.5%ZrO_2包覆样品的放电比容量为248.3 m Ah·g-1,容量保持率为88.9%,高于原样的195.9 m Ah·g-1和87.4%。
