Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high energy sodium-ion batteries(SIBs).However,inevitably complicated phase transitions and sluggish kinet ics during ins...Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high energy sodium-ion batteries(SIBs).However,inevitably complicated phase transitions and sluggish kinet ics during insertion and removal of Na+in P_(2)-type layered transition metal oxides generate structura instability and severe capacity decay.To get rid of such a dilemma,we report a structural optimization strategy to promote P2-type layered transition metal oxides with more(010)active planes as an efficien cathode for SIBs.As a result,as-prepared hexagonal-prism P2-type layered Na_(0.71)Ni_(0.16)Li_(0.09)Co_(0.16)Mn0.6O_(2)cathode with more(010)active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C,impressive rate capability of 52.7 m Ah/g at 10 C,and long-term cycling stability(capacity retention of 95.6%ove200 cycles).The outstanding electrochemical performance benefited from the unique hexagonal-prism with more(010)active facets,which can effectively shorten the diffusion distances of Na+,increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology character ization,Rietveld refinement,GITT,density functional theory calculations and operando XRD.展开更多
The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes h...The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes has become a stumbling block for achieving stable cycling in LMBs.In this work,a Li-containing polyethylene oxide(LPEO)was introduced between LAGP and electrodes as a buffer layer to regulate the interfacial compatibility and reduce interfacial impedance,inhibiting the side reactions.Moreover,ether-oxygen bond on LPEO chain can coordinate with Li+and guide the transportation of Li+,achieving fast Li+diffusion between Li1+xAlxGe2-x(PO4)3(LAGP)and electrodes.Specifically,the growth of lithium dendrites is effectively suppressed in LAGP with LPEO modification,which would lead to remarkable cycling stability and rate capability.Therefore,the Li|LPEO-LAGP|Li battery can cycle stably for more than 600 h at 0.1 mA cm−2.In addition,long-term performance of Li|LPEO-LAGP|LiFePO4(LFP)battery was achieved at a rate of 0.4 C,and capacity retention is more than 74%after 200 cycles.The Li|LPEO-LAGP|LiNi0.8Co0.1Mn0.1O2 also realized the steady operation in the voltage range of 2.8-4.3 V.展开更多
Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applica...Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries(DISBs) possess higher energy density,especially owning high power density for its higher operating voltage(> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier(artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG(covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage.Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.展开更多
P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances.There are strenuous attempts to balance the structure stability,phase transition as well as desirabl...P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances.There are strenuous attempts to balance the structure stability,phase transition as well as desirable electrochemical performances by inducing anion/cation ions,changing morphology,adjusting valence,etc.In this work,several same-period elements of Sc,Ti,V,Cr,Fe,Cu and Zn are doped into Na_(0.50)Li_(0.08)Mn_(0.60)Co_(0.16)Ni_(0.16)O_(2)cathodes,which are manipulated by ions radii and valence state,further studied by operando X-ray powder diffraction patterns(XRD).As a result,the Cu^(2+)doped cathode performed higher rate capacities(as high as 86 mAh/g even at 10 C)and more stable structures(capacity retention of~89.4%for 100 cycles),which owing to the synergistic effect among the tightened TMO_(2)layer,enlarged d-spacing,reduce O-O electrostatic repulsion,ameliorate lattice distortion as well as mitigate ordering of Na^(+)/vacancy.展开更多
Effective design of nanoheterostructure anode with high ion/electron migration kinetics can give electrode with superior electrochemical performance.However,the design and preparation of nanoheterostructure composites...Effective design of nanoheterostructure anode with high ion/electron migration kinetics can give electrode with superior electrochemical performance.However,the design and preparation of nanoheterostructure composites with high-capacity and long cycling life in half and pouch full cells remain a big challenge.Here,a novel micro-pore MnS/Mn_(2)SnS_(4)heterostructure nanowire were in situ encapsulated into the N and S elements co-doped amorphous carbon tubes(abbreviated as(MnS/Mn_(2)SnS_(4))@N,S-ACTs)and showed superior energy storage properties in Na-/Li-ion half cells and pouch full cells.The Na-/Li-storage capabilities improvement are attribute to the strong synergistic effect between MnS/Mn_(2)SnS_(4)heterostructure and N,S-ACTs protective layer,the former induces an local built-in electric field between Mn_(2)Sn S_(4)and MnS during charging/discharging,accelerating interfacial ion/electron diffusion dynamics,the latter effective maintains the morphology and volume evolution during Na~+/Li~+charging/discharging,achieving a long-term cycling stability(e.g.,high discharge capacity of 79.2 mAh/g with the capacity retention of 79.3%can be gained after 2200 cycles at 3 C in(Mn S/Mn_(2)Sn S_(4))@N,S-ACTs//LiFePO_(4)pouch full cells;a high capacity of~34 mAh/g at 10 C can be got with a Coulombic efficiency of 100%after 1000 cycles in pouch(Mn S/Mn_(2)Sn S_(4))@N,S-ACTs//Na_(3)V_(2)(PO_(4))_(2)O_(2)F full cells.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52372188,51902090)Henan Key Research Project Plan for Higher Education Institutions(No.23A150038)+6 种基金2023 Introduction of Studying Abroad Talent Program“111”Project(No.D17007)Henan Provincial Key Scientific Research Project of Colleges and Universities(No23A150038)Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National Students’Platform for Innovation and Entrepreneurship Training Program(No.201910476010)the China Postdoctoral Science Foundation(No.2019 M652546)the Henan Province Postdoctoral StartUp Foundation(No.1901017)。
文摘Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high energy sodium-ion batteries(SIBs).However,inevitably complicated phase transitions and sluggish kinet ics during insertion and removal of Na+in P_(2)-type layered transition metal oxides generate structura instability and severe capacity decay.To get rid of such a dilemma,we report a structural optimization strategy to promote P2-type layered transition metal oxides with more(010)active planes as an efficien cathode for SIBs.As a result,as-prepared hexagonal-prism P2-type layered Na_(0.71)Ni_(0.16)Li_(0.09)Co_(0.16)Mn0.6O_(2)cathode with more(010)active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C,impressive rate capability of 52.7 m Ah/g at 10 C,and long-term cycling stability(capacity retention of 95.6%ove200 cycles).The outstanding electrochemical performance benefited from the unique hexagonal-prism with more(010)active facets,which can effectively shorten the diffusion distances of Na+,increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology character ization,Rietveld refinement,GITT,density functional theory calculations and operando XRD.
基金supported by the National Natural Science Foundation of China(Grant Nos.52372188,51902090)Henan Key Research Project Plan for Higher Education Institutions(No.24A150019,23A150038)+5 种基金2023 Introduction of studying abroad talent program,“111 Project”(No.D17007)Henan Provincial Key Scientific Research Project of Colleges and Universities(No.23A150038)Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National Students,Platform for Innovation and Entrepreneurship Training Program(No.201910476010)the China Postdoctoral Science Foundation(No.2019 M652546)the Henan Province Postdoctoral Start-Up Foundation(No.1901017).
文摘The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes has become a stumbling block for achieving stable cycling in LMBs.In this work,a Li-containing polyethylene oxide(LPEO)was introduced between LAGP and electrodes as a buffer layer to regulate the interfacial compatibility and reduce interfacial impedance,inhibiting the side reactions.Moreover,ether-oxygen bond on LPEO chain can coordinate with Li+and guide the transportation of Li+,achieving fast Li+diffusion between Li1+xAlxGe2-x(PO4)3(LAGP)and electrodes.Specifically,the growth of lithium dendrites is effectively suppressed in LAGP with LPEO modification,which would lead to remarkable cycling stability and rate capability.Therefore,the Li|LPEO-LAGP|Li battery can cycle stably for more than 600 h at 0.1 mA cm−2.In addition,long-term performance of Li|LPEO-LAGP|LiFePO4(LFP)battery was achieved at a rate of 0.4 C,and capacity retention is more than 74%after 200 cycles.The Li|LPEO-LAGP|LiNi0.8Co0.1Mn0.1O2 also realized the steady operation in the voltage range of 2.8-4.3 V.
基金financially supported by the National Natural Science Foundation of China (Nos. 51672071, 51802085, 51772296 and 51902090)“111 Project” (No. D17007)+2 种基金the National students' platform for innovation and entrepreneurship training program (No. 201910476010)the China Postdoctoral Science Foundation (No. 2019 M652546)the Henan Province Postdoctoral StartUp Foundation (No. 1901017)。
文摘Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries(DISBs) possess higher energy density,especially owning high power density for its higher operating voltage(> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier(artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG(covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage.Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.
基金financially supported by the National Natural Science Foundation of China(Nos.52263010,51902090)Henan Key Research Project Plan for Higher Education Institutions(No.23A150038)+5 种基金2023 Introduction of studying abroad talent program,“"111"Project(No.D17007)Henan Provincial Key Scientific Research Project of Colleges and Universities(No.23A150038)Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National students'platform for innovation and entrepreneurship training program(No.201910476010)the China Postdoctoral Science Foundation(No.2019 M652546)the Henan Province Postdoctoral Start-Up Foundation(No.1901017).
文摘P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances.There are strenuous attempts to balance the structure stability,phase transition as well as desirable electrochemical performances by inducing anion/cation ions,changing morphology,adjusting valence,etc.In this work,several same-period elements of Sc,Ti,V,Cr,Fe,Cu and Zn are doped into Na_(0.50)Li_(0.08)Mn_(0.60)Co_(0.16)Ni_(0.16)O_(2)cathodes,which are manipulated by ions radii and valence state,further studied by operando X-ray powder diffraction patterns(XRD).As a result,the Cu^(2+)doped cathode performed higher rate capacities(as high as 86 mAh/g even at 10 C)and more stable structures(capacity retention of~89.4%for 100 cycles),which owing to the synergistic effect among the tightened TMO_(2)layer,enlarged d-spacing,reduce O-O electrostatic repulsion,ameliorate lattice distortion as well as mitigate ordering of Na^(+)/vacancy.
基金financial support from the project funded by National Natural Science Foundation of China(Nos.52372188,51902090)2023 Introduction of studying abroad talent program,Science Technology Program of Jilin Province(No.20220508141RC)+5 种基金the 111 Project(No.B13013)China Postdoctoral Science Foundation(No.2019M652546)Henan Province Postdoctoral Start-Up Foundation(No.1901017)Henan Normal University Doctoral Start-Up Project Foundation,“111”project(No.D17007)Henan Center for Outstanding Overseas Scientists(No.GZS2018003)the Dalian Revitalization Talents Program(No.2022RG01)。
文摘Effective design of nanoheterostructure anode with high ion/electron migration kinetics can give electrode with superior electrochemical performance.However,the design and preparation of nanoheterostructure composites with high-capacity and long cycling life in half and pouch full cells remain a big challenge.Here,a novel micro-pore MnS/Mn_(2)SnS_(4)heterostructure nanowire were in situ encapsulated into the N and S elements co-doped amorphous carbon tubes(abbreviated as(MnS/Mn_(2)SnS_(4))@N,S-ACTs)and showed superior energy storage properties in Na-/Li-ion half cells and pouch full cells.The Na-/Li-storage capabilities improvement are attribute to the strong synergistic effect between MnS/Mn_(2)SnS_(4)heterostructure and N,S-ACTs protective layer,the former induces an local built-in electric field between Mn_(2)Sn S_(4)and MnS during charging/discharging,accelerating interfacial ion/electron diffusion dynamics,the latter effective maintains the morphology and volume evolution during Na~+/Li~+charging/discharging,achieving a long-term cycling stability(e.g.,high discharge capacity of 79.2 mAh/g with the capacity retention of 79.3%can be gained after 2200 cycles at 3 C in(Mn S/Mn_(2)Sn S_(4))@N,S-ACTs//LiFePO_(4)pouch full cells;a high capacity of~34 mAh/g at 10 C can be got with a Coulombic efficiency of 100%after 1000 cycles in pouch(Mn S/Mn_(2)Sn S_(4))@N,S-ACTs//Na_(3)V_(2)(PO_(4))_(2)O_(2)F full cells.