Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials...Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.展开更多
Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid el...Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.展开更多
Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical s...Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical spherical MnO2 containing coherent amorphous/crystalline domained by a simple yet effective redox precipitation reaction at room temperature.Further,flower-like CoMn2O4 constructed by single-crystalline spinel nanosheets has been fabricated using MnO2 as precursor.This mild methodology avoids undesired particle aggregation and loss of active surface area in conventional hydrothermal or solid-state processes.Moreover,both MnO2 and CoMn2O4 nanosheets manifest superior lithium-ion storage properties,rendering them promising applications in LIBs and other energy-related fields.展开更多
Lithium manganese oxides(Li Mn2 O4, LMO) have attracted significant attention as important cathode materials for lithium-ion batteries(LIBs), which require fast charging based on their intrinsic electrochemical proper...Lithium manganese oxides(Li Mn2 O4, LMO) have attracted significant attention as important cathode materials for lithium-ion batteries(LIBs), which require fast charging based on their intrinsic electrochemical properties. However, these properties are limited by the rapid fading of cycling retention, particularly at high temperatures, because of the severe Mn corrosion triggered by the chemical reaction with fluoride(F-) species existing in the cell. To alleviate this issue, three types of silyl ether(Si–O)-functionalized task-specific additives are proposed, namely methoxytrimethylsilane, dimethoxydimethylsilane, and trimethoxymethylsilane. Ex-situ NMR analyses demonstrated that the Si-additives selectively scavenged the F-species as Si forms new chemical bonds with F via a nucleophilic substitution reaction due to the high binding affinity of Si with F-, thereby leading to a decrease in the F concentration in the cell. Furthermore, the addition of Si-additives in the electrolyte did not significantly affect the ionic conductivity or electrochemical stability of the electrolyte, indicating that these additives are compatible with conventional electrolytes. In addition, the cells cycled with Si-additives exhibited improved cycling retention at room temperature and 45 °C. Among these candidates, a combination of MTSi and the LMO cathode was found to be the most suitable choice in terms of cycling retention(71.0%), whereas the cell cycled with the standard electrolyte suffered from the fading of cycling retention triggered by Mn dissolution(64.4%). Additional ex-situ analyses of the cycled electrodes using SEM, TEM, EIS, XPS, and ICP-MS demonstrated that the use of Si-additives not only improved the surface stability of the LMO cathode but also that of the graphite anode, as the Si-additives prevent Mn corrosion. This inhibits the formation of cracks on the surface of the LMO cathode, facilitating the formation of a stable solid electrolyte interphase layer on the surface of the graphite anode. Therefore, Si-additives modified by Si–O functional groups can be effectively used to increase the overall electrochemical performance of the LMO cathode material.展开更多
Assisted by graphene oxide(GO),nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indica...Assisted by graphene oxide(GO),nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4(S2)was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.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
Anode material for lithium ion battery is prepared by chemical oxidation of natural graphite. After oxidation, the properties of natural graphite are modified, such as surface structure, the content of graphite phases...Anode material for lithium ion battery is prepared by chemical oxidation of natural graphite. After oxidation, the properties of natural graphite are modified, such as surface structure, the content of graphite phases, the number of micropores and its stability. thus the modified natural graphite can be used as anode material for commercial lithium ion battery. The reversible capacity is increased from 100 mAh/g to above 300 mAh/g, and its cycling properly is also satisfactory.展开更多
Based on synthesizing pure spinel type lithium manganese oxides,the derivations such as LiMn1.5Ti0.5-O4,LiMn1.5Fe0.5O4,LiMn1 .5Ni0.5O4 and LiMn1.5Zn0.5O4 were prepared using solid- step-sintering method. The structure...Based on synthesizing pure spinel type lithium manganese oxides,the derivations such as LiMn1.5Ti0.5-O4,LiMn1.5Fe0.5O4,LiMn1 .5Ni0.5O4 and LiMn1.5Zn0.5O4 were prepared using solid- step-sintering method. The structures were characterized by using XRD,SEM and laser granulometer. The electrochemical measurement results show that the elemen t of iron or nickel can raise the discharging plateau voltage of LiMn2O4,an d element titanium improves the electrochemistry property of LiMn2O4 little,while element zinc destroys the electrochemistry property of LiMn2O4. The i nfluence of elements of titanium,iron,nickel,or zinc on the structure of LiMn 2O4 pure phase was discussed from the viewpoint of structural chemistry.展开更多
A SnO-graphite composite material, which can deliver high capacities and good cycling stability compared with unsupported SnO, was described. This material prepared via chemical co-precipitation reaction in the presen...A SnO-graphite composite material, which can deliver high capacities and good cycling stability compared with unsupported SnO, was described. This material prepared via chemical co-precipitation reaction in the presence of graphite consists of high dispersion of SnO with a size of about several hundred nanometers in the graphite. The phase structure was analyzed by X-ray diffraction (XRD). The morphology and the element distribution were examined by scanning electron microscopy (SEM) equipped with energy spectrum. The results show that the SnO-graphite composites produced by slowly hydrolysis have higher rechargeable capacities than pure graphite and better cycling performance than SnO.展开更多
A novel soft chemical approach was developed to synthesize tin oxide-based powders. The microstructure, morphology, and electrochemical performance of the materials were investigated by X-ray diffraction, scanning ele...A novel soft chemical approach was developed to synthesize tin oxide-based powders. The microstructure, morphology, and electrochemical performance of the materials were investigated by X-ray diffraction, scanning electron microscope and electrochemical methods. The results show that the particles of tin oxide-based materials form an interconnected network structure like mesoporous material. The average size of the particles is about 200 nm. The materials deliver a charge capacity of more than 570 mA·h·g-1. And the capacity loss per cycle is about 0.15% after being cycled for 30 times. The good electrochemical performance indicates that tin oxide-based materials are promising anodes for lithium ion batteries.展开更多
Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific sur...Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific surface area testing, galvanostatic cycling and electrochemical impedance spectroscopy. The XRD analysis shows that the sample exhibits pure spinel phase. The substitution of Co, La for Mn and Cl for O in the LiMn2O4 stabilizes the structural integrity of the spinel host, which in turn increases the electrochemical cycleability. The electrochemical experiments confirm that the capacity of the LiCo0.02La0.01Mn1.97O3.98Cl0.02 electrode maintains 90.6% of the initial capacity at 180th cycle.展开更多
We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide (rCO) nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dis...We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide (rCO) nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dispersed MnO nanoparticles with finely tuned size on rGO surface without the use of surfactant. The MnO/rGO composite enables a fully charge/discharge in 2 min to gain a reversible specific capacity of 546 (mA-h)/g which is 45 higher than the theoretical value of commercial graphite anode.展开更多
With the increasing demands for electrical energy storage technologies,rechargeable zinc ion batteries(ZIBs)have been rapidly developed in recent years owing to their high safety,low cost and high energy storage capab...With the increasing demands for electrical energy storage technologies,rechargeable zinc ion batteries(ZIBs)have been rapidly developed in recent years owing to their high safety,low cost and high energy storage capability.The cathode is an essential part of ZIBs,which hosts zinc ions and determines the capacity,rate and cycling performance of the battery.The mainstream cathodes for ZIBs are oxidebased materials with tunnel,layer or 3 D crystal structures.In this review,we mainly focus on the latest advanced oxide-based cathode materials in ZIBs,including manganese oxides,vanadium oxides,spinel compounds,and other metal oxide based cathodes.In addition,the mechanisms of zinc storage and recent development in cathode design have been discussed in detail.Finally,current challenges and perspectives for the future research directions of oxide-based cathodes in ZIBs are presented.展开更多
Ribbon-like Cu doped V6O(13) was synthesized via a simple solvothermal approach followed by heat treatment in air.As an cathode material for lithium ion battery,the ribbon-like Cu doped V6O(13 )electrode exhibited...Ribbon-like Cu doped V6O(13) was synthesized via a simple solvothermal approach followed by heat treatment in air.As an cathode material for lithium ion battery,the ribbon-like Cu doped V6O(13 )electrode exhibited good capacity retention with a reversible capacity of over 313 m Ah·g^-1 for up to 50 cycles at 0.1C,as well as a high charge capacity of 306 m Ah·g^-1 at a high current rate of 1 C,in comparison to undoped V6O(13 )electrode(267 m Ah·g^-1 at 0.1C and 273 m Ah·g^-1 at 1 C).The high rate capability and better cycleability of the doped electrode can be attributed to the influence of the Cu ions on the mophology and the electronic conductivity of V6O(13) during the lithiation and delithiation process.展开更多
Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully...Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully applied as enhanced anodes for lithium-ion batteries(LIBs).The CuO-Co_(3)O_(4)-RGO sandwiched nanostructures exhibit a reversible capacity of~847 mA·h·g^(-1)after 200 cycles’cycling at 100 mA·g^(-1)with a capacity retention of 79%.The CuO-Co_(3)O_(4)-RGO compounds show superior electrochemical properties than the comparative CuO-Co_(3)O_(4),Co_(3)O_(4)and CuO anodes,which may be ascribed to the following reasons:the hybridizing multicomponent can probably give the complementary advantages;the mutual benefit of uniformly distributing nanospheres across the layered RGO nanosheets can avoid the agglomeration of both the RGO nanosheets and the CuO-Co_(3)O_(4) nanospheres;the 3D storage structure as well as the graphene wrapped composite could enhance the electrical conductivity and reduce volume expansion effect associated with the discharge-charge process.展开更多
In this manuscript, we have demonstrated the delicate design and synthesis of bimetallic oxides nanoparticles derived from metal–oleate complex embedded in 3D graphene networks(MnO/CoMn_2O_4 GN), as an anode mater...In this manuscript, we have demonstrated the delicate design and synthesis of bimetallic oxides nanoparticles derived from metal–oleate complex embedded in 3D graphene networks(MnO/CoMn_2O_4 GN), as an anode material for lithium ion batteries. The novel synthesis of the MnO/CoMn_2O_4 GN consists of thermal decomposition of metal–oleate complex containing cobalt and manganese metals and oleate ligand, forming bimetallic oxides nanoparticles, followed by a selfassembly route with reduced graphene oxides. The MnO/CoMn_2O_4 GN composite, with a unique architecture of bimetallic oxides nanoparticles encapsulated in 3D graphene networks, rationally integrates several benefits including shortening the di usion path of Li^+ ions, improving electrical conductivity and mitigating volume variation during cycling. Studies show that the electrochemical reaction processes of MnO/Co Mn_2O_4 GN electrodes are dominated by the pseudocapacitive behavior, leading to fast Li^+ charge/discharge reactions. As a result, the MnO/CoMn_2O_4 GN manifests high initial specific capacity, stable cycling performance, and excellent rate capability.展开更多
Nano-LiMn2O4 cathode materials with nano-sized particles are synthesized via a citric acid assisted sol-gel route. The structure, the morphology and the electrochemical properties of the nano-LiMn204 are investigated....Nano-LiMn2O4 cathode materials with nano-sized particles are synthesized via a citric acid assisted sol-gel route. The structure, the morphology and the electrochemical properties of the nano-LiMn204 are investigated. Compared with the micro-sized LiMn2O4, the nano-LiMn2O4 possesses a high initial capacity (120 mAh/g) at a discharge rate of 0.2 C (29.6 mA/g). The nano-LiMn2O4 also has a good high-rate discharge capability, retaining 91% of its capacity at a discharge rate of 10 C and 73~ at a discharge rate of 40 C. In particular, the nano-LiMn2O4 shows an excellent high-rate pulse discharge capability. The cut-off voltage at the end of 50-ms pulse discharge with a discharge rate of 80 C is above 3.40 V, and the voltage returns to over 4.10 V after the pulse discharge. These results show that the prepared nano-LiMn2O4 could be a potential cathode material for the power sources with the capability to deliver very high-rate pulse currents.展开更多
Vanadium pentoxide (V205) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and el...Vanadium pentoxide (V205) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and electronic conductivities. A porous composite of V2Os-SnO2/carbon nanotubes (CNTs) was prepared by a hydrothermal method and followed by thermal treatment. The small particles of V205, their porous structure and the coexistence of SnO2 and CNTs can all facilitate the diffusion rates of the electrons and lithium ions. Electrochemical impedance spectra indicated higher ionic and electric conductivities, as compared to commercial V205. The VzOs-SnOz/CNTs composite gave a reversible discharge capacity of 198 mAh.g- 1 at the voltage range of 2.05-4.0 V, measured at a current rate of 200 mA.g-1, while that of the commercial V205 was only 88 mAh.g-1, demonstrating that the porous V2Os-SnOz/CNTs composite is a promising candidate for high-performance lithium secondary batteries.展开更多
Here,an extremely cost-effective and simple method is proposed in order to morphologically selftransform stain less steel from a completely inactive material to a fully operati onal,nanowire-structured,3D anode materi...Here,an extremely cost-effective and simple method is proposed in order to morphologically selftransform stain less steel from a completely inactive material to a fully operati onal,nanowire-structured,3D anode material for lithium ion batteries.The reagentless process of a single heating step of the plain stainless steel in a partially reduci ng atmosphere,converts the stain less steel into an active anode via metal-selective oxidation,creating vast spinel-structured nanowires directly from the electrochemically in active surface.The simple process allows the complete utilizati on of the 3D mesh structure as the electrochemically-active spinel nanowires greatly enhance the active surface area.The novel material and architecture exhibits high capacities(-1000 mAh/g after-400 cycles),long cycle life(>1100 cycles)and fast rate performance(>2C).Simple modulation of the substrate can result in very high areal and volumetric capacities.Thus,areal capacities greater than 10 mAh/cm^(2) and volumetric capacities greater than 1400 mAh/cm^(3) can be achieved.Using the proposed method,the potential reduction in cost from the use of battery-grade graphite is at least an order of magnitude,with considerable better results achieved in terms of capacity and intrinsic structural benefits of the substrate,which include direct contact of the active material with the current collector,lack of delamination and binder-free performance.This work provides a new paradigm and a key step in the long route to replace the commercial graphite anode as the next-geneation anode material.展开更多
基金supported by the grants from the Chinese Academy of Sciences(124GJHZ2023031MI)the National Natural Science Foundation of China(52173274)+1 种基金the National Key R&D Project from the Ministry of Science and Technology(2021YFA1201603)the Fundamental Research Funds for the Central Universities.
文摘Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.
基金The authors would like to acknowledge the financial support from National Nat-ural Science Foundation of China (U2004199)Excellent Youth Foundation of Henan Province (202300410373)+2 种基金China Postdoctoral Science Foundation (2021T140615 and 2020M672281)Natural Science Foundation of Henan Province (212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.
基金Project(JCYJ20170817110251498)supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen,ChinaProject(2016TQ03C919)supported by the Guangdong Special Support for the Science and Technology Leading Young Scientist,ChinaProject(21603094)supported by the National Natural Science Foundation of China
文摘Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical spherical MnO2 containing coherent amorphous/crystalline domained by a simple yet effective redox precipitation reaction at room temperature.Further,flower-like CoMn2O4 constructed by single-crystalline spinel nanosheets has been fabricated using MnO2 as precursor.This mild methodology avoids undesired particle aggregation and loss of active surface area in conventional hydrothermal or solid-state processes.Moreover,both MnO2 and CoMn2O4 nanosheets manifest superior lithium-ion storage properties,rendering them promising applications in LIBs and other energy-related fields.
基金supported by National Research Foundation of Korea grant from the Korean government (MSIP) (NRF2019R1C1C1002249, and NRF-2017M1A2A2044506)。
文摘Lithium manganese oxides(Li Mn2 O4, LMO) have attracted significant attention as important cathode materials for lithium-ion batteries(LIBs), which require fast charging based on their intrinsic electrochemical properties. However, these properties are limited by the rapid fading of cycling retention, particularly at high temperatures, because of the severe Mn corrosion triggered by the chemical reaction with fluoride(F-) species existing in the cell. To alleviate this issue, three types of silyl ether(Si–O)-functionalized task-specific additives are proposed, namely methoxytrimethylsilane, dimethoxydimethylsilane, and trimethoxymethylsilane. Ex-situ NMR analyses demonstrated that the Si-additives selectively scavenged the F-species as Si forms new chemical bonds with F via a nucleophilic substitution reaction due to the high binding affinity of Si with F-, thereby leading to a decrease in the F concentration in the cell. Furthermore, the addition of Si-additives in the electrolyte did not significantly affect the ionic conductivity or electrochemical stability of the electrolyte, indicating that these additives are compatible with conventional electrolytes. In addition, the cells cycled with Si-additives exhibited improved cycling retention at room temperature and 45 °C. Among these candidates, a combination of MTSi and the LMO cathode was found to be the most suitable choice in terms of cycling retention(71.0%), whereas the cell cycled with the standard electrolyte suffered from the fading of cycling retention triggered by Mn dissolution(64.4%). Additional ex-situ analyses of the cycled electrodes using SEM, TEM, EIS, XPS, and ICP-MS demonstrated that the use of Si-additives not only improved the surface stability of the LMO cathode but also that of the graphite anode, as the Si-additives prevent Mn corrosion. This inhibits the formation of cracks on the surface of the LMO cathode, facilitating the formation of a stable solid electrolyte interphase layer on the surface of the graphite anode. Therefore, Si-additives modified by Si–O functional groups can be effectively used to increase the overall electrochemical performance of the LMO cathode material.
基金supported by 973(2011CB935900,2010CB631303)NSFC(21231005,51071087)+4 种基金111 Project(B12015)MOE(IRT13R30)the Research Fund for the Doctoral Program of Higher Education of China(20120031110001)Tianjin Sci&Tech Project(10SYSYJC27600)the Nature Science Foundation of Tianjin(11JCYBJC07700)
文摘Assisted by graphene oxide(GO),nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4(S2)was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.
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.
文摘Anode material for lithium ion battery is prepared by chemical oxidation of natural graphite. After oxidation, the properties of natural graphite are modified, such as surface structure, the content of graphite phases, the number of micropores and its stability. thus the modified natural graphite can be used as anode material for commercial lithium ion battery. The reversible capacity is increased from 100 mAh/g to above 300 mAh/g, and its cycling properly is also satisfactory.
文摘Based on synthesizing pure spinel type lithium manganese oxides,the derivations such as LiMn1.5Ti0.5-O4,LiMn1.5Fe0.5O4,LiMn1 .5Ni0.5O4 and LiMn1.5Zn0.5O4 were prepared using solid- step-sintering method. The structures were characterized by using XRD,SEM and laser granulometer. The electrochemical measurement results show that the elemen t of iron or nickel can raise the discharging plateau voltage of LiMn2O4,an d element titanium improves the electrochemistry property of LiMn2O4 little,while element zinc destroys the electrochemistry property of LiMn2O4. The i nfluence of elements of titanium,iron,nickel,or zinc on the structure of LiMn 2O4 pure phase was discussed from the viewpoint of structural chemistry.
文摘A SnO-graphite composite material, which can deliver high capacities and good cycling stability compared with unsupported SnO, was described. This material prepared via chemical co-precipitation reaction in the presence of graphite consists of high dispersion of SnO with a size of about several hundred nanometers in the graphite. The phase structure was analyzed by X-ray diffraction (XRD). The morphology and the element distribution were examined by scanning electron microscopy (SEM) equipped with energy spectrum. The results show that the SnO-graphite composites produced by slowly hydrolysis have higher rechargeable capacities than pure graphite and better cycling performance than SnO.
文摘A novel soft chemical approach was developed to synthesize tin oxide-based powders. The microstructure, morphology, and electrochemical performance of the materials were investigated by X-ray diffraction, scanning electron microscope and electrochemical methods. The results show that the particles of tin oxide-based materials form an interconnected network structure like mesoporous material. The average size of the particles is about 200 nm. The materials deliver a charge capacity of more than 570 mA·h·g-1. And the capacity loss per cycle is about 0.15% after being cycled for 30 times. The good electrochemical performance indicates that tin oxide-based materials are promising anodes for lithium ion batteries.
基金Project(20273047) supported by the National Natural Science Foundation of China
文摘Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific surface area testing, galvanostatic cycling and electrochemical impedance spectroscopy. The XRD analysis shows that the sample exhibits pure spinel phase. The substitution of Co, La for Mn and Cl for O in the LiMn2O4 stabilizes the structural integrity of the spinel host, which in turn increases the electrochemical cycleability. The electrochemical experiments confirm that the capacity of the LiCo0.02La0.01Mn1.97O3.98Cl0.02 electrode maintains 90.6% of the initial capacity at 180th cycle.
基金financially supported by NSAF(No.U1530155)Ministry of Science and Technology(MOST)of China,US–China Collaboration on Cutting-edge Technology Development of Electric Vehicle,the Nation Key Basic Research Program of China(No.2015CB251100)Beijing Key Laboratory of Environmental Science and Engineering(No.20131039031)
基金This work was supported by the National Natural Science Foundation of China (No.21373197), the 100 Talents Program of the Chinese Academy of Sciences, USTC Startup and the Fundamental Research Funds for the Central Universities (WK2060140018).
文摘We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide (rCO) nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dispersed MnO nanoparticles with finely tuned size on rGO surface without the use of surfactant. The MnO/rGO composite enables a fully charge/discharge in 2 min to gain a reversible specific capacity of 546 (mA-h)/g which is 45 higher than the theoretical value of commercial graphite anode.
基金funded by the Australian Research Council Project(grant no.LP190100113)the award of a Future Fellow from Australian Research Council(FT170100224)。
文摘With the increasing demands for electrical energy storage technologies,rechargeable zinc ion batteries(ZIBs)have been rapidly developed in recent years owing to their high safety,low cost and high energy storage capability.The cathode is an essential part of ZIBs,which hosts zinc ions and determines the capacity,rate and cycling performance of the battery.The mainstream cathodes for ZIBs are oxidebased materials with tunnel,layer or 3 D crystal structures.In this review,we mainly focus on the latest advanced oxide-based cathode materials in ZIBs,including manganese oxides,vanadium oxides,spinel compounds,and other metal oxide based cathodes.In addition,the mechanisms of zinc storage and recent development in cathode design have been discussed in detail.Finally,current challenges and perspectives for the future research directions of oxide-based cathodes in ZIBs are presented.
基金Funded by the Program for New Century Excellent Talents in University of Ministry of Education,(No.NCET-12-0655)the Guangxi Natural Science Foundation(No.2014GXNSFFA118004)
文摘Ribbon-like Cu doped V6O(13) was synthesized via a simple solvothermal approach followed by heat treatment in air.As an cathode material for lithium ion battery,the ribbon-like Cu doped V6O(13 )electrode exhibited good capacity retention with a reversible capacity of over 313 m Ah·g^-1 for up to 50 cycles at 0.1C,as well as a high charge capacity of 306 m Ah·g^-1 at a high current rate of 1 C,in comparison to undoped V6O(13 )electrode(267 m Ah·g^-1 at 0.1C and 273 m Ah·g^-1 at 1 C).The high rate capability and better cycleability of the doped electrode can be attributed to the influence of the Cu ions on the mophology and the electronic conductivity of V6O(13) during the lithiation and delithiation process.
基金financially supported by the National Natural Science Foundation of China (21471100, 22005199)the Shenzhen Natural Science Fundation (20200813081943001)the Natural Science Foundation of Guangdong Province,China(2021A1515010241, 2021A1515010142)
文摘Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully applied as enhanced anodes for lithium-ion batteries(LIBs).The CuO-Co_(3)O_(4)-RGO sandwiched nanostructures exhibit a reversible capacity of~847 mA·h·g^(-1)after 200 cycles’cycling at 100 mA·g^(-1)with a capacity retention of 79%.The CuO-Co_(3)O_(4)-RGO compounds show superior electrochemical properties than the comparative CuO-Co_(3)O_(4),Co_(3)O_(4)and CuO anodes,which may be ascribed to the following reasons:the hybridizing multicomponent can probably give the complementary advantages;the mutual benefit of uniformly distributing nanospheres across the layered RGO nanosheets can avoid the agglomeration of both the RGO nanosheets and the CuO-Co_(3)O_(4) nanospheres;the 3D storage structure as well as the graphene wrapped composite could enhance the electrical conductivity and reduce volume expansion effect associated with the discharge-charge process.
基金financial support from National Natural Science Foundation of China (No. 21373006 and No. 51801030)the Science and Technology Program of Suzhou (SYG201732)+4 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)the project of Scientific and Technologic Infrastructure of Suzhou (SZS201708)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (17KJB430029)One-hundred Young Talents (Class A) of Guangdong University of Technology (No. 220413198)Natural Science Foundation of Guangdong Providence (No. 2018A030310571)
文摘In this manuscript, we have demonstrated the delicate design and synthesis of bimetallic oxides nanoparticles derived from metal–oleate complex embedded in 3D graphene networks(MnO/CoMn_2O_4 GN), as an anode material for lithium ion batteries. The novel synthesis of the MnO/CoMn_2O_4 GN consists of thermal decomposition of metal–oleate complex containing cobalt and manganese metals and oleate ligand, forming bimetallic oxides nanoparticles, followed by a selfassembly route with reduced graphene oxides. The MnO/CoMn_2O_4 GN composite, with a unique architecture of bimetallic oxides nanoparticles encapsulated in 3D graphene networks, rationally integrates several benefits including shortening the di usion path of Li^+ ions, improving electrical conductivity and mitigating volume variation during cycling. Studies show that the electrochemical reaction processes of MnO/Co Mn_2O_4 GN electrodes are dominated by the pseudocapacitive behavior, leading to fast Li^+ charge/discharge reactions. As a result, the MnO/CoMn_2O_4 GN manifests high initial specific capacity, stable cycling performance, and excellent rate capability.
基金supported by the National Natural Science Foundation for Postdoctoral Scientists of China (Grant No. 20090451554)
文摘Nano-LiMn2O4 cathode materials with nano-sized particles are synthesized via a citric acid assisted sol-gel route. The structure, the morphology and the electrochemical properties of the nano-LiMn204 are investigated. Compared with the micro-sized LiMn2O4, the nano-LiMn2O4 possesses a high initial capacity (120 mAh/g) at a discharge rate of 0.2 C (29.6 mA/g). The nano-LiMn2O4 also has a good high-rate discharge capability, retaining 91% of its capacity at a discharge rate of 10 C and 73~ at a discharge rate of 40 C. In particular, the nano-LiMn2O4 shows an excellent high-rate pulse discharge capability. The cut-off voltage at the end of 50-ms pulse discharge with a discharge rate of 80 C is above 3.40 V, and the voltage returns to over 4.10 V after the pulse discharge. These results show that the prepared nano-LiMn2O4 could be a potential cathode material for the power sources with the capability to deliver very high-rate pulse currents.
基金supported by the National Natural Science Foundation of China (No. 51001098)the Institute of Metal Research of CAS (No. 09NBA211A1)
文摘Vanadium pentoxide (V205) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and electronic conductivities. A porous composite of V2Os-SnO2/carbon nanotubes (CNTs) was prepared by a hydrothermal method and followed by thermal treatment. The small particles of V205, their porous structure and the coexistence of SnO2 and CNTs can all facilitate the diffusion rates of the electrons and lithium ions. Electrochemical impedance spectra indicated higher ionic and electric conductivities, as compared to commercial V205. The VzOs-SnOz/CNTs composite gave a reversible discharge capacity of 198 mAh.g- 1 at the voltage range of 2.05-4.0 V, measured at a current rate of 200 mA.g-1, while that of the commercial V205 was only 88 mAh.g-1, demonstrating that the porous V2Os-SnOz/CNTs composite is a promising candidate for high-performance lithium secondary batteries.
文摘Here,an extremely cost-effective and simple method is proposed in order to morphologically selftransform stain less steel from a completely inactive material to a fully operati onal,nanowire-structured,3D anode material for lithium ion batteries.The reagentless process of a single heating step of the plain stainless steel in a partially reduci ng atmosphere,converts the stain less steel into an active anode via metal-selective oxidation,creating vast spinel-structured nanowires directly from the electrochemically in active surface.The simple process allows the complete utilizati on of the 3D mesh structure as the electrochemically-active spinel nanowires greatly enhance the active surface area.The novel material and architecture exhibits high capacities(-1000 mAh/g after-400 cycles),long cycle life(>1100 cycles)and fast rate performance(>2C).Simple modulation of the substrate can result in very high areal and volumetric capacities.Thus,areal capacities greater than 10 mAh/cm^(2) and volumetric capacities greater than 1400 mAh/cm^(3) can be achieved.Using the proposed method,the potential reduction in cost from the use of battery-grade graphite is at least an order of magnitude,with considerable better results achieved in terms of capacity and intrinsic structural benefits of the substrate,which include direct contact of the active material with the current collector,lack of delamination and binder-free performance.This work provides a new paradigm and a key step in the long route to replace the commercial graphite anode as the next-geneation anode material.