To obtain intrinsic overcharge boundary and investigate overcharge mechanism,here we propose an innovative method,the step overcharge test,to reduce the thermal crossover and distinguish the overcharge thermal behavio...To obtain intrinsic overcharge boundary and investigate overcharge mechanism,here we propose an innovative method,the step overcharge test,to reduce the thermal crossover and distinguish the overcharge thermal behavior,including 5%state of charge(SOC)with small current overcharge and resting until the temperature equilibrium under adiabatic conditions.The intrinsic thermal response and the self-excitation behaviour are analysed through temperature and voltage changes during the step overcharge period.Experimental results show that the deintercalated state of the cathode is highly correlated to self-heating parasitic reactions.Before reaching the upper limit of Negative/Positive(N/P)ratio,the temperature changes little,the heat generation is significantly induced by the reversible heat(endothermic)and ohmic heat,which could balance each other.Following that the lithium metal is gradually deposited on the surface of the anode and reacts with electrolyte upon overcharge,inducing selfheating side reaction.However,this spontaneous thermal reaction could be“self-extinguished”.When the lithium in cathode is completely deintercalated,the boundary point of overcharge is about 4.7 V(~148%SOC,>40℃),and from this point,the self-heating behaviour could be continuously triggered until thermal runaway(TR)without additional overcharge.The whole static and spontaneous process lasts for 115 h and the side reaction heat is beyond 320,000 J.The continuous self-excitation behavior inside the battery is attributed to the interaction between the highly oxidized cathode and the solvent,which leads to the dissolution of metal ions.The dissolved metal ions destroy the SEI(solid electrolyte interphase)film on the surface of the deposited Li of anode,which induces the thermal reaction between lithium metal and the solvent.The interaction between cathode,the deposited Li of anode,and solvent promotes the temperature of the battery to rise slowly.When the temperature of the battery reaches more than 60℃,the reaction between lithium metal and solvent is accelerated.After the temperature rises rapidly to the melting point of the separator,it triggers the thermal runaway of the battery due to the short circuit of the battery.展开更多
Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-pr...Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-programmed reduction, and thermogravimetric analysis. It is found that the flower-like CuO microspheres, which are composed of CuO nanosheets, possess an average diameter of 4.2 μm and a Brunauer–Emmett–Teller surface area of 12.6 m2/g. Compared with the flower-like CuO, the obtained flower-like CuO/graphene composite shows an enhanced electrochemical performance with a higher capacity of 603 mA-h/g at 0.1 C rate and 382 mA-h/g at 1 C rate, and exhibits a better cycle stability with a high capacity retention of 95.5 % after 50 cycles even though at 1 C rate.展开更多
An efficient synthesis of carbon nanofibers by pyrolysis of as-prepared polypyrrole nanowires was reported. Under the subsequent KOH activation, a significant morphology variation was detected and the obtained sample ...An efficient synthesis of carbon nanofibers by pyrolysis of as-prepared polypyrrole nanowires was reported. Under the subsequent KOH activation, a significant morphology variation was detected and the obtained sample took on a ribbon-like structure. The morphology and structure of the carbon nanofibers and carbon nanoribbons were characterized. When the as-prepared one-dimensional carbon nanostructures were used as anode materials in lithium ion batteries, both of them exhibited superior cyclical stability and good rate properties. After 50 cycles, the reversible capacity of carbon nanofibers electrode maintained 530 mA·h/g. Concerning carbon nanoribbons, the reversible capacity is always larger than 850 mA·h/g and the reversible capacity retention after 23 cycles is 86%.展开更多
Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galva...Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.展开更多
NA novel smelting reduction process based on FeO-SiO2-Al2O3 slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and t...NA novel smelting reduction process based on FeO-SiO2-Al2O3 slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0：1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO-SiO2-Al2O3 slag system for the smelting process is appropriate under the conditions of m（FeO）：m（SiO2）=0.58：1？1.03：1, and 17.19%？21.52% Al2O3 content. The obtained alloy was mainly composed of Fe-Co-Cu-Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.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
Nanostructured metal oxides derived from metal organic frameworks have been shown to be promising materials for application in high energy density lithium ion batteries. In this work, porous nanostructured ZnCo2O4and ...Nanostructured metal oxides derived from metal organic frameworks have been shown to be promising materials for application in high energy density lithium ion batteries. In this work, porous nanostructured ZnCo2O4and Co3O4were synthesized by a facile and cost-effective approach via the calcination of MOF-74 precursors and tested as anode materials for lithium ion batteries. Compared with Co3O4, the electrochemical properties of the obtained porous nanostructured ZnCo2O4exhibit higher specific capacity, more excellent cycling stability and better rate capability. It demonstrates a reversible capacity of 1243.2 m Ah/g after 80 cycles at 100 m A/g and an excellent rate performance with high average discharge specific capacities of 1586.8, 994.6, 759.6 and 509.2 m Ah/g at 200, 400, 600 and 800 m A/g, respectively.The satisfactory electrochemical performances suggest that this porous nanostructured ZnCo2O4is potentially promising for application as an efficient anode material for lithium ion batteries.展开更多
A new SnO2-Fe2O3/SWCNTs（single-walled carbon nanotubes） ternary nanocomposite was first synthesized by a facile hydrothermal approach.SnO2 and Fe2O3 nanoparticles（NPs） were homogeneously located on the surface of ...A new SnO2-Fe2O3/SWCNTs（single-walled carbon nanotubes） ternary nanocomposite was first synthesized by a facile hydrothermal approach.SnO2 and Fe2O3 nanoparticles（NPs） were homogeneously located on the surface of SWCNTs,as confirmed by X-ray diffraction（XRD）,transmission electron microscope（TEM） and energy dispersive X-ray spectroscopy（EDX）.Due to the synergistic effect of different components,the as synthesized SnO2-Fe2O3/SWCNTs composite as an anode material for lithium-ion batteries exhibited excellent electrochemical performance with a high capacity of 692 mAh·g-1 which could be maintained after 50 cycles at 200 mA·g-1.Even at a high rate of2000 mA·g-1,the capacity was still remained at 656 mAh·g-1.展开更多
A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted un...A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.展开更多
The physical fundamentals and influences upon electrode materials＇ open-circuit voltage （OCV） and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate t...The physical fundamentals and influences upon electrode materials＇ open-circuit voltage （OCV） and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries （LIBs）, and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.展开更多
With the assistance of nonionic surfactant （OP-10） and surface-selective surfactant （CH3COOH）, anatase TiO2 was prepared as an anode material for lithium ion batteries. The morphology, the crystal structure, and t...With the assistance of nonionic surfactant （OP-10） and surface-selective surfactant （CH3COOH）, anatase TiO2 was prepared as an anode material for lithium ion batteries. The morphology, the crystal structure, and the electrochemical properties of the prepared anatase TiO2 were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, electrochemical impedance spectroscopy （EIS）, and galvanostatic charge and discharge test. The result shows that the prepared anatase TiO2 has high discharge capacity and good cyclic stability. The maximum discharge capacity is 313 mAh.g^-1, and there is no significant capacity decay from the second cycle.展开更多
Ultrathin MoS2 nanosheets were prepared in high yield using a facile and effective hydrothermal intercalation and exfoliation route. The products were characterized in detail using X-ray diffraction, scanning electron...Ultrathin MoS2 nanosheets were prepared in high yield using a facile and effective hydrothermal intercalation and exfoliation route. The products were characterized in detail using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The results show that the high yield of MoS2 nanosheets with good quality was successfully achieved and the dimensions of the immense nanosheets reached 1 μm-2/zm. As anode material for Li-ion batteries, the as-prepared MoS2 nanosheets electrodes exhibited a good initial capacity of 1190 mAh.g-l and excellent cyclic stability at constant current density of 50 mA.g-1. After 50 cycles, it still delivered reversibly sustained high capacities of 750 mAh.g-1.展开更多
TiO2-coated SnO2 （TCS） hollow spheres, which are new anode materials for lithium ion （Li-ion） batteries, were prepared and characterized with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transm...TiO2-coated SnO2 （TCS） hollow spheres, which are new anode materials for lithium ion （Li-ion） batteries, were prepared and characterized with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, cyclic voltammetry （CV）, and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniforrrdy coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.展开更多
Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), ...Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.展开更多
Si-based materials have been extensively studied because of their high theoretical capacity,low working potential,and abundant reserves,but serious initial irreversible capacity loss and poor cyclic performance result...Si-based materials have been extensively studied because of their high theoretical capacity,low working potential,and abundant reserves,but serious initial irreversible capacity loss and poor cyclic performance resulting from large volume change of Si during lithiation and delithiation processes restrict their widespread application.Herein,we report the preparation of multi-shell coated Si(DS-Si)nanocomposites by in-situ electroless deposition method using Si granules as the active materials and copper sulfate as Cu sources.The ratio of Si and Cu was readily tuned by varying the concentration of copper sulfate.The multi-shell(Cu@CuxSi/SiO2)coating on Si surface promotes the formation of robust and dense SEI films and the transportation of electron.Thus,the obtained DS-Si composites exhibit an initial coulombic efficiency of 86.2%,a capacity of 1636 mAh g^-1 after 100 discharge-charge cycles at 840 mA g^-1,and an average charge capacity of 1493 mAh g^-1 at 4200 mA g^-1.This study provides a low-cost and large-scale approach to the preparation of nanostructured Si-metal composites anodes with good electrochemical performance for lithium ion batteries.展开更多
The tmiform layered Li（Ni2/8Co3/8Mn3/8）O2, Li（Ni3/8Co2/8Mn3/8）O2, and Li（Ni3/8Co3/8Mn2/8）O2 cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of c...The tmiform layered Li（Ni2/8Co3/8Mn3/8）O2, Li（Ni3/8Co2/8Mn3/8）O2, and Li（Ni3/8Co3/8Mn2/8）O2 cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of calcination temperature and transition metal contents on the structure and electrochemical properties of the Li-Ni-Co-Mn-O were systemically studied. The results of XRD and electrochemical performance measurement show that the ideal preparation conditions were to prepare the Li（Ni3/8Co3/8Mn2/8）O2 cathode material calcined at 900℃ for 10 h. The well-ordered Li（Ni3/8Co3/8Mn2/8）O2 synthesized under the optimal conditions has the I003/I104 ratio of 1.25 and the R value of 0.48 and delivers the initial discharge capacity of 172.9 mA·h·g^-1, the discharge capacity of 166.2 mA·h·g^-1 after 20 cycles at 0.2C rate, and the impedance of 558 Ω after the first cycle. The decrease of Ni content results in the decrease of discharge capacity and the bad cycling performance of the Li-Ni-Co-Mn-O cathode materials, but the decreases of Mn content and Co content to a certain extent can improve the electrochemical properties of the Li-Ni-Co-Mn-O cathode materials.展开更多
As a promising high capacity anode material for lithium ion batteries, the lithium insertion performance and possible insertion mechanism of binary alloy of NiSi2 were discussed. The initial lithium insertion of cryst...As a promising high capacity anode material for lithium ion batteries, the lithium insertion performance and possible insertion mechanism of binary alloy of NiSi2 were discussed. The initial lithium insertion of crystal NiSi2 can reach up to 600 mAh·g-1, but large irreversible capacity occurrs simultaneously for serious structure transformation and the irreversible phase forms. XRD and XPS were employed to detect the crystal structure and composition changes produced by lithium insertion. The lithium insertion-extraction behavior of NiSi2 electrode is similar to that of silicon after the first discharge. The structure stability seems related to the non-stoichimometric Ni-Si compound formed by lithium insertion into NiSi2.展开更多
Graphene was produced via a soft chemistry synthetic route for lithium ion battery applications. The sample was characterized by X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron micr...Graphene was produced via a soft chemistry synthetic route for lithium ion battery applications. The sample was characterized by X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron microscopy and transmission electron microscopy, respectively. The electrochemical performances of graphene as anode material were measured by cyclic voltammetry and galvanostatic charge/ discharge cycling. The experimental results showed that the graphene possessed a thin wrinkled paper-like morphology and large specific surface area （342 m2 · g ^-1）. The first reversible specific capacity of the graphene was as high as 905 mA· h · g ^-1 at a current density of 100 mA · g ^-1. Even at a high current density of 1000 or 2000 mA · g ^-1, the graphene maintained good cycling stability, indicating that it is a promising anode material for high-performance lithium ion batteries.展开更多
Lithium ion batteries（LIBs） are currently best energy storage devices providing rechargeable electrical storage to wide variety of applications – from portable electronics to automobiles. Though, these batteries ar...Lithium ion batteries（LIBs） are currently best energy storage devices providing rechargeable electrical storage to wide variety of applications – from portable electronics to automobiles. Though, these batteries are fully adopted, widely used and commercialized, but researchers are still extensively working on their constituent materials and developing technology to improve their performance. A major part of related research activities is devoted to the electrode of the battery for improvement in its performance thereby addressing issues like safety, lifetime, specific capacity, energy density and most importantly abundance and cost. There are number of cathode materials that have been proposed and tested at laboratory scale and subsequently utilized in commercialized batteries ever since the appearance of LIBs. Owing to the availability of improved computational resources in the last decade, first principles calculation has become a reliable tool and played a vital role to predict the material properties of electrodes prior to their experimental analysis. This review gives a comprehensive insight and thorough analysis of the global research efforts related to the cathode materials based on first principles framework, sheds light on current status of knowledge and explores the ways forward.展开更多
NiO nanoparticles with average particles size of 30 nm are synthesized using a one-pot metal–organic framework-combustion（MOF-C） technique, for use as an anode material in rechargeable lithium ion batteries（LIBs）...NiO nanoparticles with average particles size of 30 nm are synthesized using a one-pot metal–organic framework-combustion（MOF-C） technique, for use as an anode material in rechargeable lithium ion batteries（LIBs）. The structural and electronic properties of these nanoparticles are studied using various techniques, including powder X-ray diffraction（PXRD）, transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, X-ray photoelectron spectroscopy（XPS）, and N_2 adsorption/desorption studies. The as-synthesized NiO nanoparticles sustained reversible stable capacities of 748 and 410 mAh/g at applied current densities of 500 and 1000 m A/g, respectively, after 100 cycles. Furthermore, the anode displays a notable rate capability, achieving a stable capacity of ~200 mAh/g at a high current density of10 A/g. These results indicate that the size of the NiO nanoparticles and their high surface area influence their electrochemical properties. Specifically, this combustion strategy is clearly favorable for improving the cyclability and rate capability of various metal oxides in rechargeable battery electrodes.展开更多
基金funded by the National Key Research and Development Program of China(2018YFB0104400)supported by the Beijing Natural Science Foundation(2214066)。
文摘To obtain intrinsic overcharge boundary and investigate overcharge mechanism,here we propose an innovative method,the step overcharge test,to reduce the thermal crossover and distinguish the overcharge thermal behavior,including 5%state of charge(SOC)with small current overcharge and resting until the temperature equilibrium under adiabatic conditions.The intrinsic thermal response and the self-excitation behaviour are analysed through temperature and voltage changes during the step overcharge period.Experimental results show that the deintercalated state of the cathode is highly correlated to self-heating parasitic reactions.Before reaching the upper limit of Negative/Positive(N/P)ratio,the temperature changes little,the heat generation is significantly induced by the reversible heat(endothermic)and ohmic heat,which could balance each other.Following that the lithium metal is gradually deposited on the surface of the anode and reacts with electrolyte upon overcharge,inducing selfheating side reaction.However,this spontaneous thermal reaction could be“self-extinguished”.When the lithium in cathode is completely deintercalated,the boundary point of overcharge is about 4.7 V(~148%SOC,>40℃),and from this point,the self-heating behaviour could be continuously triggered until thermal runaway(TR)without additional overcharge.The whole static and spontaneous process lasts for 115 h and the side reaction heat is beyond 320,000 J.The continuous self-excitation behavior inside the battery is attributed to the interaction between the highly oxidized cathode and the solvent,which leads to the dissolution of metal ions.The dissolved metal ions destroy the SEI(solid electrolyte interphase)film on the surface of the deposited Li of anode,which induces the thermal reaction between lithium metal and the solvent.The interaction between cathode,the deposited Li of anode,and solvent promotes the temperature of the battery to rise slowly.When the temperature of the battery reaches more than 60℃,the reaction between lithium metal and solvent is accelerated.After the temperature rises rapidly to the melting point of the separator,it triggers the thermal runaway of the battery due to the short circuit of the battery.
基金Project (20110490594) supported by China Postdoctoral Science Foundation
文摘Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-programmed reduction, and thermogravimetric analysis. It is found that the flower-like CuO microspheres, which are composed of CuO nanosheets, possess an average diameter of 4.2 μm and a Brunauer–Emmett–Teller surface area of 12.6 m2/g. Compared with the flower-like CuO, the obtained flower-like CuO/graphene composite shows an enhanced electrochemical performance with a higher capacity of 603 mA-h/g at 0.1 C rate and 382 mA-h/g at 1 C rate, and exhibits a better cycle stability with a high capacity retention of 95.5 % after 50 cycles even though at 1 C rate.
基金Projects (51204209,51274240) supported by the National Natural Science Foundation of China
文摘An efficient synthesis of carbon nanofibers by pyrolysis of as-prepared polypyrrole nanowires was reported. Under the subsequent KOH activation, a significant morphology variation was detected and the obtained sample took on a ribbon-like structure. The morphology and structure of the carbon nanofibers and carbon nanoribbons were characterized. When the as-prepared one-dimensional carbon nanostructures were used as anode materials in lithium ion batteries, both of them exhibited superior cyclical stability and good rate properties. After 50 cycles, the reversible capacity of carbon nanofibers electrode maintained 530 mA·h/g. Concerning carbon nanoribbons, the reversible capacity is always larger than 850 mA·h/g and the reversible capacity retention after 23 cycles is 86%.
基金Project (20771100) supported by the National Natural Science Foundation of China
文摘Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.
基金Project(JS-211)supported by the State-Owned Enterprise Electric Vehicle Industry Alliance,China
文摘NA novel smelting reduction process based on FeO-SiO2-Al2O3 slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0：1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO-SiO2-Al2O3 slag system for the smelting process is appropriate under the conditions of m（FeO）：m（SiO2）=0.58：1？1.03：1, and 17.19%？21.52% Al2O3 content. The obtained alloy was mainly composed of Fe-Co-Cu-Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.
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Jiangsu provincial financial support of Fundamental Conditions and Science and Technology for people’s livelihood for Jiangsu key laboratory of Advanced Metallic Materials(grant number BM2007204)the National Natural Science Foundation of China(grant number 21475021,21427807)+1 种基金the Natural Science Foundation of Jiangsu Province(grant number BK20141331)the Fundamental Research Funds for the Central Universities(grant number2242016K40083)
文摘Nanostructured metal oxides derived from metal organic frameworks have been shown to be promising materials for application in high energy density lithium ion batteries. In this work, porous nanostructured ZnCo2O4and Co3O4were synthesized by a facile and cost-effective approach via the calcination of MOF-74 precursors and tested as anode materials for lithium ion batteries. Compared with Co3O4, the electrochemical properties of the obtained porous nanostructured ZnCo2O4exhibit higher specific capacity, more excellent cycling stability and better rate capability. It demonstrates a reversible capacity of 1243.2 m Ah/g after 80 cycles at 100 m A/g and an excellent rate performance with high average discharge specific capacities of 1586.8, 994.6, 759.6 and 509.2 m Ah/g at 200, 400, 600 and 800 m A/g, respectively.The satisfactory electrochemical performances suggest that this porous nanostructured ZnCo2O4is potentially promising for application as an efficient anode material for lithium ion batteries.
基金supported by the National Key Project on Basic Research(Grant No.2011CB935904)the National Natural Science Foundation of China(Grant No.21171163,91127020)NSF for Distinguished Young Scholars of Fujian Province(Grant No.2013J06006)
文摘A new SnO2-Fe2O3/SWCNTs（single-walled carbon nanotubes） ternary nanocomposite was first synthesized by a facile hydrothermal approach.SnO2 and Fe2O3 nanoparticles（NPs） were homogeneously located on the surface of SWCNTs,as confirmed by X-ray diffraction（XRD）,transmission electron microscope（TEM） and energy dispersive X-ray spectroscopy（EDX）.Due to the synergistic effect of different components,the as synthesized SnO2-Fe2O3/SWCNTs composite as an anode material for lithium-ion batteries exhibited excellent electrochemical performance with a high capacity of 692 mAh·g-1 which could be maintained after 50 cycles at 200 mA·g-1.Even at a high rate of2000 mA·g-1,the capacity was still remained at 656 mAh·g-1.
基金Project(50302016) supported by the National Natural Science Foundation of China
文摘A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.
基金supported by the National Natural Science Foundation of China(Grant Nos.51325206 and 51372228)National Basic Research Program of China(Grant No.2012CB932900)Shanghai Pujiang Program,China(Grant No.14PJ1403900)
文摘The physical fundamentals and influences upon electrode materials＇ open-circuit voltage （OCV） and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries （LIBs）, and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.
基金supported by the National Natural Science Foundation of China(No.20873046)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.200805740004)the Project of Guangdong Province(No.2009B050700039)
文摘With the assistance of nonionic surfactant （OP-10） and surface-selective surfactant （CH3COOH）, anatase TiO2 was prepared as an anode material for lithium ion batteries. The morphology, the crystal structure, and the electrochemical properties of the prepared anatase TiO2 were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, electrochemical impedance spectroscopy （EIS）, and galvanostatic charge and discharge test. The result shows that the prepared anatase TiO2 has high discharge capacity and good cyclic stability. The maximum discharge capacity is 313 mAh.g^-1, and there is no significant capacity decay from the second cycle.
基金supported by the Grants from National Natural Science Foundation of China(No.51172191,51002129 and 11074211)the National Basic Research Program of China(2012CB921303)the Hunan Provincial Innovation Foundation for Graduate(No.CX2012B265)
文摘Ultrathin MoS2 nanosheets were prepared in high yield using a facile and effective hydrothermal intercalation and exfoliation route. The products were characterized in detail using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The results show that the high yield of MoS2 nanosheets with good quality was successfully achieved and the dimensions of the immense nanosheets reached 1 μm-2/zm. As anode material for Li-ion batteries, the as-prepared MoS2 nanosheets electrodes exhibited a good initial capacity of 1190 mAh.g-l and excellent cyclic stability at constant current density of 50 mA.g-1. After 50 cycles, it still delivered reversibly sustained high capacities of 750 mAh.g-1.
基金financially supported by the National Natural Science Foundation of China (No.20873046)the Specialized Research Fund for the Doctoral Program of HigherEducation (No.200805740004)Natural Science Foundation of Guangdong Province (No.10351063101000001)
文摘TiO2-coated SnO2 （TCS） hollow spheres, which are new anode materials for lithium ion （Li-ion） batteries, were prepared and characterized with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, cyclic voltammetry （CV）, and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniforrrdy coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.
基金supported by the National Key Project for Basic Research of China (No. 2005CB623605)the National Natural Science Foundation of China (No. 11074039)the National Science Foundation for Young Scholars (No.11004032)
文摘Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.
基金supported by the China Postdoctoral Science Foundation(2018M632575)the National Natural Science Foundation of China(21875197 and 21621091)the National Key Research and Development of China(2016YFB0100202)。
文摘Si-based materials have been extensively studied because of their high theoretical capacity,low working potential,and abundant reserves,but serious initial irreversible capacity loss and poor cyclic performance resulting from large volume change of Si during lithiation and delithiation processes restrict their widespread application.Herein,we report the preparation of multi-shell coated Si(DS-Si)nanocomposites by in-situ electroless deposition method using Si granules as the active materials and copper sulfate as Cu sources.The ratio of Si and Cu was readily tuned by varying the concentration of copper sulfate.The multi-shell(Cu@CuxSi/SiO2)coating on Si surface promotes the formation of robust and dense SEI films and the transportation of electron.Thus,the obtained DS-Si composites exhibit an initial coulombic efficiency of 86.2%,a capacity of 1636 mAh g^-1 after 100 discharge-charge cycles at 840 mA g^-1,and an average charge capacity of 1493 mAh g^-1 at 4200 mA g^-1.This study provides a low-cost and large-scale approach to the preparation of nanostructured Si-metal composites anodes with good electrochemical performance for lithium ion batteries.
基金supported by the Natural Science Foundation of Hunan Province, China (No. 07JJ6082)
文摘The tmiform layered Li（Ni2/8Co3/8Mn3/8）O2, Li（Ni3/8Co2/8Mn3/8）O2, and Li（Ni3/8Co3/8Mn2/8）O2 cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of calcination temperature and transition metal contents on the structure and electrochemical properties of the Li-Ni-Co-Mn-O were systemically studied. The results of XRD and electrochemical performance measurement show that the ideal preparation conditions were to prepare the Li（Ni3/8Co3/8Mn2/8）O2 cathode material calcined at 900℃ for 10 h. The well-ordered Li（Ni3/8Co3/8Mn2/8）O2 synthesized under the optimal conditions has the I003/I104 ratio of 1.25 and the R value of 0.48 and delivers the initial discharge capacity of 172.9 mA·h·g^-1, the discharge capacity of 166.2 mA·h·g^-1 after 20 cycles at 0.2C rate, and the impedance of 558 Ω after the first cycle. The decrease of Ni content results in the decrease of discharge capacity and the bad cycling performance of the Li-Ni-Co-Mn-O cathode materials, but the decreases of Mn content and Co content to a certain extent can improve the electrochemical properties of the Li-Ni-Co-Mn-O cathode materials.
基金This work was supported by the National Natural Science Foundation of China (No. 50502009).
文摘As a promising high capacity anode material for lithium ion batteries, the lithium insertion performance and possible insertion mechanism of binary alloy of NiSi2 were discussed. The initial lithium insertion of crystal NiSi2 can reach up to 600 mAh·g-1, but large irreversible capacity occurrs simultaneously for serious structure transformation and the irreversible phase forms. XRD and XPS were employed to detect the crystal structure and composition changes produced by lithium insertion. The lithium insertion-extraction behavior of NiSi2 electrode is similar to that of silicon after the first discharge. The structure stability seems related to the non-stoichimometric Ni-Si compound formed by lithium insertion into NiSi2.
基金Funded by the Chongqing University Scientific&Technological Innovation Fund for Graduates(No.CDJXS12130006)
文摘Graphene was produced via a soft chemistry synthetic route for lithium ion battery applications. The sample was characterized by X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron microscopy and transmission electron microscopy, respectively. The electrochemical performances of graphene as anode material were measured by cyclic voltammetry and galvanostatic charge/ discharge cycling. The experimental results showed that the graphene possessed a thin wrinkled paper-like morphology and large specific surface area （342 m2 · g ^-1）. The first reversible specific capacity of the graphene was as high as 905 mA· h · g ^-1 at a current density of 100 mA · g ^-1. Even at a high current density of 1000 or 2000 mA · g ^-1, the graphene maintained good cycling stability, indicating that it is a promising anode material for high-performance lithium ion batteries.
基金Higprovide financial support vide 6509/Punjab/NRPU/R&D/HEC/2016
文摘Lithium ion batteries（LIBs） are currently best energy storage devices providing rechargeable electrical storage to wide variety of applications – from portable electronics to automobiles. Though, these batteries are fully adopted, widely used and commercialized, but researchers are still extensively working on their constituent materials and developing technology to improve their performance. A major part of related research activities is devoted to the electrode of the battery for improvement in its performance thereby addressing issues like safety, lifetime, specific capacity, energy density and most importantly abundance and cost. There are number of cathode materials that have been proposed and tested at laboratory scale and subsequently utilized in commercialized batteries ever since the appearance of LIBs. Owing to the availability of improved computational resources in the last decade, first principles calculation has become a reliable tool and played a vital role to predict the material properties of electrodes prior to their experimental analysis. This review gives a comprehensive insight and thorough analysis of the global research efforts related to the cathode materials based on first principles framework, sheds light on current status of knowledge and explores the ways forward.
基金supported by National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(2014R1A2A1A10050821)
文摘NiO nanoparticles with average particles size of 30 nm are synthesized using a one-pot metal–organic framework-combustion（MOF-C） technique, for use as an anode material in rechargeable lithium ion batteries（LIBs）. The structural and electronic properties of these nanoparticles are studied using various techniques, including powder X-ray diffraction（PXRD）, transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, X-ray photoelectron spectroscopy（XPS）, and N_2 adsorption/desorption studies. The as-synthesized NiO nanoparticles sustained reversible stable capacities of 748 and 410 mAh/g at applied current densities of 500 and 1000 m A/g, respectively, after 100 cycles. Furthermore, the anode displays a notable rate capability, achieving a stable capacity of ~200 mAh/g at a high current density of10 A/g. These results indicate that the size of the NiO nanoparticles and their high surface area influence their electrochemical properties. Specifically, this combustion strategy is clearly favorable for improving the cyclability and rate capability of various metal oxides in rechargeable battery electrodes.
