Separators have been gaining increasing attention to improve the performance of lithium ion batteries(LIBs),especially for high safe and long cycle life.However,commercial polyolefin separators still face the problems...Separators have been gaining increasing attention to improve the performance of lithium ion batteries(LIBs),especially for high safe and long cycle life.However,commercial polyolefin separators still face the problems of rapid capacity decay and safety issues due to the poor wettability with electrolytes and low thermal stability.Herein,a novel composite separator is proposed by introducing a surfactant of sodium dodecyl thiosulfate(SDS)into the polytetrafluoroethylene(PTFE)substrate with the binder of polyacrylic acid(PAA)through the suction filtration method.The introduction of PAA/SDS enhances the adsorption energy between PTFE substrate and electrolyte through density functional theory calculations,which improves wettability and electrolyte uptake of the separator significantly.The asachieved composite separator enables the LIBs to own high Li^(+)conductivity(0.64×10^(-3)S cm^(-1))and Li^(+)transference number(0.63),further leading to a high capacity retention of 93.50%after 500 cycles at 1 C.In addition,the uniform and smooth surface morphology of Li metal employed the composite separator after cycling indicates that the lithium dendrites can be successfully inhibited.This work indicates a promising route for the preparation of a novel composite separator for high safe LIBs.展开更多
3D urchin-like Co3O4 have been successfully prepared by calcination of the urchin-like precursors, which were synthesized through a facile hydrothermal route. The morphology and structure of the 3D urchin-like Co3O4 h...3D urchin-like Co3O4 have been successfully prepared by calcination of the urchin-like precursors, which were synthesized through a facile hydrothermal route. The morphology and structure of the 3D urchin-like Co3O4 have been characterized by field emission scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, and X-ray powder diffraction. The as-synthesized Co3O4 products are of urchin-like structures with approximated 5-7 μm in diameter, and are composed of numerous nanoparticles chains with the particles diameter of about 15 nm. This kind of urchin-like Co3O4 exhibits superior energy storage properties with the high capacity of 1.369 Ah/g and its good cyclic stability shows great potential in the rechargeable Li-ion battery.展开更多
In order to improve the electrochemical performance of polyoxomolybdate Na3[AlMo6O24H6](NAM) as the cathode material of lithium ion battery, the NAM materials with small particle size were synthesized by elevatingth...In order to improve the electrochemical performance of polyoxomolybdate Na3[AlMo6O24H6](NAM) as the cathode material of lithium ion battery, the NAM materials with small particle size were synthesized by elevatingthe synthesistemperaturein the solution.The as-prepared NAM materials were investigated by FT-IR, XRD, SEM and EIS. Their discharge-charge and cycle performance were also tested. The resultsshowthat the particle size decreasesto less than10μm at the temperature ofhigher than 40℃.When synthesized at 80℃,the NAMwiththe smallest particle size (-3μm)exhibitsthe best electrochemical performance such ashigh initial discharge capacity of 409 mA·h/gandcoulombic efficiency of 95% in the first cycle at 0.04C.展开更多
The polyoxovanadate(NH4)7[MnV13O38](AMV) was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dis...The polyoxovanadate(NH4)7[MnV13O38](AMV) was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dispersive X-ray spectroscopy. In order to improve the electrochemical performance of AMV, the particle size of as-prepared AMV is decreased to nanoscale by re-precipitation in the water-ethanol solution. The results of the electrochemical impedance spectra and the 4-pin probe measurements show that the electrical conductivity of AMV is improved by decreasing the particle size. The nanoparticle AMV shows higher initial discharge capacity and energy density than the as-prepared AMV when cycled at 0.5C. On the other hand, the nanoparticle AMV exhibits higher rate capability than the as-prepared AMV.展开更多
The requirement of energy-storage equipment needs to develop the lithium ion battery(LIB) with high electrochemical performance. The surface modification of commercial LiFePO_4(LFP) by utilizing zeolitic imidazolate f...The requirement of energy-storage equipment needs to develop the lithium ion battery(LIB) with high electrochemical performance. The surface modification of commercial LiFePO_4(LFP) by utilizing zeolitic imidazolate frameworks-8(ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances.In this work, the carbonized ZIF-8(C_(ZIF-8)) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/C_(ZIF-8) sample. The N_2 adsorption and desorptionisotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/C_(ZIF-8) cathode-active material delivers a discharge specific capacity of 159.3 m Ah g^(-1) at 0.1 C and a discharge specific energy of 141.7 m Wh g^(-1) after 200 cycles at 5.0 C(the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity,the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/C_(ZIF-8) cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.展开更多
Nickel/cobalt-layered double hydroxides(Ni Co-LDH) have been attracted increasing interest in the applications of anode materials for lithium ion battery(LIB), but the low cycle stability and rate performance are stil...Nickel/cobalt-layered double hydroxides(Ni Co-LDH) have been attracted increasing interest in the applications of anode materials for lithium ion battery(LIB), but the low cycle stability and rate performance are still limited its practice applications. To achieve high performance LIB, the surface-confined strategy has been applied to design and fabricate a new anode material of NiCo-LDH nanosheet anchored on the surface of Ti3C2 MXene(Ni Co-LDH/Ti3C2). The ultra-thin, bended and wrinkled α-phase crystal with an interlayer spacing of 8.1 ? can arrange on the conductive substrates Ti3C2 MXene directly, resulting in high electrolyte diffusion ability and low internal resistance. Furthermore, chemical bond interactions between the highly conductive Ti3C2 MXene and Ni Co-LDH nanosheets can greatly increase the ion and electron transport and reduce the volume expansion of NiCo-LDH during Li ion intercalation. As expected,the discharge capacity of 562 m Ah g-1 at 5.0 A g-1 for 800 cycles without degradation can be achieved,rate capability and cycle performance are better than that of NiCo-LDH(~100 mAh g-1). Furthermore, the density function theory(DFT) calculations were performed to demonstrate that Ni Co-LDH/Ti3C2 system can be used as a highly desirable and promising anode material for lithium ion battery.展开更多
Nb2O5-carbon nanocomposite is synthesized through a facile one-step hydrothermal reaction from sucrose as the carbon source, and stuclled as an anode material for high-performance lithium ion battery. The structural c...Nb2O5-carbon nanocomposite is synthesized through a facile one-step hydrothermal reaction from sucrose as the carbon source, and stuclled as an anode material for high-performance lithium ion battery. The structural characterizations reveal that the nanocomposite possesses a core-shell structure with a thin layer of carbon shell homogeneously coated on the Nb2O5 nanocrystals. Such a unique structure enables the composite electrode with a long cycle life by preventing the Nb2O5 from volume change and pulverization during the charge-discharge process. In addition, the carbon shell efficiently improves the rate capability. Even at a current density of 500 mA.g-1, the composite electrode still exhibits a specific capacity of ~100 mAh.g-1. These results suggest the possibility to utilize the Nb2O5-carbon core-shell composite as a high performance anode material in the practical application of lithium ion battery.展开更多
This paper investigates the mechanism of Li insertion into interphase Ni3Sn in Ni-Sn alloy for the anode of lithium ion battery by means of the first-principles plane-wave pseudopotential. Compared with other phases, ...This paper investigates the mechanism of Li insertion into interphase Ni3Sn in Ni-Sn alloy for the anode of lithium ion battery by means of the first-principles plane-wave pseudopotential. Compared with other phases, it is found that the Ni3Sn has larger relative expansion ratio and lower electrochemical potential, with its specific plateaus voltage around 0.3 eV when lithium atoms are filled in all octahedral interstitial sites, and the relative expansion ratio increasing dramatically when the lithiated phase transits from octahedral interstitial sites to tetrahedral interstitial sites. So this phase is a devastating phase for whole alloy electrode materials.展开更多
The rate performance and cycle stability of graphitized needle coke(GNC)as anode are still limited by the sluggish kinetics and volume expansion during the Li ions intercalation and de-intercalation process.Especially...The rate performance and cycle stability of graphitized needle coke(GNC)as anode are still limited by the sluggish kinetics and volume expansion during the Li ions intercalation and de-intercalation process.Especially,the output of energy density for lithium ion batteries(LIBs)is directly affected by the delithiation capacity below 0.5 V.Here,the mildly expanded graphitized needle coke(MEGNC)with the enlarged interlayer spacing from 0.346 to 0.352 nm is obtained by the two-step mild oxidation intercalation modification.The voltage plateau of MEGNC anode below 0.5 V is obviously broadened as compared to the initial GNC anode,contributing to the enhancement of Li storage below the low voltage plateau.Moreover,the coin full cell and pouch full cell configured with MEGNC anode exhibit much enhanced Li storage ability,energy density and better cycling stability than those full cells configured with GNC and commercial graphite anodes,demonstrating the practical application value of MEGNC.The superior anode behaviors of MEGNC including the increased effective capacity at low voltage and superior cyclic stability are mainly benefited from the enlarged interlayer spacing,which not only accelerates the Li ions diffusion rate,but also effectively alleviates the volume expansion and fragmentation during the Li ions intercalation process.In addition,the above result is further confirmed by the density functional theory simulation.This work provides an effective modification strategy for the NC-based graphite to enhance the delithiation capacity at a low voltage plateau,dedicated to improving the energy density and durability of LIBs.展开更多
Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electroch...Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure(XAFS) techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure (XANES) spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure (EXAFS) revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface(SEI) on the anode.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
Binary carbon mixtures, carbon black ECP 600JD(ECP) combined with vapor grown carbon fiber(VGCF) or carbon nanotube(CNT), or graphene(Gr) in different mass ratios, are investigated as the conductive additives for the ...Binary carbon mixtures, carbon black ECP 600JD(ECP) combined with vapor grown carbon fiber(VGCF) or carbon nanotube(CNT), or graphene(Gr) in different mass ratios, are investigated as the conductive additives for the cathode material polyoxomolybadate Na_3[AlMo_6O_(24)H_6](NAM). Field emission scanning electron microscopy and energy dispersive X-ray spectroscopy show that the surfaces of NAM particles are covered homogeneously with the binary conductive additive mixtures except the combination of ECP and CNT. The optimum combination is the mixture of ECP and VGCF, which shows higher discharge capacity than the combinations of ECP and CNT or Gr. Initial discharge capacities of 364, 339, and 291 m A·h/g are obtained by the combination of ECP and VGCF in the mass ratios of 2:1, 1:1, and 1:2, respectively. The results of electrochemical impedance spectra and 4-pin probe measurements demonstrate that the combination of ECP and VGCF exhibits the highest electrical conductivity for the electrode.展开更多
In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepare...In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy(SEM) were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^+ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.展开更多
Lithium ion battery has typical character of distributed parameter system, and can be described precisely by partial differential equations and multi-physics theory because lithium ion battery is a complicated electro...Lithium ion battery has typical character of distributed parameter system, and can be described precisely by partial differential equations and multi-physics theory because lithium ion battery is a complicated electrochemical energy storage system. A novel failure prediction modeling method of lithium ion battery based on distributed parameter estimation and single particle model is proposed in this work. Lithium ion concentration in the anode of lithium ion battery is an unmeasurable distributed variable. Failure prediction system can estimate lithium ion concentration online, track the failure residual which is the difference between the estimated value and the ideal value. The precaution signal will be triggered when the failure residual is beyond the predefined failure precaution threshold, and the failure countdown prediction module will be activated. The remaining time of the severe failure threshold can be estimated by the failure countdown prediction module according to the changing rate of the failure residual. A simulation example verifies that lithium ion concentration in the anode of lithium ion battery can be estimated exactly and effectively by the failure prediction model. The precaution signal can be triggered reliably, and the remaining time of the severe failure can be forecasted accurately by the failure countdown prediction module.展开更多
A chemical deposition was supposed to be an effwient method in preparation of nano-sized Sn/ MWNTs. The nanoconmposites of MWNTs and Sn/ MWNTs were both used as anodes of lithium ion battery. The special capacities an...A chemical deposition was supposed to be an effwient method in preparation of nano-sized Sn/ MWNTs. The nanoconmposites of MWNTs and Sn/ MWNTs were both used as anodes of lithium ion battery. The special capacities and coulomb efficiencies of Snl MWNTs were studied by means of electrochemical methods. The coating of Sn on MWNTs observed by TEM was amorphous and nano-sized. The reversible capacity of Sn/ MWNTs , which was much larger than that of MWNTs , was 824 mAh/ g in the 1 st charge and discharge cycle. The coulomb efficiency of Sn/ MWNTs in the 1 st cycle was increased by 16% compared with that of MWNTs. The additional Sn, which was 37wt% of total Sn/ MWNTs' weight, introduced the additional reversible lithiation capacity at least 250 mAh/ g in the 40 charge and discharge cycles. The dispersing degree of Sn on MWNTs was the main reason for the influence of the electrochemical perfomance of the Sn/ MWNTs . Sn/ MWNTs is proved to be a promising candidate as an anode of lithium ion battery.展开更多
The mechanism of lithium intercalation/deintercalation for phase Al0.8Ni3Sn0.2 as anode material used in lithium ion battery was studied carefully based on the first-principle plane wave pseudo-potential method. The c...The mechanism of lithium intercalation/deintercalation for phase Al0.8Ni3Sn0.2 as anode material used in lithium ion battery was studied carefully based on the first-principle plane wave pseudo-potential method. The calculated results indicated that SnNi Al alloy had high theoretical capacity when used as anode material, however, there was high initial irreversible capacity loss because of the large volume expansion. Therefore the technological parameters during preparing the Sn-Ni-Al anode should be controlled strictly to make the content of Al0.8Ni3Sn0.2 phase as low as possible and to make the anode consist of promising Sn-Ni and AI-Ni phases. For comparison, an experiment based on magnetron sputtering was done. The result showed that the calculation is in good agreement with the experiment. We found that the first-principle investigation method is of far-reaching significance in synthesising new commercial anode materials with high capacity and good cycle performance.展开更多
In this study, novel Carbon aerogel (CA)/Co<sub>3</sub>O<sub>4</sub>/Carbon (C) composites with a double protective structure are synthesized through a solvothermal method and in-situ polymeriz...In this study, novel Carbon aerogel (CA)/Co<sub>3</sub>O<sub>4</sub>/Carbon (C) composites with a double protective structure are synthesized through a solvothermal method and in-situ polymerization. The morphology and structure are characterized by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Fourier transform infrared spectroscopy (FTIR). The loading content of active anode material <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> in the composite is investigated by thermogravimetry, and the electrochemical properties of the composite are characterized by electrochemical impedance spectroscopy (EIS). The SEM results show that the nano-sized spherical <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> particle is adhered to the inner Carbon aerogel (CA). The HRTEM result indicates the thickness of the prepared Carbon (C) up to 40 nm. Nano-sheet is coated on the surface of the <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> particle. Compared with the pure <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> anode materials, the Carbon aerogel (CA)/<span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub>/Carbon (C) composites have better transport kinetics for both electron and lithium-ion in EIS testing results, which may contribute to its higher specific capacity and higher first coulomb efficiency. Due to the unique structure of the composite material with double protection against the volume expansion of <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> when charged, the Carbon aerogel (CA)/<span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub>/Carbon (C) composite material exhibits better cycle stability with a discharge capacity of 1180 mAh/g after 50 cycles. Therefore, the double protection strategy is verified as an effective method to improve the electrochemical performance of transition metal oxide with carbon composite as an anode material in lithium battery.展开更多
As the key component of electrochemical energy storage devices, an electrode with superior ions transport pores is the important premise for high electrochemical performance. In this paper, we developed a unique solut...As the key component of electrochemical energy storage devices, an electrode with superior ions transport pores is the important premise for high electrochemical performance. In this paper, we developed a unique solution process to prepare freestanding TiO_2/graphene hydrogel electrode with tunable density and porous structures. By incorporating room temperature ionic liquids(RTILs), even upon drying, the non-volatile RTILs that remained in the gel film would preserve the efficient ion transport channels and prevent the electrode from closely stacking, to develop dense yet porous structures. As a result, the dense TiO_2/graphene gel film as an electrode for lithium ion battery displayed a good gravimetric electrochemical performance and more importantly a high volumetric performance.展开更多
Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anode...Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.展开更多
Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and p...Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.展开更多
基金supported by the Science Foundation of the National Key Laboratory of Science and Technology on Advanced Composites in Special Environmentsthe National Natural Science Foundation of China(12002109)+1 种基金the China Postdoctoral Science Foundation(2020M670898)the Heilongjiang Postdoctoral Fund(LBH-Z20060)。
文摘Separators have been gaining increasing attention to improve the performance of lithium ion batteries(LIBs),especially for high safe and long cycle life.However,commercial polyolefin separators still face the problems of rapid capacity decay and safety issues due to the poor wettability with electrolytes and low thermal stability.Herein,a novel composite separator is proposed by introducing a surfactant of sodium dodecyl thiosulfate(SDS)into the polytetrafluoroethylene(PTFE)substrate with the binder of polyacrylic acid(PAA)through the suction filtration method.The introduction of PAA/SDS enhances the adsorption energy between PTFE substrate and electrolyte through density functional theory calculations,which improves wettability and electrolyte uptake of the separator significantly.The asachieved composite separator enables the LIBs to own high Li^(+)conductivity(0.64×10^(-3)S cm^(-1))and Li^(+)transference number(0.63),further leading to a high capacity retention of 93.50%after 500 cycles at 1 C.In addition,the uniform and smooth surface morphology of Li metal employed the composite separator after cycling indicates that the lithium dendrites can be successfully inhibited.This work indicates a promising route for the preparation of a novel composite separator for high safe LIBs.
基金This work was supported by the National Natural Science Foundation of China (No.11074254), the Ministry of Science and Technology of China (No.2005CB623603), the Hundred Talent Program of Chinese Academy of Sciences, and the President Foundation of Hefei Institute of Physical Sciences.
文摘3D urchin-like Co3O4 have been successfully prepared by calcination of the urchin-like precursors, which were synthesized through a facile hydrothermal route. The morphology and structure of the 3D urchin-like Co3O4 have been characterized by field emission scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, and X-ray powder diffraction. The as-synthesized Co3O4 products are of urchin-like structures with approximated 5-7 μm in diameter, and are composed of numerous nanoparticles chains with the particles diameter of about 15 nm. This kind of urchin-like Co3O4 exhibits superior energy storage properties with the high capacity of 1.369 Ah/g and its good cyclic stability shows great potential in the rechargeable Li-ion battery.
文摘In order to improve the electrochemical performance of polyoxomolybdate Na3[AlMo6O24H6](NAM) as the cathode material of lithium ion battery, the NAM materials with small particle size were synthesized by elevatingthe synthesistemperaturein the solution.The as-prepared NAM materials were investigated by FT-IR, XRD, SEM and EIS. Their discharge-charge and cycle performance were also tested. The resultsshowthat the particle size decreasesto less than10μm at the temperature ofhigher than 40℃.When synthesized at 80℃,the NAMwiththe smallest particle size (-3μm)exhibitsthe best electrochemical performance such ashigh initial discharge capacity of 409 mA·h/gandcoulombic efficiency of 95% in the first cycle at 0.04C.
文摘The polyoxovanadate(NH4)7[MnV13O38](AMV) was synthesized and characterized by X-ray diffraction pattern, Fourier transform infrared spectra, and field emission scanning electron microscope equipped with energy dispersive X-ray spectroscopy. In order to improve the electrochemical performance of AMV, the particle size of as-prepared AMV is decreased to nanoscale by re-precipitation in the water-ethanol solution. The results of the electrochemical impedance spectra and the 4-pin probe measurements show that the electrical conductivity of AMV is improved by decreasing the particle size. The nanoparticle AMV shows higher initial discharge capacity and energy density than the as-prepared AMV when cycled at 0.5C. On the other hand, the nanoparticle AMV exhibits higher rate capability than the as-prepared AMV.
基金supported by the Scientific and Technological Development Project of the Beijing Education Committee(No.KZ201710005009)
文摘The requirement of energy-storage equipment needs to develop the lithium ion battery(LIB) with high electrochemical performance. The surface modification of commercial LiFePO_4(LFP) by utilizing zeolitic imidazolate frameworks-8(ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances.In this work, the carbonized ZIF-8(C_(ZIF-8)) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/C_(ZIF-8) sample. The N_2 adsorption and desorptionisotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/C_(ZIF-8) cathode-active material delivers a discharge specific capacity of 159.3 m Ah g^(-1) at 0.1 C and a discharge specific energy of 141.7 m Wh g^(-1) after 200 cycles at 5.0 C(the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity,the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/C_(ZIF-8) cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.
基金Rachadapisek Sompoch project,Chulalongkorn University(CU_GR_62_14_62_02)the Energy Conservation and Promotion Fund Office,Ministry of Energy+2 种基金the NSFC(grant 51421091)National Science Foundation for Distinguished Young Scholars for Hebei Province of China(grant E2016203376)Asahi Glass Foundation。
文摘Nickel/cobalt-layered double hydroxides(Ni Co-LDH) have been attracted increasing interest in the applications of anode materials for lithium ion battery(LIB), but the low cycle stability and rate performance are still limited its practice applications. To achieve high performance LIB, the surface-confined strategy has been applied to design and fabricate a new anode material of NiCo-LDH nanosheet anchored on the surface of Ti3C2 MXene(Ni Co-LDH/Ti3C2). The ultra-thin, bended and wrinkled α-phase crystal with an interlayer spacing of 8.1 ? can arrange on the conductive substrates Ti3C2 MXene directly, resulting in high electrolyte diffusion ability and low internal resistance. Furthermore, chemical bond interactions between the highly conductive Ti3C2 MXene and Ni Co-LDH nanosheets can greatly increase the ion and electron transport and reduce the volume expansion of NiCo-LDH during Li ion intercalation. As expected,the discharge capacity of 562 m Ah g-1 at 5.0 A g-1 for 800 cycles without degradation can be achieved,rate capability and cycle performance are better than that of NiCo-LDH(~100 mAh g-1). Furthermore, the density function theory(DFT) calculations were performed to demonstrate that Ni Co-LDH/Ti3C2 system can be used as a highly desirable and promising anode material for lithium ion battery.
基金supported by Nano Special Plan from Shanghai Municipal Science and Technology Plan of Commission(No.l052nm06900)
文摘Nb2O5-carbon nanocomposite is synthesized through a facile one-step hydrothermal reaction from sucrose as the carbon source, and stuclled as an anode material for high-performance lithium ion battery. The structural characterizations reveal that the nanocomposite possesses a core-shell structure with a thin layer of carbon shell homogeneously coated on the Nb2O5 nanocrystals. Such a unique structure enables the composite electrode with a long cycle life by preventing the Nb2O5 from volume change and pulverization during the charge-discharge process. In addition, the carbon shell efficiently improves the rate capability. Even at a current density of 500 mA.g-1, the composite electrode still exhibits a specific capacity of ~100 mAh.g-1. These results suggest the possibility to utilize the Nb2O5-carbon core-shell composite as a high performance anode material in the practical application of lithium ion battery.
基金supported by the National Natural Science Foundation of China (Grant No 50771046)the Key Program of Natural Science Foundation of Guangdong Province of China (Grant No 05200534)+1 种基金the Program for Tackling Key Problems of Guangdong Province of China (Grant No 2006A10704003)the Program for Tackling Key Problems of Guangzhou City of China (GrantNo 2006Z3-D2031)
文摘This paper investigates the mechanism of Li insertion into interphase Ni3Sn in Ni-Sn alloy for the anode of lithium ion battery by means of the first-principles plane-wave pseudopotential. Compared with other phases, it is found that the Ni3Sn has larger relative expansion ratio and lower electrochemical potential, with its specific plateaus voltage around 0.3 eV when lithium atoms are filled in all octahedral interstitial sites, and the relative expansion ratio increasing dramatically when the lithiated phase transits from octahedral interstitial sites to tetrahedral interstitial sites. So this phase is a devastating phase for whole alloy electrode materials.
基金supported by the National Natural Science Foundation of China(21776309,22122807 and 21706283)。
文摘The rate performance and cycle stability of graphitized needle coke(GNC)as anode are still limited by the sluggish kinetics and volume expansion during the Li ions intercalation and de-intercalation process.Especially,the output of energy density for lithium ion batteries(LIBs)is directly affected by the delithiation capacity below 0.5 V.Here,the mildly expanded graphitized needle coke(MEGNC)with the enlarged interlayer spacing from 0.346 to 0.352 nm is obtained by the two-step mild oxidation intercalation modification.The voltage plateau of MEGNC anode below 0.5 V is obviously broadened as compared to the initial GNC anode,contributing to the enhancement of Li storage below the low voltage plateau.Moreover,the coin full cell and pouch full cell configured with MEGNC anode exhibit much enhanced Li storage ability,energy density and better cycling stability than those full cells configured with GNC and commercial graphite anodes,demonstrating the practical application value of MEGNC.The superior anode behaviors of MEGNC including the increased effective capacity at low voltage and superior cyclic stability are mainly benefited from the enlarged interlayer spacing,which not only accelerates the Li ions diffusion rate,but also effectively alleviates the volume expansion and fragmentation during the Li ions intercalation process.In addition,the above result is further confirmed by the density functional theory simulation.This work provides an effective modification strategy for the NC-based graphite to enhance the delithiation capacity at a low voltage plateau,dedicated to improving the energy density and durability of LIBs.
基金financially supported by NSFC (Grant Nos.21621091,21373008)the National Key Research and Development Program of China (2016YFB0100202)
文摘Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure(XAFS) techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure (XANES) spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure (EXAFS) revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface(SEI) on the anode.
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Binary carbon mixtures, carbon black ECP 600JD(ECP) combined with vapor grown carbon fiber(VGCF) or carbon nanotube(CNT), or graphene(Gr) in different mass ratios, are investigated as the conductive additives for the cathode material polyoxomolybadate Na_3[AlMo_6O_(24)H_6](NAM). Field emission scanning electron microscopy and energy dispersive X-ray spectroscopy show that the surfaces of NAM particles are covered homogeneously with the binary conductive additive mixtures except the combination of ECP and CNT. The optimum combination is the mixture of ECP and VGCF, which shows higher discharge capacity than the combinations of ECP and CNT or Gr. Initial discharge capacities of 364, 339, and 291 m A·h/g are obtained by the combination of ECP and VGCF in the mass ratios of 2:1, 1:1, and 1:2, respectively. The results of electrochemical impedance spectra and 4-pin probe measurements demonstrate that the combination of ECP and VGCF exhibits the highest electrical conductivity for the electrode.
基金Project(50604018)supported by the National Natural Science Foundation of China
文摘In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy(SEM) were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^+ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.
基金This work was supported by the Fundamental Research Funds for the Central Universities (No.2017JBM003), the National Natural Science Foundation of China (No.61575053, No.61504008), and the Specialized Research Fund for the Doctoral Program of Higher Education of China (No.20130009120042).
文摘Lithium ion battery has typical character of distributed parameter system, and can be described precisely by partial differential equations and multi-physics theory because lithium ion battery is a complicated electrochemical energy storage system. A novel failure prediction modeling method of lithium ion battery based on distributed parameter estimation and single particle model is proposed in this work. Lithium ion concentration in the anode of lithium ion battery is an unmeasurable distributed variable. Failure prediction system can estimate lithium ion concentration online, track the failure residual which is the difference between the estimated value and the ideal value. The precaution signal will be triggered when the failure residual is beyond the predefined failure precaution threshold, and the failure countdown prediction module will be activated. The remaining time of the severe failure threshold can be estimated by the failure countdown prediction module according to the changing rate of the failure residual. A simulation example verifies that lithium ion concentration in the anode of lithium ion battery can be estimated exactly and effectively by the failure prediction model. The precaution signal can be triggered reliably, and the remaining time of the severe failure can be forecasted accurately by the failure countdown prediction module.
基金Funded by the National Basic Research Programof China( No.2003CB61570)
文摘A chemical deposition was supposed to be an effwient method in preparation of nano-sized Sn/ MWNTs. The nanoconmposites of MWNTs and Sn/ MWNTs were both used as anodes of lithium ion battery. The special capacities and coulomb efficiencies of Snl MWNTs were studied by means of electrochemical methods. The coating of Sn on MWNTs observed by TEM was amorphous and nano-sized. The reversible capacity of Sn/ MWNTs , which was much larger than that of MWNTs , was 824 mAh/ g in the 1 st charge and discharge cycle. The coulomb efficiency of Sn/ MWNTs in the 1 st cycle was increased by 16% compared with that of MWNTs. The additional Sn, which was 37wt% of total Sn/ MWNTs' weight, introduced the additional reversible lithiation capacity at least 250 mAh/ g in the 40 charge and discharge cycles. The dispersing degree of Sn on MWNTs was the main reason for the influence of the electrochemical perfomance of the Sn/ MWNTs . Sn/ MWNTs is proved to be a promising candidate as an anode of lithium ion battery.
基金Project supported by the National Natural Science Foundation of China (Grant No. 50771046)China Postdoctoral Science Foundation (Grant No. 20080440764)Guangdong Province Natural Science Foundation (Grant No. 9451063101002082)
文摘The mechanism of lithium intercalation/deintercalation for phase Al0.8Ni3Sn0.2 as anode material used in lithium ion battery was studied carefully based on the first-principle plane wave pseudo-potential method. The calculated results indicated that SnNi Al alloy had high theoretical capacity when used as anode material, however, there was high initial irreversible capacity loss because of the large volume expansion. Therefore the technological parameters during preparing the Sn-Ni-Al anode should be controlled strictly to make the content of Al0.8Ni3Sn0.2 phase as low as possible and to make the anode consist of promising Sn-Ni and AI-Ni phases. For comparison, an experiment based on magnetron sputtering was done. The result showed that the calculation is in good agreement with the experiment. We found that the first-principle investigation method is of far-reaching significance in synthesising new commercial anode materials with high capacity and good cycle performance.
文摘In this study, novel Carbon aerogel (CA)/Co<sub>3</sub>O<sub>4</sub>/Carbon (C) composites with a double protective structure are synthesized through a solvothermal method and in-situ polymerization. The morphology and structure are characterized by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Fourier transform infrared spectroscopy (FTIR). The loading content of active anode material <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> in the composite is investigated by thermogravimetry, and the electrochemical properties of the composite are characterized by electrochemical impedance spectroscopy (EIS). The SEM results show that the nano-sized spherical <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> particle is adhered to the inner Carbon aerogel (CA). The HRTEM result indicates the thickness of the prepared Carbon (C) up to 40 nm. Nano-sheet is coated on the surface of the <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> particle. Compared with the pure <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> anode materials, the Carbon aerogel (CA)/<span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub>/Carbon (C) composites have better transport kinetics for both electron and lithium-ion in EIS testing results, which may contribute to its higher specific capacity and higher first coulomb efficiency. Due to the unique structure of the composite material with double protection against the volume expansion of <span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub> when charged, the Carbon aerogel (CA)/<span style="white-space:normal;">Co</span><sub style="white-space:normal;">3</sub><span style="white-space:normal;">O</span><sub style="white-space:normal;">4</sub>/Carbon (C) composite material exhibits better cycle stability with a discharge capacity of 1180 mAh/g after 50 cycles. Therefore, the double protection strategy is verified as an effective method to improve the electrochemical performance of transition metal oxide with carbon composite as an anode material in lithium battery.
基金supported by grants from the National Natural Science Foundation of China(21303251)Innovation Program of Shanghai Municipal Education Commission(16SG17)the Shenzhen Science and Technology Foundation(JCYJ201419122040621)
文摘As the key component of electrochemical energy storage devices, an electrode with superior ions transport pores is the important premise for high electrochemical performance. In this paper, we developed a unique solution process to prepare freestanding TiO_2/graphene hydrogel electrode with tunable density and porous structures. By incorporating room temperature ionic liquids(RTILs), even upon drying, the non-volatile RTILs that remained in the gel film would preserve the efficient ion transport channels and prevent the electrode from closely stacking, to develop dense yet porous structures. As a result, the dense TiO_2/graphene gel film as an electrode for lithium ion battery displayed a good gravimetric electrochemical performance and more importantly a high volumetric performance.
基金National Research Foundation,Grant/Award Number:2022R1A2C1092273。
文摘Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.
基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110762Research Grants Council of the Hong Kong Special Administrative Region,China,Grant/Award Number:R6005‐20Shenzhen Key Laboratory of Advanced Energy Storage,Grant/Award Number:ZDSYS20220401141000001。
文摘Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.