A surfactant-modified composite separator for high safe lithium ion battery

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.

The Surface Coating of Commercial LiFePO_4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

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.

Nb_2O_5-carbon core-shell nanocomposite as anode material for lithium ion battery

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.

First-principles study of interphase Ni_3Sn in Sn-Ni alloy for anode of lithium ion battery

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.

NiCo-LDH/Ti3C2 MXene hybrid materials for lithium ion battery with high-rate capability and long cycle life

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.

Boosting of reversible capacity delivered at a low voltage below 0.5 V in mildly expanded graphitized needle coke anode for a high-energy lithium ion battery

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.

Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

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.

Preparation of Anode Material for Lithium Ion Battery by Chemical Oxidation

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.

Effect of binary conductive additive mixtures on electrochemical performance of polyoxomolybdate as cathode material of lithium ion battery

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.

Nano-sized Sn/MWNTs and MWNTs Served as the Anode of Lithium Ion Battery

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.

First-principle study on phase Al_(0.8)Ni_3Sn_(0.2) in Sn-Ni-Al alloy as anode for lithium ion battery

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.

Unique Double Carbon Protection Structured Co₃O₄Anode for Lithium Ion Battery

In this study, novel Carbon aerogel (CA)/Co3O4/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 Co3O4 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 Co3O4 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 Co3O4 particle. Compared with the pure Co3O4 anode materials, the Carbon aerogel (CA)/Co3O4/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 Co3O4 when charged, the Carbon aerogel (CA)/Co3O4/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.

Engineering two-dimensional pores in freestanding TiO_2/graphene gel film for high performance lithium ion battery

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.

Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries

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.

Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

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.

The efficiency and toxicity of dodecafluoro-2-methylpentan-3-one in suppressing lithium-ion battery fire

Currently,the effective and clean suppression of lithium-ion battery(LIB)fires remains a challenge.The present work investigates the use of various inhibitor doses(Xin)of dodecafluoro-2-methylpentan-3-one(C_(6) F_(12)O)in 300 Ah LIBs,and systematically examines the thermal and toxic hazards of the extinguished batteries via real scale combustion and gas analysis.The inhibitor is shown to be completely effective.The inhibition mechanism involves a combination of chemical inhibition and physical cooling.While the chemical inhibition effect tends to saturate with increasing Xin,the physical cooling remains effective at higher inhibitor doses.However,extinguishing the battery fire with a high Xin of C_(6)F_(12)O is found to incur serious toxicity problems.These results are expected to provide a guideline for the design of inhibitor doses for the suppression of LIB fires.

Performance improvement of lithium-ion battery by pulse current

Periodically changed current is called pulse current.It has been found that using the pulse current to charge/discharge lithium-ion batteries can improve the safety and cycle stability of the battery.In this short review,the mechanisms of pulse current improving the performance of lithium-ion batteries are summarized from four aspects:activation,warming up,fast charging and inhibition of lithium dendrites.Related content may help us use the pulse current to improve the performance of lithium-ion batteries and further optimize pulse current technology.

Investigation on step overcharge to self-heating behavior and mechanism analysis of lithium ion batteries

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.

Carbon combustion synthesis of lithium cobalt oxide as cathode material for lithium ion battery

Lithium cobalt oxide （LiCoO2） was synthesized by carbon combustion synthesis （CCS） using carbon as fuel. X-ray diffraction （XRD） and scanning electron microscope （SEM） measurements showed that carbon combustion led to the formation of layered structure of LiCoO2 and the particle size could be controlled by carbon content. For the LiCoO2 sample prepared at 800℃ for 2 h, at molar ratio of C/Co = 0.5, the particle-size distribution fell in the narrow range of 3-5 μm. Electrochemical tests indicated this LiCoO2 sample delivered an initial discharge capacity of 148 mAh/g with capacity retention rate higher than 97% after 10 cycles.