Smart materials for safe lithium-ion batteries against thermal runaway

In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.

Empowering the Future: Exploring the Construction and Characteristics of Lithium-Ion Batteries

Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li . Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO4, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.

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.

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.

Regulating the non-effective carriers transport for high-performance lithium metal batteries

The absence of control over carriers transport during electrochemical cycling,accompanied by the deterioration of the solid electrolyte interphase(SEI)and the growth of lithium dendrites,has hindered the development of lithium metal batteries.Herein,a separator complexion consisting of polyacrylonitrile(PAN)nanofiber and MIL-101(Cr)particles prepared by electrospinning is proposed to bind the anions from the electrolyte utilizing abundant effective open metal sites in the MIL-101(Cr)particles to modulate the transport of non-effective carriers.The binding effect of the PANM separator promotes uniform lithium metal deposition and enhances the stability of the SEI layer and long cycling stability of ultra-high nickel layered oxide cathodes.Taking PANM as the Li||NCM96 separator enables high-voltage cycling stability,maintaining 72%capacity retention after 800 cycles at a charging and discharging rate of 0.2 C at a cut-off voltage of 4.5 V and 0°C.Meanwhile,the excellent high-rate performance delivers a specific capacity of 156.3 mA h g^(-1) at 10 C.In addition,outstanding cycling performance is realized from−20 to 60°C.The separator engineering facilitates the electrochemical performance of lithium metal batteries and enlightens a facile and promising strategy to develop fast charge/discharge over a wide range of temperatures.

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.

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.

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.

A new review of single-ion conducting polymer electrolytes in the light of ion transport mechanisms

With the depletion of fossil fuels and the demand for high-performance energy storage devices,solidstate lithium metal batteries have received widespread attention due to their high energy density and safety advantages.Among them,the earliest developed organic solid-state polymer electrolyte has a promising future due to its advantages such as good mechanical flexibility,but its poor ion transport performance dramatically limits its performance improvement.Therefore,single-ion conducting polymer electrolytes(SICPEs)with high lithium-ion transport number,capable of improving the concentration polarization and inhibiting the growth of lithium dendrites,have been proposed,which provide a new direction for the further development of high-performance organic polymer electrolytes.In view of this,lithium ions transport mechanisms and design principles in SICPEs are summarized and discussed in this paper.The modification principles currently used can be categorized into the following three types:enhancement of lithium salt anion-polymer interactions,weakening of lithium salt anion-cation interactions,and modulation of lithium ion-polymer interactions.In addition,the advances in single-ion conductors of conventional and novel polymer electrolytes are summarized,and several typical highperformance single-ion conductors are enumerated and analyzed in what way they improve ionic conductivity,lithium ions mobility,and the ability to inhibit lithium dendrites.Finally,the advantages and design methodology of SICPEs are summarized again and the future directions are outlined.

Loosely coordinating diluted highly concentrated electrolyte toward -60℃ Li metal batteries

Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

基于ISSA-CNN-BiGRU-Attention的锂电池健康状态评估

健康状态(SOH)预测对于电池管理系统至关重要。针对电池健康状态评估建模复杂、预测误差大等问题,准确的SOH预测仍需要改进。本文结合容量增量分析(ICA)和差分电压分析(DVA)方法,提出了一种改进麻雀优化算法(ISSA)-卷积神经网络(CNN)-双向门控递归单元(BiGRU)-注意力机制(Attention)的锂电池健康状态评估方法。通过对容量增量(IC)曲线和差分电压(DV)曲线进行高斯滤波处理,避免了噪声的影响。通过马里兰大学先进的生命周期工程中心(CALCE)数据进行处理,从滤波后的IC和DV曲线上提取一组新的电池老化特征,所提4个老化特征与SOH之间的Pearson相关系数在0.9以上。使用ISSA-CNN-BiGRU-Attention方法来构建电池SOH的预测模型,将所提方法与CNN、BiGRU、CNN-BiGRU等方法进行比较,实验结果表明,该方法的MAE与RMSE误差最大值分别为0.00544和0.00717,对比其他模型,具有优秀的鲁棒性和准确性,具有更好的实际使用价值。

Preparation and electrochemical properties of Y-doped Li_3V_2(PO_4)_3 cathode materials for lithium batteries

Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.

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.

Rare Earth Elements-Doped LiCoO_2 Cathode Material for Lithium-Ion Batteries

Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01～0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).

A ternary phased SnO_2-Fe_2O_3/SWCNTs nanocomposite as a high performance anode material for lithium ion batteries

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.

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.

Preparation of anatase TiO_2 with assistance of surfactant OP-10 and its electrochemical properties as an anode material for lithium ion batteries

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.

In-situ synthesis of interconnected SWCNT/OMC framework on silicon nanoparticles for high performance lithium-ion batteries

In spite of silicon has a superior theoretical capacity, the large volume expansion of Si anodes during Li^+ insertion/extraction is the bottle neck that results in fast capacity fading and poor cycling performance. In this paper, we report a silicon, single-walled carbon nanotube, and ordered mesoporous carbon nanocomposite synthesized by an evaporation-induced self-assembly process, in which silicon nanoparticles and single-walled carbon nanotubes were added into the phenolic resol with F-127 for co-condensation. The ordered mesoporous carbon matrix and single-walled carbon nanotubes network could effectively accommodate the volume change of silicon nanoparticles, and the ordered mesoporous structure could also provide efficient channels for the fast transport of Li-ions. As a consequence, this hybrid material exhibits a reversible capacity of 861 mAh g^(-1) after 150 cycles at a current density of 400 mAg^(-1). It achieves significant improvement in the electrochemical performance when compared with the raw materials and Si nanoparticle anodes.

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.