Chloride ion battery:A new emerged electrochemical system for next-generation energy storage

In the scope of developing new electrochemical concepts to build batteries with high energy density,chloride ion batteries(CIBs)have emerged as a candidate for the next generation of novel electrochemical energy storage technologies,which show the potential in matching or even surpassing the current lithium metal batteries in terms of energy density,dendrite-free safety,and elimination of the dependence on the strained lithium and cobalt resources.However,the development of CIBs is still at the initial stage with unsatisfactory performance and several challenges have hindered them from reaching commercialization.In this review,we examine the current advances of CIBs by considering the electrode material design to the electrolyte,thus outlining the new opportunities of aqueous CIBs especially combined with desalination,chloride redox battery,etc.With respect to the developing road of lithium ion and fluoride ion batteries,the possibility of using solid-state chloride ion conductors to replace liquid electrolytes is tentatively discussed.Going beyond,perspectives and clear suggestions are concluded by highlighting the major obstacles and by prescribing specific research topics to inspire more efforts for CIBs in large-scale energy storage applications.

Water molecules and oxygen-vacancy modulation of vanadium pentoxide with fast kinetics toward ultrahigh power density and durable flexible all-solid-state zinc ion battery

Aqueous zinc ion battery(ZIB)with many virtues such as high safety,cost-effective,and good environmental compatibility is a large-scale energy storage technology with great application potential.Nevertheless,its application is severely hindered by the slow diffusion of zinc ions in desirable cathode materials.Herein,a technique of water-incorporation coupled with oxygen-vacancy modulation is exploited to improve the zinc ions diffusion kinetics in vanadium pentoxide(V_(2)O_5)cathode for ZIB.The incorporated water molecules replace lattice oxygen in V_(2)O_5,and function as pillars to expand interlayer distance.So the structural stability can be enhanced,and the zinc ions diffusion kinetics might also be promoted during the repeated intercalation/deintercalation.Meanwhile,the lattice water molecules can effectively enhance conductivity due to the electronic density modulation effect.Consequently,the modulated V_(2)O_5(H-V_(2)O_5)cathode behaves with superior rate capacity and stable durability,achieving 234 mA h g^(-1)over 9000 cycles even at 20 A g^(-1).Furthermore,a flexible all-solid-state(ASS)ZIB has been constructed,exhibiting an admirable energy density of 196.6 Wh kg^(-1)and impressive power density of 20.4 kW kg^(-1)as well as excellent long-term lifespan.Importantly,the assembled flexible ASS ZIB would be able to work in a large temperature span(from-20 to 70℃).Additionally,we also uncover the energy storage mechanism of the H-V_(2)O_5 electrode,offering a novel approach for creating high-kinetics cathodes for multivalent ion storage.

Paper-based aqueous Al ion battery with water-in-salt electrolyte

Low-cost,flexible and safe battery technology is the key to the widespread usage of wearable electronics,among which the aqueous Al ion battery with water-in-salt electrolyte is a promising candidate.In this work,a flexible aqueous Al ion battery is developed using cellulose paper as substrate.The water-in-salt electrolyte is stored inside the paper,while the electrodes are either printed or attached on the paper surface,leading to a lightweight and thin-film battery prototype.Currently,this battery can tolerate a charge and discharge rate as high as 4 A g^(-1) without losing its storage capacity.The charge voltage is around 2.2 V,while the discharge plateau of 1.6–1.8 V is among the highest in reported aqueous Al ion batteries,together with a high discharge specific capacity of~140 mAh g^(-1).However,due to the water electrolysis side reaction,the faradaic efficiency can only reach 85%with a cycle life of 250 due to the dry out of electrolyte.Benefited from using flexible materials and aqueous electrolyte,this paper-based Al ion battery can tolerate various deformations such as bending,rolling and even puncturing without losing its performance.When two single cells are connected in series,the battery pack can provide a charge voltage of 4.3 V and a discharge plateau as high as 3–3.6 V,which are very close to commercial Li ion batteries.Such a cheap,flexible and safe battery technology may be widely applied in low-cost and large-quantity applications,such as RFID tags,smart packages and wearable biosensors in the future.

Electric Vehicles Lithium-Polymer Ion Battery Dynamic Behaviour Charging Identification and Modelling Scheme

Lithium-ion batteries are considered the substantial electrical storage element for electric vehicles(EVs). The battery model is the basis of battery monitoring, efficient charging, and safety management. Non-linearmodelling is the key to representing the battery and its dynamic internal parameters and performance. This paperproposes a smart scheme to model the lithium-polymer ion battery while monitoring its present charging currentand terminal voltage at various ambient conditions (temperature and relative humidity). Firstly, the suggestedframework investigated the impact of temperature and relative humidity on the charging process using the constantcurrent-constant voltage (CC-CV) charging protocol. This will be followed by monitoring the battery at thesurrounding operating temperature and relative humidity. Hence, efficient non-linear modelling of the EV batterydynamic behaviour using the Hammerstein-Wiener (H-W) model is implemented. The H-W model is considered ablack box model that can represent the battery without any mathematical equivalent circuit model which reducesthe computation complexity. Finally, the model beholds the boundaries of the charging process, not affecting onthe lifetime of the battery. Several dynamic models are applied and tested experimentally to ensure theeffectiveness of the proposed scheme under various ambient conditions where the temperature is fixed at40°C and the relative humidity (RH) at 35%, 52%, and 70%. The best fit using the H-W model reached 91.83% todescribe the dynamic behaviour of the battery with a maximum percentage of error 0.1 V which is in goodagreement with the literature survey. Besides, the model has been scaled up to represent a real EV and expressedthe significance of the proposed H-W model.

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.

Emerging rechargeable aqueous aluminum ion battery:Status,challenges,and outlooks

Aluminum ion battery(AIB)technology is an exciting alternative for post-lithium energy storage.AIBs based on ionic liquids have enabled advances in both cathode material development and fundamental understanding on mechanisms.Recently,unlocking chemistry in rechargeable aqueous aluminum ion battery(AAIB)provides impressive prospects in terms of kinetics,cost,safety considerations,and ease of operation.To review the progress on AAIB,we discuss the critical issues on aluminum electrochemistry in aqueous system,cathode material design to overcome the drawbacks by multivalent aluminum ions,and challenges on electrolyte design,aluminum stripping/plating,solid-electrolyte interface(SEI)formation,and design of cathode materials.This review aims to stimulate exploration of high-performance AAIB and rationalize feasibility grounded on underlying reaction mechanisms.

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.

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.

β-MnO_(2) with proton conversion mechanism in rechargeable zinc ion battery

Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,the under-debate proton reaction mechanism and unsatisfactory electrochemical performance limit their applications.Nanorod b-MnO_(2) synthesized by hydrothermal method is used to investigate the reaction mechanism.As cathode materials for RAZIB,the Zn//b-MnO_(2) delivers 355 mA h g^(-1)(based on cathode mass)at0.1 A g^(-1),and retain 110 mA h g^(-1) after 1000 cycles at 0.2 A g^(-1).Different from conventional zinc ion insertion/extraction mechanism,the proton conversion and Mn ion dissolution/deposition mechanism of b-MnO_(2) is proposed by analyzing the evolution of phase,structure,morphology,and element of b-MnO_(2) electrode,the pH change of electrolyte and the determination of intermediate phase MnO OH.Zinc ion,as a kind of Lewis acid,also provides protons through the formation of ZHS in the proton reaction process.This study of reaction mechanism provides a new perspective for the development of Zn//MnO_(2) battery chemistry.

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.

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.

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.

Engineering optimization approach of nonaqueous electrolyte for sodium ion battery with long cycle life and safety

Electrolyte design strategies are closely related to the capacities, cycle life and safety of sodium–ion batteries. In this study, we aimed to optimize electrolyte with the focus on engineering aspects. The basic physicochemical properties including ionic conductivity, viscosity,wettability and thermochemical stability of the electrolytes using Na PF6 as the solute and the mixed solvent with different components of EMC,DMC or DEC in PC or EC were systematically measured. Ah pouch cell with NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)/hard carbon electrodes was used to evaluate the performance of the prepared electrolytes. By using the Inductive Coupled Plasma Emission Spectrometer(ICP), X-ray photoelectron spectroscopy(XPS), Thermogravimetric-differential scanning calorimetry(TG-DSC) and Accelerating Rate Calorimeter(ARC), we show that an optimized electrolyte can effectively promote the formation of a protective interfacial layer on two electrodes, which not only retards parasitic reactions between the electrodes and electrolyte but also suppresses dissolution of metal ions from the cathode. With an optimized electrolyte, a NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)/hard carbon cell can attain 56.16% capacity retention under the low temperature of -40℃, and can be able to retain 80%capacity retention after more than 2500 cycles while presenting excellent thermal safety.

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.

Bi_(2)S_(3) for Aqueous Zn Ion Battery with Enhanced Cycle Stability

Aqueous Zn ion batteries(ZIBs)are promising in energy storage due to the low cost,high safety,and material abundance.The development of metal oxides as the cathode for ZIBs is limited by the strong electrostatic forces between O2−and Zn2+which leads to poor cyclic stability.Herein,Bi2S3 is proposed as a promising cathode material for rechargeable aqueous ZIBs.Improved cyclic stability and fast diffusion of Zn2+is observed.Also,the layered structure of Bi2S3 with the weak van der Waals interaction between layers offers paths for diffusion and occupancy of Zn2+.As a result,the Zn/Bi2S3 battery delivers high capacity of 161 mAh g−1 at 0.2 A g−1 and good cycling stability up to 100 cycles with ca.100%retention.The battery also demonstrates good cyclic performance of ca.80.3%over 2000 cycles at 1 A g−1.The storage mechanism in the Bi2S3 cathode is related to the reversible Zn ion intercalation/extraction reactions and the capacitive contribution.This work indicates that Bi2S3 shows great potential as the cathode of ZIBs with good performance and stability.

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.

An all-organic aqueous potassium dual-ion battery

Benefiting from the environmental friendliness of organic electrodes and the high security of aqueous electrolyte,an all-organic aqueous potassium dual-ion full battery(APDIB) was assembled with 21 M potassium bis(fluoroslufonyl)imide(KFSI) water-in-salt as the electrolyte.The APDIB could deliver a reversible capacity of around 50 mAh g^(-1) at 200 mA g^(-1)(based on the weight of total active materials),a long cycle stability over 900 cycles at 500 mA g^(-1) and a high coulombic efficiency of 98.5%.The reaction mechanism of APDIB during the charge/discharge processes is verified:the FSI-could associate/disassociate with the nitrogen atom in the polytriphenylamine(PTPAn) cathode,while the K^(+) could react with C=O bonds in the 3,4,9,10-perylenetetracarboxylic diimide(PTCDI) anode reversibly.Our work contributes toward the understanding the nature of water-into-salt electrolyte and successfully constructed all-organic APDIB.

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.

Modeling the dynamic behavior of a lithium-ion battery for electric vehicles using numerical optimization

In order to simulate the dynamical behavior of a lithium ion traction battery used in elec tric vehicles, an equivalent circuit based battery model was established. The methodology in the guide document of the ADVISOR software was used to determine the initial parameters of the model as a function of state of charge （ SoC ） over an experimental data set of the battery. A numerically nonlinear least squares algorithm in SIMULINK design optimization toolbox was applied to further op timize the model parameters. Validation results showed that the battery model could well describe the dynamic behavior of the lithinm ion battery in two different battery loading situations.

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.