Self-actuating protection mechanisms for safer lithium-ion batteries

Safety issue is still a problem nowadays for the large-scale application of lithium-ion batteries(LIBs)in electric vehicles and energy storage stations.The unsafe behaviors of LIBs arise from the thermal run-away,which is intrinsically triggered by the overcharging and overheating.To improve the safety of LIBs,various protection strategies based on self-actuating reaction control mechanisms(SRCMs)have been proposed,including redox shuttle,polymerizable monomer additive,potential-sensitive separator,thermal shutdown separator,positive-temperature-coefficient electrode,thermally polymerizable addi-tive,and reversible thermal phase transition electrolyte.As build-in protection mechanisms,these meth-ods can sensitively detect either the temperature change inside battery or the potential change of the electrode,and spontaneously shut down the electrode reaction at risky conditions,thus preventing the battery from going into thermal runaway.Given their advantages in enhancing the intrinsic safety of LIBs,this paper overviews the research progresses of SRCMs after a brief introduction of thermal runaway mechanism and limitations of conventional thermal runaway mitigating measures.More importantly,the current states and issues,key challenges,and future developing trends of SRCTs are also discussed and outlined from the viewpoint of practical application,aiming at providing insights and guidance for developing more effective SRCMs for LIBs.

Anode surface engineering of zinc-ion batteries using tellurium nanobelt as a protective layer for enhancing energy storage performance

Over the years,zinc-ion batteries(ZIBs)have attracted attention as a promising next-generation energy storage technology because of their excellent safety,long cycling performance,eco-friendliness,and high-power density.However,issues,such as the corrosion and dissolution of the Zn anode,limited wet-tability,and lack of sufficient nucleation sites for Zn plating,have limited their practical application.The introduction of a protective layer comprising of tellurium(Te)nanobelts onto the surface of Zn anode has emerged as a promising approach to overcome these limitations and improve the electrochemical behav-ior by enhancing the safety and wettability of ZIBs,as well as providing numerous nucleation sites for Zn plating.In the presence of a Te-based protective layer,the energy power density of the surface-engineered Zn anode improved significantly(ranging from 310 to 144 W h kg^(-1),over a power density range of 270 to 1,800 W kg^(-1)),and the lifespan capability was extended.These results demonstrate that the proposed strategy of employing Te nanobelts as a protective layer holds great promise for enhancing the energy storage performance of zIBs,making them even more attractive as a viable energy storage solution forthefuture.

Thermally insulating and fire-retardant bio-mimic structural composites with a negative Poisson's ratio for battery protection

Battery safety has attracted considerable attention worldwide due to the rapid development of wearable electronics and the steady increase in the production and use of electric vehicles.As battery failures are often associated with mechanical-thermal coupled behaviors,protective shielding materials with excellent mechanical robustness and flame-retardant properties are highly desired to mitigate thermal runaway.However,most of the thermal insulating materials are not strong enough to protect batteries from mechanical abuse,which is one of the most critical scenarios with catastrophic consequences.Here,inspired by wood,we have developed an effective approach to engineer a hierarchical nanocomposite via self-assembly of calcium silicate hydrate and polyvinyl alcohol polymer chains(referred as CSH wood).The versatile protective material CSH wood demonstrates an unprecedented combination of light weight(0.018 g cm-3),high stiffness(204 MPa in the axial direction),negative Poisson's ratio(-0.15),remarkable toughness(6.67×105 J m-3),superior thermal insulation(0.0204 W m-1 K-1 in the radial direction),and excellent fire retardancy(UL94-V0).When applied as a protective cover or a protective layer within battery packages,the tough CSH wood can resist high-impact load and block heat diffusion to block or delay the spread of fire,therefore significantly reducing the risk of property damage or bodily injuries caused by battery explosions.This work provides new pathways for fabricating advanced thermal insulating materials with large scalability and demonstrates great potential for the protection of electronic devices.

Tuning Li nucleation and growth via oxygen vacancy-enriched 3D flexible self-supporting protection layer of P-Mn_(3)O_(4-x)for advanced lithium-sulfur batteries

Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resulting from the uncontrollable generation and growth of Li dendrites.Herein,an innovative 3D flexible self-supporting Li anode protection layer of P-Mn_(3)O_(4-x)is constructed via a facile solvothermal method followed by an annealing process.Benefiting from the rich oxygen vacancies coupled with the 3D flexible self-supporting skeleton,abundant lithiophilic sites and high ionic conductivity are obtained,which succeed in guiding Li+homogeneous adsorption and redistribution,accelerating Li+diffusion rate,inducing Li+uniform deposition and nucleation.DFT calculations and experimental results conclusively demonstrate such a protection mechanism.Meanwhile,the effective anchoring and catalytic nature of polar P-Mn_(3)O_(4-x)can also be applied as an immobilization-diffusion-conversion host to improve polysulfides redox.Taking advantage of these merits,super-stable functions for Li symmetric cell matched with P-Mn_(3)O_(4-x)layer are achieved,which exhibits an ultralong lifespan of>5000 h with an ultralow overpotential of 20 m V,far lower than that of bare Li symmetric cell(overpotential of 800 m V only after 250 h)at high current densities of 5 m A cm^(-2)and high plating/stripping capacity of 10 m A h cm^(-2).Even in Li|P-Mn_(3)O_(4-x)||S full cell at 1 C,a high initial discharge specific capacity of 843.1 m A h g^(-1)is still delivered with ultralow capacity fading rate of 0.07%per cycle after 250 cycles,further confirming the synergistic regulation of P-Mn_(3)O_(4-x)for Li nucleation behavior.This work illustrates a sufficient guarantee of 3D protection layer coupled with oxygen vacancies in guiding Li diffusion and nucleation behavior and provides new guidance for promoting the development of advanced Li-S batteries.

A Mixed Ether Electrolyte for Lithium Metal Anode Protection in Working Lithium-Sulfur Batteries

Lithium-sulfur(Li-S) battery is considered as a promising energy storage system to realize high energy density.Nevertheless,unstable lithium metal anode emerges as the bottleneck toward practical applications,especially with limited anode excess required in a working full cell.In this contribution,a mixed diisopropyl ether-based(mixed-DIPE) electrolyte was proposed to effectively protect lithium metal anode in Li-S batteries with sulfurized polyacrylonitrile(SPAN) cathodes.The mixed-DIPE electrolyte improves the compatibility to lithium metal and suppresses the dissolution of lithium polysulfides,rendering significantly improved cycling stability.Concretely,Li | Cu half-cells with the mixed-DIPE electrolyte cycled stably for 120 cycles,which is nearly five times longer than that with routine carbonate-based electrolyte.Moreover,the mixedDIPE electrolyte contributed to a doubled life span of 156 cycles at 0.5 C in Li | SPAN full cells with ultrathin 50 μm Li metal anodes compared with the routine electrolyte.This contribution affords an effective electrolyte formula for Li metal anode protection and is expected to propel the practical applications of high-energy-density Li-S batteries.

Polymer engineering for electrodes of aqueous zinc ion batteries

With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.

Revisiting aluminum current collector in lithium-ion batteries:Corrosion and countermeasures

With the large-scale service of lithium-ion batteries(LIBs),their failures have attracted significant attentions.While the decay of active materials is the primary cause for LIB failures,the degradation of auxiliary materials,such as current collector corrosion,should not be disregarded.Therefore,it is necessary to conduct a comprehensive review in this field.In this review,from the perspectives of electrochemistry and materials,we systematically summarize the corrosion behavior of aluminum cathode current collector and propose corresponding countermeasures.Firstly,the corrosion type is clarified based on the properties of passivation layers in different organic electrolyte components.Furthermore,a thoroughgoing analysis is presented to examine the impact of various factors on aluminum corrosion,including lithium salts,organic solvents,water impurities,and operating conditions.Subsequently,strategies for electrolyte and protection layer employed to suppress corrosion are discussed in detail.Lastly and most importantly,we provide insights and recommendations to prevent corrosion of current collectors,facilitate the development of advanced current collectors and the implementation of next-generation high-voltage stable LIBs.

Analysis of thermal management and anti-mechanical abuse of multi-functional battery modules based on magneto-sensitive shear thickening fluid

Electric vehicles(EVs)have garnered significant attention as a vital driver of economic growth and environmental sustainability.Nevertheless,ensuring the safety of high-energy batteries is now a top priority that cannot be overlooked during large-scale applications.This paper proposes an innovative active protection and cooling integrated battery module using smart materials,magneto-sensitive shear thickening fluid(MSTF),which is specifically designed to address safety threats posed by lithium-ion batteries(LIBs)exposed to harsh mechanical and environmental conditions.The theoretical framework introduces a novel approach for harnessing the smoothed-particle hydrodynamics(SPH)methodology that incorporates the intricate interplay of non-Newtonian fluid behavior,capturing the fluid-structure coupling inherent to the MSTF.This approach is further advanced by adopting an enhanced Herschel-Bulkley(H-B)model to encapsulate the intricate rheology of the MSTF under the influence of the magnetorheological effect(MRE)and shear thickening(ST)behavior.Numerical simulation results show that in the case of cooling,the MSTF is an effective cooling medium for rapidly reducing the temperature.In terms of mechanical abuse,the MSTF solidifies through actively applying the magnetic field during mechanical compression and impact within the battery module,resulting in 66%and 61.7%reductions in the maximum stress within the battery jellyroll,and 31.1%and 23%reductions in the reaction force,respectively.This mechanism effectively lowers the risk of short-circuit failure.The groundbreaking concepts unveiled in this paper for active protection battery modules are anticipated to be a valuable technological breakthrough in the areas of EV safety and lightweight/integrated design.

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.

Electrolyte for lithium protection: From liquid to solid

Lithium battery with high energy density and enhanced safety is undoubtedly the ideal choice for consumer electronics and electric vehicles.Metal anode such as lithium has been considered as the most effective way to enhance the energy density as it provides ultra-high theoretical capacity and the lowest redox potential.However,due to the low coulombic efficiency as well as safety concerns originated from dendrite issue of lithium,its further commercial utilization is hindered.Dendrite growth is a common phenomenon in metal electrodeposition while the plating process of Li is more complicated than other metals for its high reactivity nature.As a matter of fact,the Li plating process is accompanied with the generation of solid electrolyte interphase(SEI)in which the electrolyte plays a vital role.In this paper,recent advances of electrolytes for Li protect application are reviewed,from liquid to gel polymer and solid state,on which we find that although tremendous progress has been accomplished,there are still great challenges before Li metal anode could be commercially used.

Research on thin grid materials of lead-acid batteries

A detailed investigation on Pb-Ca-Sn alloys was made in order to choose suitable grid alloys materials for thin plate lead-acid batteries. The electrochemical performances of alloys were investigated by electrochemical corrosion experiment, scanning electron microscope (SEM), and cyclic voltammetry (CV) test. The results indicate that Pb-Ca-Sn-Bi-Cu alloys can be used to make the grids used for thin grid lead-acid batteries, the content of bismuth has primary effects on the corrosion resistance of grid alloys, the composition of alloys plays an important role on batteries performance, and appropriate scale of elements can be choosed to obtain optimal electrochemical performance. The lead-acid batteries using this kind of grid show good performance by cycle life test.

Experiments Study on Charge Technology of Lead-Acid Electric Vehicle Batteries

The basic theory of the fast charge and several charge methods are introduced. In order to heighten charge efficiency of valve-regulated lead-acid battery and shorten the charge time, five charge methods are investigated with experiments done on the Digatron BNT 400-050 test bench. Battery current, terminal voltage, capacity, energy and terminal pole temperature during battery experiment were recorded, and corresponding curves were depicted. Battery capacity-time ratio, energy efficiency and energy-temperature ratio are put forward to be the appraising criteria of lead-acid battery on electric vehicle （EV）. According to the appraising criteria and the battery curves, multistage-current/negative-pulse charge method is recommended to charge lead-acid EV battery.

Gas treatment protection of metallic lithium anode

The effects of different coating layers on lithium metal anode formed by reacting with different controlled atmospheres（argon,CO_2–O_2（2：1）,N_2,and CO_2–O_2–N_2（2：1：3））have been investigated.The obtained XRD,second ion mass spectroscopy（SIMS）,and scanning probe microscope（SPM）results demonstrate the formation of coating layers composed of Li_2CO_3,Li_3N,and the mixture of them on lithium tablets,respectively.The Li/Li symmetrical cell and Li/S cell are assembled to prove the advantages of the protected lithium tablet on electrochemical performance.The comparison of SEM and SIMS characterizations before/after cycles clarifies that an SEI-like composition formed on the lithium tablets could modulate the interfacial stabilization between the lithium foil and the ether electrolyte.

Boosting Zn||I_(2) Battery’s Performance by Coating a Zeolite‑Based Cation‑Exchange Protecting Layer

The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(−)-shuttling and dynamic parasitic reactions on Zn anodes.Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes,modifying Zn anodes’surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes.Herein,a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes.The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn^(2+),while blocking anions and electrolyte from passing through.This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge,anode corrosion/passivation,and Zn dendrite growth,awarding the Zn||I_(2) batteries with ultra-long cycle life(91.92%capacity retention after 5600 cycles at 2 A g^(−1)),high coulombic efficiencies(99.76%in average)and large capacity(203–196 mAh g^(−1) at 0.2 A g^(−1)).This work provides a highly affordable approach for the construction of high-performance Zn-I_(2) aqueous batteries.

Upcycling of phosphogypsum waste for efficient zinc-ion batteries

Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.

PREPARATION OF LEAD-ACID BATTERY USING ELECTROPLATED RETICULATED SiC AS THE POSITIVE CURRENT COLLECTOR

The possibility of using Pb-electroplated reticulated SiC as the positive current collector for lead-acid batteries was investigated. Reticulated SiC with two aperture sizes (3 and 2mm) were tested as the substrate of positive electrode. It was found that the reticulated SiC has an excellent corrosion resistance in H2SO4 solution, and the Pb layer electroplated on reticulated SiC showed analogous electrochemical behavior to metal Pb. Preliminary test of the battery performance indicated that the utilization efficiency of the positive active mass of new designed batteries are improved compared with the conventional batteries. The improvement could be ascribed to the high specific surface area of the reticulated structured positive current collector, which was further supported by the even better performance of the battery made from a smaller aperture size (2mm) reticulated SiC as the substrate of the positive electrode.

Self-Discharge in Valve-Regulated Sealed Lead-Acid Batteries

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Study of the Charge Acceptance of Small-Size Sealed Lead-Acid Batteries

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Mathematical Model and Experiment of Temperature Effect on Discharge of Lead-Acid Battery for PV Systems in Tropical Area

This paper presents Mathematical Model and Experiment of Temperature effect on Charge and Discharge of Lead-Acid Battery performance in PV system power supply. To test temperature effect on battery discharge cycles, a temperature range of tropical area from 25 - 60 degrees Celsius in a simulator is set up for testing. This temperature range is normally practical for battery usage. This allows the battery to determine the parameters of the battery quickly and high accurate. A Mathematical Model with MATLAB Program is written and constructed as block diagram using the equations of battery the parameters. By running program, the effects of various parameters are investigated. The results showed that time of discharge the battery is longer. Then, the experiment is set up by battery VRLA 12 V 20 AH. The results confirmed the mathematical model simulations.

Anode Interfacial Issues in Solid-State Li Batteries:Mechanistic Understanding and Mitigating Strategies

All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.