Simple electrode assembly engineering:Toward a multifunctional lead-acid battery

Electrochemical energy storage is a promising technology for the integration of renewable energy.Lead-acid battery is perhaps among the most successful commercialized systems ever since thanks to its excellent cost-effectiveness and safety records.Despite of 165 years of development,the low energy density as well as the coupled power and energy density scaling restrain its wider application in real life.To address this challenge,we optimized the configuration of conventional Pb-acid battery to integrate two gas diffusion electrodes.The novel device can work as a Pb-air battery using ambient air,showing a peak power density of 183 mW cm^(−2),which was comparable with other state-of-the-art metal-O_(2)batteries.It can also behave as a fuel cell,simultaneously converting H_(2)and air into electricity with a peak power density of 75 mW cm^(−2).Importantly,this device showed little performance degradation after 35 h of the longevity test.Our work shows the exciting potential of lead battery technology and demonstrates the importance of battery architecture optimization toward improved energy storage capacity.

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.

Application of a Sulfur Removal Hydrometallurgical Process in a Lead-Acid Battery Recycling Plant in Costa Rica

This study presents the implementation of a desulphurization process for lead recycling under different chemical and physical conditions using pyro-metallurgical processes. Desulphurization was done using a hydrometallurgical process using sodium carbonate as a desulphurization agent and different lead-bearing loads compositions. Waste characterization included: SO2 concentrations in the stack emissions, total lead content in the furnace ash, the total lead content in the slag, and the toxicity characteristic leaching procedure (TCLP). A significant reduction in SO2 emissions was achieved (~55% reduction) where mean SO2 concentrations changed from 2193 ± 135 ppm to 1006 ± 62 ppm after the implementation of the modified processes. The desulfurized lead paste (i.e. the metallic fraction lead of the battery) of the modified process exhibited an improvement in the concentration of the lead in the TCLP test, with an average value of 1.5 ppm which is below US EPA limit of 5 ppm. The traditional process TCLP mean value for the TCLP was 54.2 ppm. The total lead content in the bag house ashes shows not significant variations, when comparing the desulphurization (67.6% m/m) and non-desulphurization process (64.9% m/m). The total lead mean content in the slag was higher in the desulphurization process (2.49% m/m) than the traditional process (1.91% m/m). Overall, the implementation of a new desulphurization method would potentially increase the operation costs in 10.3%. At the light of these results, a combination of hydrometallurgical and pyro-metallurgical processes in the recycling of lead-acid batteries can be used to reduce the environmental impact of these industries but would increase the operational costs of small lead recyclers.

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.

Effect of lead foam grid on performance of lead-acid battery

In order to increase the specific energy and specific power of a lead-acid battery, lead foam grid was prepared by electrodepositing Pb-Sn alloy on a copper foam substrate and used as negative current collector for a lead acid battery whose capacity was limited by the negative plate. Comparing the effect of the cast grid, under the same conditions, the mass of lead foam grid decreases by 35%, and the area of lead foam contacted with active material increases by about 20 times. Under 2 h rate discharge condition, with a high current （3 0 I2） e and low-temperature （-10 ℃, I2） discharge system, the lead foam grid markedly boosts the discharge performance of lead acid battery. It increases not only the negative electrode mass specific capacity by 27%,37% and 29%,but also the utilization efficiency of the negative active material by 5%. Compared with the negative electrode of cast grid, XRD and SEM results show that after 20 cycles at the state of charge, the sponge lead in the negative lead foam electrode has smaller crystals and less PbSO4 on its surface. Meanwhile, at the state of full discharge, the PbSO4 crystals are smaller and occur less on the surface of lead foam electrode. This indicates its active material reacts more uniformly.

Prussian Blue Analogue‑Templated Nanocomposites for Alkali‑Ion Batteries:Progress and Perspective

Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

From waste to wealth:Coal tar residue derived carbon materials as low-cost anodes for potassium-ion batteries

Carbon materials are widely recognized as highly promising electrode materials for various energy storage system applications.Coal tar residues(CTR),as a type of carbon-rich solid waste with high value-added utilization,are crucially important for the development of a more sustainable world.In this study,we employed a straightforward direct carbonization method within the temperature range of 700-1000℃to convert the worthless solid waste CTR into economically valuable carbon materials as anodes for potassium-ion batteries(PIBs).The effect of carbonization temperature on the microstructure and the potassium ions storage properties of CTR-derived carbons(CTRCs)were systematically explored by structural and morphological characterization,alongside electrochemical performances assessment.Based on the co-regulation between the turbine layers,crystal structure,pore structure,functional groups,and electrical conductivity of CTR-derived carbon carbonized at 900℃(CTRC-900H),the electrode material with high reversible capacity of 265.6m Ah·g^(-1)at 50 m A·g^(-1),a desirable cycling stability with 93.8%capacity retention even after 100 cycles,and the remarkable rate performance for PIBs were obtained.Furthermore,cyclic voltammetry(CV)at different scan rates and galvanostatic intermittent titration technique(GITT)have been employed to explore the potassium ions storage mechanism and electrochemical kinetics of CTRCs.Results indicate that the electrode behavior is predominantly governed by surface-induced capacitive processes,particularly under high current densities,with the potassium storage mechanism characterized by an“adsorption-weak intercalation”mechanism.This work highlights the potential of CTR-based carbon as a promising electrode material category suitable for high-performance PIBs electrodes,while also provides valuable insights into the new avenues for the high value-added utilization of CTR.

Aligned Ion Conduction Pathway of Polyrotaxane‑Based Electrolyte with Dispersed Hydrophobic Chains for Solid‑State Lithium–Oxygen Batteries

A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.

Sulfolane‑Based Flame‑Retardant Electrolyte for High‑Voltage Sodium‑Ion Batteries

Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.

Ideal Bi‑Based Hybrid Anode Material for Ultrafast Charging of Sodium‑Ion Batteries at Extremely Low Temperatures

Sodium-ion batteries have emerged as competitive substitutes for low-temperature applications due to severe capacity loss and safety concerns of lithium-ion batteries at−20°C or lower.However,the key capability of ultrafast charging at ultralow temperature for SIBs is rarely reported.Herein,a hybrid of Bi nanoparticles embedded in carbon nanorods is demonstrated as an ideal material to address this issue,which is synthesized via a high temperature shock method.Such a hybrid shows an unprecedented rate performance(237.9 mAh g^(−1) at 2 A g^(−1))at−60℃,outperforming all reported SIB anode materials.Coupled with a Na_(3)V_(2)(PO_(4))_(3)cathode,the energy density of the full cell can reach to 181.9 Wh kg^(−1) at−40°C.Based on this work,a novel strategy of high-rate activation is proposed to enhance performances of Bi-based materials in cryogenic conditions by creating new active sites for interfacial reaction under large current.

Photo‑Energized MoS_(2)/CNT Cathode for High‑Performance Li–CO_(2)Batteries in a Wide‑Temperature Range

Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.

Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Efficient and Stable Photoassisted Lithium‑Ion Battery Enabled by Photocathode with Synergistically Boosted Carriers Dynamics

Efficient and stable photocathodes with versatility are of significance in photoassisted lithium-ion batteries(PLIBs),while there is always a request on fast carrier transport in electrochemical active photocathodes.Present work proposes a general approach of creating bulk heterojunction to boost the carrier mobility of photocathodes by simply laser assisted embedding of plasmonic nanocrystals.When employed in PLIBs,it was found effective for synchronously enhanced photocharge separation and transport in light charging process.Additionally,experimental photon spectroscopy,finite difference time domain method simulation and theoretical analyses demonstrate that the improved carrier dynamics are driven by the plasmonic-induced hot electron injection from metal to TiO_(2),as well as the enhanced conductivity in TiO2 matrix due to the formation of oxygen vacancies after Schottky contact.Benefiting from these merits,several benchmark values in performance of TiO2-based photocathode applied in PLIBs are set,including the capacity of 276 mAh g^(−1) at 0.2 A g^(−1) under illumination,photoconversion efficiency of 1.276%at 3 A g^(−1),less capacity and Columbic efficiency loss even through 200 cycles.These results exemplify the potential of the bulk heterojunction strategy in developing highly efficient and stable photoassisted energy storage systems.

Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Porous Organic Cage‑Based Quasi‑Solid‑State Electrolyte with Cavity‑Induced Anion‑Trapping Effect for Long‑Life Lithium Metal Batteries

Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.

Co/Co_(7)Fe_(3)heterostructures with controllable alloying degree on carbon spheres as bifunctional electrocatalyst forrechargeable zinc-air batteries

Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.

Recycling technologies of spent lithium-ion batteries and future directions:A review

Lithium-ion batteries(LIBs)are the most popular energy storage devices due to their high energy density,high operating voltage,and long cycle life.However,green and effective recycling methods are needed because LIBs contain heavy metals such as Co,Ni,and Mn and organic compounds inside,which seriously threaten human health and the environment.In this work,we review the current status of spent LIB recycling,discuss the traditional pyrometallurgical and hydrometallurgical recovery processes,and summarize the existing short-process recovery technologies such as salt-assisted roasting,flotation processes,and direct recycling.Finally,we analyze the problems and potential research prospects of the current recycling process,and point out that the multidisciplinary integration of recycling will become the mainstream technology for the development of spent LIBs.

Electrode/Electrolyte Optimization‑Induced Double‑Layered Architecture for High‑Performance Aqueous Zinc‑(Dual)Halogen Batteries

Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.