Trend of Developing Aqueous Liquid and Gel Electrolytes for Sustainable,Safe,and High‑Performance Li‑Ion Batteries

Current lithium-ion batteries(LIBs)rely on organic liquid electrolytes that pose significant risks due to their flammability and toxicity.The potential for environmental pollution and explosions resulting from battery damage or fracture is a critical concern.Water-based(aqueous)electrolytes have been receiving attention as an alternative to organic electrolytes.However,a narrow electrochemicalstability window,water decomposition,and the consequent low battery operating voltage and energy density hinder the practical use of aqueous electrolytes.Therefore,developing novel aqueous electrolytes for sustainable,safe,high-performance LIBs remains challenging.This Review first commences by summarizing the roles and requirements of electrolytes–separators and then delineates the progression of aqueous electrolytes for LIBs,encompassing aqueous liquid and gel electrolyte development trends along with detailed principles of the electrolytes.These aqueous electrolytes are progressed based on strategies using superconcentrated salts,concentrated diluents,polymer additives,polymer networks,and artificial passivation layers,which are used for suppressing water decomposition and widening the electrochemical stability window of water of the electrolytes.In addition,this Review discusses potential strategies for the implementation of aqueous Li-metal batteries with improved electrolyte–electrode interfaces.A comprehensive understanding of each strategy in the aqueous system will assist in the design of an aqueous electrolyte and the development of sustainable and safe high-performance batteries.

Gel electrolytes containing several kinds of particles used in quasi-solid-state dye-sensitized solar cells

Composite gel electrolytes containing several kinds of particles used as the quasi-solid-state electrolytes in dye-sensitized solar cells (DSSCs) were reported. Mesoporous particles (MCM-41) with unique structures composed of ordered nanochannels were served as a new kind of gelator for quasi-solid-state electrolytes. MCM-41, hydrophobic fumed silica Aerosil R972 and TiO2 nanopatricles P25 were dispersed into gel electrolytes respectively. The solar energy-to-electricity conversion efficiency of these cells is 4.65%, 6.85% and 5.05% respectively under 30 mW·cm-2 illumination. The preparation methods and the particles sizes exert an influence on the performance of corresponding solar cells. Owing to unique pore structures and high specific BET surface area, mesoporous silica MCM-41 was expected to have the potential to afford conducting nanochannels for redox couple diffusion.

A series of conducting gel electrolytes for quasi-solid-state quantum dot-sensitized solar cells with boosted electron transfer processes

To pursue electron-generation stability with no sacrifice of photovoltaic performance has been a persistent objective for all kinds of solar cells. Here, we demonstrate the experimental realization of this objective by quasi-solid-state quantum dot-sensitized solar cells from a series of conducting gel electrolytes composed of polyacrylamide（PAAm） matrix and conductive polymers [polyaniline（PANi）, polypyrrole（PPy） or polythiophene（PT）]. The reduction of Sx2- occurred in both interface and three dimensional framework of conducting gel electrolyte as a result of the electrical conduction of PANi, PPy and PT toward refluxed electrons from external circuit to Pt electrode. The resulting solar cells can yield the solarto-electrical conversion efficiency of 2.33%, 2.25% and 1.80% for PANi, PPy and PT based gel electrolytes,respectively. Those solar cells possessed much higher efficiency than that of 1.74% based on pure PAAm gel electrolyte owing to the enhanced kinetics for Sx2- ？ S2- conversion. More importantly, the stability of quasi-solid-state solar cell is significantly advanced, arising from the localization of liquid electrolyte into the three dimensional framework and therefore reduced leakage and volatilization.

Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

Progress in Gel Polymer Electrolytes for Sodium-Ion Batteries

Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.

Bifunctional TiO_(2-x)nanofibers enhanced gel polymer electrolyte for high performance lithium metal batteries

Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.

Research progress on gel polymer electrolytes for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have become a promising candidate for advanced energy storage system owing to low cost and high theoretical specific energy.In the last decade,in pursuit of Li-S batteries with enhanced safety and energy density,the investigation on the electrolytes has leaped form liquid organic electrolytes to solid polymer ones.However,such solid-state Li-S battery system is greatly limited by unfavorable ionic conductivity,poor interfacial contact and narrow electrochemical windows on account of the absence of any liquid components.To address these issues,gel polymer electrolytes(GPEs),the incorporation of liquid electrolytes into solid polymer matrixes,have been newly developed.Although the excellent ionic transport and low interfacial resistance provided by GPEs have prompted numerous researchers to make certain progress on high-performance Li-S coins,a comprehensive review on GPEs for Li-S batteries remains vacant.Herein,this review focuses on recent development and progress on GPEs in view of their physical and chemical properties for the applications in Li-S batteries.Studies on the components including solid hosts,liquid solutions and fillers of GPEs are systematically summarized with particular emphasis on the relationship between components and performance.Finally,current challenges and directional outlook for fabricating GPEs-based Li-S batteries with outstanding performance are outlined.

A self-standing,UV-cured semi-interpenetrating polymer network reinforced composite gel electrolytes for dendrite-suppressing lithium ion batteries

A self-standing,flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion batteries.The multi-functional composite semi-interpenetrating polymer network(referred to as“Cs-IPN”)electrolyte membrane was fabricated by combining a UV-cured ethoxylated trimethylolpropane triacrylate(ETPTA)macromer with alumina nanoparticles in the presence of liquid electrolyte and thermoplastic linear poly(ethylene oxide)(PEO).The polymer electrolyte membrane exhibits a semi-interpenetrating polymer network structure and a higher room temperature ionic conductivity,which impart the electrolyte with a significant cycling(120 mAh g^(-1)after 200 cycles)and a remarkable rate(137 mAh g^(-1)at 0.1℃,130 mAh g^(-1)at 0.5℃,119 mAh g^(-1)at 1℃ and 100 mAh g^(-1)at 2℃)performance in Li/LiFePO4 battery.More importantly,the polymer electrolyte possesses superior ability to inhibit the growth of lithium dendrites,which makes it promising for next generation lithium ion batteries.

All-Climate Stretchable Dendrite-Free Zn-Ion Hybrid Supercapacitors Enabled by Hydrogel Electrolyte Engineering

Hybrid supercapacitors have shown great potentials to fulfill the demand of future diverse applications such as electric vehicles and portable/wearable electronics.In particular,aqueous zinc-ion hybrid supercapacitors(ZHSCs)have gained much attention due to their low-cost,high energy density,and environmental friendliness.Nevertheless,typical ZHSCs use Zn metal anode and normal liquid electrolyte,causing the dendrite issue,restricted working temperature,and inferior device flexibility.Herein,a novel flexible Zn-ion hybrid supercapacitor(FZHSC)is developed by using activated carbon(AC)anode,δ-MnO_(2) cathode,and innovative PVA-based gel electrolyte.In this design,heavy Zn anode and its dendrite issue are avoided and layered cathode with large interlayer spacing is employed.In addition,flexible electrodes are prepared and integrated with an anti-freezing,stretchable,and compressible hydrogel electrolyte,which is attained by simultaneously using glycerol additive and freezing/thawing technique to regulate the hydrogen bond and microstructure.The resulting FZHSC exhibits good rate capability,high energy density(47.86 Wh kg^(−1);3.94 mWh cm^(−3)),high power density(5.81 kW kg^(−1);480 mW cm^(−3)),and excellent cycling stability(~91%capacity retention after 30000 cycles).Furthermore,our FZHSC demonstrates outstanding flexibility with capacitance almost unchanged even after various continuous shape deformations.The hydrogel electrolyte still maintains high ionic conductivity at ultralow temperatures(≤−30℃),enabling the FZHSC cycled well,and powering electronic timer robustly within an all-climate temperature range of−30~80℃.This work highlights that the promising Zn metal-free aqueous ZHSCs can be designed with great multifunctionality for more practical application scenarios.

A gel polymer electrolyte with IL@UiO-66-NH_(2) as fillers for high-performance all-solid-state lithium metal batteries

All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4) full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.

Molecular Reactivity and Interface Stability Modification in In-Situ Gel Electrolyte for High Performance Quasi-Solid-State Lithium Metal Batteries

Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.

Novel Amphiphilic Polymer Gel Electrolytes Based on PEG-b-GMA-co-MMA

1 Results Gel polymer electrolytes for lithium battery have been widely investigated recently because of their high ion conductivity at room temperature. We synthesized and characterized novel gel electrolytes based on amphiphilic copolymethacrylates containing different lengths of ethylene oxide (EO) chain as ionophilic units and methyl methacrylate (MMA) chain as ionophobic units[1]. Their electrochemical properties were also measured.1H NMR and FTIR analysis results elucidated that PEG-b-glycidyl met...

PREPARATION OF STAR NETWORK PEG-BASED GEL POLYMER ELECTROLYTES FOR ELECTROCHROMIC DEVICES

An amorphous,colorless,and highly transparent star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized from the poly(ethylene glycol)(PEG),pentaerythritol,and dichloromethane by Williamson reaction.FTIR and ~1H-NMR measurement demonstrated that the polymer repeating units were C[CH_2-OCH_2O-(CH_2CH_2O)_m-CH_2O-(CH_2CH_2O)_n-CH_2O]_4.The polymer host held well mechanical properties for pentaerythritol cross-linking.The gel polymer electrolytes based on Lithium pe...

Solid-state Al-air battery with an ethanol gel electrolyte

Hydrogel electrolyte is especially suitable for solid-state Al-air batteries targeted for various portable applications, which may, however, lead to continuous Al corrosion during battery standby. To tackle this issue, an ethanol gel electrolyte is developed for Al-air battery for the first time in this work, by using KOH as solute and polyethylene oxide as gelling agent. The ethanol gel is found to effectively inhibit Al corrosion compared with the water gel counterpart, leading to stable Al storage. When assembled into an Al-air battery, the ethanol gel electrolyte achieves a much improved discharge lifetime and specific capacity, which are 5.3 and 4.1 times of the water gel electrolyte at 0.1 mA cm^(-2), respectively.By studying the gel properties, it is found that a lower ethanol purity can improve the battery power output, but at the price of decreased discharge efficiency. On the contrary, a higher polymer concentration will decrease the power output, but can bring extra benefit to the discharge efficiency. As for the gel thickness, a moderate value of 1 mm is preferred to balance the power output and energy efficiency. Finally, to cater the increasing market of flexible electronics, a flexible Al-air battery is developed by impregnating the ethanol gel into a paper substrate, which can function normally even under serious deformation or damage.

A UV cross-linked gel polymer electrolyte enabling high-rate and high voltage window for quasi-solid-state supercapacitors

Serving as a promising alternative to liquid electrolyte in the application of portable and wearable devices,gel polymer electrolytes(GPEs)are expected to obtain more preferable properties rather than just be satisfied with the merits of high safety and deformability.Here,an easy-operated method is employed to fabricate cross-linked composite polymer membranes used for GPEs assisted by UV irradiation,in which N-doped carbon quantum dots(N-CQDs)and TiO2are introduced as photocatalysts and additives to improve the performances of GPEs.Specifically,N-CQDs participate as a cross-linker to construct the inner porous structure,and TiO2nanoparticles serve as a stabilizer to improve the electrochemical stability of GPEs under high voltage(3.5 V).The excellent thermal and mechanical stability of the membrane fabricated in this work guarantee the safety of the supercapacitors(SCs).This GPE based SC not only exhibits prominent rate performance(105%capacitance retention at the current density of 40A g^(-1))and cyclic stability(85%at 1 A g^(-1)under 3.5 V after 20,000 cycles),but also displays remarkable energy density(42.88 Wh kg^(-1))with high power density(19.3 k W kg^(-1)).Moreover,the superior rate and cycling performances of the as-prepared GPE based flexible SCs under flat and bending state confirm the feasibility of its application in flexible energy storage devices.

Gelation mechanisms of gel polymer electrolytes for zinc-based batteries

Zinc-based batteries(ZBs)have been deemed as a potential substitute for lithium-ion batteries due to its unique advantages of abundant resources,low cost and acceptable energy density.Despite great progress in designing electrode materials has been made,the development of high-performance ZBs still remain challenges,such as the dendrite growth of zinc anode,hydrogen evolution reaction,limited electrochemical stability window,water evaporation and liquid leakage.Gel polymer electrolytes(GPEs),including hydrous GPEs with low content of active water and anhydrous GPEs without the presence of water,are proposed to avoid these problems.Furthermore,employing GPEs is conductive to fabricate flexible devices owing to the good mechanical strength.To date,most of researches focus on discovering new GPEs and exploring its application on flexible or wearable devices.Recent reviews also have outlined the polymer matrixes and advances of GPEs in various battery systems.Given this,herein,we seek to summarize the gelation mechanisms of GPEs,involving physical gel of polymer,chemical crosslinking of polymer and chemical polymerization of monomers.Peculiarly,the preparation methods are also classified.In addition,not only the features and central conundrum of GPEs are analyzed but also the corresponding strategies are discussed,contributing to design GPEs with ideal properties for high-performance ZBs.

High-performance PVDF-HFP based gel polymer electrolyte with a safe solvent in Li metal polymer battery

Poly(vinylidenefluoride-co-hexafluoropropylene)(PVDF-HFP)based gel polymer electrolytes are widely studied owing to their electrochemical stability and high dielectric constant.However,most gel polymer electrolytes show unsatisfied safety and interface compatibility due to excessive absorption of volatile and flammable liquid solvents.Herein,by using a safe solvent(N-methyl-2-pyrrolidone)with higher boiling(203℃)and flash points(95℃),we initiatively fabricate a flexible PVDF-HFP based gel polymer electrolyte.The obtained gel polymer electrolyte demonstrates a high ionic conductivity of 7.24×10^−4 S cm−1,an electrochemical window of 5.2 V,and a high lithium transference number of 0.57.As a result,the synthesized polymer electrolyte exhibits a capacity retention of 70%after 500 cycles at 0.5 C,and a discharge capacity of 86 mAh g−1 even at a high current rate of 10 C for LiFePO4 based Li metal batteries.Moreover,a stable Li plating/stripping for more than 500 h is achieved under 0.1 mAh at both room temperature and 70℃.Our results indicate that the PVDF-HFP polymer electrolyte is promising for manufacturing safe and high-performance Li metal polymer batteries.

A novel permselective organo-polysulfides/PVDF gel polymer electrolyte enables stable lithium anode for lithium–sulfur batteries

Lithium-sulfur(Li-S)battery can satisfy the need of the future power battery market because of its high energy density,but the hidden dangers caused by lithium anode have seriously hindered their commercialization.Herein,an innovative gel polymer electrolyte(GPE)composed of polyvinylidene fluoride(PVDF)and organo-polysulfide polymer(PSPEG)is proposed,which could be used in semisolid-state Li-S batteries for protection of Li anodes.Particularly,organo-polysulfide polymer could chemically/electrochemically generate both inorganic and organic components simultaneously in-situ once contacting fresh Li metal surface and/or during discharging processes.And these inorganic/organic components could participate in the formation of the SEI layer and finally constitute a stable and flexible hybrid SEI layer on the surface of Li metal anode.Moreover,the organic components were permselective to lithium ions against anions.Therefore,PVDF/PSPEG GPE ensures the ideal chemical and electrochemical properties for Li-S batteries.Our work demonstrates an effective solution to solve the problems about Li anodes and contributes to the development of the safe Li metal batteries.

Thermotolerant and fireproof gel polymer electrolyte toward high-performance and safe lithium-ion battery

Poly(ethylene oxide)(PEO)and its derivatives based gel polymer electrolytes(GPEs)are severely limited in advanced and safe lithium-ion batteries(LIBs)owing to the intrinsically high flammability of liquid electrolytes and PEO.Directly adding flame retardants to the GPEs can suppress their flammability and thus improve the safety of LIBs,but results in deteriorative electrochemical performance.Herein,a novel GPE with chemically bonded flame retardant(i.e.diethyl vinylphosphonate)in cross-linked polyethylene glycol diacrylate matrix,featuring both high-safety and high-performance,is designed.This as-prepared GPE storing the commercial 1 mol L^(-1) LiPF6 electrolyte resists high temperature of 200℃and cannot be ignited as well as possesses a high ionic conductivity(0.60 m S cm^(-1))and good compatibility with lithium.Notably,the LiFePO_(4)/Li battery with this GPE delivers a satisfactory capacity of 142.2 m A h g^(-1) and a superior cycling performance with a capacity retention of 96.3%and a coulombic efficiency of close to 100%for 350 cycles at 0.2 C under ambient temperature.Furthermore,the battery can achieve steady charge–discharge for 100 cycles with a coulombic efficiency of 99.5%at 1 C under 80℃and run normally even at a high temperature of 150℃or under the exposure to butane flame.Differential scanning calorimetry manifests significantly improved battery safety compared to commercial battery systems.This work provides a new pathway for developing next-generation advanced LIBs with enhanced performance and high safety.

A symmetric MnO_2/MnO_2 flexible solid state supercapacitor operating at 1.6V with aqueous gel electrolyte

The demand of microelectronic devices postulated high energetic flexible energy storage devices. Flexible solid state supercapacitor is flawless possible candidate to fulfill the requirement of microelectronic devices. This investigation provides practical evidence of the use of flexible solid state supercapacitors based on MnOelectrodes with polyvinylpyrrolidone(PVP)-Li ClOgel electrolyte. Initially, different acid mediated growths of MnOhave been carried. Later, the electrochemical performances of MnOelectrodes have been carried out. Impressively, the fabricated symmetric flexible solid state supercapacitor(FSS-SC) device demonstrates the highest operating potential window of 1.6 V with extended cycling stability. Moreover, the cell exhibits high energy density of 23 Wh/kg at power density of 1.9 k W/kg. It is interesting to note that the device shows excellent flexibility upon bending at angle of 180° for number of times. These results clearly evidenced those symmetric FSS-SC devices based on MnOelectrodes are promising energy storage devices for microelectronic applications.