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.

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.

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.

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.

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.

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...

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.

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.

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.

Fibrous gel polymer electrolyte for an ultrastable and highly safe flexible lithium-ion battery in a wide temperature range

Replacement of flammable liquid electrolytes with gel polymer electrolytes(GPEs)is a promising route to improve the safety of lithium-ion batteries(LIBs).However,polymer-based electrolytes have limited suitability at low/high temperatures due to the instability of the polymer at high temperatures and the low ionic conductivity of the gel state at low temperatures.Herein,an integrated design of electrodes/fibrous GPEs modified with graphene oxide(GO)is reported.Due to the integrated structure of electrodes/GPEs,the strong interface affinity between electrodes and GPEs ensures that the GPEs spun on electrodes do not shrink at high temperatures(160-180℃),thus preventing a short circuit of electrodes.Moreover,after GO modification,oxygen-containing functional groups of GO can accelerate Li^(+)transport of GO-GPEs even at a low temperature of−15℃.When these GPEs are applied to flexible LIBs,the LIBs show excellent electrochemical performance,with satisfactory cycling stability of 82.9%at 1 C after 1000 cycles at 25℃.More importantly,at a high temperature of 160℃,the LIBs can also discharge normally and light the green light-emitting diode.Furthermore,at a low temperature of−15℃,92.7%of its room-temperature capacity can be obtained due to the accelerated Li^(+)transport caused by GO modification,demonstrating the great potential of this electrolyte and integrated structure for practical gel polymer LIB applications.

A lithiated gel polymer electrolyte with superior interfacial performance for safe and long-life lithium metal battery

Rechargeable lithium metal batteries(LMBs)have gained much attention recently.However,the short lifespan and safety issues restrict their commercial applications.Here we report a novel gel polymer electrolyte(GPE)based on lithiated poly(vinyl chloride-r-acrylic acid)(PVCAALi)to realize dendritesuppressing and long-term stable lithium metal cycling.PVC chains ensure the quick gelation process and high electrolyte uptake,and lithiated PAA segments enable the increase of mechanical strength,acceleration of lithium-ion transmission and improvement of interfacial compatibility.PVCAALi GPE showed much higher mechanical strength compared with other free-standing GPEs in previous works.It displays a superior ionic conductivity of 1.50 m S cm^(-1) and a high lithium-ion transference number of 0.59 at room temperature.Besides,the lithiated GPE exhibits excellent interfacial compatibility with lithium metal anodes.Lithium symmetrical cells with PVCAALi GPE yield low hysteresis of 50 m V over1000 h at 1.0 m A cm^(-2).And the possible mechanism of the lithiated GPE with improved lithium-ion transfer and interfacial property was discussed.Accordingly,both the Li4Ti5O12/Li and lithium-sulfur(Li-S)cells assembled with PVCAALi GPE show outstanding electrochemical performance,retaining high discharge capacities of 133.8 m Ah g^(-1) and 603.8 m Ah g^(-1) over 200 cycles,respectively.This work proves excellent application potential of the highly effective and low-cost PVCAALi GPE in safe and long-life LMBs.

Performance Improvement of Polyvinyl Formal Based Gel Polymer Electrolyte for Lithium-Ion Batteries by Coating Al2O3

Al2O3/PVFM/Al2O3 trilayer membranes are prepared by means of simple coating of PVA-Al2O3 solution onto both sides of PVFM thin membranes, which is prepared via phase inversion method. The characteristics of the trilayer membranes and gel polymer electrolytes are investigated using FESEM, tensile testing apparatus, thermal shrinkage test, EIS and charge-discharge test. When inorganic Al2O3 particles are used to coat the PVFM membrane, drawbacks associated with gel-type membranes, namely, poor mechanical strength and thermal stability are greatly improved. Lithium ion cell with the Al2O3/PVFM/Al2O3 based GPE matched with LiFePO4 shows excellent electrochemical performance.

Novel Semi-IPN Gel Electrolyte for Polymer Lithium-ion Battery

A new type of semi-IPN gel electrolyte was prepared by thermal polymerization in this article.The cross-linked PEG200 (MXPEG) was prepared by condensation reaction in the presence of methacryloxypropyltrimethoxysilane (MAPTMS),the condensation product was then blent with PMMA and polymerized to form polymer blends with semi-IPN fabric.Differential scanning calorimetry and X-ray diffraction spectroscopy were used to investigate the thermal transition behavior of the polymer blends prepared.Ion-conducting behaviors and the electrochemical stability window for semi-IPN gel electrolyte were investigated by means ofimpedance spectroscopy and linear sweep voltammetry.The Arrhenius-type relationship was observed in the temperature dependence ofionic conductivity.All the properties shows that the prepared semi-IPN gel electrolyte possesses certain levels of electrolye salt and plasticizer were expected to have applications of gel polymer electrolyte for lithium polymer secondary batteries.

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...

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.

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.

Crosslinked solubilizer enables nitrate-enriched carbonate polymer electrolytes for stable,high-voltage lithium metal batteries

High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density batteries.However,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium.N,N-dimethylacrylamide(DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate(LiNO3)in carbonate-based electrolytes and to form gel polymer electrolytes(GPEs)through in situ polymerization.The Lit solvation structure of the GPEs is regulated using LiNO3 and DMAA,which suppresses the decomposition of LiPFe and facilitates the formation of an inorganic-rich solid electrolyte interface.Consequently,the Coulombic efficiency(CE)of the LillCu cell assembled with a GPE increases to 98.5%at room temperature,and the high-voltage LillNCM622 cell achieves a capacity retention of 80.1%with a high CE of 99.5%after 400 cycles.The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.

Thiol-ene crosslinked cellulose-based gel polymer electrolyte with good structural integrity for high cycling performance lithium-metal battery

Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.

SiO_(2) nanofiber composite gel polymer electrolyte by in-situ polymerization for stable Li metal batteries

Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.