Preparation Of Gel Polymer Electrolyte Research Articles

In situ 형성 고분자 젤 전해질 기반 WO₃/NiO 전기변색소자의 제작

In situ 형성 고분자 젤 전해질 기반 WO₃/NiO 전기변색소자의 제작

Advancing Lithium Battery Performance through Gel Electrolytes: Investigating EC-Based Blends with HNBR and PEC for Enhanced Conductivity

Li-ion batteries (LiBs), the most established rechargeable energy storage devices, are currently at closing the gap of their theoretical capacity. That is the main reason why Lithium metal batteries (LMB) have recently regained interest, mainly because of the higher theoretical energy densities achievable with this technology. Therefore, the development of new electrode and electrolyte materials is essential for improving battery performance. Solid polymer electrolytes (SPEs) have been presented as safer alternatives for liquid electrolytes which are used commercially in these devices as they tend to be non-flammable, have enough mechanical strength to resist lithium dendrite growth, and do not leak. However, solid polymer electrolytes are less conductive than liquid electrolytes. Improved ionic conductivity in solid electrolyte materials can be obtained through the use of solid-state gel polymer electrolytes (GPEs). These materials combine the ionic conductivity of liquid electrolytes with the increased safety of SPE resulting in electrolytes with high ionic conductivity and good mechanical stability.1 This study introduces a novel approach to creating in-situ gel polymer electrolytes (GPEs) from solid polymer electrolytes (SPEs) using melt processing followed by sample heating. 2, 3This method capitalizes on the easy processability of SPEs. Initially, the SPE was prepared by blending two polymers with LiTFSI (bis(trifluoromethanesulfonyl)imide) through extrusion mixing. The sample was then converted into a GPE via a controlled heating step. Compared to the initial SPE, the resultant GPE possessed improved thermal and electrochemical properties. In this presentation, we will provide supportive data derived from IR, DSC, and NMR analyses to highlight the differences linked to changes in salt-polymer interactions in the GPE. Verdier, N.; Lepage, D.; Zidani, R.; Prebe, A.; Ayme-Perrot, D.; Pellerin, C.; Dolle, M.; Rochefort, D., Cross-linked polyacrylonitrile-based elastomer used as gel polymer electrolyte in Li-ion battery. ACS Applied Energy Materials 2019, 3 (1), 1099-1110.Ma, C.; Cui, W.; Liu, X.; Ding, Y.; Wang, Y., In situ preparation of gel polymer electrolyte for lithium batteries: Progress and perspectives. InfoMat 2021.Verdier, N.; Foran, G.; Lepage, D.; Prébé, A.; Aymé-Perrot, D.; Dollé, M., Challenges in Solvent-Free Methods for Manufacturing Electrodes and Electrolytes for Lithium-Based Batteries. Polymers 2021, 13 (3), 323.√

Characterization of alginate hydrogel electrolytes for use in symmetric supercapacitor based on polypyrrole-modified electrodes

The use of biopolymers for the preparation of gel polymer electrolytes (GPEs) to construct high-performance energy storage devices contributes to the development of new sustainable materials. Herein, an alginate-based gel electrolyte was used in the construction of a supercapacitor, to aim for an environmentally friendly device. Alginate was crosslinked with calcium ions (ALG-Ca2+) resulting in gels with good mechanical properties and ionic conductivity, suitable for their use as electrolyte and separator for a symmetric supercapacitor, assembled in a coin cell architecture and using polypyrrole as the electrode. The device presented a specific cell capacitance of 39.5 F g-1 at 0.2 A g − 1, and durability of 70.9% after 2000 galvanostatic charge-discharge (GCD) cycles. Based on these properties, three devices were connected in series and demonstrated to be able to light up a 3.0 V LED. The influence of temperature on supercapacitor performance was verified by varying the temperature from 10 to 60 °C and evaluating the characteristic cyclic voltammograms and GCD profiles. The devices were able to operate in the temperature range of 10 to 60 °C, with no loss of their capacity properties.

(Digital Presentation) Post-Treatment Study on Blended Polymer for Solid-State Lithium Batteries

The widely used Li batteries (LiBs) is the most established rechargeable energy storage device. Therefore, the development of new electrode and electrolyte materials is essential for improving battery performance. Solid polymer electrolytes (SPEs) have been presented as safer alternatives for liquid electrolytes as they tend to be non-flammable, have enough mechanical strength to resist dendrite growth, and do not leak. However, these materials tend to be less conductive than liquid electrolytes. This problem can be solved by solid-state gel polymer electrolytes (GPEs), which have lately received more attention. In fact, present a possible solution to this dilemma as they combine the ionic conductivity of liquid electrolytes with the increased safety of SPE to develop of electrolytes with high ionic conductivity and good mechanical stability.1 This work presents a preparation of in-situ GPE from SPE which produce by dry process in order to take advantage of the easy processability of SPE and the higher ionic conductivity of GPE.2, 3 The initial SPE was prepared by combining two polymers with LiTFSI (bis(trifluorormethanesulfonyl)imide) via extrusion mixing. This method of GPE processing was also found to improve other aspects of the electrolyte such as thermal and electrochemical properties which were characterized using cycling voltammetry, electrochemical impedance spectroscopy, and thermal gravimetric analysis. Additionally, the salt-polymer interaction in the GPE was characterized using FTIR, NMR, and the homogeneity of the polymer blend study by SEM-EDX. The cell of LFP/electrolyte/ Li metal showed a high capacity near to the theoretical one at C/20 at temperature 60 C. Additionally, the ionic conductivity of the electrolyte is around 10-5 S/cm. These first results confirmed that this blend of the polymers is a good electrolyte candidate for lithium batteries. Verdier, N.; Lepage, D.; Zidani, R.; Prebe, A.; Ayme-Perrot, D.; Pellerin, C.; Dolle, M.; Rochefort, D., Cross-linked polyacrylonitrile-based elastomer used as gel polymer electrolyte in Li-ion battery. ACS Applied Energy Materials 2019, 3 (1), 1099-1110.Ma, C.; Cui, W.; Liu, X.; Ding, Y.; Wang, Y., In situ preparation of gel polymer electrolyte for lithium batteries: Progress and perspectives. InfoMat 2021.Verdier, N.; Foran, G.; Lepage, D.; Prébé, A.; Aymé-Perrot, D.; Dollé, M., Challenges in Solvent-Free Methods for Manufacturing Electrodes and Electrolytes for Lithium-Based Batteries. Polymers 2021, 13 (3), 323.

In-situ preparation of gel polymer electrolytes in a fully-assembled lithium ion battery through deeply-penetrating high-energy electron beam irradiation

Several in-situ preparation methods of gel polymer electrolytes (GPEs) to develop long-lasting and safe lithium ion batteries (LIBs) recently have been reported. However, the reported in-situ methods still have technical gaps for practical industrial uses in terms of processing time, integrity with the current production line, and scalability. Here, we report an in-situ method to prepare crosslinked poly(vinylene carbonate-co-cyanoethyl acrylate) (PVCEA) GPEs using 10 MeV electron beam (EB) irradiation in a fully-assembled metallic housing LIB that can be processed in a short time without any initiator or thermal treatment. The successful in-situ formation of PVCEA GPEs was achieved at absorbed doses above 16 kGy (irradiation time of 56 s), leading to intimately integrated GPEs with the electrodes, while ensuring stable charge and discharge performance. The prepared PVCEA GPE exhibited a higher transference number (tLi+ = ca. 0.53) and a wider electrochemical operation window (up to 5.0 V) than those of a liquid electrolyte (LE), while providing good ionic conductivity (1.17 mS/cm at 20 °C). Furthermore, the PVCEA GPE-based LIB prepared at an optimized dose of 16 kGy showed comparable retention capacity of 83 % at 0.5C to the conventional LE-based LIB after 300 cycles at 25 °C, and more importantly, better cycling durability at elevated temperature of 60 °C in comparison to the LE-based LIB. This study suggests that the combination of radiation-sensitive precursor formulation and high-energy EB with high penetration ability can provide a promising solution for industrial production of high-performing and safe LIBs.

A simple low-cost method to prepare gel electrolytes incorporating graphene oxide with increased ionic conductivity and electrochemical stability

It has been reported that the existence of graphene oxide (GO) provides a fast-conducting pathway, promoting ionic conductivity in solid polymer electrolytes. However, the preparation of gel polymer electrolytes with GO has been less discussed. In addition, gel polymer electrolytes are usually prepared by adding polymers to organic solvent-based electrolyte solutions. In this study, we propose a facile method for preparing composite gel polymer electrolytes using gelators in low molecular weight (exhibited the liquid state) poly(ethylene glycol) (PEG)-based electrolytes. Mixing GO in PEG-based electrolytes results in precipitation due to significant aggregation of GO. However, PEG/GO composite gel electrolytes are obtained with an inexpensive organogelator, 1,3:2,4-dibenzylidene-d-sorbitol (DBS). The DBS gels entrap the GO and prevent its aggregation. The prepared composite gel electrolytes with GO show higher ionic conductivity and a wider electrochemical stability window, indicating that these electrolytes would be suitable for electrochemical devices.

In situ preparation of gel polymer electrolyte for lithium batteries: Progress and perspectives

AbstractThe practical applications of Li‐ion batteries (LIBs) are challenged by their safety concerns when using liquid electrolytes (LEs). Solid‐state gel polymer electrolytes (GPEs) can address this challenge and have drawn increased attention recently. Normally, GPEs are prepared separately and then assembled into cells, which undoubtedly result in dissatisfactory solid/solid interfacial compatibility and low ionic conductivity. Fortunately, in situ GPEs are proposed to address the above challenges and simplify the preparation process. Typically, LE precursor is injected into the cells and gradually transformed into a quasi‐solid gel state under the conditions of thermal or chemical initiators. Consequently, the obtained in situ GPEs could fully infiltrate the electrode and better interface contact of gel electrolyte/electrode is thus inherited. In this review, the authors focus on the in situ GPEs used in lithium batteries (LBs), and summarize recent progress of the design, synthesis, and applications of in situ GPEs. Based on the different ways of triggering polymerization, there are mainly three methods: thermochemical gelation, polymerization by additional chemical initiators, and cross‐linking initiated by LiO bond. Composite GPEs based on in situ solidification method are introduced as a promising strategy to improve the electrochemical performances. Finally, up‐to‐date research progresses are discussed, and perspectives are provided on the development and challenges of in situ GPEs to meet the requirements for their practical applications in LBs.image

Performance Improvement of PVDF-HFP-Based Gel Polymer Electrolyte with the Dopant of Octavinyl-Polyhedral Oligomeric Silsesquioxane.

Gel polymer electrolytes have the advantages of both a solid electrolyte and a liquid electrolyte. As a transitional product before which a solid electrolyte can be comprehensively used, gel polymer electrolytes are of great research value. They can reduce the risk of spontaneous combustion and explosion caused by leakage during the use of conventional liquid electrolytes. Poly(vinylidene-fluoride-co-hexafluoropropylene) (PVDF–HFP), a material with excellent performance, has been widely utilized in the preparation of gel polymer electrolytes. Here, PVDF–HFP-based gel polymer membranes with polyvinyl pyrrolidone (PVP) pores were prepared using a phase inversion method, and Octavinyl-polyhedral oligomeric silsesquioxane (OVAPOSS) was doped to improve its temperature resistance as well as its ionic conductivity, to enhance its safety and electrochemical performance. The final prepared polymer membrane had a porosity of 85.06% and still had a certain mechanical strength at 160 °C without any shrinkage. The gel polymer electrolyte prepared with this polymer membrane had an ionic conductivity of 1.62 × 10−3 S·cm−1 at 30 °C, as well as an electrochemical window of about 5.5 V. The LiCoO2-Li button half-cell prepared therefrom had a specific capacity of 141 mAh·g−1 at a rate of 1C. The coulombic efficiency remained above 99% within 100 cycles and the capacity retention rate reached 99.5%, which reveals an excellent cycling stability.

Gel Polymer Electrolyte Based on Methyl Methacrylate and Ethyl Methacrylate for Lithium-Ion Batteries

This article deals with gel polymer electrolytes (GPEs) composed of methacrylate-based copolymers. The experiment is based on the preparation of GPE with copolymers, measurement of their electrochemical properties, and following measurements with negative electrode LTO (Li4Ti5O12) and positive electrode NMC (LiNi0.33Mn0.33Co0.33O2). The functionality of electrolyte was verified by cyclic voltammetry and measurement of capacity.

In-situ preparation of gel polymer electrolyte with glass fiber membrane for lithium batteries

A poly (butyl acrylate) (PBA) based gel polymer electrolyte supported by glass fiber membrane (GF-PBA) has been successfully prepared by in-situ polymerization. It is demonstrated that the GF-PBA possesses high ion conductivity (2.52 × 10−4 S cm−1 at room temperature), superior electrochemical stability (5.04 V), high Li ion transport number (0.56) and high thermal stability (>342 °C). Compared with traditional polypropylene and cellulose membranes, glass fiber membrane exhibits excellent electrochemical and thermal stability. Spectroscopy results show that the silicon-oxygen bonds in the glass fiber can promote the dissociation of lithium salts to facilitate Li+ transport. Furthermore, the LiFePO4/GF-PBA/Li cells prepared by in-situ polymerization exhibit low interfacial resistance, excellent cycling stability and superior rate capability at room temperature.

Preparation of gel polymer electrolyte with high lithium ion transference number using GO as filler and application in lithium battery

High lithium ion transference number (tLi+) is one of the requirements of polymer electrolytes for utilization in lithium secondary batteries. Herein, graphene oxide (GO) is used as a filler to fabricate the homogeneous gel polymer electrolyte (GPE) for pursuing high tLi+. The effect of GO on the whole properties of gel polymer electrolytes including conductivity, lithium ion transference number, electrochemical window, electrochemical stability, and cycling performance are explored. Impressively, the GPE containing 0.3 wt% of GO (labeled as GPE-0.3%) demonstrates a high lithium ion transference number of 0.79 and improved electrochemical stability. The LFP/Li battery with GPE-0.3% as the separator shows excellent electrochemical cycle stability and Coulomb efficiency at 25 °C. The discharge specific capacity retention rate of this battery is 94.4% after 100 cycles at 0.2C. All these features make the gel polymer electrolyte useful as a separator of lithium metal batteries for high-performance lithium ion conductors, which exhibits high safety.

Tripropyl Chitosan Iodide-Based Gel Polymer Electrolyte as Quasi Solid-State Dye Sensitized Solar Cells

Electrolyte as one of the major components in dye sensitized solar cells (DSSCs) plays an important role in dye regeneration and as the inner charge carrier transport between electrodes. Gel polymer electrolyte is a potential alternative to liquid electrolytes which suffer of leakage and solvent evaporation. In this present research, functionalization of chitosan by the quaternization reaction of chitosan with iodopropane forming tripropyl chitosan iodide is proposed for the preparation of gel polymer electrolyte. Tripropyl chitosan iodide was characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Four different polymer electrolytes were tested at different compositions in presence of iodide/triiodide redox salt and imidazolium ionic liquid in DSSCs configurations. The results show that the gel polymer electrolyte containing the tripropyl chitosan iodide in presence of 1-propyl-3-methylimidazolium iodide ionic liquid showed better performance with power conversion efficiency of 0.415% as compared to the gel polymer electrolyte film without ionic liquid with power conversion efficiency of 0.075%. The results shown the synergistic effects of the polycationic tripropyl chitosan iodide with the ionic liquid 1-propyl-3-methylimidazolium iodide on the photovoltaic performance.

Electrochemical and Thermal Properties of Gel Polymer Electrolytes Modified by Flame Retardants

Flame retardants can solve a problem with flammability of electronic devices. This article deals with preparation of gel polymer electrolytes, which are used in lithium batteries, modified by flame retardants. Gel polymer electrolytes with selected additives, were prepared by different methods. Electrochemical and thermal properties were measured of all prepared gel polymer electrolytes.

Electrochemical Properties of Gel Polymer Electrolytes with Flame Retardant Used as Solvent

This paper deals with a method of preparation of gel polymer electrolytes modified by flame retardants. The method is characterized that as a solvent, one type of flame retardant is used here. Other components from basic chemical composition of a gel electrolyte didn’t change. The work is focused on measuring electrochemical and electrical properties of gel polymer electrolyte. Electrochemical properties were measured by linear voltammetry and impedance spectroscopy.

Gel Polymer Electrolytes for Lithium Cells Based on Various Methacrylates

Variety of methacrylates was used as the component for preparation of gel polymer electrolytes for lithium batteries. The monomers containing short aliphatic chain were indicated as suitable and their conductivity was in the range from 1 to 6 mS/cm. The good mechanical properties of them seemed important.

Conductivity or rheology? Tradeoff for competing properties in the fabrication of a gel polymer electrolyte based on chitosan-barbiturate derivative

Chitosan-barbiturate (Ch-Ba) derivative was synthesized to afford organosolubility. Attachment of Ba onto the Ch backbone was confirmed by 1H NMR with peaks at 8.2 and 11.1 ppm, and FTIR with bands at 1679 and 1739 cm−1 belonging to the Ba ring. This derivative was used as a host polymer in the preparation of gel polymer electrolytes. The components of the gel consist of tetrapropylammonium iodide (TPAI) as the salt, SiO2 nanofiller (NF) as the mechanical stabilizer, and dimethyl sulfoxide (DMSO) as the solvent. The necessary formulation required to produce the gel was studied using response surface models by means of artificial neural networks. Electrochemical and rheological behaviors were studied and the simulated model predicted conductivities were as high as 8.51 mS cm−1 while still maintaining a solid-like gel structure in the region where storage modulus dominated loss modulus, G″/G′ < 1.

A PEO-based gel polymer electrolyte for lithium ion batteries

This paper illustrates a simpler method for the preparation of gel polymer electrolytes.

Degradable cellulose acetate/poly-l-lactic acid/halloysite nanotube composite nanofiber membranes with outstanding performance for gel polymer electrolytes

The biodegraded cellulose acetate (CA)/poly-l-lactic acid (PLLA)/halloysite nanotube composite nanofiber membranes were fabricated for the preparation of gel polymer electrolytes (GPEs) used in lithium-ion batteries.

Research on Composite Quasi-Solid Polymer Electrolytes

Lithium-ion batteries are dominated the fields of power sources for future electrochemical device attribute to their high energy density, high working voltage, high efficiency, long life and memory-effect-free [1]. Solid-state polymer have been employed to develop rechargeable lithium-ion batteries which have little security problems caused by liquid electrolyte leakage. In recent years, Soft matter ionic conductors such as gel polymer electrolytes (GPEs) have been emerging as a suitable class of materials due to their ability to deliver substantially higher Li+ transport number [2]. In general, conventional GPEs are prepared using a predesigned frame via solution casting of liquid state mixtures (i.e., lithium salt and polymers dissolved in organic solvents), followed by solvent evaporation for solidification. However, the cumbersome preparation processes, and low lithium transport numbers are usually inadequate for practical application. To relieve the preparation problem, in situ synthesis process has been increasingly attracted extensive attention in the preparation of GPEs. The as prepared GPEs are also known as composite polymer electrolytes, because they combine the cohesive features typical of solid systems with liquid-like transport properties. The composite quasi-solid polymer electrolytes were prepared by in situ thermal polymerization using trimethylolpropane trimethylacrylate (TMPTMA) [3, 4] or triethylene glycol diacetate-2-propenoic acid butyl ester copolymer (TEGDA-BA) [5, 6] as monomer. The preparation processes, electrochemical performance and interfacial properties of polymer electrolytes were studied.TMPTMA-based gel polymer electrolytes were prepared by using TMPTMA as a monomer, lauroyl peroxide (LPO) as a thermal initiator, 1M LiFP6 / (EC:DMC:EMC =1:1:1, V/V/V) liquid electrolyte solvent and plastic crystal electrolyte (containing 4 mol% LiTFSI in the succinonitrile) as plasticizer, respectively.The influencing factors of the electrochemical performance, such as polymerization temperature, liquid electrolyte content and initiator content, were systematically discussed and the process parameters were optimized. The high ionic conduction (>10-3 S cm-1) of gel polymer electrolytes was mainly due to the liquid electrolyte trapped in the pores highly dispersed in the polymer framework.The homogeneous and stable liquid state electrolyte was obtained by magnetic stirring the precursors. After the gel reaction, the precursor liquid electrolyte became a viscous gel and showed little flow even tipping the vial at a certain angle.The polymer electrolytes has a wider electrochemical voltage window was stable approximately up to 5 V versus Li/Li+ without an irreversible oxidation.The discharge capacity vs. the cycle number had been studied employing LiCoO2, Li[Li1/6Ni1/4Mn7/12]O2, LiFePO4 as the active cathode material and lithium metal as the anode. The Li/GPEs/ LiCoO2 display a high initial discharge capacity of 134.1 mAh g-1, as well as an excellent rate capability (83% remaining capacity after 100 cycles).TMPTMA-based and TEGDA-BA-based composite polymer electrolytes have been successfully prepared in situ thermal polymerization. The polymer electrolytes have higher ionic conductivities, electrochemical stability and excellent charge/discharge galvanostatic cycling performance at room-temperature. The excellent properties of polymer electrolytes make it significant potential material for next generation lithium ion batteries.Acknowledgements This work was supported by the 973 project (2013CB934001), NSF of China (51172024, 51372022)References[1] L.Z. Fan, Y.S. Hu, J. Maier. Adv. Funct. Mater., 2007, 17, 2800.[2] E.H. Kil , K.H. Choi. K.Y. Cho, S.Y. Lee. Adv. Mater., 2013, 25, 1395.[3] D. Zhou, L.Z. Fan, H.H. Fan, Q. Shi. Electrochim. Acta, 2013, 89, 334.[4] Q.J. Wang, H.H. Fan, L.Z. Fan, Q. Shi. Electrochim. Acta, 2013, In press.[5] H.H. Fan, H.X. Li, L.Z. Fan. J. Power Sources, 2013, Accepted.[6] Q.J. Wang, H.F. Ni, W.L. Song, L.Z. Fan. J. Power Sources, 2013,in press.

Preparation and characterization of electrospun poly(acrylonitrile) fibrous membrane based gel polymer electrolytes for lithium-ion batteries

Electrospun, non-woven membrane of high molecular weight poly(acrylonitrile) (PAN) is demonstrated as an efficient host matrix for the preparation of gel polymer electrolytes for lithium-ion batteries. Electrospinning process parameters are optimized to get a fibrous membrane of PAN consisting of bead-free, uniformly dispersed thin fibers with diameter in the range 880–1260 nm. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of 1 M LiPF 6 in a mixture of organic solvents and the gel polymer electrolyte shows ionic conductivity of 1.7 × 10 −5 S cm −1 at 20 °C. Electrochemical performance of the gel polymer electrolyte at 20 °C is evaluated in lithium-ion cell with lithium cobalt oxide cathode and graphite anode. Good performance with a low capacity fading on charge–discharge cycling is demonstrated.