Composite Polymer Electrolyte Membranes Research Articles

A highly ionic conductive poly(methyl methacrylate) composite electrolyte with garnet-typed Li6.75La3Zr1.75Nb0.25O12 nanowires

Composite solid polymer electrolytes, integrating advantages (inflammability and electrochemical stability) of inorganic parts and virtues (lower interfacial resistance, flexibility and handy preparation) of polymer matrix, present a promising prospect for safe high-energy solid-state lithium energy storage systems. Herein, one-dimensional garnet-typed Li6.75La3Zr1.75Nb0.25O12 nanowires are successfully synthesized, and the nanowires are complexed with poly(methyl methacrylate), lithium perchlorate to fabricate composite solid polymer electrolyte membranes via a facile solution-casting method. The ionic conductivity is sharply increased from 5.98 × 10−7 of filler-free solid electrolyte to 2.20 × 10−5 S cm−1 of composite solid polymer electrolyte at room temperature, because the interaction between nanowires and polymer chains provide more free volume and special ionic conductive channels. In the meantime, the composite solid polymer electrolytes exhibit the wide electrochemical window and good stability against lithium anode. The feasibility of composite solid polymer electrolyte is examined in LiCoO2/Li configuration at 0.2 C under 60 and 70 °C, the cells deliver discharge capacity of 134.6 and 143.6 mAh g−1 at first cycle and kept 92.3%, 71.8% retention after 80 and 65 cycles respectively. The results indicate that the as-prepared composite solid polymer electrolytes will be a promising candidate for solid-state lithium batteries in the future.

Poly(ethylene oxide)-Li10SnP2S12 Composite Polymer Electrolyte Enables High-Performance All-Solid-State Lithium Sulfur Battery.

Composite polymer electrolyte membranes are fabricated by the incorporation of Li10SnP2S12 into the poly(ethylene oxide) (PEO) matrix using a solution-casting method. The incorporation of Li10SnP2S12 plays a positive role on Li-ionic conductivity, mechanical property, and interfacial stability of the composite electrolyte and thus significantly enhances the electrochemical performance of the solid-state Li-S battery. The optimal PEO-1%Li10SnP2S12 electrolyte presents a maximum ionic conductivity of 1.69 × 10-4 S cm-1 at 50 °C and the highest mechanical strength. The possible mechanism for the enhanced electrochemical performance and mechanical property is analyzed. The uniform distribution of Li10SnP2S12 in the PEO matrix inhibits crystallization and weakens the interactions among the PEO chains. The PEO-1%Li10SnP2S12 electrolyte exhibits lower interfacial resistance and higher interfacial stability with the lithium anode than the pure PEO/LiTFSI electrolyte. The Li-S cell comprising the PEO-1%Li10SnP2S12 electrolyte exhibits outstanding electrochemical performance with a high discharge capacity (ca. 1000 mA h g-1), high Coulombic efficiency, and good cycling stability at 60 °C. Most importantly, the PEO-1%Li10SnP2S12-based cell possesses attractive performance with a high specific capacity (ca. 800 mA h g-1) and good cycling stability even at 50 °C, whereas the PEO/LiTFSI-based cell cannot be successfully discharged because of the low ionic conductivity and high interfacial resistance of the PEO/LiTFSI electrolyte.

Garnet-doped composite polymer electrolyte with high ionic conductivity for dendrite-free lithium batteries

Abstract Solid polymer electrolytes are promising candidates to replace the extensively used flammable liquid electrolytes in lithium batteries. However, pure polymer electrolytes seldom meet practical requirements because of their relatively low ionic conductivity and poor mechanical properties. Herein, we report a garnet (Li6.4La3Zr1.4Ta0.6O12, LLZTO)-doped composite polymer electrolyte (CPE) membrane for high performance lithium batteries. The CPE is composed of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(ethylene glycol) methyl ether methacrylate (POEGMA) polymer with the addition of ceramic particles LLZTO. It not only has high ionic conductivity of 1.00 × 10−3 S cm−1 after the activation of liquid electrolyte at room temperature, but also surprisingly restrains the growth of Li dendrites. Its electrochemical stability window is up to 4.7 V (vs. Li+/Li). Moreover, LiFePO4/Li batteries using the CPE exhibit excellent cycling performance and superior rate capability.

100 MeV O7+ ion irradiation induced electrochemical enhancement in NiBTC metal-organic framework based composite polymer electrolytes incorporated with ionic liquid

Nickel 1,3,5-benzenetricarboxylate (NiBTC) metal-organic framework (MOF), has been synthesized by solvothermal method and dispersed in Poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer. The composite polymer electrolyte membranes were irradiated with 100 MeV O7+ swift heavy ion (SHI) at different fluences and ionic liquid (IL) BMIMBF4 has been incorporated after irradiation. Increasing % uptake of IL has been observed upon IL incorporation as SHI irradiation can enlarge the micropore volumes of NiBTC-MOF by inducing missing linker defects. FTIR spectra depict shifting of carboxylate vibrational modes with increasing fluence suggesting elongation of metal-linker molecular bonds in NiBTC-MOF due to interaction of BF4- anion of IL with unsaturated Ni metal nodes with increasing uptake of IL. Non-Debye relaxation ion dynamics has been revealed from dielectric modulus spectra and optimum ionic conductivity of 9.9 × 10−3 Scm−1 is achieved for the nanocomposite membrane at the fluence of 3.3 × 1012 ions cm−2 at 380 K. The frequency dependent AC conductivity increases with increasing fluence due to higher IL uptake as well as chain scission of the polymer segments. The electrochemical stability of the nanocomposite membrane increases with increasing fluence and attains a maximum value of 6.1 V at 3.3 × 1012 ions cm−2.

Unitized Configuration Design of Thermally Stable Composite Polymer Electrolyte for Lithium Batteries Capable of Working Over a Wide Range of Temperatures

Solid‐state electrolytes that can meet the requirements of high‐safety lithium batteries at high temperature aroused much attention in electrochemical energy storage.Nevertheless, the low ionic conductivity at ambient temperature and poor mechanical strength limit their practical applications. Through unitized configurationdesign, herein, a unique safe and flexible composite polymer electrolyte membrane comprising of inorganic ceramic particles (Li6.75La3Zr1.75Nb0.25O12, LLZNO), polyvinylidene fluoride (PVDF), and lithium perchlorate (LiClO4) are fabricated. Benefitting from the strongly coupled effects via interfacial chemical reactions and the synergistic effects between LLZNOand PVDF, the LLZNO‐based composite electrolyte wetted by ionic liquid exhibits a high ionic conductivity of 1.5 × 10−3 S cm−1 at 25 °C. Moreover, the electrolyte is able to be thermally stable at relatively high temperatures. A LiFePO4 (+) // Li (−) lithium battery using the as‐prepared LLZNO‐based composite electrolyte achieves a good electrochemical stability at ambient temperature, 80 °C and even 120 °C. This work provides an effective way to the fabrication of high‐performance, flexible electrolyte membranes for lithium batteries and other energy‐storage devices that are capable of working over a wide range of temperatures

Development of all-solid-state battery based on lithium ion conductive polymer nanofiber framework

A thin, flexible, and safe composite polymer electrolyte membrane composed of lithium ion conductive nanofiber framework and polymer electrolyte matrix is demonstrated as an innovative solid-state electrolyte for potential use in high-performance rechargeable all-solid-state lithium ion battery. Due to this unique structural integrity, the composite solid polymer electrolyte indicates excellent mechanical stability, remarkable improvements in the ion conductivity (approximately 10−4 S cm−1 at room temperature) and the lithium ion transference number (approximately 0.5), and the significant battery performance in terms of good charge-discharge cycling behavior and moderate rate capability. Finally, a high-voltage multi-stacked battery with the solid polymer composite electrolytes is developed and can readily produce a doubled cell potential of 6.8 V, promising future batteries operated at high-voltage with high energy densities.

Performance improvement of electrolytic air dehumidification systems with high‐water‐uptake polymer electrolyte membranes

ABSTRACTElectrolytic dehumidification with polymer electrolyte membranes (PEMs) is innovative as it enables portable, accurate, and efficient air dehumidification. However, during operation, the dehydration of the PEM results in a severe decrease in its dehumidification performance. In this study, for the purposes of improving the water retention, we developed two types of composite PEMs, Nafion Membrane 212 (N212)–SiO2 and Nafion–SiO2. The hydration parameters (λ; H2O–SO3H) of N212–SiO2 and Nafion–SiO2 were increased by 20–61 and 40–92%, respectively, compared to that of Nafion 212. System experimental results show that in air with a 45% relative humidity, the dehumidification rates of N212–SiO2 and Nafion–SiO2 elements improved by 17 and 8%, respectively, and the respective increases in energy efficiency were 22 and 16%. In addition, the effect of the PEM water content on the dehumidification performance was more pronounced than those of other influencing factors such as the proton conduction resistance. The use of high‐water‐uptake PEMs positively helped optimize the electrolytic dehumidification, especially under low air humidities. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47676.

Characterization of polymer/liquid crystal composite based electrolyte membranes for sodium ion battery applications

A novel PEO/E8 liquid crystal based composite solid polymer electrolyte membranes complexed with NaIO4 salt were prepared by the solution casting technique. The composite-salt complexations were examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, micro-Raman and X-ray photoelectron spectroscopy (XPS) studies. Differential scanning calorimetry (DSC) studies confirmed the decrease of percentage of crystalline portion in the matrix of electrolyte membranes upon that addition of NaIO4. The EIS studies evidenced for the increase of ionic conductivity of the electrolytes upon increase of NaIO4 concentration and in the present study, PEO/E8 electrolyte complexed with 10 wt% of NaIO4 demonstrated higher room temperature ionic conductivity of 1.05 × 10−7 S/cm.

High-Rate and Large-Capacity Lithium Metal Anode Enabled by Volume Conformal and Self-Healable Composite Polymer Electrolyte.

The widespread implementation of lithium‐metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite‐related failure. Here a solid–liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self‐healing polymer and Li+‐conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm−2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm−2 at 10 mA cm−2 could also be obtained. Furthermore, the Li|Li4Ti5O12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self‐healing functionality of CPE, providing a novel approach and a significant step toward cost‐effective and large‐scalable LMBs.

Electrospun poly(vinylidene fluoride)/cellulose acetate/AgTiO2 nanofibers polymer electrolyte membrane for lithium ion battery

Polymer electrolyte membrane based on cellulose acetate/AgTiO2 seems propitious for lithium ion battery (LIB) separator due to its superior thermal stability and hydrophilic property. Herein, we report the preparation of novel electrospun poly(vinylidine fluoride)/cellulose acetate/AgTiO2 hybrid nanofibers polymer electrolyte membrane by electrospinning for LIB application. For the preparation of PVdF/CA-AgTiO2 nanofibers membrane, silver doped titania (Ag-TiO2) nanoparticles were incorporated in electrospinning solution of poly(vinylidine fluoride) (PVdF)/cellulose acetate (CA). The PVdF/CA-AgTiO2 nanofibers membrane was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red spectroscopy (FTIR), thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses. PVdF/CA-AgTiO2 nanofibers membrane shows excellent thermal stability, high porosity and super electrolyte compatibility. The prepared cell LiFePO4/PVdF/CA-Ag-TiO2/Li delivered excellent cyclic stability with high discharge capacity and coulombic efficiency of 100% after 50 cycles at 0.1C. High ionic conductivity and good overall electrochemical performances enlightens the approach of making hybrid organic cellulose-based composite polymer electrolyte membrane is promising candidate for lithium ion battery.

Energy material - the role of silicotungstic acid and fly ash in sulfonated poly (ether sulfone) composites for PEMFC applications

The composite polymer electrolyte membranes were prepared from sulfonated poly (ether sulfone) (SPES), silicotungstic acid (STA) and fly ash (FA). Post sulfonation process was adopted to synthesize SPES using sulphuric and chlorosulfonic acid. The prepared electrolyte membranes were examined by water uptake capacity, swelling ratio, ion-exchange ability, proton conductivity, thermal stability and electrochemical performance for evaluating the pertinence of these membranes in fuel cell applications. As such the pristine membrane restricts with the proton conductivity of 0.042 S cm−1 at 30 °C and 0.060 S cm−1 at 90 °C while the polymer composite membrane, SP-STA-FA-10 reveals the maximum conductivity of 0.054 S cm−1 at 30 °C and 0.073 S cm−1 at 90 °C. It also exhibits good thermal stability than that of the pure membrane. The membrane electrode assemblies (MEAs) have been successfully developed from SPES as well as SP-STA-FA-10 membranes and their electrochemical performance were studied the wide range of current density. Herein, the composite membranes derived from SPES, STA and FA can be viable candidates for fuel cell applications.

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 °C, 130 mAh g−1 at 0.5 °C, 119 mAh g−1 at 1 °C and 100 mAh g−1 at 2 °C) 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.

Fast surface proton conduction on acid-doped polymer nanofibers in polymer electrolyte composite membranes

Fast surface proton conduction on the acid-doped nanofibers was demonstrated to achieve low membrane resistance under low relative humidity or unfumidified conditions for future fuel cell applications. Polymer electrolyte composite membranes composed of phytic acid-doped polybenzimidazole nanofibers embedded in sulfonated polyimide were designed and fabricated. Scanning transmission electron microscopic observation and proton conductivity measurements of uniaxially-aligned nanofiber composite membranes revealed that the phosphoric acid groups in the doped acid and sulfonic acid groups of the polymer electrolyte matrix were aggregated at the surface of the nanofibers to construct effective proton conductive pathway. In addition to low membrane resistance based on fast surface proton conduction on the acid-doped nanofibers, distinguished gas barrier property and improved membrane stability of the acid-doped nanofiber composite membrane will promise high-performing fuel cells, especially by fabricating ultra-thin polymer electrolyte membrane that can be efficiently operated at low relative humidity.

High Performance Composite Polymer Electrolytes Doped With Spherical-Like and Honeycomb Structural Li0.1Ca0.9TiO3 Particles.

The spherical-like and honeycomb structural Li0.1Ca0.9TiO3 particles are prepared by spray drying combined with following calcination confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive X-ray spectrometer (EDS). The poly (vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP))-based composite polymer electrolytes (CPEs) modified with the particles are fabricated by phase inversion and activation processes. The characterization results show that the as-prepared CPE membranes possess the smoothest surface and most abundant micropores with the lowest crystallinity with adding the particles into the polymer matrix, which results in high ionic conductivity (3.947 mS cm−1) and lithium ion transference number (0.4962) at ambient temperature. The interfacial resistance can be quickly stabilized at 508 Ω after 5 days storage and the electrochemical working window is up to 5.2 V. Moreover, the mechanical strength of the membranes gains significant improvement without lowering the ionic conductivity. Furthermore, the assembled coin cell can also deliver high discharge specific capacity and preserve steady cycle performance at different current densities. Those outstanding properties may be ascribed to the distinctive structure of the tailored spherical-like and honeycomb structural Li0.1Ca0.9TiO3 particles, which can guarantee the desirable CPEs as a new promising candidate for the polymer electrolyte.

Enhanced thermal and electrochemical properties of poly(vinylidene fluoride-co-hexafluoropropylene)-based composite polymer electrolytes doped with CaTiO3 dielectric ceramics

Poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP))-based composite polymer electrolytes (CPEs) doped with different amounts of CaTiO3 inorganic fillers are prepared by phase inversion. With adding the CaTiO3 fillers into the P(VDF-HFP) polymer matrix, the CPE membranes show more abundant and uniform micro-pore structure with lower crystallinity, better thermal stability and mechanical strength. The characterization results show that the ionic conductivity at room temperature and electrochemical working window of the CPE doped with 5 wt% CaTiO3 fillers (CPE-5) can be up to about 3.557 mS cm−1 and 5.1 V, respectively. The interfacial resistance of the Li/CPE-5/Li simulated cell can quickly stabilize at 750 Ω after 5 days storage, and the assembled LiCoO2/CPE-5/Li coin cell shows excellent rate and cycle performance. Moreover, the CPE-5 membrane can still well maintain the original micro-pore structure after 100 cycles at 1.0 C without visible cracks. Those results suggest that the as-fabricated CPE doped with 5 wt% CaTiO3 inorganic fillers may become a promising polymer electrolyte for the lithium ion battery

Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (Wavg ~ 5 × 106) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO4) and lithium garnet oxide Li6.28Al0.24La3Zr2O12 (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li+ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li+ conductivity of 4.40 × 10−4 S cm−1 and wide electrochemical window (4.5 V) is observed for PEO8/LiClO4 + 20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO2 as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g−1/142 mAh g−1 at 25 °C with 0.06 C-rate.

Effect of IL incorporation on ionic transport in PVdF-HFP-based polymer electrolyte nanocomposite doped with NiBTC-metal-organic framework

Ni-based metal-organic framework (MOF), nickel 1,3,5-benzene tricarboxylate (NiBTC) has been synthesized by solvothermal method and incorporated with ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) at varying weight ratios to use as nanofiller in the polymer matrix of poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP). The structural properties of MOF-NiBTC-based composite polymer electrolyte system upon IL incorporation have been investigated by XRD, FTIR, BET, scanning EXAFS and XANES techniques. Shifting of vibrational modes of –COOH groups is observed from FTIR spectra due to strong interaction of Ni metal cluster with BF4− anion of the IL. Local coordination structure and oscillation periodicity of Ni K-edge are investigated in R-space and k-space from the EXAFS as well as XANES spectra. Asymmetric oscillatory behavior with reduction in coordination number is observed upon IL incorporation due to strong interaction of guest IL with the host MOF-NiBTC. Dielectric relaxation and scaling of AC conductivity have been analyzed in the temperature range of 300–380 K and frequency range of 42 Hz–5 MHz. Non Debye type dielectric relaxation dynamics is observed due to short range hopping of ions. Ion concentration and temperature independent scaling behaviors are followed by the composite polymer electrolyte membranes. Optimum ionic conductivity of 6.5 × 10−3 S cm−1 and electrochemical stability up to 5.7 V have been obtained at 50 wt% of IL incorporation in the porous nanocomposite electrolyte system.

Preparation of monodispersed ZrO2 nanoparticles and their applications in poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolytes

AbstractTo improve the electrochemical performance of pure poly[(vinylidene fluoride)‐co‐hexafluoropropylene] (P(VDF‐HFP))‐based gel polymer electrolytes, different amounts of monodispersed ZrO2 nanoparticles were introduced to fabricate P(VDF‐HFP)/ZrO2 composite polymer electrolytes (CPEs) using the phase inversion method and activated processes, in which the monodispersed ZrO2 nanoparticles were synthesized by an easy route without any chelating agents or surfactants, and confirmed using scanning electron microscopy, particle size distribution measurement and X‐ray diffraction. The characterization results show that the as‐fabricated CPE membranes present not only an abundant porous structure, but also an improved mechanical strength. In particular, sample CPE‐5 presents the best properties when the doped content of the monodispersed ZrO2 nanoparticles reaches 5 wt% in the polymer matrix, in which the liquid uptake and ionic conductivity at room temperature are about 192.4% and 3.926 mS cm−1, and the electrochemical working window and thermal decomposition temperature can increase to 5.1 V and 420 °C, respectively. Moreover, an assembled LiCoO2/CPE‐5/Li coin cell can deliver excellent rate and cycling performance, in which the discharge specific capacity of the cell can show about 83.95% capacity retention at 2.0 C after 85 cycles. © 2018 Society of Chemical Industry

Preparation and characterization of nanocomposite ionic liquid-based gel polymer electrolyte for safe applications in solid-state lithium battery

Gel electrolyte is one of the most direct and appropriate ways to solve the safety problem of battery before the most challenging technological hurdles to all solid-state batteries have not yet been overcame. A major challenge towards gel polymer electrolyte (GPE) is making an electrolyte that is effectively combine with electrochemical performance, thermal safety and the stability to lithium. Here, PVDF-HFP-LiTFSI/SiO2/EMITFSI polymer electrolyte composite membrane (ILGPE) is prepared via solution casting method, in which nano-silica and ionic liquid positively effect on the performance of polymer electrolytes, such as ionic conductivity, electrochemical stability and thermal safety stability. It remarkably enhances the interface compatibility between ILGPEs and lithium metal. Significantly, we characteristically elucidate the possible transmission mechanism and interaction within the materials of ILGPE. Furthermore, Li/LiFePO4 battery based on such ILGPEs can exhibit fascinating interfacial stability and cycling performance. Herein, cells based on ILGPEs can overcome the drawbacks of solid electrolytes and volatile organic liquid electrolytes, which suggest a promising method for highly secure lithium batteries with appreciably enhanced performance.

Effect of different contents of organic-inorganic hybrid particles poly(methyl methacrylate)[sbnd]ZrO2 on the properties of poly(vinylidene fluoride-hexafluoroprolene)-based composite gel polymer electrolytes

Poly(vinylidene fluoride-hexafluoroprolene) (P(VDF-HFP))-based composite polymer electrolyte (CPE) membranes doped with organic-inorganic hybrid particles poly(methyl methacrylate)ZrO2 (PMMA-ZrO2) are fabricated by phase inversion, in which PMMA is firstly successfully grafted onto the surface of the homemade nano-ZrO2 particles via in situ polymerization confirmed by FT-IR. XRD and DSC patterns show that adding PMMA-ZrO2 into the polymer matrix can decrease the crystallinity of the CPE membranes and TG curves indicate the CPE membranes possess desirable thermal stability. It can be found that the CPE membrane presents a uniform surface with abundant interconnected micro-pores when the added amount of PMMA-ZrO2 increases to 5 wt % vs. polymer matrix, in which the ionic conductivity at room temperature and tensile strength can be up to 3.595 mS cm−1 and 26.18 MPa, respectively. In particular, the CPE membrane shows the minimum deformation of about 8% after being exposed at 160 °C for 1 h, and the electrochemical working window of the assembled Li/CPE/SS cell can be stable at 5.1 V (vs Li/Li+) at room temperature. Moreover, the LiCoO2/CPE/Li coin cell can deliver a specific capacity of 114.5 mAh g−1 with 79.13% capacity retention at 2.0 C after 110 cycles. The results suggest that the as-fabricated P(VDF-HFP)-based CPE doped with 5 wt % organic-inorganic hybrid particles PMMA-ZrO2 can be a promising polymer electrolyte for lithium ion batteries.