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PVDF-HFP
JOURNAL OF ELECTRONIC MATERIALS · 2021 ·Vol. 50 ·期 9 ·5049-5056 · IF 1.938

Effects of Components in Solvent-Enhanced PVDF-HFP-Based Polymer Electrolyte on Its Electrochemical Performance

Wang Yihe,Qin Faxiang

Lithium (Li) metal has been considered as a potential substitute for the graphite anode in Li-ion batteries to further boost their energy density. Polymer electrolytes (PEs) are expected to be applied in Li metal batteries (LMB) to replace liquid electrolytes due to safety concerns. Among others, poly(vinylidene fluoride- co -hexafluoropropylene) (PVDF-HFP)-based electrolytes offer clear advantages such as improved processability and chemical/electrochemical stability. However, Li dendrite growth in LMBs and the low Li-ion conductivity of solid polymer electrolytes (SPEs) still hinder their practical applications. To address this issue, it has been proposed that solvent-enhanced PVDF-HFP-based polymer electrolytes (SPPEs) with a tuned amount of residual N -methyl-2-pyrrolidone (NMP) could provide improved ionic conductivity and outstanding chemical/electrochemical stability. We report herein the effects of different salts, polymer, and additives on the electrochemical performance and interface stability of SPPEs. We demonstrate that lithium salts and blended polymers play a pivotal role in the electrochemical performance of SPPEs. In addition, additives exert a remarkable effect on the stripping/plating behaviors of metallic lithium anode in SPPEs. SPPEs with adequate LiNO 3 are found to be stable with lower overpotentials at 0.5 mA cm −2 on cycling of symmetrical Li cells. These results highlight novel SPPE strategies for optimizing the ionic conductivity and stabilizing the lithium metal anodes.

研究领域: 材料科学 · 电化学 · 能源存储 · 电池技术
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TALANTA · 2024 · IF 5.6

Cu superparticle-based aggregation induced enhancement strategy with PVDF-HFP/CeVO4 NP sensing interface for miR-103a detection

Fangyan Ji,Peilin Wang,Zhenrun Li,Kaixiang Ji,Dongyu Wang,Qiang Ma

Aggregation-induced emission (AIE) has been widely used in research on electrochemiluminescence (ECL) due to its excellent luminescence intensity. In this work, copper superparticles (Cu SPs) were used to construct ECL biosensor to detect the microRNA-103a (miRNA-103a) in triple-negative breast cancer (TNBC) tumor tissues. Firstly, GSH-capped copper clusters were used as precursors to prepare Cu SPs by the AIE effect. Compared with clusters, Cu SPs possessed higher luminescence performance and energy stability, making them an ideal choice for ECL nanoprobe. The film of PVDF-HFP/CeVO 4 NPs was constructed and modified with CPBA and GSH as the sensing interface (PCCG). The PCCG film displayed good conductivity and hydrophilicity, and desirable mechanical stability. Moreover, the PCCG film can induce high carrier mobility rates and dissociate large amounts of the co-reactant K 2 S 2 O 8 to enhance the ECL intensity of Cu SPs. As a result, the prepared ECL sensor with the catalyzed hairpin assembly (CHA) strategy was employed to quantify miRNA-103a in the range of 100 fM to 100 nM. The biosensor provided a novel analytical approach for the clinical diagnosis of TNBC.

研究领域: 生物传感器 · 癌症诊断 · 纳米技术 · 生物医学工程 · 分析化学
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POLYMER · 2023 · IF 4.6

A flexible, highly conductive, tough ionogel electrolyte containing LiTFSI salt and ionic liquid [EMIM][TFSI] based on PVDF-HFP for high-performance supercapacitors

Ying Wei,Wei Chen,Xinyi Ge,Jiayi Liang,Zheng Xing,Qingguo Zhang,Zhong-Xia Wang

Ionogel electrolytes (IGEs) with chemical and thermal stability properties have attracted considerable attention for all-solid-state energy storage devices, particularly for high-performance supercapacitors (SCs). However, achieving high conductivity, flexibility, and toughness, as well as deformation and impact resistance in special cases, is challenging with the typical polymer based on ionic liquids (ILs). Here, an effective gelation strategy is proposed for the preparation of free-standing LiTFSI/[EMIM][TFSI]/PVDF-HFP ionogels (IGs) by double-additive induced physical cross-linking. The mechanical and electrochemical properties of the IGs can be synergistically optimized by the cross-linking and entanglement of LiTFSI and [EMIM][TFSI] with the PVDF-HFP network. The target IGs simultaneously exhibit excellent deformation capacity (over 50 %), high ionic conductivity (10.3 × 10 −3  S cm −1 at 25 °C), hardness (H: 728.6 kPa), and Young's modulus (E: 11.4 MPa), which can exhibit the specific capacitance of 274. 55 F g −1 , energy density of 38.13 Wh kg −1 and maximum power density of 2499.93 W kg −1 in the fabricated symmetric supercapacitor . The results will motivate us to further explore their applications for flexible electronic devices, wearable electronic skin, and flexible energy storage.

研究领域: 材料科学 · 电化学 · 高分子物理 · 能源存储 · 柔性电子学 · 纳米复合材料
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

PVDF-HFP/LiTFSI based composite solid state electrolyte with different micromorphology of Li6.25Ga0.25La3Zr2O12 doping

Jingxuan Cai,Tao Liu,Chuwei Liu,Guoqiang Liu

Solid electrolytes are safer alternatives to liquid electrolytes. Adding Ga to lithium lanthanum zirconium oxide (LLZO) garnet-like solid-state electrolytes effectively improves their performance. The properties of solid-state electrolytes prepared using the two mainstream methods, namely, electrospinning and sol-gel, vary and directly affect the electrochemical performance of assembled batteries. In this study, we prepared Li 6.25 Ga 0.25 La 3 Zr 2 O 12 (Ga-LLZO) nanoparticles and nanofibers using the sol-gel and electrospinning methods, respectively. The battery was also assembled with composite film consisting of the poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer substrate within Ga-LLZO ceramic fillers. The electrolyte of the battery prepared by Ga-LLZO nanofibers has better conductivity. We fabricated a Li|10 wt% Ga-LLZO nanofiber/PVDF-HFP/60 wt% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)|LiFePO 4 button battery using the optimal concentration. The device demonstrated a stable cycle lasting up to 700 h, a Coulombic efficiency of 98%, a capacity retention rate of 96.5%, and an electrochemical window up to 5 V vs Li/Li + at room temperature. Over time, a suitable contact interface generated a positive feedback loop. The ionic conductivity was 1.1 × 10 −4 S·cm −1 . The newly prepared electrolyte films aid the fabrication of future solid electrolytes.

CAS / MDL: 25249-54-1 9003-39-8
研究领域: 材料科学 · 电化学 · 能源存储
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Dual polymer (PVDF-HFP and PES) matrix / Li6.4La3Zr1.4Ta0.6O12 composite solid electrolyte with good stability for solid state lithium ion batteries operating at different temperatures

Xi Wu,Xiaohua Jie,Xinghua Liang,Qicheng Hu,Liuyan Zhang,Jin Wang,Shufang Wu

Solid state lithium-ion batteries (SSLIBs) with high safety and high energy density are promising novel energy storage devices. However, the performance of SSLIBs would descend under a wide work temperature range. A flexible ceramic-polymer composite solid electrolyte membrane was created by solution casting to obtain good stability of SSLIBs at different temperatures. The PVDF-HFP-PES-LiClO 4 -Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) composite solid electrolyte shows excellent electrochemical performances in the temperature range of 20 to 60 o C. The ionic conductivity of PVDF-HFP-PES-LiClO 4 -LLZTO (PPLL) is 4.26 × 10 -4 , 4.97 × 10 -4 , 5.26 × 10 -4 , 5.59 × 10 -4 and 5.97 × 10 -4 S cm -1 at 20, 30, 40, 50 and 60 o C, respectively. The PPLL was employed in LiFePO 4 (LFP)/PPLL/Li batteries, and their properties were tested at 0.2 C. The test results show that the LFP/PPLL/Li battery has a good charge-discharge, rate, and cyclic performance at 20 - 60 o C. After 150 cycles with 0.2C at 30 o C and 60 o C, the capacity retention rates of 75.6% and 86.4%, respectively. This work provides an effective strategy for designing and preparing SSLIBs.

研究领域: 材料科学 · 电化学 · 能源存储
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Journal of Energy Storage · 2023 · IF 9.4

Construction and performance of PVDF-HFP-matrix comb-like gel copolymer electrolyte for high-performance quasi-solid-state lithium-metal batteries

Lingguang Yi,Xiaoyi Chen,Changfei Zou,Jiali Liu,Xilin Cao,Xiyuan Tao,Zihao Zang,Liping Zheng,Li Liu,Xianyou Wang

Rechargeable lithium metal batteries (LMBs) have encountered bottlenecks in energy density , durability, and safety issues. Designing functional polymer electrolytes has been considered as an effective way to develop high-performance of LMBs. In this study, PVDF-HFP-matrix polymeric electrolytes blended with co polymer P(MMA- co -PEGMEMA) (PPxPy) via a simple one-pot free-radical polymerization are successfully designed and prepared. It has been found that the PPxPy electrolytes can construct different comb -like networks via systematically tuning monomer ratios. The tailored PP5P5 gel electrolyte exhibited high ionic conductivity of 0.74 × 10 −3  S cm −1 at room temperature (RT), an enlarged electrochemical window up to 4.77 V, high lithium-ion transference number t Li+ of 0.65, and good mechanical property with Yang's modulus up to 131 MPa. Benefited from these good properties, the Li||LiFePO 4 batteries assembled with PP5P5 gel electrolyte achieved an exceptional discharge capacity of 152 mAh g −1 with nearly 100 % Coulombic efficiency after 150 cycles at 1C. Furthermore, the Li|PP5P5|NCM811 cell exhibits excellent reversible specific capacity of 188 mAh g −1 at 0.1C. Consequently, it can be anticipated the as-prepared functional polymer structure to provide a reliable method for the preparation of polymer electrolytes in quasi-solid-state batteries with high-energy-density.

CAS / MDL: 872-50-4 26915-72-0
研究领域: 材料科学 · 电化学 · 能源存储
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ACS Applied Materials & Interfaces · 2018 · IF 8.097

Durable Sodium Battery with a Flexible Na3Zr2Si2PO12–PVDF–HFP Composite Electrolyte and Sodium/Carbon Cloth Anode

Qiang Yi,Wenqiang Zhang,Shaoqing Li,Xinyuan Li,Chunwen Sun

High-performance electrolytes and electrode materials play a critical role in advanced sodium-ion batteries with higher energy densities. In this work, we prepared a poly(methyl methacrylate)-filled composite electrolyte (named as GHSE) by in situ polymerization of methyl methacrylate in the porous Na3Zr2Si2PO12–polymer vinylidene fluoride–hexafluoropropylene composite membrane for the first time. The GHSE membrane exhibits a high ionic conductivity (2.78 × 10–3 S cm–1), wide electrochemical window (∼4.9 V), high Na+ ion transference number (∼0.63), good thermal stability and flexibility, as well as smaller interfacial resistance. Moreover, a composite Na/C anode was prepared, which shows good dendrite suppression ability. The full cell Na0.67Ni0.23Mg0.1Mn0.67O2 |GHSE|Na/C exhibits excellent rate capability with an initial discharge capacity of 96 mAh g–1 even at a higher current density of 192 mA g–1 and excellent cyclability for 600 cycles. These results suggest that the GHSE and Na/C anode are promising electrolyte and anode materials for Na-ion batteries, respectively.

研究领域: 材料科学 · 电化学 · 能源存储
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JOURNAL OF POWER SOURCES · 2023 · IF 9.2

Reinforcing interfacial compatibility of LLZTO/PVDF-HFP composite electrolytes by chemical interaction for solid-state lithium metal batteries

Tong Duan,Hongwei Cheng,Qiangchao Sun,Yanbo Liu,Wei Nie,Yuehua Chu,Qian Xu,Xionggang Lu

Composite electrolytes (CEs) have a significant potential for achieving excellent safety and energy density in solid-state lithium metal batteries owing to applicable ionic conductivity, easy fabrication, and good electrochemical properties. However, achieving good interfacial compatibility between inorganic fillers and polymer matrix remains challenging. Herein, we design a Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 filler modified with isopropyl tri(dioctyl pyrophosphate) titanate for poly (vinylidene fluoride-co-hexafluoropropylene) electrolyte (denoted as Ti@LLZTO/PVDF-HFP). We reveal the enhanced mechanism of a modified interface on the electrochemical performance by combining experimental results and theoretical calculations. The reinforced interface can facilitate the uniform dispersion of filler in the polymer matrix as well as dissociate more lithium salt, which enables enhanced ionic conductivity (6.86 × 10 −5  S cm −1  at 30 °C). Besides, the Ti@LLZTO can immobilize the anions in lithium salt via hydrogen bonding interactions and the Ti–O chemical bonding. Consequently, the Li||Ti@LLZTO/PVDF-HFP||Li cell shows great cyclability over 1550 h at 0.1 mA cm −2 , 0.1 mAh cm −2 . Moreover, the Li||Ti@LLZTO/PVDF-HFP||LFP cell achieves superior cycling stability at 0.5 C with a high Coulombic efficiency of 98.8 %. This work provides an insightful understanding of designing good interfacial compatibility for advanced composite electrolytes.

研究领域: 材料科学 · 电化学 · 电池技术
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JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

Mussel stimulated modification of flexible Janus PAN/PVDF-HFP nanofiber hybrid membrane for advanced lithium-ion batteries separator

Mao Guo,Jing Xiong,Xuanyang Jin,Shengjun Lu,Yufei Zhang,Jian Xu,Haosen Fan

Bicomponent polyacrylonitrile/Poly(vinylidene fluoride-co-hexafluoropropylene) (PAN/PVDF-HFP) Janus nanofibers based hybrid membrane was successfully prepared by parallel electrospinning technology. Subsequently, modified PAN/PVDF-HFP hybrid membrane (M-PAN/PVDF-HFP) was further fabricated via mimicking the adhesive of mussel by coating dopamine alternative through polymerization of catechol and tetraethylenepentamine (TEPA) in weakly alkali solution. M-PAN/PVDF-HFP maintains the abundant pore structure of the electrospun hybrid membrane and further provides excellent electrolyte infiltration with high porosity (82.09%) and outstanding electrolyte retention (553.23%). Simultaneously, the mechanical strength of the separator was significantly improved (14.36 MPa). Electrochemical studies displayed that the M-PAN/PVDF-HFP composite membrane delivered superior ion conductivity (2.81 mS/cm) and wide electrochemical stability window (∼5.25 V). The cell assembled by M-PAN/PVDF-HFP separator presented outstanding rate capability with high specific capacity of 147 mAh/g at 1 C and excellent cycle stability with discharge capacity of 120 mAh/g at 1 C after 600 cycles. Furthermore, M-PAN/PVDF-HFP separator exhibited ultra-flexibility with remarkable electrochemical performance after repeated bending for 500 to 1000 time. This work provides new insights into polyamine modified hybrid membranes for the potential practical applications in lithium-ion batteries separator.

研究领域: 材料科学 · 电化学 · 纳米技术 · 能源存储
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Water flow-driven high piezo-photocatalytic efficacy in superthin and densely porous GO-TiO2/PVDF-HFP composite film for ROS generation

Jialin Zhuang,Yechen Wang,Liping Lin,Jiaying Xiao,Jiahui Cai,Yingmo Hu,Qi An

Reactive oxygen species (ROS) as highly oxidative substances play significant roles in environmental matter cycling. Despite their high potential in environmental regulation, effective artificial ROS generation techniques are still in the primary stage. In this study, we propose an effective piezo-photocatalytic film for ROS generation in water flow and under light irradiation. The high ROS generation capability stem from the special suprathin and highly porous structure obtained using our developed spray-drying technique to prepare the composite film. During the spray process, optimized component of graphene oxide, TiO 2 nanoparticles, and Poly(vinylidene fluoride- co -hexafluoropropylene) (PVDF-HFP) polymer chains self-organized to effective piezoelectrically and photocatalytically active assemblies, and highly porous structures are formed during the drying process. Especial mechanical sensibility to deform is realized in response to external force as weak as 0.2 N. The enhanced piezoelectricity of the PVDF-HFP microdomain, the narrowed band gap, and the electron transfer across the interfacial heterojunction between graphene and TiO 2 all contribute to the especially high piezo-photocatalytic capabilities. Water flow can effectively trigger the piezoelectric field generation in the film, which remarkably boost extractable charge carriers generated upon light irradiation. 88.05 % degradation efficiency of Rhodamine B during 15 min and 95.2 % degradation efficiency of ciprofloxacin in 120 min are realized, along with bacteriostat capabilities. The application potential of the composite are demonstrated in dest-top laundry process and the treated stained water can be used to cultivate plant. We expect the strategy to develop into a novel form of cleaning technique.

CAS / MDL: 13463-67-7
研究领域: 环境科学 · 材料科学 · 纳米技术 · 催化 · 水处理 · 高分子科学 · 光化学
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Materials Today Chemistry · 2023 · IF 7.3

Flexible core-shell PAN/CNTs@PVDF-HFP/Uio-66-NH2 hybrid nanofibers membrane for advanced lithium-ion batteries separator

Mao Guo,Siyang Dong,Jing Xiong,Xuanyang Jin,Pengfei Wan,Shengjun Lu,Yufei Zhang,Jian Xu,Haosen Fan

Flexible core-shell polyacrylonitrile (PAN)/carbon nanotubes (CNTs)@Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/Uio-66-NH 2 (PC@PU) hybrid nanofiber membrane was prepared by coaxial electrospinning technology. PAN polymer and CNTs particles were used as core to improve the membrane structure stability for further ensuring the thermal stability of the separator. PVDF-HFP and Uio-66-NH 2 nanoparticles were applied to reinforce the affinity of separator to electrolyte. The PC@PU composite membrane delivered high thermal stability and fantastic electrolyte affinity (545.76%). Furthermore, compared with Celgard 2325 commercial membrane, the PC@PU composite membrane exhibited higher porosity (80.22%) and higher Li + conductivity (3.43 mS/cm), leading to superior rate performance and long-term cycle stability. The cell with the PC@PU hybrid membrane displayed high specific capacity of 143 mAh/g at 1C and only 0.0259% capacity attenuation of each cycle after 1000 cycles. In addition, the PC@PU composite membrane demonstrated remarkable flexibility, and the cells with bent separators exhibited outstanding electrochemical performance. Hence, the PC@PU hybrid nanofiber membrane can pave a way for the further application in the field of secondary batteries separator.

研究领域: 材料科学 · 电化学 · 纳米技术 · 能源存储
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MOLECULES · 2023 ·Vol. 28 ·期 13 ·4998 · IF 4.6

Electrospun Sandwich-like Structure of PVDF-HFP/Cellulose/PVDF-HFP Membrane for Lithium-Ion Batteries

Xingfu Zi,Hongming Wu,Jiling Song,Weidi He,Lu Xia,Jianbing Guo,Sihai Luo,Wei Yan

Cellulose membranes have eco-friendly, renewable, and cost-effective features, but they lack satisfactory cycle stability as a sustainable separator for batteries. In this study, a two-step method was employed to prepare a sandwich-like composite membrane of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/cellulose/ PVDF-HFP (PCP). The method involved first dissolving and regenerating a cellulose membrane and then electrospinning PVDF-HFP on its surface. The resulting PCP composite membrane exhibits excellent properties such as high porosity (60.71%), good tensile strength (4.8 MPa), and thermal stability up to 160 °C. It also has exceptional electrolyte uptake properties (710.81 wt.%), low interfacial resistance (241.39 Ω), and high ionic conductivity (0.73 mS/cm) compared to commercial polypropylene (PP) separators (1121.4 Ω and 0.26 mS/cm). Additionally, the rate capability (163.2 mAh/g) and cycling performance (98.11% after 100 cycles at 0.5 C) of the PCP composite membrane are superior to those of PP separators. These results demonstrate that the PCP composite membrane has potential as a promising separator for high-powered, secure lithium-ion batteries.Keywords:lithium-ion batteries;separator;cellulose;electrospinning;interfacial compatibility;cycle stability

研究领域: 材料科学 · 能源技术
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