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PVDF-HFP
IONICS · 2020 ·Vol. 26 ·期 9 ·4489-4497 · IF 2.394

Poly(vinylidenefluoride-hexafluoropropylene)/cellulose/carboxylic TiO2 composite separator with high temperature resistance for lithium-ion batteries

Li Ling,Li Haijuan,Wang Yan,Zheng Shuaizhi,Zou Youlan,Ma Zengsheng

To improve the safety performance of lithium-ion batteries, the research of composite separator with high temperature resistance is one of the strategies. Herein, a poly(vinylidene fluoride-hexafluoropropylene)/cellulose/carboxylic titanium dioxide (PVDF-HFP/cellulose/C-TiO 2 ) composite separator is prepared by the phase inverse method. The composite separator has higher porosity (63.65%) and electrolyte uptake (210.3%) than PP separator, exhibiting good heat resistance that can keep its shape and size under 160 °C for 0.5 h. Additionally, it has a superior ionic conductivity of 1.24–1.49 mS cm −1 and a lower charge transfer impedance at a room temperature, which brings about better cycle and rate performance. Promisingly, the cell assembled with the PVDF-HFP/cellulose/C-TiO 2 composite separator has a high electrochemical working window and a high current charge of ability, and can undergo 10 charge-discharge cycles normally under 120 °C. The PVDF-HFP/cellulose/C-TiO 2 composite separator has promising potentials for high current and voltage charging, which can improve the safety performance of the lithium-ion battery.

研究领域: 材料科学 · 电化学 · 电池技术
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2026 · IF 4.6

Preparation of high ionic conducting Sc and B co-doped NASICON-type Li1.3Al0.3Ti1.7(PO4)3 and its application in PVDF-HFP-based solid hybrid electrolytes for lithium-ion batteries

Yudi Guo,Jiaming Li,Erqing Zhao

Sc and B doping enlarges the electrolyte lattice and reduces grain boundaries. • The LASBTP003 electrolyte shows an optimal ionic conductivity of 0.882 mS/cm. • PVDF-HFP-LITFSI-SN-10LASBTP003 SCE displays enhanced electrochemical performance. • Li/SCE/ LiFePO 4 full cell shows an excellent long-term cycling stability. NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP), with excellent air stability, a wide electrochemical window and low cost, is an attractive electrolyte for lithium-ion batteries (LIBs). However, its low electrical conductivity and poor interface contact impede its practical applications. Herein, LATP was doped with Sc and B elements, and the properties of the resultant LATP-based solid electrolytes were thoroughly studied. The structural characterization suggests that doping of Sc and B densifies the electrolyte structure, enlarges the lattice, and reduces grain boundaries. The optimized Li 1.3 Al 0.24 Sc 0.03 B 0.03 Ti 1.7 (PO 4 ) 3 (LASBTP003) achieves a high ionic conductivity of 8.82 × 10 −4  S/cm, equivalent to 4-fold that of pure LATP. The composition of LASBTP003 electrolyte with PVDF-HFP and SN results in PVDF-HFP-LITFSI-SN-LASBTP003 solid composite electrolyte with enhanced ionic conductivity of 8.89 × 10 −5  S/cm, attributed to the reduced PVDF-HFP crystallization and established lithium-ion migration pathways at LASBTP003/PVDF-HFP interface. PVDF-HFP-LITFSI-SN-10LASBTP003 also displays a wide electrochemical window of 4.85 V and a high Li-ion transference number of 0.41. The Li/ PVDF-HFP-LITFSI-SN-10LASBTP003/Li symmetric battery delivers a long cycling of 1800 h under a current density of 0.1 mA/cm 2 . Moreover, LiFePO 4 /PVDF-HFP-LITFSI-SN-10LASBTP003/Li full cell delivers a long-term cycling stability, with a capacity retention of 86.92% after 1000 cycles at 0.5C. Overall, the proposed PVDF-HFP-LITFSI-SN-10LASBTP003 has great potential for LIB applications. Download: Download high-res image (195KB) Download: Download full-size image

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Polymers · 2024 ·Vol. 16 ·期 21 ·2972 · IF 4.7

Bilayer Heterostructure Electrolytes Were Prepared by a UV-Curing Process for High Temperature Lithium-Ion Batteries

Qiankun Hun,Lingxiao Lan,Xuanan Lu,Qicheng Hu,Xinghua Liang,Yifeng Guo,Yujiang Wang

Solid-state electrolytes are widely anticipated to revitalize high-energy-density and high-safety lithium-ion batteries. However, low ionic conductivity and high interfacial resistance at room temperature pose challenges for their practical application. In this work, the dual-matrix concept is applied to the design of a bilayer heterogeneous structure. The electrolyte in contact with the cathode blends PVDF-HFP and oxidation-resistant PAN. In contrast, the electrolyte in contact with the anode blends PVDF-HFP and reduction-resistant PEO. A UV-curing process was used to fabricate the bilayer heterostructure electrolyte. The heterostructure electrolyte exhibits an ionic conductivity of 4.27 × 10−4S/cm and a Li+transference number of 0.68 at room temperature. Additionally, when assembled into LiFePO4/CPEs/Li batteries, it shows a high initial discharge capacity at room temperature (168 mAh g−1at 0.1 C and 60 mAh g−1at 2 C), with a capacity retention of 93.3% after 100 cycles at a current density of 0.2 C. Notably, at 60 °C, the battery maintains a discharge capacity of 90 mAh g−1at 2 C, with a capacity retention of 97.4% after 100 cycles at 0.2 C. Therefore, solid-state batteries using this bilayer heterogeneous structure electrolyte demonstrate promising performance, including effective capacity output and cycling stability.

CAS / MDL: 7791-03-9
研究领域: 材料科学 · 电化学 · 能源存储
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Sandwiched composite electrolyte with excellent interfacial contact for high-performance solid-state sodium-ion batteries

Wenting Wang,Wenyong Yuan,Zhongjun Zhao,Pengfei Zhou,Pengju Zhang,Minghui Ding,Jiahai Bai,Junying Weng

Solid-state sodium-ion batteries have attracted significant attention due to their rich resources, high safety, and high energy density. However, the lower ionic conductivity and inferior interfacial contact between solid-state electrolytes (SSEs) and electrodes limit their practical applications. Herein, polyvinylideneuoride- co -hexauoropropylene (PVDF-HFP) membrane is selected and a novel sandwiched composite PVDF-HFP/Na 2.5 Zr 1.95 Ce 0.05 Si 2.2 P 0.8 O 11.3 F 0.7 /PVDF-HFP (G-NZC0.05SPF0.7-G) SSEs is well designed. The ionic conductivity of Na 3 Zr 2 Si 2 PO 12 is enhanced by Ce 4+ /F − co-doping. The effects of Ce 4+ and F − doping on the crystal structure, density, and ionic conductivity for Na 3 Zr 2 Si 2 PO 12 are well investigated. The optimal NZC0.05SPF0.7 delivers a high ionic conductivity of 1.39 × 10 −3 S cm −1 at 25 ℃. Moreover, the PVDF-HFP membrane can significantly enhance the interface compatibility between NZC0.05SPF0.7 and electrodes. The as-prepared G-NZC0.05SPF0.7-G exhibits a large ionic conductivity of 1.07 × 10 −3 S cm −1 at 25 ℃, wide electrochemical stability window up to 4.5 V, high critical current density of 1.2 A cm −2 , and stable Na plating/stripping over 600 h at 0.3 A cm −2 . The solid-state Na 0.67 Mn 0.47 Ni 0.33 Ti 0.2 O 2 /G-NZC0.05SPF0.7-G/Na battery delivers a remarkable cycling stability and rate capability at 25 ℃, indicating that the as-prepared G-NZC0.05SPF0.7-G has a promising application for solid-state SIBs. This study demonstrates an effective strategy to develop advanced solid-state electrolytes for solid-state SIBs.

研究领域: 材料科学 · 电化学 · 能源存储 · 电池技术
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Advanced Science · 2021 ·Vol. 8 ·期 15 ·2003241 · IF 16.806

A Stretchable and Safe Polymer Electrolyte with a Protecting-Layer Strategy for Solid-State Lithium Metal Batteries

Shengzhao Zhang,Taibo Liang,Donghuang Wang,Yanjun Xu,Yongliang Cui,Jingru Li,Xiuli Wang,Xinhui Xia,Changdong Gu,Jiangping Tu

An elastic and safe electrolyte is demanded for flexible batteries. Herein, a stretchable solid electrolyte comprised of crosslinked elastic polymer matrix, poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP), and flameproof triethyl phosphate (TEP) is fabricated, which exhibits ultrahigh elongation of 450%, nonflammability and ionic conductivity above 1 mS cm −1 . In addition, in order to improve the interface compatibility between the electrolyte and Li anode and stabilize the solid-electrolyte interphase (SEI), a protecting layer containing poly(ethylene oxide) (PEO) is designed to effectively prevent the anode from reacting with TEP and optimize the chemical composition in SEI, leading to a tougher and more stable SEI on the anode. The LiFePO 4 /Li cells employing this double-layer electrolyte exhibit an 85.0% capacity retention after 300 cycles at 1 C. Moreover, a flexible battery based on this solid electrolyte is fabricated, which can work in stretched, folded, and twisted conditions. This design of a stretchable double-layer solid electrolyte provides a new concept for safe and flexible solid-state batteries.

研究领域: 材料科学 · 电化学 · 储能技术 · 高分子科学 · 锂电池
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ACS Applied Energy Materials · 2022 · IF 6.959

Modified Poly(vinylidene fluoride-co-hexafluoropropylene) Polymer Electrolyte for Enhanced Stability and Polymer Degradation Inhibition toward the Li Metal Anode

Maoxia Yang,Baiqing Zhao,Jianying Li,Shaomin Li,Gen Zhang,Shiqi Liu,Yanhua Cui,Hao Liu

Solid polymer electrolytes (SPEs) are flexible, low cost, and easily scalable for battery manufacturing. These merits make SPEs one of the most practical solid-state electrolytes. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), which has good mechanical properties and good thermal stability, is considered a promising polymer for SPEs. However, PVDF-HFP is unstable due to the dehydrofluorination side reaction when PVDF-HFP-based electrolytes cycle with Li metal. This reaction leads to the deterioration of the electrolyte–electrode interface. In this work, the PVDF-HFP polymer electrolyte is modified with LiOH during the synthesis of SPEs (pre-dehydrofluorination). The modified electrolyte delivers significantly enhanced stability toward the Li metal anode. The electrochemical stable window is extended from 4.75 to 5.00 V, and the stable cycle time of the galvanostatic test of Li symmetric cells at 0.1 mA cm–2 increases from about 100 h to over 500 h. Ex situ scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analyses indicate that the polymer degradation is suppressed after modification, and a stable interface containing more LiF and inorganic sulfur compounds forms between the electrolyte and Li metal; the interface could effectively suppress Li dendrite growth. Combining electrochemical results with ex situ SEM and XPS analysis, it is observed that the pre-dehydrofluorination is the reason for inhibiting polymer degradation and suppressing Li dendrite growth toward the Li metal anode. These findings will promote the development of safe all-solid-state Li metal batteries.

研究领域: 材料科学 · 电化学 · 电池技术 · 固态电解质
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Asymmetric supercapacitor comprising a core-shell TiNb2O7@MoS2/C anode and a high voltage ionogel electrolyte

Meng Yao,Ao Liu,Chunxian Xing,Bosen Li,Shanshan Pan,Jiahe Zhang,Peipei Su,Haitao Zhang

Supercapacitors have emerged as appealing alternatives to rechargeable energy storage devices in renewable energy generation and storage systems due to their ultra-high power characteristics. However, their broad applications are hindered by their low energy density characteristic. Therefore, the designs of electrodes with high rate and high specific capacitance and electrolytes with wide-potential window are extremely crucial. A novel core–shell heterostructure, TiNb 2 O 7 as the core and C-encapsulated MoS 2 as the shell, was demonstrated. As a result of synergistic effects induced by the core–shell heterostructure, this nanoarchitectural anode exhibited a high rate capability and an excellent cyclic stability, 99% capacity was retented after 500 cycles. Moreover, a nanocomposite ionogel electrolyte composed of ionic liquid (IL), poly(vinylidene fluoride-co-hexafluoropropene)-hexafluoropropylene (PVDF-HFP) and SiO 2 was prepared. In our study, optimized solid lithium-ion capacitors (SLICs) exhibited an impressive energy density of 147.2 Wh kg −1 at 60 °C and an outstanding ultra-long term stability, 93.7% capacity was retented after 10,000 cycles at 1 A g −1 . These outstanding performances could be ascribed to the widened potential window and remarkable ionic conductivity of the ionogel electrolyte. The effective combination of nanoarchitectural anodes and a nanocomposite ionogel provides a novel and profound direction for the fabrication of highly safe and reliable solid lithium-ion capacitors with an enhanced high energy density.

研究领域: 能源存储 · 材料科学 · 电化学 · 纳米技术
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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

A self-supporting solid electrolyte membrane with fibrous network structure for solid state lithium metal batteries

Shijie Lu,Xiaorong Chu,Chunli Li,Zhikun Zhao,Jianxiong Xiao,Borong Wu,Daobin Mu

High ionic conductivity and good interface compatibility have always been two major bottlenecks for solid-state electrolytes. Herein, a composite electrolyte membrane comprising poly (propylene carbonate), PVDF-HFP and Li 6 · 3 La 3 Zr 1 · 4 Ta 0 · 6 O 12 is successfully prepared via electrospinning. With the assistance of succinonitrile, the synthesized solid-state electrolyte exhibits high ionic conductivity (1.32 × 10 −3  S cm −1 at room temperature), oxidation potential up to 4.5 V vs Li/Li + and high Li + transference number (0.81). This desirable performance is attributed to the combination of PPC with good Li + conduction ability and PVDF-HFP with excellent mechanical properties, forming a continuous transport framework within the electrolyte. The introduced active fillers and small molecular additive not only benefit to fast Li + mobility, but also reinforce the stability towards Li metal. Li symmetric cell using the solid-state electrolyte can last for 800 h at a current density of 1.0 mA cm −2 with a low overpotential. The NCM811 cell using the electrolyte membrane shows high initial discharge specific capacity (184.3 mAh g −1 at 1 C) and good capacity retention (80.1% after 300 cycles at 30 °C).

研究领域: 材料科学 · 电化学 · 电池技术 · 纳米技术
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Nano Energy · 2024 · IF 16.8

Soft-metal bonding-enabled recyclable and anti-interference flexible multilayer piezoelectric sensor for tractor tire strain monitoring

Chun-Xiao Xing,Qiu-Bo Zhang,Zhong-Hao Wang,Jun-Xian Guo,Mao-Lin Li,De-Hai Yu,Ya-Dong Wang,Quan Zhou,Wei Tang,Zhen Li,Zhi-Zhu He

Real-time efficient sensing of machine-soil interactions, especially precise tire-ground contact information, plays a critical role in cultivation, seeding, and harvesting for smart agriculture. However, the complicated agricultural environment poses a considerable challenge to traditional rigid sensors, which cannot suffer from both large deformation and electromagnetic interference . Here, we report a novel soft-metal BiInSn bonding-enabled recyclable and anti-interference flexible multilayer piezoelectric sensor for monitoring tractor tire strain. The printed BiInSn-ink electrode fully wraps the surface fibers of porous BaTiO 3 /PVDF-HFP electrospun films only through a low pressure at low temperature due to its unique thermal-softening effects, which of the adhesion strength is superior to the intrinsic tension limit of the film. The compact multilayer piezoelectric sensor is thus easily prepared, remarkably increasing the output voltage compared to a single-layer case (up to 300% for three layers). Benefiting from the low melting point of the BiInSn alloy, the sensors are easily recyclable compared to conventional metal electrodes prepared with copper, silver, and gold. In addition, its high electrical conductivity also enables the shielding layer to achieve ultrahigh shielding effectiveness of 2100 dB mm −1 . This sensor can be demonstrated for tire strain sensing under complex operating conditions such as plowing, harrowing, and fertilizer application . These findings serve as a foundation for accelerating the development of smart agriculture.

CAS / MDL: 12047-27-7 111-27-3
研究领域: 材料科学 · 电子学 · 农业工程 · 传感器 · 智能农业
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Polymer solid electrolytes with ultra-stable cycles and high-capacity retention for all-solid-state Li-metal battery

Jingshun Wang,Yongquan Zhang,Zengxu Chen,Shuo Fan,Qihui Zhang,Yue Zhang,Tiandong Zhang,Changhai Zhang,Qingguo Chi

Polymer electrolytes have become widely popular on account of their low expenses, reduced weight, simple processing, and excellent safety features. However, polymer electrolytes have yet to find use in commercial batteries because of their limited mechanical durability and poor ionic conductivity . In this paper, an ultra-stable cycles and interfaces blending polymer electrolyte (BPE) suitable for all solid-state Li metal batteries was prepared by blending three polymers: polymethyl methacrylate (PMMA), polyvinylidene fluoride hexafluoropropylene (PVDF-HFP), and polyethylene oxide (PEO). Microstructure characterization showed numerous amorphous areas with strong interfacial strength of the BPE. The BPE3 exhibited a maximum of 15.65 MPa in tensile strength. BPE2 have excellent electrochemical performance, such as wide electrochemical windows (up to 4.7 V vs Li/Li + ), high lithium ion transference numbers (up to 0.75), high ion conductivity (up to 1.87 × 10 -4 S cm −1 at 60 °C), and excellent interface stability. By assembling all state-solid LiFePO 4 /BPE2/Li batteries for electrochemical testing, BPE2 exhibit high electrochemical characteristics. BPE2 discharge specific capacity is as high as 154.7 mAh g −1 at 1C. The BPE2 underwent 200 cycles at 0.5C and 400 cycles at 1C, with capacity retention rates of 95.7 % and 96.6 %, respectively. BPE is a promising electrolyte candidate for flexible lithium metal batteries.

研究领域: 材料科学 · 电化学 · 电池技术 · 聚合物科学
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