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PVDF
Advanced Energy Materials · 2023 ·Vol. 13 ·期 36 ·2302139 · IF 27.8

Sulfur–Carbon Electrode with PEO-LiFSI-PVDF Composite Coating for High-Rate and Long-Life Lithium–Sulfur Batteries

Ling Li,Jong Seok Nam,Min Soo Kim,Yifan Wang,Shaohua Jiang,Haoqing Hou,Il-Doo Kim

To address the problem of the serious capacity fading in lithium–sulfur batteries, a multi-functional PEO(polyethylene oxide)/LiFSI (lithium bis(fluorosulfonyl)imide)/PVDF (polyvinylidene fluoride) (PLP) gel polymer electrolyte is exploited by coating PLP on a carbon nanotubes (CNTs) based sulfur cathode (PLP-S/CNTs) with a controlled thermal annealing process. The annealing process leads to the conformal infusion of PLP through the matrix of S/CNTs with retaining the amorphous phase of the PLP, which enhance the rate performance compared to the bare S/CNTs. The PLP coating drives the transformation of more elemental sulfur to Li 2 S 2 /Li 2 S without forming intermediary product by restraining soluble-polysulfides formation. Furthermore, the PLP coating successfully inhibits the dissolution of Li 2 S x ( x > 4) in PEO and prevents the loss of active material in the cathode, which is confirmed by density functional theory calculations. Comprehensively, the PLP coating applied to the surface of the S/CNTs cathode exhibit significantly suppressed shuttle effect and greatly improve long-term cycle stability of the lithium–sulfur battery. The synthesized PLP-coated S/CNTs composite cathode demonstrates a high specific capacity of 573.6 mAh g −1 at a current density of 0.5 C after 1 000 cycles, even achieving 318.1 mAh g −1 at an extremely high C-rate (6 C). which is unprecedented performance among the reported studies on coating technology.

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Polymers · 2023 ·Vol. 15 ·期 12 ·2688 · IF 5

Effect of High-Entropy Spinel Ferrite (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4 Doping Concentration on the Ferroelectric Properties of PVDF-Based Polymers

Jiale Qiao,Zhaoting Liu,Haiwei Mu,Chao Liu

Polyvinylidene fluoride (PVDF)-based dielectric energy storage materials have the advantages of environmental friendliness, high power density, high operating voltage, flexibility, and being light weight, and have enormous research value in the energy, aerospace, environmental protection, and medical fields. To investigate the magnetic field and the effect of high-entropy spinel ferrite (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4nanofibers (NFs) on the structural, dielectric, and energy storage properties of PVDF-based polymers, (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4NFs were prepared via the use of electrostatic spinning methods, and (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4/PVDF composite films were prepared via the use of the coating method. The effects of a 0.8 T parallel magnetic field, induced for 3 min, and the content of high-entropy spinel ferrite on the relevant electrical properties of the composite films are discussed. The experimental results show that, structurally, the magnetic field treatment causes the originally agglomerated nanofibers in the PVDF polymer matrix to form a linear fiber chain with different fiber chains parallel to each other along the magnetic field direction. Electrically, the introduction of the magnetic field enhanced the interfacial polarization, and the (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4/PVDF composite film with a doping concentration of 10 vol% had a maximum dielectric constant of 13.9, as well as a low energy loss of 0.068. The high-entropy spinel ferrite (Mn0.2Zr0.2Cu0.2Ca0.2Ni0.2)Fe2O4NFs and the magnetic field influenced the phase composition of the PVDF-based polymer. The α-phase and γ-phase of the cohybrid-phase B1 vol% composite films had a maximum discharge energy density of 4.85 J/cm3and a charge/discharge efficiency of 43%.Keywords:high-entropy spinel ferrite;polymer;dielectric;ferroelectric;energy density

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2023 ·Vol. 34 ·期 17 ·1-20 · IF 2.8

Effect of HNT@PANI hybrid nanoparticles on performance enhancement of electrospun PVDF nanofiber mat for flexible piezoelectric nanogenerators

Qi Zhijia,Zhang Shengsheng,Huang Jiaju,Li Juan,Jiang Junjiong,Fan Ping,Yang Jintao

Flexible PVDF-based piezoelectric nanogenerators (PENGs) are promising mechanical energy harvesters for powering wearable devices and portable electronics. In this work, a new hybrid nanocomposite was prepared by coating polyaniline on the surface of halloysite nanotube (HNT@PANI) and PENGs were fabricated by using electrospun nanocomposite fiber mats comprising HNT@PANI and poly(vinylidene fluoride) (PVDF). The rough surface of PANI outer layer and its electronegative properties favors a large interface and a strong interfacial interaction with PVDF matrix, which efficiently improves the β-phase crystal content and the crystallinity of PVDF simultaneously, resulting in an enhanced output performance in the fibrous nanocomposite PENGs. When the nanocomposite fiber mats are composed of 1 wt% HNT@PANI nanoparticles, the open-circuit voltage of the PENG is up to 30 V, which is six times higher than that of pure PVDF, and it can also light up 17 red LEDs. Furthermore, the open-circuit voltage was found unchanged after being subjected to continuous tapping for 5 weeks in the durability test. In addition, the PENG can charge a capacitor to 4.4 V within 60 s. This flexible self-powered PENG with good durability and high outputs has the potential to be used as a self-charging power source and applied in the field of wearable flexible electronic devices.

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Journal of Central South University · 2022 ·Vol. 29 ·期 9 ·2980-2990 · IF 2.392

Fast-ionic conductor Li2.64(Sc0.9Ti0.1)2(PO4)3 doped PVDF-HFP hybrid gel-electrolyte for lithium ion batteries

Wang Zhen-yu,Li Cong,Huang Ying-de,He Zhen-jiang,Yan Cheng,Mao Jing,Dai Ke-hua,Zheng Jun-chao

With increasing demand on energy density of lithium-ion battery, wide electrochemical window and safety performance are the crucial request for next generation electrolyte. Gel-electrolyte as a pioneer for electrolyte solidization development aims to solve the safety and electrochemical window problems. However, low ionic conductivity and poor physical performance prohibit its further application. Herein, a fast-ionic conductor (Li 2.64 (Sc 0.9 Ti 0.1 ) 2 (PO 4 ) 3 ) (LSTP) was added into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) base gel-electrolyte to enhance mechanical properties and ionic conductivity. Evidences reveal that LSTP was able to weaken interforce between polymer chains, which increased the ionic conductibility and decreased interface resistance during the cycling significantly. The obtained LiFePO 4 /hybrid gel-electrolyte/Li-metal coin cell exhibited excellent rate capacity (145 mA·h/g at 1 C , 95 mA·h/g at 3 C , 28 °C) which presented a potential that can be comparable with commercialized liquid electrolyte system.

CAS / MDL: 7790-69-4 5593-70-4
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Journal of Materiomics · 2022 · IF 8.589

Fabrication of intra porous PVDF fibers and their applications for heavy metal removal, oil absorption and piezoelectric sensors

Gajula Prasad,Xiongwei Lin,Junwei Liang,Yingbang Yao,Tao Tao,Bo Liang,Sheng-Guo Lu

Intra porous fibrous membranes have enhanced metal ionic adsorption and oil separation abilities than those of intra nonporous fibrous membrane. In this paper, we prepared highly intra porous fibrous poly (vinylidene fluoride) (PVDF) membranes using an innovated water-mediated electrospinning approach. FTIR-ATR and XRD techniques confirmed the conversion of non-polar α - phase to polar β-phase in electrospun membranes. The porous fibrous membrane M–16 had adsorbed oil almost 120% and metal adsorption around 15%, 12%, 5%, 13% respectively for Pb 2+ , Cd 2+ , Cu 2+ and Zn 2+ , which are larger than the counterpart of nonporous M–18. The nonporous fibrous membranes have better peak to peak output voltage ( V p - V p ) 2 to 3 times than the porous fibrous membranes (M–16). The results show apparent potential applications in wastewater/oil spill treatment as well as piezoelectric sensors.

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Journal of Environmental Chemical Engineering · 2022 · IF 7.968

Fabrication of a Ag/CNQDs/g-C3N4-PVDF photocatalytic composite membrane with excellent photocatalytic and self-cleaning properties

Chen Li,Tianyi Sun,Guohui Yi,Dashuai Zhang,Yan Zhang,Xiaoxue Lin,Jinrui Liu,Zaifeng Shi,Qiang Lin

A highly efficient visible light-driven photocatalytic membrane composed of Ag/CNQDs/g-C 3 N 4 and PVDF membranes was successfully prepared by vacuum filter crosslinking. This new type of photocatalytic membrane possessed both excellent photocatalytic degradation performance and photocatalytic self-cleaning properties. The Ag/CNQDs/g-C 3 N 4 photocatalyst coating amount of 10 mg had the highest photocatalytic degradation of norfloxacin (NOR), and the quasi-first-order kinetic constant ( k ) value was 0.0138 min −1 . Moreover, the mechanism of the photocatalytic reaction was also discussed. In addition, bovine serum albumin (BSA) as the simulated pollutant was applied to evaluate the self-cleaning property of the Ag/CNQDs/g-C 3 N 4 -PVDF composite membrane. After contamination with BSA, the water flux of the composite membrane decreased from 3880 L (m 2 h) −1 to 800 L (m 2 h) −1 . Then, the maximum pure water flux of the Ag/CNQDs/g-C 3 N 4 -PVDF photocatalytic composite membrane recovered 87% (3360 L (m 2 h) −1 ) within 90 min of visible light irradiation, indicating that the Ag/CNQDs/g-C 3 N 4 -PVDF photocatalytic composite membrane had excellent self-cleaning properties.

CAS / MDL: 68-04-2
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JOURNAL OF MATERIALS SCIENCE · 2022 ·Vol. 57 ·期 24 ·11274-11288 · IF 4.682

Hierarchical microstructure and performance of PVDF/PMMA/SiO2 lithium battery separator fabricated by thermally-induced phase separation (TIPS)

Yang Bin,Yang Yingdong,Xu Xiang,Ke Yuchao,Pan Yang,Su Lifen,Wang Yingying,Wang Shuqing,Qian Jiasheng,Xia Ru,Fu Enfa

Lithium-ion batteries (LIBs) have attracted more and more attention in recent years because of their renewable, clean energy and high-cost performance. Polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA) were expected to be used in the preparation of LIB separator due to their excellent comprehensive properties. In this work, a series of PVDF/PMMA LIB separators were prepared by thermally-induced phase separation (TIPS), which is a simple method of fabricating microporous films. In order to improve the comprehensive performance, SiO 2 was adopted to modify the composite films with various filling proportions by solution method. Results of DSC and XRD tests showed that SiO 2 nanoparticles could significantly reduce the crystallinity of the films, but hardly changed the morphology of PVDF. With an increase in SiO 2 content, both porosity and electrolyte uptake rate for the composite films increased, but an excessive loading of SiO 2 tended to agglomerate inside the films. The porosity and electrolyte uptake rate for composite film containing 3% SiO 2 were found to be the highest. As SiO 2 loading increased, both first charge–discharge capacity and efficiency of the composite films were enhanced with the discharge cycle stability enhanced simultaneously. When 3% SiO 2 was incorporated, the PVDF/PMMA/SiO 2 composite film displayed the best comprehensive performance of the battery among all film samples examined. This study presents a facile way of manufacturing LIB separators with relatively ideal overall battery performance.

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CERAMICS INTERNATIONAL · 2022 · IF 5.532

Core@double-shell structured fillers for increasing dielectric constant and suppressing dielectric loss of PVDF-based composite films

Dajun Hou,Jing Zhou,Wen Chen,Pengchao Zhang,Jie Shen,Zelang Jian

High dielectric constant polymer dielectrics have attracted a great deal of attention in flexible electronics. However, it appears to be a paradox for polymer dielectrics that the enhancement of their dielectric constant often comes along with the increase of dielectric loss. Hence, we reported core@double shell structured filler/poly(vinylidene fluoride) (PVDF) composites to overcome this paradox. The hybrid filler with BaTiO 3 (BT) as the core, conductive carbon as the inner shell, and insulating polydopamine (PDA) as the outer shell was synthesized. As a result, the BT@C@PDA/PVDF composites at the filler content of 11 vol% exhibit an outstanding dielectric performance with a dielectric constant of 45 and a dielectric loss of 0.053 at 10 3  Hz. This phenomenon can be attributed to the increased interfacial polarization induced by the inner carbon shell and the conductive paths blockade caused by the outside PDA shell inside the BT@C@PDA/PVDF composites. This work reveals that rational design of core@double shell structured hybrid fillers maybe a promising way to optimize the overall dielectric performance of the PVDF-based composites.

CAS / MDL: 62-31-7 77-86-1
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Polymers · 2022 ·Vol. 14 ·期 10 ·1950 · IF 4.967

Incorporation of Poly(Ionic Liquid) with PVDF-HFP-Based Polymer Electrolyte for All-Solid-State Lithium-Ion Batteries

Zhefei Ruan,Yuzhe Du,Hongfei Pan,Ruiming Zhang,Fangfang Zhang,Haolin Tang,Haining Zhang

A solid-state polymer electrolyte membrane is formed by blending poly(vinylidene fluoride-co-hexafluoropropylene) with the synthesized copolymer of poly(methyl methacrylate-co-1-vinyl-3-butyl-imidazolium bis(trifluoromethanesulfonyl)imide, in which lithium bis(trifluoromethane)sulfonimide molecules are applied as the source of lithium ions. The accordingly formed membrane that contains 14 wt.% of P(MMA-co-VBIm-TFSI), 56 wt.% of PVDF-HFP, and 30 wt.% of LiTFSI manifests the best electrochemical properties, achieving an ionic conductivity of 1.11 × 10−4S·cm−1at 30 °C and 4.26 × 10−4S·cm−1at 80 °C, a Li-ion transference number of 0.36, and a wide electrochemical stability window of 4.7 V (vs. Li/Li+). The thus-assembled all-solid-state lithium-ion battery of LiFePO4/SPE/Li delivers a discharge specific capacity of 148 mAh·g−1in the initial charge–discharge cycle at 0.1 C under 60 °C. The capacity retention of the cell is 95.2% after 50 cycles at 0.1 C and the Coulombic efficiency remains close to 100% during the cycling process.Keywords:solid polymer electrolyte;all-solid-state;lithium-ion battery;ion conduction;polymer composite

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CHINESE JOURNAL OF POLYMER SCIENCE · 2022 ·Vol. 40 ·期 5 ·515-525 · IF 3.815

Simultaneously Improved Dielectric Constant and Breakdown Strength of PVDF-based Composites with Polypyrrole Nanowire Encapsuled Molybdenum Disulfide Nanosheets

Luo Hua-Bin,Pan Xiao-Ren,Yang Jing-Hui,Qi Xiao-Dong,Wang Yong

High-performance dielectric polymer composites have received increasing attention due to their important applications in the field of energy storage. The rational structural design of hybrid fillers can lead to a balance between high dielectric constant and insulation in composites. In this work, novel hybrid fillers were fabricated by in situ synthesizing one-dimensional polypyrrole nanowires (PPynws) on the two-dimensional molybdenum disulfide (MoS 2 ), which integrated the good ion polarization ability of PPynws and the high insulation and adjustable band gap of MoS 2 . Compared with the binary poly(vinylidene fluoride) (PVDF)/MoS 2 composites, the PVDF/MoS 2 -PPynws composites exhibited remarkably improved dielectric constant and breakdown strength, while the dielectric loss was still maintained at a low level. An optimal ternary composite with 1 wt% MoS 2 -PPynws showed a high dielectric constant (15@1kHz), suppressed dielectric loss (0.027@1kHz), and high breakdown strength (422.1 MV/m). PPynws inducing strong interfacial polarization and the highly insulated MoS 2 nanosheets extending the breakdown path mainly contributed to the synchronously enhanced dielectric constant and breakdown strength. This intriguing synthesis method of PVDF/MoS 2 -PPynws nanocomposite will open up new opportunities for fabricating nanostructured polymer composites to produce high dielectric materials.

CAS / MDL: 1317-33-5
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

3D Printing-Enabled In-Situ Orientation of BaTi2O5 Nanorods in β-PVDF for High-Efficiency Piezoelectric Energy Harvesters

Xingang Liu,Yinghao Shang,Jingfeng Liu,Zhuzhu Shao,Chuhong Zhang

Piezoelectric energy harvesters (PEHs) with a three-dimensional (3D) structure are arousing increasing interest because of the ability to efficiently convert mechanical energy into electricity catering for self-powered systems. Among them, 3D PEHs composed of 1–3-type piezoelectric composites which exploit one-dimensional (1D) piezoceramic fillers rather than conventional powders are particularly attractive. However, an issue involving the orientation of the 1D fillers to utilize the piezoelectric effect renders the 3D structural design for high-efficiency energy conversion more challenging. Herein, for the first time, we introduce the fused deposition modeling (FDM) 3D printing to the flexible construction of poly(vinylidene fluoride) (PVDF)-based 3D PEHs by incorporating 1D BaTi2O5 (BT2) nanorods as piezoelectric fillers. The shearing force generated by FDM successfully realizes the in situ uniform orientation of BT2 nanorods in the PVDF (98% β crystals) matrix along the nozzle extrusion direction. Besides, by coupling 3D printing with the appealing piezoelectric anisotropy feature of BT2 nanorods, the 3D PEH is able to generate different piezoelectric responses to the same applied external force from X, Y, and Z directions. Furthermore, an optimized 3D conical array structure is constructed to amplify the effective deformation of the PEH to enhance its piezoelectric output. As expected, customized PEH can continuously power commercial electronic devices and monitor various human motions, indicating 3D printing as a multifunctional strategy to fabricate 3D PEHs with 1–3-type piezoelectric composite materials for self-powering microelectronic applications.

CAS / MDL: 513-77-9 143314-16-3
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Journal of Advanced Ceramics · 2022 ·Vol. 11 ·期 2 ·331-344 · IF 11.534

Porous, multi-layered piezoelectric composites based on highly oriented PZT/PVDF electrospinning fibers for high-performance piezoelectric nanogenerators

Du Xiangxin,Zhou Zheng,Zhang Zhao,Yao Liqin,Zhang Qilong,Yang Hui

Piezoelectric nanogenerators (PENGs) that can harvest mechanical energy from ambient environment have broad prospects for multi-functional applications. Here, multi-layered piezoelectric composites with a porous structure based on highly oriented Pb(Zr 0.52 Ti 0.48 )O 3 /PVDF (PZT/PVDF) electrospinning fibers are prepared via a laminating method to construct high-performance PENGs. PZT particles as piezoelectric reinforcing phases are embedded in PVDF fibers and facilitate the formation of polar β phase in PVDF. The multi-layered, porous structure effectively promotes the overall polarization and surface bound charge density, resulting in a highly efficient electromechanical conversion. The PENG based on 10 wt% PZT/PVDF composite fibers with a 220 µm film thickness outputs an optimal voltage of 62.0 V and a power of 136.9 µW, which are 3.4 and 6.5 times those of 10 wt% PZT/PVDF casting film-based PENG, respectively. Importantly, the PENG shows a high sensitivity of 12.4 V·N −1 , presenting a significant advantage in comparison to PENGs with other porous structures. In addition, the composites show excellent flexibility with a Young’s modulus of 227.2 MPa and an elongation of 262.3%. This study shows a great potential application of piezoelectric fiber composites in flexible energy harvesting devices.

CAS / MDL: 68-12-2
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