Zhicheng Zhang

Electric energy storage properties of poly(vinylidene fluoride)

High discharged energy density observed in poly(vinylidene fluoride) (PVDF) based copolymers has attracted considerable research interests in the past years. Crystalline properties exhibit great influence on their dielectric and energy storageproperties. To understand how crystalline properties influence the energy storageproperties of PVDF, PVDF films with three different crystal forms are investigated in this paper. It is shown that γ -PVDF is allowed to work under higher electric fields than α - and β -PVDF in the absence of phase transition in α -PVDF and early polarization saturation in β -PVDF. Consequently, γ -PVDF exhibits the highest energy density of 14 J / cm 3 under 500 MV/m electric field.

High-field antiferroelectric behaviour and minimized energy loss in poly(vinylidene-co-trifluoroethylene)-graft-poly(ethyl methacrylate) for energy storage application

In this work, we report a novel antiferroelectric-like performance at high poling fields obtained in poly(ethyl methacrylate) (PEMA) grafted poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) series copolymers for application as high energy density and low loss capacitor dielectrics films. Compared with the pristine P(VDF-TrFE) random copolymer, an enhanced discharged energy density but a lowered energy loss has been observed as more PEMA is grafted. This novel antiferroelectric-like behavior at high poling field was explained by the crystalline impediment and polarization confinement effect induced by PEMA side chains. The highest discharged energy density of 14 J cm−3 and a low loss of 30% at 550 MV m−1 are achieved in the sample containing 22 wt% PEMA. This finding represents one of the effective routes to design potential dielectric polymer films for high energy storage applications.

One-pot synthesis of carbon coated Fe3O4 nanosheets with superior lithium storage capability

Hybrid nanosheet structures based on carbon coated metal oxides still attract promising interest as high-performance electrode materials for next-generation lithium-ion batteries (LIBs). In this study, we develop a simple one-pot solution method to synthesize large-scale flat Fe3O4 nanosheet hybrid structures coated with an amorphous carbon overlayer (denoted as Fe3O4@C NSs) followed by a thermal annealing treatment. It is found that the refluxing temperature plays an important role in adjusting the morphology of the Fe3O4@C hybrid. Increasing the temperature from 140 °C to 200 °C will lead to flower-like hybrid structures constructed by Fe3O4 nanoflakes gradually growing, rupturing, and finally evolving into flat and completely separate nanoflakes with large size at 200 °C. When evaluated as an anode material for LIBs, the hybrid Fe3O4@C NSs demonstrate a high reversible capacity of 1232 mA h g−1 over 120 cycles at a current density of 200 mA g−1, and remarkable rate capability.

Controlled hydrogenation of P(VDF-co-CTFE) to prepare P(VDF-co-TrFE-co-CTFE) in the presence of CuX (X = Cl, Br) complexes

An environmentally friendly and controllable P(VDF-co-CTFE) hydrogenation route involving the transition-metal complex mediated radical chain transfer reaction is successfully developed to synthesize P(VDF-co-CTFE-co-TrFE). The typical transition metal catalysts of ATRP reaction could be applied in this process.

Tuning phase transition and ferroelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) via grafting with desired poly(methacrylic ester)s as side chains

For potential application in high energy storage capacitors with high energy density and low energy loss, three sets of poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] grafted with poly(methacrylic ester)s, including poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(butyl methacrylate) (PBMA) copolymers, are designed and investigated carefully. Due to their intermediate polarity, relatively high glass transition temperature, and excellent compatibility with PVDF chains, the poly(methacrylic ester) segments introduced could not only dramatically weaken the coupling interactions of oriented polar crystals, but could also accelerate the reversal switching of polar crystal domains along the applied electric field, which leads to well hindered remnant polarization. As a result, the displacement–electric field (D–E) hysteresis behaviors of the graft copolymers could be tuned from typical ferroelectric to either antiferroelectric or linear shape under high electric field. Meanwhile, significantly reduced energy loss and effectively improved energy discharging efficiency were obtained. Compared with PMMA and PBMA, PEMA with intermediate polarity and grafting length exhibits more suitable confinement of the F–P transition of P(VDF-TrFE-CTFE), and thus more desirable energy storage properties are observed in the resultant copolymers. These findings may help to deeply understand the ferroelectric nature of PVDF based fluoropolymers and design new energy storage capacitor materials with high discharged energy density and low energy loss.

Chemical bonding-induced low dielectric loss and low conductivity in high-K poly(vinylidenefluoride-trifluorethylene)/graphene nanosheets nanocomposites.

Blending high-permittivity (εr) ceramic powders or conductive fillers into polymers to form 0-3-type composites has been regarded as one of the most promising processes to achieve high-dielectric-permittivity materials with excellent processing performance. The high dielectric loss and conductivity induced by the interface between the matrix and fillers as well as the leakage current have long been a great challenge of dielectric composites, and the resolution of these challenges is still an open question. In this work, poly(vinylidenefluoride-trifluorethylene with double bonds)/graphene nanosheets (P(VDF-TrFE-DB)/GNS) terpolymer nanocomposites were fabricated via a solution-cast process. GNSs were functionalized with KH550 to improve the dispersion in the terpolymer matrix solution and crosslinked with P(VDF-TrFE-DB) by a free-radical addition reaction in the nanocomposites. Compared with neat terpolymer, significantly increased dielectric permittivity and a low loss were observed for the composites. For instance, at 1 kHz the P(VDF-TrFE-DB)/GNS composites with 4 vol % GNS possessed a dielectric permittivity of 74, which is over seven times larger than that of neat terpolymer. However, a rather low dielectric loss (0.08 at 1 kHz) and conductivity (3.47 × 10(-7) S/m at 1 kHz) are observed in the P(VDF-TrFE-DB)/GNS composites containing up to 12 vol % GNS. The covalent bonding constructed between P(VDF-TrFE-DB) and GNS is responsible for the reduced aspect ratio of the GNS and the crystalline properties of P(VDF-TrFE-DB) as well as the improved compatibility between them. As a result, the high-dielectric-loss conductivity of polymer composites, mainly induced by conduction loss and the interface polarization between the matrix and filler, were effectively restricted. Meanwhile, the 3D network established between P(VDF-TrFE-DB) and GNS endows the P(VDF-TrFE-DB)/GNS composites at high temperature with excellent mechanical and dielectric properties. Besides preparing high-performance dielectric composites, this facile route may also be utilized to fabricate high-performance nanocomposites by inhibiting the poor compatibility between fillers and polymeric matrix.

Crystalline properties dependence of dielectric and energy storage properties of poly(vinylidene fluoride-chlorotrifluoroethylene)

Thermal quenching at various temperatures has been employed to fabricate poly(vinylidene fluoride- c o -chlorotrifluoroethylene) films with varied crystalline properties in an attempt to significantly improve their dielectric and energy storage properties. It has been shown that the film quenched at lower temperature possesses lower crystallinity and crystal grain size. The dielectric constant and dielectric loss of corresponding films are improved at low frequency and reduced at high frequency due to the response of dipoles in amorphous phase. The breakdown strength and polarization of the film quenched at lower temperature are larger than that quenched at higher temperature. Therefore, the low quenching temperature favors the high energy density both under the consistent electric field and the breakdown electric field.

Fabrication of Stretchable Nanocomposites with High Energy Density and Low Loss from Cross-Linked PVDF Filled with Poly(dopamine) Encapsulated BaTiO3

In this report, a simple solution-cast method was employed to prepare poly(dopamine) (PDA) encapsulated BaTiO3 (BT) nanoparticle (PDA@BT) filled composites using PVDF matrix cross-linked by the free radical initiator. The effects of both the particle encapsulation and matrix cross-linking on the mechanical and dielectric properties of the composites were carefully investigated. The results suggested that the introduction of BT particles improved permittivity of the composites to ∼30 at 100 Hz when particle contents of only 7 wt % were utilized. This was attributed to the enhanced polarization, which was induced by high permittivity ceramic particles. Compared to bare BT, PDA@BT particles could be dispersed more homogeneously in the matrix, and the catechol groups of PDA layer might form chelation with free ions present in the matrix. The latter might depress the ion conduction loss in the composites. Other results revealed that the formation of hydrogen-bonding between the PDA layer and the polymer, especially the chemical cross-linking across the matrix, resulted in increased Young modulus by ∼25%, improved breakdown strength by ∼40%, and declined conductivity by nearly 1 order of magnitude when compared to BT filled composites. The composite films filled with PDA@BTs indicated greater energy storage capacities by nearly 190% when compared to the pristine matrix. More importantly, the excellent mechanical performance allowed the composite films to adopt uni- or biaxially stretching, a crucial feature required for the realization of high breakdown strength. This work provided a facile strategy for fabrication of flexible and stretchable dielectric composites with depressed dielectric loss and enhanced energy storage capacity at low filler loadings (<10 wt %).

Significantly improving dielectric and energy storage properties via uniaxially stretching crosslinked P(VDF-co-TrFE) films

Recently, tuning the normal ferroelectric performance of poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-co-TrFE)) to either relaxor ferroelectric or anti-ferroelectric behavior by confining the relaxation of ferroelectric crystal domains physically or chemically has attracted considerable interest to achieve high discharged electric energy density (Ue) and low energy loss (Ul) for energy storage applications in high pulse capacitors. To improve the dielectric and energy storage properties as well as reduce the energy loss induced by the ferroelectric relaxation of P(VDF-co-TrFE), unsaturation containing P(VDF-co-TrFE) films were uniaxially stretched after crosslinking with peroxide in this work. P(VDF-co-TrFE) containing unsaturation was synthesized via controlled hydrogenation and dehydrochlorination of commercially available poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)). The properties of the films obtained were characterized with differential scanning calorimetry (DSC), X-ray diffraction (XRD), dielectric constant and electric displacement–electric field (D–E) hysteresis loop measurements. Compared with the as-cast and as-crosslinked films, the stretched films exhibit a significantly enhanced dielectric constant, breakdown field (Eb > 500 MV m−1) and Ue but depressed energy loss. This could be attributed to the enhanced film quality, optimized crystalline properties, improved orientation uniformity of crystal domains as well as accelerated ferroelectric relaxation induced by the crosslinking and mechanical stretching. The best performance was achieved for the stretched film with a dielectric constant of 15 at 1 kHz, a relatively high Ue of 17.5 J cm−3 and a low energy loss of about 30% at 575 MV m−1.

Synthesis of fluoropolymer containing tunable unsaturation by a controlled dehydrochlorination of P(VDF-co-CTFE) and its curing for high performance rubber applications

Fluoropolymer containing unsaturation, an important intermediate for many reactions such as radical addition and Michael addition reaction, could be either utilized to synthesize fluoropolymer with desired functions or cured for rubber applications, which has rarely been investigated because of the absence of a synthetic strategy. A facile method to synthesize fluoropolymer with tunable unsaturation via controlled dehydrochlorination of commercially available poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) catalyzed by tertiary monoamines under mild conditions has been reported in this work. The resultant copolymers are carefully characterized with nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and thermal gravimetric analysis (TGA). It has been shown that the elimination could be well controlled by employing proper solvent, catalyst and reaction conditions. The typical side reactions catalyzed with amines, such as Michael addition reaction and main chain scission during the dehydrofluorination of fluoropolymer, could be avoided in the present reaction system. The kinetics results indicate that the elimination reaction is in a bi-molecular mechanism (E2), which is well recognized in strong base-catalyzed elimination of halogenated hydrocarbon. The concentration, alkalinity and steric bulk of the catalysts, the polarity and capability to absorb HCl acid of solvents, and the reaction time and temperature exhibit dominant influences on the dehydrochlorination of P(VDF-co-CTFE). The fluoropolymer containing unsaturation is readily cured with peroxide, and the crosslinked fluoropolymer exhibits excellent solvent resistance and mechanical properties.