锂电池用聚偏氟乙烯粘结剂

锂电池用粘结剂是制造锂电池的重要材料之一,可直接影响其性能.介绍了锂电池用粘结剂应具备的特性、种类及存在的问题;叙述了日本专利中,偏氟乙烯作为锂电池用粘结剂和用偏氟乙烯与第二及第三单体的共聚改性、聚偏氟乙烯与其他聚合物共混改性等的方法.     

Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries

A composite anode material of silicon/graphite/multi-walled carbon nanotubes (MWNTs) for Li-ion batteries was prepared by ball milling. This composite anode material showed a discharge capacity of 2274 mAh/g in the first cycle, and after 20 charge-discharge cycles, a reversible capacity of 584 mAh/g was retained, much higher than 218 mAh/g for silicon/graphite composite. It was observed that silicon particles were homogeneously embedded into the “lamellar structures” of flaked graphite particles, and the silicon/graphite composite particles were further wrapped by a MWNTs network. The improvement in the electrochemical properties of the composite anode material was mainly attributed to the excellent resiliency and good electric conductivity of the MWNTs network.     

Microporous poly(acrylonitrile-methyl methacrylate) membrane as a separator of rechargeable lithium battery

We studied microporous poly(acrylonitrile-methyl methacrylate), AMMA, membrane as the separator of Li/LiMn₂O₄ cell. The porous AMMA membrane was prepared by the phase inversion method with N,N-dimethylformamide (DMF) as the solvent and water as the non-solvent. We observed that morphology of the resulting membrane was strongly affected by the concentration of polymer solution: low concentration produced finger-like pores with dense skin on two surfaces of the membrane, while high concentration yielded open voids with dense layer on the other surface of the membrane. Regardless of their morphology, both membranes could be rapidly wetted by the liquid electrolyte (1.0 m LiBF₄ dissolved in 1:3 wt.% mixture of ethylene carbonate (EC) and γ-butyrolactone (GBL)), and could be swollen at elevated temperatures, which resulted in the formation of a microporous gel electrolyte (MGE). It was shown that the resulting MGE not only had high ionic conductivity and but also had good compatibility with metal lithium even at 60 °C. Cyclic voltammetric test showed that the MGE had an electrochemical window of 4.9 V versus Li⁺/Li. At room temperature, the Li/MGE/LiMn₂O₄ cell showed excellent cycliability with a specific capacity of 121-125 mA h g⁻¹ LiMn₂O₄. It was shown that even at 60 °C good mechanical strength of the MGE remained. Therefore, the MGE is suitable for the application of battery separator at elevated temperatures.     

Multiple melting in blends of poly(vinylidene fluoride) with isotactic poly(ethyl methacrylate)

Multiple melting phenomena have been studied in blends of poly(vinylidene fluoride) (PVF₂) with low molar mass isotactic poly(ethyl methacrylate) (it-PEMA). In all blends, as well as in pure PVF₂, a transition (T₁) was observed prior to the main melting point (T₂). T₁ is probably connected with the melting of secondarily-crystallized material. In addition to this, a high temperature melting endotherm (T₃) was observed, which could be ascribed completely to recrystallization of PVF₂. The highest transition (T₄) was caused by melting of the σ form of PVF₂. From Hoffman-Weeks plots—T₂ vs. crystallization temperature, T_c — it could be concluded that no thermody amic depression of the melting point of PVF₂ occurred in the blends. The stabilities of PVF₂ crystallites in the various blends were derived from the slopes of Hoffman-Weeks plots and were in good agreement with lamellar thicknesses found from SAXS measurements.     

Morphological and infra-red studies on highly oriented poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Highly oriented melt drawn films of poly(vinylidene fluoride) (PVDF) and blends of poly(vinylidene fluoride) and poly(methyl methacrylate) (PMMA) have been studied by transmission electron microscopy, electron diffraction and infra-red spectroscopy. Infra-red spectra show the second moment of the orientation function for PVDF samples to be greater than 0.94. Using such a sample, the transition dipole directions relative to the chain axis have been calculated. Electron microscopic studies of the PVDF/PMMA blends show a transformation for pure PVDF from a lamellar morphology to a mixture of lamellar and needle-like crystals for the 80/20 blend. The 60/40 blend shows a pure needle-like morphology. The β phase content for this blend is dependent upon the composition and thermal history. An increase in the β phase content is observed with the addition of PMMA. After annealing at 110°C, the 50/50 blend shows a lamellar β phase morphology. A significant increase in the segmental orientation of PVDF is also observed.     

Purification and carbon-film-coating of natural graphite as anode materials for Li-ion batteries

A process of modification of natural graphite materials as anode for lithium ion batteries was attempted. The process started with the treatment of natural graphite with concentrated hydrochloric acid and concentrated sulfuric acid in a thermal autoclave, followed by the in situ polymerization of resorcinol-formaldehyde resin to coat the graphite, then heat-treatment. SEM, XRD, Raman and electrochemical charge-discharge analysis showed that the surface defects and impurities on natural graphite were eliminated by purification of the concentrated acids, and carbon-film encapsulation modified the surface structure of the graphite and reduced its BET surface area. The as-obtained natural graphite sample presented an initial charge-discharge coulombic efficiency of 88.4% and a reversible capacity of 355.8 mAh g⁻¹. The proposed process paves a way to prepare a promising anode material with excellent performance with low cost of natural graphite for rechargeable lithium ion batteries.     

Effect of poly(vinylidene fluoride) binder crystallinity and graphite structure on the mechanical strength of the composite anode in a lithium ion battery

We have evaluated the mechanical strength of a series of composites consisting of carbon particles bound together by poly(vinylidene fluoride) (PVDF), which is closely related to the carbonaceous anode in a lithium ion battery. We used a balanced beam scrape adhesion tester and evaluated the influence of carbon particle structure, the chemical properties of PVDF, and the processing parameters of annealing temperature and casting solvent on the adhesion of the composite film to a copper substrate. The composite prepared with amorphous carbon shows over 10 times higher adhesion strength than those fabricated from other graphite materials. This results from chemical binding that is intermediate between semi-ionic and covalent C-F bonds, as detected by X-ray photoelectron spectroscopy. To address the effect of the crystalline phase of the binder on the adhesion strength, we investigated PVDF crystallinity in the composite films using differential scanning calorimetry. Samples with higher crystallinity show higher adhesion strength, independent of annealing temperature and casting solvent. The scratch adhesion was also measured for swollen electrodes immersed in 3:7 volume ratio of ethylene carbonate:ethyl methyl carbonate (EC:EMC) at different temperatures. After being swollen, the composite films prepared from PVDF modified with hydroxyl functional groups show higher adhesion strengths than the others due to their low uptake of the electrolyte solvent.     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Investigation on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends by solution casting

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by solution casting. The crystallization behavior and hydrophilicity of ternary blends were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and contact angle test. According to morphological analysis, the surface was full of typical spherulitic structure of PVDF and the average diameter was in the order of 3 μm. The samples presented predominantly β phase of PVDF by solution casting. It indicated that the size of surface spherulites and crystalline phase had little change with the PMMA or PVP addition. Moreover, FTIR demonstrated special interactions among the ternary polymers, which led to the shift of the carbonyl stretching absorption band of PVP. On the other hand, the melting, crystallization temperature, and crystallinity of the blends had a little change compared with the neat PVDF in the first heating process. Except for the content of PVP containing 30 wt %, the crystallinity of PVDF decreased remarkably from 64% to 33% and the value of t_1/2 was not obtained. Besides, the hydrophilicity of PVDF was remarkably improved by blending with PMMA/PVP, especially when the content of PVP reached 30 wt %, the water contact angle displayed the lowest value which decreased from 98.8° to 51.0°. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Miscibility of C60‐containing poly(methyl methacrylate)/poly(vinylidene fluoride) blends

The miscibility of C₆₀‐containing poly(methyl methacrylate) (PMMA‐C₆₀) with poly(vinylidene fluoride) (PVDF) was studied. Two PMMA‐C₆₀ samples containing 2.6 and 7.4 wt % C₆₀ were found to be miscible with PVDF based on single glass transition temperature criterion and melting point depression of PVDF. However, the interaction parameters of the two blend systems are less negative than that of the PMMA/PVDF blend system, showing that the incorporation of C₆₀ reduces the ability of carbonyl groups of PMMA to interact with PVDF. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1393–1396, 2000     

Synthesis and characterization of porous maghemite as an anode for Li-ion batteries

The synthesis of porous maghemite via a simple glycerol-mediated solution method was successfully accomplished. Thermal analysis, X-ray diffraction and Mössbauer spectroscopy results disclosed the formation of maghemite. The morphological and structural features of maghemite were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, and nitrogen adsorption–desorption. The powder showed Brunauer–Emmett–Teller surface area of 285 m² g⁻¹ with micro-, meso- and macropores.The anode body was doctor bladed using primary powder with a binder and a conductive agent. Galvanostatic charge–discharge cycling of the porous maghemite exhibited a specific reversible capacity of approximately 1180 mAh g⁻¹ at 100 mA g⁻¹ current density, which was two times higher than that of common nanomaghemite with average particle size of 19 nm. The cell showed stability even at the high current charge–discharge rates of 3000 mA g⁻¹ and more than 94% retention. After multiple high current cycling regimes, the cell recovered to nearly full reversible capacity of ~1120 mAh g⁻¹ at 100 mA g⁻¹. The reason for this remarkable performance of the present anode was thought to be dependent upon the role of pores in increasing the surface area and resistance against volume changes during lithium insertion/extraction.     

聚偏氟乙烯共混隔膜的制备与性能

以乙二醇二甲基丙烯酸酯和丙烯腈为单体,合成了聚合物poly(AN-co-PEGDMA),然后与聚偏氟乙烯(PVDF)共混,制备了不同poly(AN-co-PEGDMA)含量的PVDF/poly(AN-co-PEGDMA)共混隔膜,利用X射线衍射、扫描电子显微镜(SEM)、差示扫描量热对共混隔膜的性能进行表征。结果表明,随着poly(AN-co-PEGDMA)含量的增加,PVDF/poly(AN-co-PEGDMA)的玻璃化转变温度逐渐提高,衍射峰的谱峰强度逐渐降低,隔膜的结晶度降低。SEM结果显示,随着poly(AN-co-PEGDMA)含量的增加共混隔膜的孔隙变大,有利于电解液的有效吸收。通过对PVDF/poly(AN-co-PEGDMA)共混隔膜电导率、吸液率的测定,表明在poly(AN-co-PEGDMA)质量分数为30%时,制得的共混隔膜的性能较佳。在此基础上,对共混隔膜构建的聚合物锂离子电池的电化学稳定窗口、电池容量和循环性能进行测试,其电化学稳定窗口为0～4.7 V(vs Li+/Li),放电电容为1.433～1.151 mAh,可以满足商业使用要求,具有广阔的应用前景。     

Physical Properties of Plasticized Poly(vinyl chloride) Blended with Poly(methyl methacrylate) Nanoparticles Synthesized by Differential Microemulsion Polymerization

In this work, poly(methyl methacrylate) (PMMA) nanoparticles synthesized by differential micro emulsion polymerization were used to improve the physical properties of plasticized poly(vinyl chloride) (PVC). PVC, plasticizer (40 phr), heat stabilizer (2 phr), and lubricant (0.2 phr) were melt-mixed with varied amount of the PMMA nanoparticles (3, 5, 7, and 9 phr) on a two-roll mill, followed by compression molding. The results showed that the tensile strength, Young's modulus, tear strength, and thermal stability were improved, but the elongation at break deteriorated with increased PMMA content. Moreover, the flammability of the plasticized PVC was not improved by the PMMA nanoparticles.     

Poly(methyl methacrylate) as masking material for microelectromechanical system (MEMS) fabrication

In the present study direct current (dc) sputtered poly(methyl methacrylate) (PMMA) films deposited on silicon substrates were evaluated as masking materials for anisotropic etching of silicon in aqueous potassium hydroxide (KOH) and tetramethyl ammonium hydroxide (TMAH) solutions. Sputtered PMMA films were characterized by FTIR to ascertain the bonding, by X‐ray photoelectron spectroscopy (XPS) for the elemental composition, and by the contact angle for measuring the adhesion of the film with the substrate. FTIR and XPS data showed the presence of a poly(tetrafluoroethylene)‐like film on the silicon substrate. The interfacial tension was calculated from the contact angle value, which was 0.82 dyne/cm, confirming good adhesion of the film and the substrate. A pattern was lithographically transferred through the masking material on the silicon substrate, and the etch rate of the masking layer was calculated from the masking time data of the films. The etch rate value of 4 Å/min obtained for the masking material is low compared to the etch rate of the conventional masking materials (60 Å/min for SiO₂ and 8 Å/min for Si₃N₄). © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 2094–2098, 2006     

Sn-Co-artificial graphite composite as anode material for rechargeable lithium batteries

Nanosized Sn-Co prepared by ultrasonic-assisted chemical reduction is milled with artificial graphite (AG) to form Sn-Co-AG composite. The as-prepared materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectrometry and Brunauer-Emmett-Telle (BET) surface area measurement. XRD patterns show that Sn-Co particles are poorly crystallized and artificial graphite has a typical hexagonal graphite structure phase. The diffraction peaks of Sn-Co particles remain the same but some of AG obviously change after milling Sn-Co with AG. BET areas of AG, Sn-Co and Sn-Co-AG are 1.569, 13.187 and 6.754 m² g⁻¹, respectively. SEM images display the as-prepared Sn-Co particles have a size distribution ranging from 20 to 70 nm in diameter. After milling Sn-Co with AG, Sn-Co particles keep similar morphology but there is a perceptible change in AG. Electrochemical tests show that Sn-Co-AG composite possesses much improved electrochemical performance than the state-of-the-art graphite. This composite has great potential as an alternative material for improving the energy density of a lithium ion secondary battery.     

Spatially‐confined crystallization of poly(vinylidene fluoride)

Nanometre‐sized poly(vinylidene fluoride) (PVDF) particle domains in a confined space were obtained by blending PVDF with excess poly(methyl methacrylate) (PMMA). When these particles were small enough they showed β‐form structure, which was different from the structure of bigger particles or PVDF bulk. However, the β‐form was thermodynamically metastable because it could eventually be transformed to a more stable phase by annealing at a certain temperature. Larger particle domains were of identical phase to the bulk, indicating that small size favours the formation of the β‐form. © 2000 Society of Chemical Industry     

Investigation of Fullerenes as High Temperature Stabilizers of Poly(methyl methacrylate) and Polystyrene

Abstract

Investigation has been made on the effects of fullerenes C₆₀ and C₇₀ on the degradation of PMMA and PS under helium and oxygen by a DSC method. The dependences of the temperature of the onset of the thermal and thermo-oxidative degradation of the polymers on concentration of C₆₀ and C₇₀ have been obtained. The temperature limits of effective inhibition of the polymers by fullerenes have been determined. The temperature limit depends on the chemical structure of polymer, namely it is considerably greater in the degradation of more stable polymer. In the thermo-oxidative degradation of the polymers with addition of fullerenes, the temperature limit of inhibition of less stable PS is much less and of more stable PMMA is considerably greater than that in the presence of well-known antioxidants. It was concluded that fullerenes are more effective high temperature inhibitors of the thermo-oxidative degradation of PMMA than well-known antioxidants. The suggestion was made that the thermo-oxidative degradation of polymers initiates the oxidation of fullerenes.     

Optical Properties of Composites Based on Poly(o-phenylenediamine), Poly(vinylenefluoride) and Double-Wall Carbon Nanotubes

In this work, synthesis and optical properties of a new composite based on poly(o-phenylenediamine) (POPD) fiber like structures, poly(vinylidene fluoride) (PVDF) spheres and double-walled carbon nanotubes (DWNTs) are reported. As increasing the PVDF weight in the mixture of the chemical polymerization reaction of o-phenylenediamine, the presence of the PVDF spheres onto the POPD fibers surface is highlighted by scanning electron microscopy (SEM). The down-shift of the Raman line from 1421 cm⁻¹ to 1415 cm⁻¹ proves the covalent functionalization of DWNTs with the POPD-PVDF blends. The changes in the absorbance of the IR bands peaked around 840, 881, 1240 and 1402 cm⁻¹ indicate hindrance steric effects induced of DWNTs to the POPD fiber like structures and the PVDF spheres, as a consequence of the functionalization process of carbon nanotubes with macromolecular compounds. The presence of the PVDF spheres onto the POPD fiber like structures surface induces a POPD photoluminescence (PL) quenching process. An additional PL quenching process of the POPD-PVDF blends is reported to be induced in the presence of DWNTs. The studies of anisotropic PL highlight a change of the angle of the binding of the PVDF spheres onto the POPD fiber like structures surface from 50.2° to 38° when the carbon nanotubes concentration increases in the POPD-PVDF/DWNTs composites mass up to 2 wt.%.     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

聚偏氟乙烯的宽频介电谱特征研究

采用熔融法制备了聚偏氟乙烯（PVDF）样品,通过X射线衍射仪、傅里叶变换红外光谱仪和宽频介电谱分析仪对PVDF样品的结构及介电性能进行了测试分析。结果表明,熔融法获得的PVDF主要含α相;在40～100℃范围内出现由玻璃化转变引起的α-PVDF的松弛现象, 在-100～-50 ℃范围内出现的δ-PVDF松弛,是由非晶区分子运动产生的极化现象。