锂离子电池用聚合物电解质的最新进展II.含液聚合物电解质

由于干态聚合物电解质目前还不能满足聚合物锂离子电池的应用要求,人们致力于开发含液体增塑剂的聚合物电解质,包括凝胶型和微孔型两类体系。本文综述了含液聚合物电解质的最新进展,重点论述了各种新体系和新方法。     

Quantum chemical studies of Li cation binding to polyalkyloxides

A quantum chemical study of the binding of Li⁺ cation to polyalkyloxides has been carried out. The lithium cation interaction with three polyalkyloxides (polyethylene oxide (PEO), polytrimethylene oxide (PTMO), and polypropylene oxide (PPO)) has been investigated using ab initio molecular orbital theory at the HF/6-31G^* level with molecular models for the polymers. Coordination by one to six oxygens was considered. In addition, higher level calculations were carried out using G3(MP2) theory for coordination of Li⁺ by one oxygen. For coordination of lithium by one oxygen, the binding energy ordering is PTMO>PPO>PEO, with PTMO having the largest lithium cation affinity. The same ordering is found for larger coordination numbers with the exception of coordination by six oxygens, where the ordering changes due to the steric interactions.     

Sol-gel preparation of a di-ureasil electrolyte doped with lithium perchlorate

Solid polymer electrolytes (SPEs) synthesized by the sol-gel process and designated as di-ureasils have been prepared through the incorporation of lithium perchlorate, LiClO₄, into the d-U(2000) organic-inorganic hybrid network. Electrolytes with lithium salt compositions of n (where n indicates the number of oxyethylene units per Li⁺ ion) between ∞ and 0.5 were characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode, thermal analysis and Fourier transform Raman (FT-Raman) spectroscopy. The conductivity results obtained suggest that this system offers a quite significant improvement over previously characterized analogues doped with lithium triflate [S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Barros, M.J. Smith, R.A. Sá Ferreira, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. Soc. 152 (2) (2005), A429]. “Free” perchlorate ions, detected in all the samples examined, are identified as the main charge carriers in the sample that yields the highest room temperature conductivity (n = 20). In the di-ureasils with n ≤ 10 ionic association is favoured and the ionic conductivity drops.     

Room-Temperature Solid-State Lithium Metal Batteries Using Metal Organic Framework Composited Comb-Like Methoxy Poly(ethylene glycol) Acrylate Solid Polymer Electrolytes

Solid polymer electrolyte with good thermal stability and flexibility is an excellent candidate for solid-state lithium metal batteries, while its low ionic conductivity caused by high crystallinity limits its application at ambient temperature. Here a metal organic framework (zeolitic imidazolate framework-8, ZIF-8) composited comb-like methoxy poly(ethylene glycol) acrylate polymer electrolyte (MCPE) with high ionic conductivity (9.96 × 10⁻⁵ S cm⁻¹ at 30 °C) is prepared by an in situ UV polymerization method. The as-prepared MCPE exhibits improved mechanical property due to the introduction of porous ZIF-8 nanofillers, which is beneficial to suppress the growth of lithium dendrites. Consequently, the LiFePO₄||MCPE||Li cells show a high capacity of 116 mAh g⁻¹ at 30 °C and 0.5 C, and maintain 89.4% of initial capacity after 150 cycles with the average Coulombic efficiency of 99.9%. These results demonstrate that the MCPE shows great potential in solid-state lithium metal batteries near room temperature.     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007     

Kinetics of methane hydrate formation in aqueous electrolyte solutions

Experimental data on the kinetics of methane hydrate formation in aqueous electrolyte solutions are reported. The experiments were carried out in a semi-batch stirred tank reactor in three NaCl and two KCl solutions as well as in a solution containing a mixture of NaCl and KCl at three different nominal temperatures from 270 to 274 K and at pressures ranging from 3.78 to 7.08 MPa. The kinetic model developed by Englezos et al. (1987a) was adapted to predict the growth of hydrates. The model is based on the crystallisation theory coupled with the two-film theory for gas absorption in the liquid phase. The kinetic rate constant which appears in the model was that obtained earlier for methane hydrate formation in pure water. The effect of the electrolytes was taken into account through the computation of the three-phase equilibrium conditions and the corresponding fugacities. Overall, the model predictions match the experimental data very well with the largest prediction error being less than 10%.     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

In situ composite of nano SiO2-P(VDF-HFP) porous polymer electrolytes for Li-ion batteries

Nano SiO₂-P(VDF-HFP) composite porous membranes were prepared as the matrix of porous polymer electrolytes through in situ composite method based on hydrolysis of tetraethoxysilane and phase inversion. SEM, TEM, DSC and AC impedance analysis were carried out. It is found that the in situ prepared nano silica was homogeneously dispersed in the polymeric matrix, enhanced conductivity and electrochemical stability of porous polymer electrolytes, and improved the stability of the electrolytes against lithium metal electrodes. The in situ composite method was found to be much better than the direct composite method in lowering the interfacial resistance between electrolyte and lithium metal electrode. Moreover, cycle test of lithium batteries using lithium metal as anode and sulfur composite material as cathode showed that the electrolyte based on in situ composite of silica presented stable charge-discharge behavior and little capacity loss of battery.     

PVdF-HFP/P123 hybrid with mesopores: a new matrix for high-conducting, low-leakage porous polymer electrolyte

Highly conducting porous polymer electrolytes comprised of poly(vinylidene-fluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123), ethylene carbonate (EC), propylene carbonate (PC), and LiClO₄ were fabricated. The PVdF-HFP/P123 hybrid polymer membranes were made with a phase inverse method and the electrolyte solution uptake was carried out in glove box to avoid the moisture contamination. It was found that when a small amount of polymer surfactant (P123) was blended into the PVdF-HFP, mesopores with well-defined sizes were formed. Impedance spectroscopy showed that the room temperature conductivity of (PVdF-HFP)/P123 polymer electrolytes increased as the content of P123 increased up to 4×10⁻³ S/cm. Nitrogen adsorption isotherms, electrolyte solution uptake, porosity measurements, and SEM micrographs showed that the enhanced conductivity was due to increase the pore volume, pore density, and electrolyte uptake. The highest conduction was found when the weight ratio of P123 to PVdF-HFP was 70%, when big channels were formed in the hybrid polymer membrane. Furthermore, blending P123 in PVDF-HFP reduced the pore size of polymer membrane, therefore, the solution leakage was also reduced. These polymer electrolytes were stable up to 4.5 V (vs Li/Li⁺) and the performance of the model lithium ion battery made by sandwiching the polymer electrolyte between a LiCoO₂ anode and a MCMB cathode, showed great promise for the use of these polymer electrolytes in lithium ion batteries.     

Ionic conductivity enhancement of the plasticized PMMA/LiClO4 polymer nanocomposite electrolyte containing clay

This work has demonstrated that the addition of an optimum content of dimethyldioctadecylammonium chloride (DDAC)-modified montmorillonite clay (Dclay) enhances the ionic conductivity of the plasticized poly(methyl methacrylate)-based electrolyte by nearly 40 times higher than the plain system. Specific interactions among silicate layer, carbonyl group (CO) and lithium cation have been investigated using Fourier-transform infrared (FTIR), solid-state NMR, alternating current impedance. The FTIR characterization confirms that both of the relative fractions of ‘complexed’ CO sites and ‘free’ anions increase with the increase of the Dclay content, indicating that strong interaction exists between the CO group and the lithium salt. In addition, the solid-state NMR demonstrates that the interaction between the PMMA and the clay mineral is insignificant. The addition of clay mineral promotes the dissociation of the lithium salt and thus, the specific interaction can be enhanced between the CO and the free lithium cation. However, the balanced attractive forces among silicate layers, CO groups, lithium cations and anions is critical to result in the higher ionic conductivity.