RESUMEN
The rational design and exploration of safe, robust, and inexpensive energy storage systems with high flexibility are greatly desired for integrated wearable electronic devices. Herein, a flexible all-solid-state battery possessing competitive electrochemical performance and mechanical stability has been realized by easy manufacture processes using carbon nanotube enhanced phosphate electrodes of LiTi2(PO4)3 and Li3V2(PO4)3 and a highly conductive solid polymer electrolyte made of polyphosphazene/PVDF-HFP/LiBOB [PVDF-HFP, poly(vinylidene fluoride-co-hexafluoropropylene)]. The components were chosen based on their low toxicity, systematic manufacturability, and (electro-)chemical matching in order to ensure ambient atmosphere battery assembly and to reach high flexibility, good safety, effective interfacial contacts, and high chemical and mechanical stability for the battery while in operation. The high energy density of the electrodes was enabled by a novel design of the self-standing anode and cathode in a way that a large amount of active particles are embedded in the carbon nanotube (CNT) bunches and on the surface of CNT fabric, without binder additive, additional carbon, or a large metallic current collector. The electrodes showed outstanding performance individually in half-cells with liquid and polymer electrolyte, respectively. The prepared flexible all-solid-state battery exhibited good rate capability, and more than half of its theoretical capacity can be delivered even at 1C at 30 °C. Moreover, the capacity retentions are higher than 75% after 200 cycles at different current rates, and the battery showed smaller capacity fading after cycling at 50 °C. Furthermore, the promising practical possibilities of the battery concept and fabrication method were demonstrated by a prototype laminated flexible cell.
RESUMEN
The effect of both nanoparticles and low molecular weight borate esters on the ionic conductivity of cross-linked polysiloxanes was systematically investigated by means of measuring conductivity spectra in the impedance regime at temperatures between -30 and 90 degrees C. Salt-in-polymer electrolytes were prepared by dissolving lithium triflate (LiSO(3)CF(3)) in comblike polysiloxanes bearing one methyl and one oligoether side group per silicon. An amount of 10 mol % of the oligoether side groups exhibited a terminal allytrimethoxysilane serving as a cross-linker moiety (T(0.1)OPS). Thus prepared polymer electrolyte membranes were completely amorphous and mechanically stable with an optimum conductivity value of 5.7 x 10(-5) S x cm(-1) at 15 wt % of lithium triflate (LiSO(3)CF(3)) at room temperature (T(0.1)OPS + 15 wt % LiSO(3)CF(3)). Further investigations concerned the influence of additives, i.e., nanosized ceramic fillers (alpha-Al(2)O(3) and SiO(2), up to 10 wt %) as well as two low molecular weight borate esters (tris(2-(2-methoxyethoxy)ethyl) borate (B2) and tris(2-(2-(2-methoxyethoxy)ethoxy)ethyl) borate (B3)) with maximum concentrations of 40 wt % as referred to polysiloxane T(0.1)OPS. The addition of borate esters resulted in a considerable increase of the conductivity, while still maintaining the mechanical stability. Optimum conductivities of 3.7 x 10(-5) and 1.6 x 10(-4) S x cm(-1) were measured for B2 and B3, respectively, at room temperature. A fit of the temperature-dependent DC conductivity by the empirical Vogel-Tammann-Fulcher (VTF) equation showed that there was an increased number density of mobile charge carriers in the case of borate esters as additives. However, the shape of the conductivity spectra in the dispersive regime changed considerably in going from nanoparticles as additives to borate esters. A careful and consistent modeling of the conductivity spectra and of the temperature dependence of the DC conductivity was done within the framework of the MIGRATION concept. The result was that the addition of borate esters to the polymer host most probably increased both number density of mobile charge carriers as well as their mobility.