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Figure 2.9 The evolutions of morphology of ceramic filler in SCEs.

      Source: Li et al. [94].

By combining the advantages of these two materials, i.e. ceramic filler and polymer material, new hybrid composite materials with high dielectric constants can be fabricated. Different types of inert ceramics had been incorporated into the polymer by blending the polymers with fillers, such as SiO₂ [101], Al₂O₃ [102], TiO₂ [103], zeolite, etc. In 1982, Weston and Steele firstly prepared a composite by mixing PEO with Al₂O₃ [104], proving that PEO after addition of fillers exhibited an improvement of mechanical properties and ionic conductivity even in a temperature exceeding 100 °C. The idea of adding ceramic fillers into polymer complex is to provide a stable solid matrix [104]. Composite polymeric materials containing fine ceramic particles are considered as heterogeneously disordered systems [105]. Later, Capuano et al. (1991) [106] studied the effects of the doping amount and particle size of LiAlO₂ powder on the conductivity of solid electrolyte. The conductivity achieved the highest after the doping amount of LiAlO₂ was around 10 wt.%. In other words, particle size of the inert ceramic material influenced to the conductivity of the SPE and which increased as the size is <10 μm [107]. As was reported, Al₂O₃ can also effectively decrease the crystallinity and glass transition temperature of PEO, proving that the decrease of polymer crystallinity promotes the improvement of ionic conductivity [102]. Liang et al. [108] reported that PEO‐PMMA‐based composite electrolyte exhibited an improvement of the ionic conductivity from 6.71 × 10⁻⁷ to 9.39 × 10⁻⁷ S/cm, in which PEO‐PMMA and nano Al₂O₃ were used as a host matrix and filler, respectively [108]. Moreover, SiO₂ is also a common inert ceramic filler material used in synthesizing SPE. A composite of a PEO matrix and SiO₂ fillers was reported and reached an ionic conductivity of 2 × 10⁻⁴ S/cm at ambient temperature, [109] with 2.5 wt.% filler loadings. In addition, SiO₂ can be designed as a three‐dimensional skeleton doped into polymers. In recent years, PEO‐Silica aerogel was reported to achieve high ionic conductivity of 6 × 10⁻⁴ S/cm and high modulus of 0.43 GPa [110]. The mechanical properties and ionic conductivity has been enhanced by controlling powder dispersion. In addition, some studies have integrated a variety of inorganic ceramics into the polymer, and the ionic conductivity has also been improved.

Fast ion conductor ceramics, also known as active inorganic electrolytes, exhibit a high ionic conductivity of up to 10⁻² S/cm at 25 °C. Composite of fast ion conductor ceramics with polymer can strengthen interfacial contact. Since 2009, polymer‐in‐ceramic (PIC) approach was introduced into the field of composite polymeric electrolytes [111]. It consists of introducing polymer salt complexes into porous ceramic structures. The studied systems exhibited excellent mechanical properties, high conductivities, and good stability vs Li metal electrodes under prolonged storage [111]. As was reported recently, composite electrolytes from “ceramic‐in‐polymer” (CIP) to PIC with different sizes of garnet particles are investigated for their effectiveness in dendrite suppression [112]. With a large specific surface area, nanoscale garnet ceramic fillers improve the transition rate of ions [113]. The PIC electrolyte with 80 vol% 5 μm Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) (PIC‐5 μm) shows the highest tensile strength of 12.7 MPa [113]. The morphology, distribution, and three‐dimensional structure of ceramic filler particles may affect the ionic conductivity of polymer composite electrolyte [114]. Cui et al. explored the different morphologies of LLZO to increase ionic transport [115]. These LLZO nanowires show an ionic conductivity of 6.05 × 10⁻⁵ S/cm at 30 °C. A polymer–ceramic composite electrolyte of PEO and Li_0.33La_0.557TiO₃ nanowires has been studied

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