All-solid-state lithium-ion batteries replace traditional liquid organic electrolytes with solid electrolytes, offering a promising solution to long-standing battery safety issues. These batteries are considered an ideal power source for electric vehicles and large-scale energy storage systems due to their high energy density and improved stability.
**Polymer Solid Electrolyte**
Polymer solid electrolytes (SPEs) consist of a polymer matrix—such as polyethylene oxide (PEO), polyacrylonitrile (PAN), or polyvinylidene fluoride (PVDF)—combined with lithium salts like LiPF6 or LiClO4. They are favored for their lightweight, flexibility, and ease of processing, making them highly attractive in the field of solid-state batteries.
Common types of SPEs include PEO, PAN, PVDF, PMMA, PPO, PVDC, and single-ion polymer electrolytes. Among these, PEO remains the most widely studied due to its good compatibility with metallic lithium and its ability to dissociate lithium salts effectively.
However, one major challenge is that ion transport in polymer electrolytes occurs mainly in the amorphous regions. At room temperature, unmodified PEO has a high degree of crystallinity, which limits ionic conductivity and hinders performance at high current densities.
To address this, researchers have focused on reducing the crystallinity of PEO. One effective method is blending it with inorganic nanoparticles such as MgO, Al2O3, SiO2, zeolite, or montmorillonite. These fillers disrupt the polymer’s ordered structure, reduce crystallinity, and enhance ion mobility. Additionally, they can absorb moisture and improve mechanical strength.
Another innovative approach involves using metal-organic frameworks (MOFs), where transition metal ions and rigid organic linkers self-assemble into porous structures. MOFs offer high surface area and stability, making them promising candidates for next-generation electrolytes.
**Oxide Solid Electrolyte**
Oxide-based solid electrolytes are divided into crystalline and glassy (amorphous) forms. Crystalline types include perovskites, NASICON, LISICON, and garnet structures, while glassy electrolytes like LiPON are commonly used in thin-film batteries.
**Oxide Crystalline Solid Electrolyte**
Crystalline oxide electrolytes are known for their chemical stability and compatibility with atmospheric conditions, making them suitable for mass production. However, improving room-temperature ionic conductivity and electrode compatibility remain key challenges. Doping with heterovalent elements and element substitution are common strategies to enhance performance.
**LiPON Electrolyte**
Developed in 1992 by Oak Ridge National Laboratory, LiPON (lithium phosphorus oxynitride) is a thin-film electrolyte with excellent properties. It exhibits a room-temperature ionic conductivity of 2.3×10â»â¶ S/cm, a wide electrochemical window of 5.5 V vs. Li/Liâº, and good thermal stability. It is compatible with various cathode materials like LiCoOâ‚‚ and LiMnâ‚‚Oâ‚„, as well as lithium metal anodes.
The ionic conductivity of LiPON depends on its amorphous structure and nitrogen content. Increasing nitrogen improves conductivity. RF magnetron sputtering is a common method for producing LiPON films, though it has limitations in controlling composition and deposition speed. Alternative methods like pulsed laser deposition and electron beam evaporation are also being explored.
**Sulfide Crystalline Solid Electrolyte**
Thio-LISICON is a well-known sulfide electrolyte with a formula of Liâ‚„â‚‹â‚“Geâ‚â‚‹â‚“PxSâ‚„. It exhibits high ionic conductivity (up to 2.2×10â»Â³ S/cm at room temperature) and negligible electronic conductivity, making it a strong candidate for solid-state batteries.
**Sulfide Glass and Glass Ceramic Electrolyte**
Sulfide-based glass and glass ceramics, such as Li₂S–P₂S₅, offer high ionic conductivity, good thermal stability, and a wide electrochemical window. By partially crystallizing the glass, researchers can further enhance ionic conductivity. This approach, pioneered by Professor Tatsumi of Osaka Prefecture University, shows great potential for use in high-power and high-temperature solid-state batteries.
Features
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