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Batteries using inorganic solid electrolytes have many advantages related to electrolyte batteries, such as electrochemical stability, thermal stability, seismic resistance, impact resistance, no leakage and pollution problems, easy miniaturization and thin film production. An excellent inorganic solid electrolyte should have the following characteristics: (1) high lithium ion conductivity and almost negligible electronic conductivity within the lithium active state and environmental temperature range; (2) Must maintain stability under electrochemical reactions, especially at the interface in contact with lithium or lithium alloy negative electrodes; (3) In order to use it, solid-state electrolytes must be environmentally friendly, non-toxic, inexpensive, and easy to prepare. It is best to have a thermal expansion coefficient that matches the electrodes on both sides, at least not significantly different.

(1) Crystalline inorganic electrolyte

At present, crystalline inorganic electrolytes have shown high ionic conductivity in many reports, which can be divided into NASICON type, LISICON type, Thio LISICON type, perovskite type and other solid electrolytes. The structure of NASICON type solid electrolytes is generally M [A2b3O12]. Although NASICON type electrolytes have high ion conductivity, their contact with metal lithium is unstable due to the easy reduction of T production by metal lithium.

LISICON also has high ion conductivity, with a typical structure of Lisa. Zn1. GeO1sThio LISl CON type electrolytes. In order to improve the ion conductivity of the electrolyte, sulfur is used to replace oxygen in LISICON type electrolytes. New materials such as Li2GeS3, Li4GeS4, Li2ZnGeS4, etc. have an ion conductivity of up to 6.5× 10-5S/cm.

Although crystalline solid electrolytes have high ion conductivity, they are generally single crystal data. When used in ceramic electrolyte sheets, their ion conductivity is significantly reduced due to the ion diffusion resistance at the grain boundary. Moreover, crystalline solid electrolytes contain ions such as T, Si, Ge * that are easily reduced by metal lithium, causing reduction reactions at the interface when in contact with metal lithium, lithium alloys, and other highly reducing negative electrodes, Electrolyte instability.

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