Solid electrolyte and preparation method thereof, and electrochemical device and electronic device comprising same
Embodiments of the present application relate to a solid electrolyte and a preparation method thereof, and an electrochemical device and an electronic device comprising the same. The solid electrolyte of the present application includes a solid electrolyte material being represented by the chemical formula of Li 1+2x−2y M y Ga 2+x P 1−x S 6 , where M is selected from the group consisting of Sr, Ba, Zn, Cd and a combination thereof, 0≤x≤0.2 and 0≤y≤0.05. Embodiments of the present application provides a solid electrolyte having good stability with lithium and ionic conductivity by forming the solid electrolyte using lower cost solid electrolyte materials and optimizing the material composition and a crystal structure thereof. At the same time, this also reduces the manufacturing costs of the solid electrolyte, and improves the structural stability of the solid electrolyte.
1. An electrolyte comprising a solid electrolyte, wherein the solid electrolyte comprises a solid electrolyte material being represented by a chemical formula of Li 1+2x−2y M y Ga 2+x P 1−x S 6 , wherein M is selected from a group consisting of Sr, Ba, Zn, Cd and a combination thereof, 0≤x≤0.2 and 0≤y≤0.05.
2. The electrolyte according to claim 1 , wherein the solid electrolyte material belongs to a monoclinic crystal system and has a crystal structure of a diamond-like structure.
3. The electrolyte according to claim 2 , wherein the crystal structure is composed of corner-sharing tetrahedral structural units.
4. The electrolyte according to claim 2 , wherein a space group of the crystal structure of the solid electrolyte material is Cc, and primitive vectors of a unit cell of the crystal structure are a=11.373±0.5 Å, b=6.946±0.5 Å and c=11.401±0.5 Å.
5. The electrolyte according to claim 1 , further comprising a binder, wherein a mass percentage of the binder is about 10% to about 20% based on a total mass of the solid electrolyte, and the binder is selected from a group consisting of polypropylene, polyethylene, poly(ethylene oxide), polyphenylene oxide, polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate ester, polyacrylic acid, polyacrylate salt, carboxymethyl cellulose sodium, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, styrene-butadiene rubber and a combination thereof.
6. The electrolyte according to claim 1 , wherein the solid electrolyte material has ionic conductivity of about 10 −6 S/cm to about 10 −4 S/cm and a lithium ion migration barrier of less than about 0.4 eV.
7. A method for preparing the electrolyte according to claim 1 , the method comprising the following steps:
mixing a lithium (Li)-containing material, an M-containing material, a gallium (Ga)-containing material, a phosphorus (P)-containing material and a sulfur (S)-containing material according to a stoichiometric ratio of Li 1+2x−2y M y Ga 2+x P 1−x S 6 to form a mixture, wherein M is selected from the group consisting of Sr, Ba, Zn, Cd and a combination thereof, 0≤x≤0.2 and 0≤y≤0.05;
heating the mixture to a solid phase reaction critical temperature, and then cooling to obtain the solid electrolyte material; and
forming the solid electrolyte by using the solid electrolyte material.
8. The method according to claim 7 , wherein the step of heating the mixture to a solid phase reaction critical temperature comprises heating the mixture to a range from about 550° C. to about 800° C.
9. The method according to claim 7 , wherein the step of forming the solid electrolyte by using the solid electrolyte material further comprises:
conducting a cold pressing or hot pressing process on the solid electrolyte material to form the solid electrolyte.
10. The method according to claim 9 , wherein the step of forming the solid electrolyte by using the solid electrolyte material further comprises: mixing a binder with the solid electrolyte material before conducting the cold pressing or hot pressing process, wherein the mass percentage of the binder is about 10% to about 20% based on the total mass of the solid electrolyte, and the binder is selected from the group consisting of polypropylene, polyethylene, poly(ethylene oxide), polyphenylene oxide, polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate ester, polyacrylic acid, polyacrylate salt, carboxymethyl cellulose sodium, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, styrene-butadiene rubber and a combination thereof.
11. An electrochemical device, comprising:
a cathode;
an anode; and
a solid electrolyte, wherein the solid electrolyte comprises a solid electrolyte material being represented by a chemical formula of Li 1+2x−2y M y Ga 2+x P 1−x S 6 , wherein M is selected from a group consisting of Sr, Ba, Zn, Cd and a combination thereof, 0≤x≤0.2 and 0≤y≤0.05.
12. The electrochemical device according to claim 11 , wherein the solid electrolyte material belongs to a monoclinic crystal system and has a crystal structure of a diamond-like structure.
13. The electrochemical device according to claim 12 , wherein the crystal structure is composed of corner-sharing tetrahedral structural units.
14. The electrochemical device according to claim 12 , wherein a space group of the crystal structure of the solid electrolyte material is Cc, and primitive vectors of a unit cell of the crystal structure are a=11.373±0.5 Å, b=6.946±0.5 Å and c=11.401±0.5 Å.
15. The electrochemical device according to claim 11 , further comprising a binder, wherein a mass percentage of the binder is about 10% to about 20% based on a total mass of the solid electrolyte, and the binder is selected from a group consisting of polypropylene, polyethylene, poly(ethylene oxide), polyphenylene oxide, polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate ester, polyacrylic acid, polyacrylate salt, carboxymethyl cellulose sodium, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, styrene-butadiene rubber and a combination thereof.
16. The electrochemical device according to claim 11 , wherein the solid electrolyte material has ionic conductivity of about 10 −6 S/cm to about 10 −4 S/cm and a lithium ion migration barrier of less than about 0.4 eV.
17. An electronic device, comprising a electrochemical device, wherein the electrochemical device comprises:
a cathode;
an anode; and
a solid electrolyte, wherein the solid electrolyte comprises a solid electrolyte material being represented by a chemical formula of Li 1+2x−2y M y Ga 2+x P 1−x S 6 , wherein M is selected from a group consisting of Sr, Ba, Zn, Cd and a combination thereof, 0≤x≤0.2 and 0≤y≤0.05.
18. The electronic device according to claim 17 , wherein the solid electrolyte material belongs to a monoclinic crystal system and has a crystal structure of a diamond-like structure, the crystal structure is composed of corner-sharing tetrahedral structural units, a space group of the crystal structure of the solid electrolyte material is Cc, and primitive vectors of a unit cell of the crystal structure are a=11.373±0.5 Å, b=6.946±0.5 Å and c=11.401±0.5 Å.
19. The electronic device according to claim 17 , further comprising a binder, wherein a mass percentage of the binder is about 10% to about 20% based on a total mass of the solid electrolyte, and the binder is selected from group consisting of polypropylene, polyethylene, poly(ethylene oxide), polyphenylene oxide, polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate ester, polyacrylic acid, polyacrylate salt, carboxymethyl cellulose sodium, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, styrene-butadiene rubber and a combination thereof.
20. The electronic device according to claim 17 , wherein the solid electrolyte material has ionic conductivity of about 10'S/cm to about 10'S/cm and a lithium ion migration barrier of less than about 0.4 eV.