Polymerized in-situ hybrid solid ion-conductive compositions
Provided herein are methods of forming solid-state ionically conductive composite materials that include particles of an inorganic phase in a matrix of an organic phase. The methods involve forming the composite materials from a precursor that is polymerized in-situ after being mixed with the particles. The polymerization occurs under applied pressure that causes particle-to-particle contact. In some embodiments, once polymerized, the applied pressure may be removed with the particles immobilized by the polymer matrix. In some implementations, the organic phase includes a cross-linked polymer network. Also provided are solid-state ionically conductive composite materials and batteries and other devices that incorporate them. In some embodiments, solid-state electrolytes including the ionically conductive solid-state composites are provided. In some embodiments, electrodes including the ionically conductive solid-state composites are provided.
1. A composition comprising:
a solid organic phase comprising a solid cross-linked polymer matrix, wherein the solid organic phase has substantially no added salts and is not ionically conductive; and
ionically conductive inorganic particles in the organic phase,
wherein the ionically conductive inorganic particles are lithium-containing inorganic particles or sodium-containing inorganic particles, wherein the composition has an ionic conductivity of at least 10 −4 S/cm at room temperature.
2. The composition of claim 1 , wherein contacting ionically conductive inorganic particles form ionically conductive pathways throughout the composition.
3. The composition of claim 1 , wherein the ionically conductive inorganic particles in the solid cross-linked polymer matrix exhibit the same crystallization temperature as pristine ionically conductive particles.
4. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise partially crystalline particles.
5. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise amorphous particles.
6. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise ceramic particles.
7. The composition of claim 1 , wherein the solid cross-linked polymer matrix comprises a polyolefin, a polysiloxane, polystyrene, a cyclic olefin polymer, poly(urethane), a poly(ureaurethane), poly(thiourethane), a poly(acrylate), a poly(methacrylate), a poly(maleimide), poly(acrylamide), a poly(methacrylamide), or a cured epoxy resin.
8. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise sulfides.
9. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise oxides.
10. The composition of claim 1 , wherein the ionically conductive inorganic particles comprise phosphates.
11. The composition of claim 1 , wherein the solid cross-linked polymer matrix comprises one or more of:
a) —CH 2 CH(H/CH 3 )(R) where R═—C(O)—O—, —C(O)—NR—, —C 6 H 4 —, or
b) —NH—C(O)—NR—, where R is H, alkyl, or aryl;
c) —NH—C(O)—O—; and
d) —NH—C(O)—S—.
12. The composition of claim 1 , wherein the solid cross-linked polymer matrix comprises a fully or partially saturated polyolefin.
13. The composition of claim 1 , wherein the solid cross-linked polymer matrix comprises polybutadiene.
14. A composition comprising:
a solid organic phase comprising a solid cross-linked polymer matrix, wherein the organic phase has substantially no added salts and is not ionically conductive; and
ionically conductive inorganic particles in the organic phase, wherein the composition has an ionic conductivity of at least 10 −4 S/cm at room temperature and wherein the solid cross-linked polymer matrix comprises a polyolefin, a polysiloxane, polystyrene, a cyclic olefin polymer, poly(urethane), a poly(ureaurethane), poly(thiourethane), a poly(acrylate), a poly(methacrylate), a poly(maleimide), poly(acrylamide), a poly(methacrylamide), or a cured epoxy resin.
15. The composition of claim 14 , wherein contacting ionically conductive inorganic particles form ionically conductive pathways throughout the composition.
16. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise partially crystalline particles.
17. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise amorphous particles.
18. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise fully crystalline particles.
19. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise sulfides.
20. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise oxides.
21. The composition of claim 14 , wherein the ionically conductive inorganic particles comprise phosphates.
22. The composition of claim 14 , wherein the solid cross-linked polymer matrix comprises a fully or partially saturated polyolefin.
23. The composition of claim 14 , wherein the solid cross-linked polymer matrix comprises polybutadiene.
24. A composition comprising:
a solid organic phase comprising a solid cross-linked polymer matrix, wherein the solid organic phase has substantially no added salts and is not ionically conductive; and
ionically conductive inorganic particles in the solid organic phase, wherein the composition has an ionic conductivity of at least 10 −4 S/cm at room temperature and wherein the ionically conductive inorganic particles are sulfide inorganic particles.
25. The composition of claim 24 , wherein contacting ionically conductive inorganic particles form ionically conductive pathways throughout the composition.
26. The composition of claim 24 , wherein the ionically conductive inorganic particles comprise partially crystalline particles.
27. The composition of claim 24 , wherein the ionically conductive inorganic particles comprise amorphous particles.
28. The composition of claim 24 , wherein the ionically conductive inorganic particles comprise ceramic particles.
29. The composition of claim 24 , wherein the solid cross-linked polymer matrix comprises one or more of:
a) —CH 2 CH(H/CH 3 )(R) where R═—C(O)—O—, —C(O)—NR—, —C 6 H 4 —, or
b) —NH—C(O)—NR—, where R is H, alkyl, or aryl;
c) —NH—C(O)—O—; and
d) —NH—C(O)—S—.