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 solid-state composition comprising:
ionically conductive inorganic particles in a non-ionically conductive polymer matrix, wherein the composition has an ion conductivity of at least 1×10 −4 S·cm −1 .
2 . The composition of claim 1 , wherein the ionically conductive inorganic particles are at least 50% by weight of the composition.
3 . The composition of claim 1 , wherein the non-ionically conductive polymer matrix comprises a polymer binder.
4 . The composition of claim 3 , wherein the polymer binder is 1-5% by weight of the composition.
5 . The composition of claim 1 , wherein the non-ionically conductive polymer matrix is free of a polymer binder.
6 . The composition of claim 1 , wherein the non-ionically conductive polymer matrix is 2.5%-60% by weight of the composition.
7 . The composition of claim 1 , wherein the non-ionically conductive polymer matrix is at least 20% by weight of the composition.
8 . The composition of claim 1 , wherein the ionically conductive inorganic particles are sulfide glass particles.
9 . The composition of claim 1 , wherein the non-ionically conductive polymer matrix is polymerized in-situ.
10 . The composition of claim 1 , wherein the polymer network comprises a backbone selected from a polyolefin, a polysiloxane, a polystyrene, and a cyclic olefin polymer.
11 . The composition of claim 1 , wherein the polymer network comprises a polydimethylsiloxane (PDMS) backbone.
12 . The composition of claim 1 , wherein the polymer network comprises a polybutadiene (PBD) backbone.
13 . The composition of claim 1 , wherein the polymer network comprises a cured epoxy resin.
14 . The composition of claim 1 , wherein the polymer network comprises urea-urethane groups, urethane groups, or thiourethane groups.
15 . The composition of claim 1 , wherein the polymer network comprises a. poly(urethane), a poly(ureaurethane), poly(thiourethane), a poly(acrylate), a poly(methacrylate), a poly(rnaleimide), poly(acrylarnide), a poly(methacrylamide), a polyolefin, or a polystyrene
16 . The composition of claim 1 , wherein the composition comprises one or more unreacted reactants or byproducts of a polymerization reaction.
17 . The composition of claim 16 , wherein the unreacted reactant comprises isocyanate functional groups.
18 . The composition of claim 17 , wherein the isocyanate functional groups are blocked.
19 . The composition of claim 16 , wherein the unreacted reactant comprises a functional group selected from: an amine functional group, an alcohol functional group, a thiol functional group, and a blocked isocyanate.
20 . The composition of claim 16 , wherein the unreacted reactant comprises one or more functional cross-linkers.
21 . The composition of claim 16 , wherein unreacted reactant comprises a radical initiator.
22 . The composition of claim 16 , wherein the unreacted reactant comprises functional groups selected from one or more of: an acrylic functional group, a methacrylic functional group, an acrylamide functional group, a methacrylamide functional group, a styrenic functional group, an alkenyl functional group, an alkynyl functional group, a vinyl functional group, allyl functional group, and a maleimide functional group.
23 . The composition claim 16 , wherein unreacted reactant comprises functional groups selected from one or more of: epoxy resins, oxiranes, glycidyl groups, and alkene oxides.
24 . The composition of claim 1 , wherein the polymer network comprises one or more of:
1) —CH 2 CH(H/CH 3 )(R) where R═—C(O)—, —C(O)—NR—, —C 6 H 4 —, or
2) —NH—C(O)—NR—, where R is H, alkyl or aryl;
3) —NH—C(O)—O—; and
4) —NH—C(O)—S—.
25 . The composition of claim , wherein the non-ionically conductive polymer matrix does not include an added salt.
26 . A battery comprising:
an anode;
a cathode; and
a solid-state electrolyte comprising the solid-state electrolyte composition of any one of claim 1 .
27 . A solid-state electrode for use in an alkali ion or alkali metal battery, comprising
an inorganic phase comprising an ionically conductive amorphous inorganic material, an electrochemically active material, and an electronically conductive additive; and
and an organic phase comprising a non-ionically conductive polymer matrix.
28 . The solid-state electrode of claim 27 , wherein the non-ionically conductive polymer matrix is crosslinked.
29 . The solid-state electrode of claim 27 , wherein the electrochemically active material is selected from the group consisting of lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP) and lithium nickel cobalt manganese oxide (NCM).
30 . The solid-state electrode of claim 27 , wherein the electrochemically active material is selected from the group consisting of a carbon-containing material, a silicon-containing material, a tin-containing material, lithium, or a lithium alloyed metal.
31 . A method of forming an ionically conductive composite comprising:
mixing polymer matrix precursors and ionically conductive inorganic particles; and
initiating cross-linking in the mixture to form a polymer matrix, wherein cross-linking increases the ionic conductivity of the mixture by a factor of at least two.
32 . The method of claim 31 , wherein the cross-linking is performed under an ambient pressure.
33 . The method of claim 31 , wherein the cross-linking is performed under an applied external pressure of at least 10 MPa.