Advanced solid electrooyte membranes and batteries made therefrom

Abstract

This disclosure relates generally to solid electrolyte membranes made from the combination of a polymer, a lithium salt group comprising of inorganic and/or organic anion, cyano molecules, a plasticizer having such a high dielectric solvent, and, optionally, a filler having nano/micron size particles to prevent the crystallization of such a polymer matrix. The resultant structures are solid electrolyte membranes exhibiting high ionic conductivity, thermal and electrochemical stability capable of enhanced cycling performance as well as high mechanical strength able to permit improved battery manufacturing properties.

What is claimed is: 
     
         1 . A solid electrolyte membrane comprising a reactive combination of constituents, said constituents comprising:
 a) at least one polymer or co-polymer selected from the group of polyacrylonitrile, polyethylene oxide, polyepoxides (epoxy resin), polymethyl methacrylate, poly(styrene-co-acrylonitrile), poly(acrylonitrile-co-butadiene-co-styrene), acrylonitrile butadiene rubber (NBR), and any combination thereof;   b) at least one lithium salt having i) an inorganic anion, ii) an organic anion, and iii) any combination of i) and ii);   c) at least one cyano-based molecule comprising i) a mono-cyano molecule, ii) a di-cyano molecule, iii) Tetracyanoethylene, iv) 2,5-Cyclohexadiene-1,4-diylidene and any cyano-derivatives thereof, or v) any combination of i), ii), iii), and iv);   d) at least one plasticizer present within at least one high dielectric solvent selected from the group of γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), acetonitrile (AN), propylene carbonate (PC), 1,3-Dioxolan-2-one, and any combination thereof; and   e) at least one nano- and/or micron-sized particle filler selected from the group of i) oxide, ii) carbide, iii) nitride, iv) halide based inorganic materials, v) lithophilic inorganic compounds, and a hybrid material selected from a metal or non-metal clay.   
     
     
         2 . The solid electrolyte membrane of  claim 1  wherein:
 b) said lithium salt having an i) inorganic anion is selected from the group of lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoro-arsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF 6 ), lithium hexafluorotantalate (LiTaF 6 ), and lithium hexafluoroniobate (LiNbF 6 ),
 ii) organic anion is selected from the group of lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium perfluorobutylsulfonate (LiC 4 F 9 SO 3 ), lithium bis(trifluoromethanesulfonyl)imide (LiC 2 F 6 NO 4 S 2 ), lithium bis (perfluoro-ethane-sulfonyl)imide (Li(CF 3 CF 2 SO 2 ) 2 N), lithium tris(trifluoromethanesulfonyl) methide (C 4 F 9 LiO 6 S 3 ), lithium pentafluoroethyltrifluoroborate (LiBF 3 (C 2 F 5 )), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ), lithium tetra(pentafluorophenyl)borate(C 24 BF 20 Li), lithium fluoroalkylphosphate (LiPF 3 (CF 3 CF 2 ) 3 ), lithium difluorophosphate, and lithium(difluorooxalato)borate; 
 
 c) i) said mono-cyano group is selected from the group of butyl cyanide, 2-methylglutaronitrile, α-methyl-valerodinitrile, and percyanoethylene, and
 ii) said di-cyano group is selected from the group of 1,4-Dicyanobutane, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,2-dicyanoethane, 1,3-dicyanopropane, 1,5-dicyanopetane, 1,6-dicyanohexane, trans-1,4-dicyano-2-butene, and trans-1,2-dicyanoethylene; and 
 
 e) iv) said halide based inorganic materials selected from the group consisting of LiAl(SiO 3 ) 2 , LiAlSi 4 O 10 , LiNO 3 , NaNO 3 , CsNO 3 , RbNO 3 , KNO 3 , AgNO 3 , NH 4 NO 3 , Ba(NO 3 ) 2 , Sr(NO 3 ) 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , Ni(NO 3 ) 2 , Co(NO 3 ) 2 , Mn(NO 3 ) 2 , Al(NO 3 ) 3 , Ce(NO 3 ) 3 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , Li O.33 La O.557 TiO 3 , Li 2 O-SiO 2 -TiO 2 -P 2 O 5 , Al 2 O 3 , SiO 2 , TiO 2 , BaTiO 3 , Ta 2 O 5 , ZrO 2 , Si 3 N 4 , SiC, PbTiO 3 , LiNbO 3 , AlN(Aluminum Nitride), Y 2 O 3 , HfO 2 , Li 2 O, Li 3 PO 4 , LiF, LiCl, Li 2 S-P 2 S 5 , and Argyrodite compounds including Li 2 S-P 2 S 5 -LiCl, and 
 v) said lithophilic inorganic compounds include cations selected from the group consisting of Al, Ag, Au, Zn, Mg, Si, Sn, Ge, In, Ba, Bi, B, Ca, Cd, Ir, Pd, Pt, Rh, Sb, Se, Sr, Te, Zn, AgO, MgO, MnO 2 , Co 3 O 4 , SnO 2 , SiO 2 , SiOx, (0.5<x<1.5), ZnO, CuO, and Cu 2 O. 
 
     
     
         3 . The solid electrolyte membrane of  claim 1  wherein said membrane is a free-standing film or a substrate-assisted film present on at least one of cathodes or anodes. 
     
     
         4 . The solid electrolyte membrane of  claim 2  wherein said membrane is a free-standing film or a substrate-assisted film present on at least one of cathodes or anodes. 
     
     
         5 . The solid electrolyte membrane of  claim 3  wherein said membrane exhibiting a thickness between 0.1 to 200 µm. 
     
     
         6 . The solid electrolyte membrane of  claim 4  wherein said membrane exhibiting a thickness between 0.1 to 200 µm. 
     
     
         7 . The solid electrolyte membrane of  claim 3  wherein said membrane is a substrate-assisted film. 
     
     
         8 . The substrate-assisted film of  claim 7  wherein said film is present on a substrate selected from the group consisting of an anode, a cathode, an anode-free substrate, a copper foil, a stainless-steel foil, and a separator. 
     
     
         9 . The substrate-assisted film of  claim 8  wherein said substrate is an anode selected from the group consisting of a-1) carbonaceous based materials such as graphite(s), hard carbon, soft carbon, carbon nanotube, silicon-graphite, carbon composite, and lithium titanate (Li 4 Ti 5 O 12 );
 a-2) lithium metal, lithium metal alloy, lithium metal composite, and any negative substrates in anode free cell configuration; and 
 a-3) a substrate without active materials including copper foil, copper mesh, stainless steel, nickel-plated copper, and any combination of anode active material free substrates. 
 
     
     
         10 . The substrate-assisted film of  claim 8  wherein said substrate is a cathode selected from the group consisting of a cathode selected from the group consisting of a) lithium metal oxides, b) high-voltage tavorite phosphate- and sulfate-based compounds, c) fluorophosphates, d) LiMSO 4 F, e) polyanionic compounds; f), Sulfur (S8) for lithium sulfur batteries and porous carbon cathode for lithium air batteries. 
     
     
         11 . The substrate-assisted film of  claim 10  wherein said: a) lithium metal oxide is selected from the group consisting of LiNiCoMnO 2 , LiNiCoAlO 2 , LiCoO 2 , LiMn 2 O 4 , LiFePO 4 , LiNi 0.5 Mn 1.5 O 4 , lithium-rich layered Li 1+x M 1-x O 2 , lithium-deficient layer-layer or layer-spinel oxide Li 1-x M 1-x O 2 , high-voltage olivine LiMPO 4 , and monolithic Li 3 M 2 (PO 4 ) 3; 
 b) high-voltage tavorite phosphate- and sulfate-based compounds selected from the consisting of LiyMxO 4 Z, wherein y = 0, 1, 2; M = Co, Ni, Mn, V, Fe; X = P, S; and Z = F, O, OH. 
 c) fluorophosphates selected from the group consisting of Li 2 MPO 4 F and Li 2-x MPO 4 F, wherein M is Co or Ni; and 
 e) polyanionic compounds are selected from the group consisting of lithium pyrophosphates, lithium diphosphates, and lithium silicates. 
 
     
     
         12 . The substrate-assisted film of  claim 8  wherein said substrate is a separator constituting materials selected from the group consisting of polyolefin, polyester, ceramic-embedded polyester, polyvinylidene fluoride (PVDF), ceramic-filled PVDF, ceramic-coated PVDF, polytriphenylamine, porous cellulose, hemi-cellulose, lignin, and ceramic-filled porous fiber. 
     
     
         13 . The solid electrolyte membrane of  claim 3  wherein said membrane is a free-standing film. 
     
     
         14 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 1 . 
     
     
         15 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 3 . 
     
     
         16 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 4 . 
     
     
         17 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 13 . 
     
     
         18 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 10 , wherein cathode-based solid electrolyte membrane comprises reactants of a) at least one mono and/or di-cyano molecule, and b) at least one lithium salt with at least one organic anion functional group, wherein the thickness of said cathode-based solid electrolyte membrane from about 0.1 µm to 200 µm. 
     
     
         19 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 9 , wherein said anode-based solid electrolyte membrane comprises reactants of a) at least one mono and/or di-cyano molecule, and b) at least one lithium salt with at least one organic anion functional group, wherein the thickness of said cathode-based solid electrolyte membrane from about 0.1 µm to 200 µm. 
     
     
         20 . A rechargeable lithium-ion battery comprising the solid electrolyte membrane of  claim 9 , wherein said anode is a copper foil and said anode-based solid electrolyte membrane comprises reactants of a) at least one mono and/or di-cyano molecule, and b) at least one lithium salt with at least one organic anion functional group, wherein the thickness of said cathode-based solid electrolyte membrane from about 0.1 µm to 200 µm.