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.

Claims

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.sub.4), lithium tetrafluoroborate (LiBF.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium hexafluoro-arsenate (LiAsF.sub.6), lithium hexafluoroantimonate (LiSbF.sub.6), lithium hexafluorotantalate (LiTaF.sub.6), and lithium hexafluoroniobate (LiNbF.sub.6), ii) organic anion is selected from the group of lithium trifluoromethanesulfonate (LiCF.sub.3SO.sub.3), lithium perfluorobutylsulfonate (LiC.sub.4F.sub.9SO.sub.3), lithium bis(trifluoromethanesulfonyl)imide (LiC.sub.2F.sub.6NO.sub.4S.sub.2), lithium bis (perfluoro-ethane-sulfonyl)imide (Li(CF.sub.3CF.sub.2SO.sub.2).sub.2N), lithium tris(trifluoromethanesulfonyl) methide (C.sub.4F.sub.9LiO.sub.6S.sub.3), lithium pentafluoroethyltrifluoroborate (LiBF.sub.3(C.sub.2F.sub.5)), lithium bis(oxalato)borate (LiB(C.sub.2O.sub.4).sub.2), lithium tetra(pentafluorophenyl)borate (C.sub.24BF.sub.20Li), lithium fluoroalkylphosphate (LiPF.sub.3(CF.sub.3CF.sub.2).sub.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.sub.3).sub.2, LiAlSi.sub.4O.sub.10, LiNO.sub.3, NaNO.sub.3, CsNO.sub.3, RbNO.sub.3, KNO.sub.3, AgNO.sub.3, NH.sub.4NO.sub.3, Ba(NO.sub.3).sub.2, Sr(NO.sub.3).sub.2, Mg(NO.sub.3).sub.2, Ca(NO.sub.3).sub.2, Ni(NO.sub.3).sub.2, Co(NO.sub.3).sub.2, Mn(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, Ce(NO.sub.3).sub.3, Li.sub.1.3Al.sub.0.3Ti.sub.1.7(PO.sub.4).sub.3, Li.sub.1.5Al.sub.0.5Ge.sub.1.5(PO.sub.4).sub.3, Li.sub.7La.sub.3Zr.sub.2O.sub.12, Li.sub.0.33La.sub.0.557TiO.sub.3, Li.sub.2O—SiO.sub.2—TiO.sub.2—P.sub.2O.sub.5, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, BaTiO.sub.3, Ta.sub.2O.sub.5, ZrO.sub.2, Si.sub.3N.sub.4, SiC, PbTiO.sub.3, LiNbO.sub.3, AlN(Aluminum Nitride), Y.sub.2O.sub.3, HfO.sub.2, Li.sub.2O, Li.sub.3PO.sub.4, LiF, LiCl, Li.sub.2S—P.sub.2S.sub.5, and Argyrodite compounds including Li.sub.2S—P.sub.2S.sub.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.sub.2, Co.sub.3O.sub.4, SnO.sub.2, SiO.sub.2, SiOx, (0.5<x<1.5), ZnO, CuO, and Cu.sub.2O.

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.sub.4Ti.sub.5O.sub.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.sub.4F, e) polyanionic compounds; f), Sulfur (S.sub.8) 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.sub.2, LiNiCoAlO.sub.2, LiCoO.sub.2, LiMn.sub.2O.sub.4, LiFePO.sub.4, LiNi.sub.0.5Mn.sub.1.5O.sub.4, lithium-rich layered Li.sub.1+xM.sub.1−xO.sub.2, lithium-deficient layer-layer or layer-spinel oxide Li.sub.1-xM.sub.1-xO.sub.2, high-voltage olivine LiMPO.sub.4, and monolithic Li.sub.3M.sub.2(PO.sub.4).sub.3; b) high-voltage tavorite phosphate- and sulfate-based compounds selected from the consisting of LiyM.sub.xO.sub.4Z, 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.sub.2MPO.sub.4F and Li.sub.2-xMPO.sub.4F, 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.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] To obtain a better understanding of the features and advantages of the disclosed subject, a reference to the following description on illustrative embodiments, which the principles of the disclosed subject are utilized, and the accompanying drawings of which:

[0020] FIG. 1 shows a graphical representation of the cycling performance of one disclosed embodiment solid electrolyte with a capacity retention at 0.5 C;

[0021] FIG. 2 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.5 C;

[0022] FIG. 3 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.5 C;

[0023] FIG. 4 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.5 C;

[0024] FIG. 5 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0025] FIG. 6 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0026] FIG. 7 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0027] FIG. 8 shows a voltage profile in relation to a solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0028] FIG. 9 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0029] FIG. 10 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C.

[0030] FIG. 11 shows a voltage profile in relation to a different solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0031] FIG. 12 shows a voltage profile in relation to a different solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0032] FIG. 13 shows a voltage profile in relation to a different solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0033] FIG. 14 shows a voltage profile in relation to a different solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0034] FIG. 15 shows a voltage profile in relation to a different solid state electrolyte embodiment disclosed herein for a 1.sup.st cycling at 0.1 C;

[0035] FIG. 16 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0036] FIG. 17 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0037] FIG. 18 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0038] FIG. 19 shows a graphical representation of the cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0039] FIG. 20 shows a graphical representation of the discharge capacity in relation to cycling performance of another disclosed solid electrolyte embodiment with a capacity retention at 0.3 C;

[0040] FIG. 21 shows a graphical representation of voltage measurements over 1,100 hours for a disclosed solid electrolyte membrane.

[0041] FIG. 22 shows a graphical representation of electrochemical stability using linear scanning voltammetry with a current density (mA/cm.sup.2) vs potential (V) with a solid electrolyte membrane comprising of PAN/PEO/LiAsF.sub.6/AN;

[0042] FIG. 23 shows a data table of ionic conductivity values for various chemical composition embodiments of disclosed solid electrolyte membranes;

[0043] FIG. 24 is a data table of tensile stress values for free-standing (FS) and solid electrolyte membrane (SEM) coated on substrate (porous cellulose membrane); and

DETAILED DESCRIPTION OF THE DRAWINGS AND PREFERRED EMBODIMENTS

[0044] All the features of this disclosure and its preferred embodiments will be described in detail in connection with the following illustrative, but non-limiting, drawings and examples. Thus, the drawings provided herein are not intended to limit the scope and breadth of the disclosed materials and devices but serve to provide a few different embodiments thereof.

Example 1. Synthesis of Solid Electrolyte Membrane, [Free Standing] PAN/LiPF.SUB.6 .or LiAsF.SUB.6 .or LiTFSI/1,3-Dicyanopropane or 2-Methylglutaronitrile or Butyl cyanide

[0045] The following materials were used for synthesis of the solid electrolyte solution: Polyacrylonitrile (PAN, MW 150,000, Sigma Aldrich), 1,3-Dioxolan-2-one, Spodumene (LiAl(SiO.sub.3).sub.2) powders, Lithium Hexafluorophosphate (LiPF.sub.6, 97%+, TCI America), Lithium Hexafluoroarsenate (LiAsF.sub.6, 99%, Alfa Aesar), and Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 98%, TCI America), 1,3-Dicyanopropane, and 2-Methylglutaronitrile (2-Metylglutaronitrile, 99%, Sigma Aldrich)

[0046] In a glove box, a solution was prepared by first melting 1,3-Dioxolan-2-one at 70° C. and then adding PAN at 9-12% of 1,3-Dioxolan-2-one by mass. For complete dissolution, the mixture was stirred with a magnetic stirrer at 70° C. for 2 hours. When PAN fully dissolved, a lithium salt (LiPF.sub.6 or LiAsF.sub.6 or LiTFSI each) of 0.8M was added to this solution and was dissolved over 1 hour of stirring under the same conditions. An addition of 1,3-Dicyanopropane or 2-Metylglutaronitrile was made at an amount of 20% of total solution by mass and the solution was stirred for another 1 hour. Finally, the filler, Spodumene (LiAl(SiO.sub.3).sub.2) powder, was added at an amount of 3% of total solution by mass and stirred for an additional 1 hour. The completed solution was cast onto a clean sheet of aluminum foil adhered to a glass plate by drawing down the material with a doctor blade. The membrane casting was dried under vacuum conditions at room temperature for 2 hours.

[0047] Coin cells 2032 were assembled using solid electrolyte membrane prepared as described above with cathode electrode (NCA, NMC811) and anode electrode (lithium metal). Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.rd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using a voltage window of 3.0V to 4.3V.

[0048] FIG. 1 shows the cycling performance of the Example 1 solid electrolyte membrane with a capacity retention (%) at 0.5 C cycling. Both cells were prepared using NCA as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN/LiPFd/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. The cells were cycled at 0.5 C and demonstrated retention of 96% even after 50 cycles.

[0049] FIG. 2 shows cycling performance with a capacity retention (%) at 0.5 C cycling. The two cells were prepared using NCA as the cathode, solid electrolyte membrane comprising Free-Standing/PAN/LiAsF.sub.6/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. These cells demonstrated retention of 95%, 93% each even after 50 cycles.

[0050] FIG. 3 shows cycling performance with a capacity retention at 0.5 C cycling. The cell was prepared using NCA as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN/LiTFSI/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. The cell demonstrated retention of 100% after 50 cycles.

[0051] FIG. 4 shows cycling performance with a capacity retention for 50 cycles at 0.5 C cycling. The cell was prepared using NCA as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN/LiPF.sub.6/2-Metylglutaronitrile, and lithium metal of 200 μm thickness as the anode. The cells demonstrated retention of 85% after 50 cycles.

Example 2. Synthesis of Solid Electrolyte Membrane, [Free Standing] PAN-PEO/LiPF.SUB.6 .or LiAsF.SUB.6./1,3-Dicyanopropane or Butyl Cyanide

[0052] The following materials were used for synthesis of the solid electrolyte solution: 1,3-Dicyanopropane, Polyacrylonitrile (PAN, MW 150,000, Sigma Aldrich), Polyethylene Oxide (PEO, Alfa Aesar) 1,3-Dioxolan-2-one, Spodumene (LiAl(SiO.sub.3).sub.2) powder, Lithium Hexafluorophosphate (LiPF.sub.6, 97%+, TCI America), and Lithium Hexafluoroarsenate (LiAsF.sub.6, 99%, Alfa Aesar).

[0053] In a glove box, a solution was prepared by first melting 1,3-Dioxolan-2-one at 70° C. and then adding PAN at 9-12% of 1,3-Dioxolan-2-one by mass. For complete dissolution, the mixture was stirred with a magnetic stirrer at 70° C. for 2 hours. When PAN fully dissolved, PEO was added at 30% of PAN by mass and stirring was continued for an hour. A lithium salt (LiPF.sub.6 or LiAsF.sub.6) of 0.8M concentration in an amount matching was added to this solution and was dissolved over 1 hour of stirring under the same conditions. An addition of 1,3-Dicyanopropane was made at an amount of 20% of total solution by mass and the solution was stirred for another 1 hour. Finally, the filler, Spodumene (LiAl(SiO.sub.3).sub.2) powder, was added at an amount of 3% of total solution by mass and stirred for an additional 1 hour. The completed solution was cast onto a clean sheet of aluminum foil adhered to a glass plate by drawing down the material with a doctor blade. The membrane casting was dried under vacuum conditions at room temperature for 2 hours to create a dried solid electrolyte.

[0054] Coin cells 2032 were assembled using solid electrolyte membrane prepared from described above with cathode electrode such as NCA, NMC811 and anode electrode such as lithium metal.

[0055] Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.rd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using voltage window of 3.0V to 4.3V.

[0056] FIG. 5 shows cycling performance with a capacity retention for 50 cycles at 0.3 C cycling. Two coin cells were prepared using LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 (NMC811) as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN-PEO/LiPF.sub.6/1,3-Dicyanopropane, and lithium metal of 200 μm thickness as the anode. The cells demonstrated retention of 103%, 98% each even after 50 cycles.

[0057] FIG. 6 shows cycling performance with a capacity retention for 10 cycles at 0.3 C cycling. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN-PEO/LiAsF.sub.6/1,3-Dicyanopropane, and lithium metal of 200 μm thickness as the anode. The cell demonstrated retention of 117% after 10 cycles.

Example 3. SEM Coating on a Highly Porous Cellulose Membrane (PCM), Pan/LiPF.SUB.6 .or LiAsF.SUB.6 .or LiTFSI or LiPF.SUB.6.-LiTFSI/Butyl Cyanide or 1,4-Dicyanobutane or 2-Metylglutaronitrile or Butyl Cyanide

[0058] The following materials were used for synthesis of the solid electrolyte solution: Polyacrylonitrile (PAN, MW 150,000, Sigma Aldrich), 1,3-Dioxolan-2-one, Spodumene (LiAl(SiO.sub.3).sub.2) powder, Lithium Hexafluorophosphate (LiPF.sub.6, 97%+, TCI America), Lithium Hexafluoroarsenate (LiAsF.sub.6, 99%, Alfa Aesar), and Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 98%, TCI America), 1,3-Dicyanopropane, Butyl cyanide (BUTYL CYANIDE, 99.5%, Sigma Aldrich), 1,4-Dicyanobutane (99%, Sigma Aldrich), and 2-Methylglutaronitrile (2-Metylglutaronitrile, 99%, Sigma Aldrich)

[0059] In a glove box, a solution was prepared by first melting 1,3-Dioxolan-2-one at 70° C. and then adding PAN at 9-12% of 1,3-Dioxolan-2-one by mass. For complete dissolution, the mixture was stirred with a magnetic stirrer at 70° C. for 2 hours. When PAN was fully dissolved, a lithium salt (LiPF.sub.6 or LiAsF.sub.6 or LiTFSI or 60% LiTFSI-40% LiPF.sub.6 each) of 0.8M concentration in an amount matching was added to this solution and was dissolved over 1 hour of stirring under the same conditions. Butyl cyanide (1%) or 1,4-Dicyanobutane (20%) or 2-Methylglutaronitrile (20)% each were then added in an amount of 0.1-20% of total solution by mass and the solution was stirred for another 1 hour. The completed solution was cast onto a porous cellulose membrane by flattening the sheet on a glass plate and drawing down the material with a doctor blade. The membrane casting was dried under vacuum conditions at room temperature for 2 hours.

[0060] Coin cells 2032 were assembled using solid electrolyte membrane prepared from described above with cathode electrode such as NCA, NMC811 and anode electrode such as lithium metal.

[0061] Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.nd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using voltage window of 3.0V to 4.3V.

[0062] FIG. 7 shows cycling performance with a capacity retention (%) for 50 cycles at 0.3 C cycling. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of Porous Cellulose Membrane (PCM)/PAN-PEO/LiPF.sub.6/1,3-Dicyanopropane (Coating on porous cellulose membrane), and lithium metal of 200 μm thickness as the anode. The cell demonstrated retention of 97% after 50 cycles.

[0063] FIG. 8 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiAsF.sub.6/1,3-Dicyanopropane, and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 208 mAh/g, 183 mAh/g, 88.0% each.

[0064] FIG. 9 shows cycling performance with the capacity retention for 18 cycles at 0.3 C cycling. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising PCM/PAN/LiTFSI/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. The cell demonstrated retention of 98.4% after 18 cycles.

[0065] FIG. 10 shows cycling performance with the capacity retention for 19 cycles at 0.3 C cycling. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising PCM/PAN/LiTFSI-LiPF.sub.6/1,3-Dicyanopropane, and lithium metal of 200 μm thickness as the anode. The cell demonstrated retention of 93.3% after 19 cycles.

[0066] FIG. 11 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiTFSI-LiPF.sub.6/Butyl cyanide and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 199 mAh/g, 180 mAh/g, 90.1% each.

[0067] FIG. 12 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiTFSI-LiPF.sub.6, and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 229 mAh/g, 210 mAh/g, 92.1% each.

[0068] FIG. 13 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiTFSI-LiPF.sub.6/1,4-dicyanobutane and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 228 mAh/g, 211 mAh/g, 92.7% each.

[0069] FIG. 14 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiTFSI-LiAsF.sub.6/2-Metylglutaronitrile and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 225 mAh/g, 207 mAh/g, 91.7% each.

[0070] FIG. 15 shows a voltage profile for 1.sup.st cycling at 0.1 C. This cell was charged and discharged at 0.1 C for one cycle. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN/LiTFSI-LiAsF.sub.6/1,4-dicyanobutane/Butyl cyanide and lithium metal of 200 μm thickness as the anode. The obtained charge capacity, discharge capacity and efficiency were 226 mAh/g, 208 mAh/g, 91.8% each.

Example 4. [SEM Coating on PCM] PAN-PEO/LiPF.SUB.6 .or LiAsF.SUB.6./1,3-Dicyanopropane or Butyl Cyanide

[0071] The following materials were used for synthesis of the solid electrolyte solution: 1,3-Dicyanopropane, Polyacrylonitrile (PAN, MW 150,000, Sigma Aldrich), Polyethylene Oxide (PEO, Alfa Aesar) 1,3-Dioxolan-2-one, Spodumene (LiAl(SiO.sub.3).sub.2) powder, Lithium Hexafluorophosphate (LiPF.sub.6, 97%+, TCI America), and Lithium Hexafluoroarsenate (LiAsF.sub.6, 99%, Alfa Aesar).

[0072] In a glove box, a solution was prepared by first melting 1,3-Dioxolan-2-one at 70° C. and adding 10% of 1,3-Dioxolan-2-one by mass of PAN. For complete dissolution, the mixture was stirred with a magnetic stirrer at 70° C. for 2 hours. When PAN was fully dissolved, PEO was added 30% of PAN by mass and stirring was continued for an hour. To this solution was added a lithium salt (LiPF.sub.6 or LiAsF.sub.6) in an amount matching that of PAN 10% of 1,3-Dioxolan-2-one by mass and was dissolved over 1 hour of stirring under the same conditions. An addition of 1,3-Dicyanopropane was made at an amount of 20% of total solution by mass and the solution was stirred for another 1 hour. The completed solution was cast onto a porous cellulose membrane by flattening the sheet on a glass plate and drawing down the material with a doctor blade. The membrane casting was dried under vacuum conditions at room for 1-2 hours.

[0073] Coin cells 2032 were assembled using solid electrolyte membrane prepared from described above with cathode electrode such as NCA, NMC811 and anode electrode such as lithium metal.

[0074] Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.nd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using voltage window of 3.0V to 4.3V.

[0075] FIG. 16 shows cycling performance with a capacity retention (%) at 0.3 C cycling.

[0076] Three cells were prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN-PEO/LiPF.sub.6/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode at 0.3 C.

[0077] FIG. 17 shows cycling performance with a capacity retention (%). The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of PCM/PAN-PEO/LiAsF.sub.6/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. The cells were cycled at 0.3 C and demonstrated retention of 98% after 19 cycles.

Example 5. [Free Standing] PAN-Polyepoxides, LiPF.SUB.6., 1,3-Dicyanopropane or Butyl Cyanide

[0078] The following materials were used for synthesis of the solid electrolyte solution: 1,3-Dicyanopropane, Polyacrylonitrile (PAN, MW 150,000, Sigma Aldrich), 1,3-Dioxolan-2-one, Polyepoxides (epoxy resin), Spodumene (LiAl(SiO.sub.3).sub.2) powder, and Lithium Hexafluorophosphate (LiPF.sub.6, 97%+, TCI America).

[0079] In a glove box, a solution was prepared by first melting 1,3-Dioxolan-2-one at 70° C. and adding 10% of 1,3-Dioxolan-2-one by mass of PAN. For complete dissolution, the mixture was stirred with a magnetic stirrer at 70° C. for 2 hours. To this solution was added LiPF.sub.6 in an amount matching that of PAN 10% of 1,3-Dioxolan-2-one by mass and was dissolved over 1 hour of stirring under the same conditions. An addition of 1,3-Dicyanopropane was made at an amount of about 20% of total solution by mass and the solution was stirred for another 1 hour. The filler Spodumene (LiAl(SiO.sub.3).sub.2) was added at an amount of 3% of total solution by mass and stirred for an additional 1 hour. After the solution was completed, polyepoxides (epoxy resin and hardener) were mixed and then added to the SEM solution at an amount of 5% of the total weight, then was quickly mixed by hand and prepared for casting.

[0080] The completed solution was cast onto the surface of a clean glass plate, and another was cast onto a sheet of aluminum foil adhered to a glass plate. The casting was completed by drawing down the material with a doctor blade. The membrane casting was dried under vacuum conditions at room temperature for 2 hours to create a dried solid electrolyte.

[0081] Coin cells 2032 were assembled using solid electrolyte membrane prepared from described above with cathode electrode such as NCA, NMC811 and anode electrode such as lithium metal.

[0082] Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.nd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using voltage window of 3.0V to 4.3V.

[0083] FIG. 18 shows cycling performance with a capacity retention (%) at 0.3 C cycling. The cell was prepared using NMC811 as the cathode, solid electrolyte membrane comprising of Free-Standing/PAN/polyepoxides/LiPF.sub.6/1,3-Dicyanopropane/Butyl cyanide, and lithium metal of 200 μm thickness as the anode. The cycle performance shows retention of 80% after 50 cycles.

Example 6. [Direct Casting onto Cathode Electrode or Anode Electrode (Silicon+Graphite) or Lithium Metal Anode] PAN/LiPF.SUB.6./1,3-Dicyanopropane and/or Butyl Cyanide

[0084] An example containing one such, or any of the above solutions, where the method of casting is applied directly to a battery electrode instead of creating free-standing film. This direct casting method was applied to a cathode electrode (LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2, NMC811), to an anode electrode (25 wt % SiOx-75% graphite blended), and to a lithium metal anode. The Solid electrolyte solution was drawn down using a doctor blade to cast directly onto a sheet of the electrode. The membrane casting was dried under vacuum conditions at room temperature for 2 hours to create a dried solid electrolyte. Such a dried electrolyte membrane on cathode electrode can be used in unison to efficiently build battery cells.

[0085] Coin cells 2032 were assembled using solid electrolyte membrane as prepared and described above with cathode electrode such as NCA, NMC811 and anode electrode such as lithium metal.

[0086] Each coin cell was cycled at 0.1 C for 1.sup.st cycle, 0.2 C for 2.sup.nd cycle and 0.3 C from 3.sup.rd cycle to the end of cycling test using voltage window of 3.0V to 4.3V.

[0087] FIG. 19 shows cycling performance with a capacity retention (%) at 0.3 C cycling. The cell was prepared by directly casting on the cathode (NMC811) with solid electrolyte membrane comprising of PAN/LiPF.sub.6/1,3-Dicyanopropane/Butyl cyanide. The cycle performance shows retention of 91% after 50 cycles.

[0088] FIG. 20 shows cycling performance with a capacity retention (%) at 0.3 C cycling. The cell was prepared by directly casting on anode electrode (SiOx+Graphite blended) with solid electrolyte membrane comprising of PAN/LiPF.sub.6/1,3-Dicyanopropane/Butyl cyanide. The cycle performance shows retention of 91% after 50 cycles.

[0089] FIG. 21 shows cycling performance of lithium symmetric cell at 1 mA/cm.sup.2. The cell was prepared by directly casting on lithium metal anode with solid electrolyte membrane comprising of PAN/LiPF.sub.6/1,3-Dicyanopropane/Butyl cyanide. The cycle performance was herein measured by increasing the potential of cell until reaching 0.2V. The cell shows excellent lifetime measurements, with 1107 hours up to 0.2V.

[0090] Material Characterization

[0091] The ionic conductivity of a solid electrolyte membrane samples in a frequency ranges from 1 Hz to 1 MHz and a voltage amplitude of 10 mV, using two Stainless steel electrodes at room temperature (25 degree Celsius) using a Biologic SP300 potentiostat.

[0092] The electrochemical stability of a solid electrolyte membrane was measured using linear sweep voltammetry method in voltage range from 0 V to 5 V at a 10 mV/s scan rate using Biologic SP300 potentiostat.

[0093] Tensile stress of solid electrolyte membrane was measured with tensile speed of 10 mm/min. Specimen size is 1 cm(width)×5 cm (length). PAN/PEO/LiAsF.sub.6/1,4-Dicyanobutane.

[0094] FIG. 22 shows electrochemical stability measurements using linear scanning voltammetry with the current density (mA/cm.sup.2) vs potential (V) with solid electrolyte membrane comprising of PAN/PEO/LiAsF.sub.6/1,4-Dicyanobutane. It was measured from 0V to 5V and shows excellent electrochemical stability as current density of 0.018 mA/cm.sup.2 at 5V.

[0095] FIG. 23 is a table of ionic conductivity values for various composition of solid electrolyte membrane. All the samples exhibited good IC values of 1×10.sup.−4 S/cm or higher. In particular, sample #5 (PAN/LiTFSI(60)-LiPF.sub.6(40)/1,3-Dicyanopropane/Butyl cyanide), sample #9 (PAN/LiTFSI(60)—LiAsF.sub.6(40)/2-Metylglutaronitrile (20%)), and sample #10 (PAN/LiTFSI(60)-LiAsF.sub.6(40)/1,4-dicyanobutane (20%) containing two kinds of lithium salt show very excellent IC values more than 1×10.sup.−3 S/cm.

[0096] FIG. 24 is a table presenting different tensile stress values of solid electrolyte membranes disclosed herein. A first, free-standing solid electrolyte membrane exhibits a tensile stress value of 0.5 MPa. In contrast, also presented is the tensile stress value for a substrate coated with a disclosed solid electrolyte membrane measured over 15 times greater than for the free-standing membrane structure. Due to such an improved mechanical property (tensile stress), the inclusion of such a substrate-coated solid electrolyte membrane as disclosed herein within a lithium ion battery manufacturing process imparts a significantly improved manufacturing processability. Such an improvement further indicates the excellent properties obtained in relation to the specific type(s) of solid electrolyte membranes described above.

[0097] With these examples, experimental test results, and descriptions, there is provided a significantly improved solid state polymer electrolyte membrane for utilization with and within battery devices. The combination of cyano molecules, lithium salts, plasticizer(s), a base polymer, and a nano- or micro-filler, has been found to accord excellent performance in every needed criterium.

[0098] It should be understood that various modifications within the scope of this invention can be made by one of ordinary skill in the art without departing from the spirit thereof. It is therefore wished that this invention be defined by the scope of the appended claims as broadly as the prior art will permit, and in view of the specification if need be.