Ultra-conductive polymer electrolytes and methods of synthesizing same

Abstract

Ultra-conductive solid-state polymer electrolytes are disclosed. A method of synthesizing the electrolytes involves doping graphene oxide sheets with ion transfer mediators, mixing the doped graphene oxide sheets into a base polymer electrolyte, and reorienting the doped graphene oxide sheets by applying an electrical field and / or a magnetic field while the polymer mixture is fluidal.

Description

ULTRA-CONDUCTIVE POLYMER ELECTROLYTES ANDMETHODS OF SYNTHESIZING SAMECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 636,991, titled “ULTRA-CONDUCTIVE POLYMER ELECTROLYTES AND METHODS OF SYNTHESIZING SAME” and filed April 22, 2024, which is incorporated herein by reference in its entirety.BACKGROUND

[0002] For safety, durability, robustness, and environmental protection reasons, it is desirable to replace organic liquid electrolytes with solid-state electrolytes. Whereas organic liquid electrolytes are prone to leakage and / or flammability, solid-state electrolytes have no issues of leakage and are generally non-volatile, mechanically and / or thermally stable, and / or non-flammable, making them much safer for both consumer electronics and large-scale energy storage applications. Polymeric solid-state electrolytes are also flexible, lightweight, and easy to handle. Unfortunately, however, solid-state electrolytes rarely match the performance of their organic liquid counterparts in terms of ionic conductivity. It follows that electrochemical storage devices utilizing solid-state electrolytes rarely match the performance of their counterparts utilizing organic liquid electrolytes in terms of specific energy, power, and capacity / capacitance.

[0003] Ionic conductivity is crucial for facilitating the movement of ions within the electrolyte. Generally, solid-state electrolytes have ionic conductivities at least an order of magnitude less than their organic liquid counterparts. Most solid-state electrolytes have ionic conductivities lower than 10'3siemens per centimeter (S / cm) at room temperature whereas most organic liquid electrolytes have ionic conductivities of at least 10'2S / cm at roomtemperature. Electrolyte systems possessing ionic conductivities greater than 10'2S / cm are referred to as “superionic” electrolytes.

[0004] There are two major groups of solid-state electrolytes: (1) polymeric electrolytes, which comprise a polymer matrix that provides a medium for ionic conduction, and (2) inorganic compound electrolytes, which comprise inorganic compounds rather than organic polymers. The ionic conductivity of solid-state electrolytes rarely reaches 10'2S / cm. Most solid-state electrolytes have ionic conductivities of less than 10'2S / cm. The low ionic conductivity of solid-state electrolytes limits their ability to replace their organic liquid electrolytes counterparts.

[0005] Generally, there are two approaches for improving the ionic conductivity of solid-state electrolytes: (1) tuning the local environment of free ions to promote easier dissociation and more frequent ion hopping and (2) creating fast transport pathways via doping inorganic particles and fibers. However, so far, both approaches have only resulted in marginal increases of ionic conductivity. Thus, there is still an unmet need for solid-state electrolytes comparable to organic liquid electrolytes in terms of ionic conductivity and methods of synthesizing same.

[0006] For supercapacitors utilizing solid-state electrolytes, if the ionic conductivity of the solid-state electrolyte can be increased by one or more orders of magnitude, the maximum power density and charge-discharge rate can potentially be increased by one or more orders of magnitude as well. By improving the ionic conductivity of the solid-state electrolyte by one or more orders of magnitude, the cell resistance, which is inversely correlated with the ionic conductivity of the electrolyte, can potentially be reduced by one or more orders of magnitude and the maximum power density and charge-discharge rate, which are inversely proportional to cell resistance, can potentially be increased by one or more orders of magnitude.

[0007] For supercapacitors, maximum specific power (Pmax) is given by Equation (1):where “Res ” is the equivalent series resistance, which is mainly a measurement of electrolyte resistance, and “F” is voltage. Notably, for supercapacitors utilizing solid-state electrolytes, if the ionic conductivity of the solid-state electrolyte can be increased by multiple orders of magnitude (or the equivalent series resistance decreased by multiple orders of magnitude), the specific power of the supercapacitors could potentially surpass that of traditional capacitors and / or internal combustion engines.

[0008] For Li-ion batteries comprising solid-state electrolytes and electronically conductive additives, the energy density and charge / discharge rate is controlled by the ionic conductivity of the electrolyte not by the electronic conductivity of the electronically conductive additive. This is because the ionic conductivity of the electrolyte is generally orders of magnitude less than the electronic conductivity of the electronically conductive additive. Thus, for Li-ion batteries utilizing solid-state electrolytes, if the ionic conductivity of the solid- state electrolyte was substantially improved (z.e., by orders of magnitude), the power and energy density at high-rate conditions could also potentially be increased by orders of magnitude.

[0009] The potential effect of substantially improving the ionic conductivity of solid- state electrolytes on the maximum specific power (x-axis) and maximum specific energy (y- axis) in supercapacitors and Li-ion batteries is schematically illustrated in FIG. 1.

[0010] For proton exchange membrane fuel cells and / or polymer electrolyte fuel cells, activation resistance, electrolyte resistance, and mass transfer resistance limit specific power. For proton exchange fuel cells and / or polymer electrolyte fuel cells utilizing solid-state electrolytes, substantially improving the ionic conductivity of the solid-state electrolyte would significantly reduce the electrolyte resistance and potentially reduce activation resistance thereby significantly improving specific power.

[0011] Other potential applications for solid-state electrolytes that are known to be limited by the low ionic conductivity of solid-state electrolytes include pure ionic circuitries (or iontronics) and ion thrusters.SUMMARY

[0012] The present disclosure is directed to ultra-conductive solid-state polymer electrolytes and methods of synthesizing same. The disclosed solid-state polymer electrolytes comprise at least partially oriented (ie., aligned) graphene oxide (GO) sheets doped with electron transfer mediators.

[0013] In accordance with aspects herein disclosed, a method is provided whereby an at least partially oriented (z.e., aligned) distribution of doped graphene oxide sheets in a solid- state polymer electrolyte is accomplished by exposing a polymer slurry comprising graphene oxide sheets doped with mediators and a base polymer to an electric field and / or a magnetic field while the slurry is still fluidal until the slurry is completely dried.

[0014] In accordance with the disclosed aspects, the solid-state polymer electrolytes have no issues of leakage and are non-volatile, mechanically and thermally stable, and nonflammable, while matching (or exceeding) the performance of their organic liquid counterparts in terms of ionic conductivity. They are also flexible, lightweight, and easy to handle.

[0015] This summary is provided to introduce and not limit the scope of the general inventive concepts, provided hereafter in further detail. The general inventive concepts encompass an improved polymer electrolyte, methods and systems of synthesizing same, and methods and systems of using same in rechargeable batteries, supercapacitors, and fuel cells.

[0016] A polymeric electrolyte comprising a base polymer electrolyte, graphene oxide, and an ion transfer mediator is disclosed.

[0017] In some embodiments, the graphene oxide is in the form of a plurality of graphene oxide sheets.

[0018] In some embodiments, the graphene oxide sheets are substantially aligned with each other.

[0019] In some embodiments, the graphene oxide sheets are substantially parallel to each each.

[0020] In some embodiments, the base polymer electrolyte comprises Polyvinylidene Fluoride (PVDF).

[0021] In some embodiments, the base polymer electrolyte is PVDF.

[0022] In some embodiments, the base polymer electrolyte comprises Bis(trifluoromethanesulfonyl)imide (TFSI).

[0023] In some embodiments, the base polymer electrolyte comprises PVDF-TFSI.

[0024] In some embodiments, the base polymer electrolyte is PVDF-TFSI.

[0025] In some embodiments, the base polymer electrolyte comprises Nation™.

[0026] In some embodiments, the base polymer electrolyte is Nafion™.

[0027] In some embodiments, the base polymer electrolyte comprises Polyvinyl Alcohol (PVA).

[0028] In some embodiments, the base polymer electrolyte is PVA.

[0029] In some embodiments, the base polymer electrolyte comprises H2SO4.

[0030] In some embodiments, the base polymer electrolyte comprises PVA and H2SO4.

[0031] In some embodiments, the base polymer electrolyte consists of PVA and H2SO4.

[0032] In some embodiments, the base polymer electrolyte comprises PTFE.

[0033] In some embodiments, the base polymer electrolyte is PTFE.

[0034] In some embodiments, the ion transfer mediator comprises a W containing ion transfer mediator.

[0035] In some embodiments, the ion transfer mediator is a W containing ion transfer mediator.

[0036] In some embodiments, the ion transfer mediator comprises SiWLi, the lithium salt of tungstosilicic acid (Li4Wi2Si04o). It may also include ferrocene, ferrocyanides, ferricyanides, Prussian Blue and analogous compounds.

[0037] In some embodiments, the ion transfer mediator is SiWLi.

[0038] In some embodiments, the ion transfer mediator comprises SiWH, or tungstosilicic acid (H4Wi2Si04o). It may also include ferrocene, ferrocyanides, ferricyanides, Prussian Blue and analogous compounds.

[0039] In some embodiments, the ion transfer mediator is SiWH.

[0040] In some embodiments, the ion transfer mediator comprises an Fe containing ion transfer mediator.

[0041] In some embodiments, the ion transfer mediator is an Fe containing ion transfer mediator.

[0042] In some embodiments, the ion transfer mediator comprises Prussian blue (ferrous ferricyanide).

[0043] In some embodiments, the ion transfer mediator is Prussian blue.

[0044] In some embodiments, the ion transfer mediator comprises Turbull’s blue.

[0045] In some embodiments, the ion transfer mediator is Turbull’s blue.

[0046] In some embodiments, the ion transfer mediator comprises organic quinone.

[0047] In some embodiments, the ion transfer mediator is organic quinone.

[0048] In some embodiments, the ion transfer mediator comprises a derivative of organic quinone.

[0049] In some embodiments, the ion transfer mediator is a derivative of organic quinone.

[0050] In some embodiments, the ion transfer mediator is selected from the group iodine, iodides, VOSO4, V2SO4, Fe(CN)6]4- Fe(CN)6]3- CuCl2, CuCl, CoCl2, C0CI3, FeBr3,FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetrachlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p- phenylenediamine, Phosphotungstic acid, Sulfanilic acid azo chromotrop (SA), or combinations thereof.

[0051] In some embodiments, the graphene oxide is doped with the ion transfer mediator.

[0052] In some embodiments, the polymeric electrolyte further comprises Styrenebutadiene rubber (SBR) glue.

[0053] In some embodiments, the polymeric electrolyte further comprises Carboxymethyl Cellulose (CMC).

[0054] In some embodiments, the polymeric electrolyte further comprises SiWH.

[0055] In some embodiments, the polymeric electrolyte further comprises HSW, which is the same as, or chemically and physically similar to, SiWH discussed above .

[0056] In some embodiments, the polymeric electrolyte has an ionic conductivity greater than 10'3siemens per centimeter (S / cm) at room temperature.

[0057] In some embodiments, the polymeric electrolyte has an ionic conductivity greater than 10'2siemens per centimeter (S / cm) at room temperature.

[0058] In some embodiments, the polymeric electrolyte has an ionic conductivity greater than 10'1siemens per centimeter (S / cm) at room temperature.

[0059] In some embodiments, the polymeric electrolyte has an ionic conductivity greater than 10 siemens per centimeter (S / cm) at room temperature.

[0060] In some embodiments, the weight ratio of the ion transfer mediator to graphene oxide is 5 to 20.

[0061] In another embodiment, a method of synthesizing a polymeric electrolyte is provided, the method comprising doping graphene oxide sheets with ion transfer mediators, mixing the doped graphene oxide sheets into a base polymer electrolyte, and reorienting the doped graphene oxide sheets in the polymer mixture.

[0062] In some embodiments, the base polymer electrolyte comprises PVDF.

[0063] In some embodiments, the base polymer electrolyte is PVDF.

[0064] In some embodiments, the base polymer electrolyte comprises TFSI.

[0065] In some embodiments, the base polymer electrolyte comprises PVDF-TFSI.

[0066] In some embodiments, the base polymer electrolyte is PVDF-TFSI.

[0067] In some embodiments, the base polymer electrolyte comprises Nafion™.

[0068] In some embodiments, the base polymer electrolyte is Nafion™.

[0069] In some embodiments, the base polymer electrolyte comprises PVA.

[0070] In some embodiments, the base polymer electrolyte is PVA.

[0071] In some embodiments, the base polymer electrolyte comprises H2SO4.

[0072] In some embodiments, the base polymer electrolyte comprises PVA and H2SO4.

[0073] In some embodiments, the base polymer electrolyte consists of PVA and H2SO4.

[0074] In some embodiments, the base polymer electrolyte comprises PTFE.

[0075] In some embodiments, the base polymer electrolyte is PTFE.

[0076] In some embodiments, the ion transfer mediators comprise W containing ion transfer mediators.

[0077] In some embodiments, the ion transfer mediators are W containing ion transfer mediators.

[0078] In some embodiments, the ion transfer mediators comprise SiWLi.

[0079] In some embodiments, the ion transfer mediators are SiWLi.

[0080] In some embodiments, the ion transfer mediators comprise SiWH.

[0081] In some embodiments, the ion transfer mediators are SiWH.

[0082] In some embodiments, the ion transfer mediators are Fe containing ion transfer mediators.

[0083] In some embodiments, the ion transfer mediators are Prussian blue.

[0084] In some embodiments, the ion transfer mediators are Turbull’s blue.

[0085] In some embodiments, the ion transfer mediators are organic quinone.

[0086] In some embodiments, the ion transfer mediators are a derivative of organic quinone.

[0087] In some embodiments, the ion transfer mediator is selected from the group iodine, iodides, VOSO4, V2SO4, Fe(CN)6]4- Fe(CN)6]3- CuCl2, CuCl, CoCl2, C0CI3, FeBr3, FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetrachlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p- phenylenediamine, Phosphotungstic acid, Sulfanilic acid azo chromotrop (SA), or combinations thereof.

[0088] In some embodiments, the step of doping graphene oxide sheets with ion transfer mediators comprises attaching ion transfer mediators to graphene oxide sheets using wet chemistry methods.

[0089] In some embodiments, the step of mixing the doped graphene oxide sheets into a base polymer electrolyte comprises using wet chemistry methods to prepare a polymer slurry.

[0090] In some embodiments, the method further comprises adding SBR glue to the polymer mixture.

[0091] In some embodiments, the method further comprises adding CarboxymethylCellulose (CMC) to the polymer mixture.

[0092] In some embodiments, the method further comprises adding SiWH to the polymer mixture.

[0093] In some embodiments, the method further comprises adding HSW to the polymer mixture.

[0094] In some embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to an electric field.

[0095] In some embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to an electric field while the polymer slurry is still fluidal.

[0096] In some embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to a magnetic field.

[0097] In some embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to a magnetic field while the polymer slurry is still fluidal.

[0098] In some embodiments, the weight ratio of the ion transfer mediator to graphene oxide is 5 to 20.

[0099] In some embodiments, the step of mixing the doped graphene oxide sheets into a base polymer electrolyte comprises dissolving PVDF into acetone by stirring on a hot plate, adding LiTFSI into the slurry, adding the doped graphene oxide into the slurry, stirring on a hot plate, and casting the slurry on a glass sheet under electrical field.[000100] In some embodiments, the weight ratio of the ion transfer mediators to the base polymer electrolyte is 0.25 to 1.[000101] In some embodiments, the suspension to solvent ratio of the polymer slurry is 0.1 g / ml to 0.2 g.ml.[000102] In some embodiments, the viscosity of the polymer slurry is 0.6 Pa- s to 0.9 Pa s.[000103] In some embodiments, the pH of the polymer slurry is 6.5 to 7.5.[000104] In some embodiments, the polymer slurry is stirred on a hot plate at 65 °C to 75°C.[000105] In some embodiments, the dielectric constant of the polymer slurry is 10 to 80.[000106] In some embodiments, the wettability of the polymer slurry is high.DESCRIPTION OF THE DRAWINGS[000107] The present invention is described in detail herein with reference to the attached drawings, wherein:[000108] FIG. 1 is a graph that illustrates the potential effect of the present invention on the maximum specific energy (y-axis) and maximum specific power (x-axis) of various electrochemical storage devices.[000109] FIG. 2 illustrates longitudinal coordination between motions of free ions in a polymer electrolyte doped with graphene oxide sheets doped with ion transfer mediators.[000110] FIG. 3 illustrates lateral coordination between motions of free ions in a polymer electrolyte doped with graphene oxide sheets doped with ion transfer mediators.[000111] FIG. 4 is a diagram showing a method of measuring the interaction between ionic and electronics flows called interface cell measurement (ICM) according to an exemplary embodiment.[000112] FIG. 5 is a graph showing electrochemical impedance spectroscopy (EIS) data for (1) an electrolyte membrane without ion transfer mediators, (2) an electrolyte membrane with ion transfer mediators, and (3) an electrolyte membrane with graphene oxide doped with ion transfer mediators.[000113] FIG. 6A is a side view of an electrical reorientation setup according to an exemplary embodiment.[000114] FIG. 6B is a plan view of an electrical reorientation setup according to an exemplary embodiment.[000115] FIG. 7A is a side view of a magnetic reorientation setup according to an exemplary embodiment.[000116] FIG. 7B is a plan view of a magnetic reorientation setup according to an exemplary embodiment.[000117] FIG. 8 is a diagram showing a method of measuring ionic and electronic conductivity simultaneously.[000118] FIG. 9 is a Bode plot showing electrochemical impedance (y-axis) as a function of frequency (x-axis) for (1) a “pristine” PVDF / LiTFSI polymer electrolyte, (2) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte, and (3) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte electrified with a static electrical field of 2,500 V / cm in the in-plane direction.[000119] FIG. 10 is a Nyquist plot showing electrochemical impedance spectroscopy (EIS) data for (1) a “pristine” PVDF / LiTFSI polymer electrolyte and (2) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte electrified with a static electrical field of 2,500 V / cm in the in-plane direction.[000120] FIG. 11 is a Bode plot showing electrochemical impedance (y-axis) as a function of frequency (x-axis) for (1) GO / Nafion™, (2) electrified GO / Nafion™, (3) electrified GO / Nafion™+SBR / CMC, (4) electrified GO / Nafion™+SiWH, and (5) commercial Nafion™.[000121] FIG. 12 is a Bode plot showing electrochemical impedance (y-axis) as a function of frequency (x-axis) for (1) PVA+H2SO4, PVA+H2SO4+GO+HSW, and (3) electrified PVA+H2SO4+GO+HSW.[000122] FIG. 13 shows a measure of ionic conductivity in PVDF / LiTFSI / GO / SiWLi electrified at 2000 to 3000 V.[000123] FIG. 14 shows DC current recorded from the sample of FIG. 13.[000124] FIG. 15 shows the effect of an electrical field on forming ultrahigh ionic conductive Nafion polymer.[000125] FIG. 16 is a transmission electron microscopy (TEM) micrograph at a low magnification showing domains of 5-10 nm in size.[000126] FIG. 17 is another TEM micrograph at an intermediate magnification showing alignment of linear particles along the indicated direction indicated by an arrow.[000127] FIG. 18 is another TEM micrograph showing semi-periodicity along the directions indicated by the two arrows.DETAILED DESCRIPTION[000128] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments belong. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the various embodiments, some currently preferred methods and materials are described herein. In the drawings, the thickness of the lines, layers, and regions can be exaggerated for clarity. It is to be noted that like numbers found throughout the figures denote like elements.[000129] As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.[000130] Unless otherwise indicated, all numbers expressing quantities of ingredients, chemical and molecular properties, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that can vary depending upon the desiredproperties sought to be obtained by the present exemplary embodiments. At the very least, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.[000131] Unless otherwise indicated, any element, property, feature, or combination of elements, properties, and features, can be used in any embodiment disclosed herein, regardless of whether the element, property, feature, or combination of elements, properties, and features was explicitly disclosed in the embodiment. It will be readily understood that features described in relation to any particular aspect described herein can be applicable to other aspects described herein provided the features are compatible with that aspect.[000132] Every numerical range given throughout this specification and claims will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.[000133] The following describes select aspects relating to improved polymeric solid- state electrolytes. The disclosed polymeric solid-state electrolytes can comprise at least partially ordered (z.e., aligned) graphene oxide sheets doped with electron transfer mediators. The following also describes methods whereby an at least partially ordered (z.e., aligned) distribution of graphene oxide sheets in a solid-state polymer electrolyte can be accomplished, as well as methods whereby the improved polymeric solid-state electrolytes can be used in supercapacitors, rechargeable batteries, and fuel cells.[000134] The ultra-conductive polymeric solid-state electrolytes and methods for synthesizing same disclosed herein provides for various improvements over conventional solid-state electrolytes and organic liquid electrolytes. The unique orientation (z.e., alignment) of graphene oxide sheets doped with electron transfer mediators provides for a polymeric solid- state electrolyte having a substantial improved ionic conductivity, which offers advantages overboth conventional solid-state electrolytes, which generally suffer from low ionic conductivity, and organic liquid electrolytes, which are prone to leakage and / or flammability.[000135] Without wishing to be bound to a theory, the inventors hypothesize that the interaction between ions and electrons flying between mediators attached to graphene oxide sheets creates coupled ions. The “flying” electrons strongly interact / correlate with free ions, which significantly reduces the activation energy for ion conduction in the electrolyte system. [000136] Turning to FIG. 2, the inventors hypothesize that ions along the graphene oxide sheet are coupled / correlated via electron exchanges between the mediators attached to the graphene oxide sheets.[000137] Turning to FIG. 3, the inventors hypothesize that ions located at different aligned graphene oxide sheets can also be correlated / coupled via electron exchanges between the mediators attached on those graphene oxide sheets.[000138] To create coupling between the ions, graphene oxide sheets, and electrons, it is believed that the ranges of the natural frequencies for the hopping on ions, the vibration of the graphene oxide sheets, and the electron exchanges must overlap. In the case of a GO-SiWLi doped PVDF / LiTFSI solid-state polymer electrolyte system, the “hopping” frequency of Li+is in the range of 106Hz and 108Hz, the vibration frequency of the multilayer (one to ten layers) graphene oxide sheet tens of nanometer in thickness is in the range of 107Hz and 1012Hz, and the electron exchange frequency of the mediator is in the range of 106Hz and 108Hz. Strong synchronizations within the solid-state electrolyte system are possible when the frequencies overlap.[000139] The inventors developed a method called interface cell measurement (ICM) to determine the optimal range for correlation between ion jump and electron exchange.[000140] Turning to FIG. 4, which schematically illustrates this method, a first (top) polymer electrolyte membrane containing free ions but no mediators and a second (bottom)polymer membrane containing ion transfer mediators but no free ions are pressed together. Both of the films are installed with four electrodes (two current supplying electrodes and two potential sensing electrodes) and both sets of electrodes are controlled independently with a potentiostat.[000141] Turning to FIG. 5, electrochemical impedance spectroscopy (EIS) data for (1) an electrolyte membrane without ion transfer mediators, (2) an electrolyte membrane with ion transfer mediators, and (3) an electrolyte membrane with graphene oxide doped with ion transfer mediators is shown.[000142] According to an exemplary embodiment, a method of synthesizing an ultra- conductive polymeric solid-state electrolyte comprises the following steps: (1) doping graphene oxide sheets with ion transfer mediators, (2) mixing the doped graphene oxide sheets into a base polymer electrolyte, and (3) reorienting (z.e., aligning) the doped graphene oxide sheets.[000143] In some embodiments, the step of doping graphene oxide nanosheets with ion transfer mediators comprises attaching ion transfer mediators to graphene oxide sheets using wet chemistry methods.[000144] It is important to control the density of mediators on the graphene oxide sheets, the polarization of the graphene oxide, and the electronic conductivity of the graphene oxide.[000145] The size, thickness, and oxidation state of the graphene oxide are also key parameters.[000146] In some embodiments, the ion transfer mediators comprise SiWLi, Prussian blue, Turbull’s blue, other analogues of Prussian blue, organic quinone, derivatives of organic quinones, iodine, iodides, VOSO4, V2SO4, Fe(CN)e]4_, Fe(CN)e]3“, CuCh, CuCl, C0CI2, C0CI3, FeBrs, FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetra-chlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p- phenylenediamine, Phosphotungstic acid, or Sulfanilic acid azo chromotrop (SA), or combinations thereof. In some embodiments, the ion transfer mediators consist of SiWLi,Prussian blue, analogues of Prussian blue, organic quinone, derivatives of organic quinones, iodine, iodides, VOSO4, V2SO4, Fe(CN)6]4-, Fe(CN)6]3- CuCl2, CuCl, C0CI2, C0CI3, FeBr3, FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetrachlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p- phenylenediamine, Phosphotungstic acid, or Sulfanilic acid azo chromotrop (SA). It is to be understood that other ion transfer mediators could be used as well and would fall within the scope of this disclosure.[000147] In some embodiments, the weight ratio of the ion transfer mediator to graphene oxide is 5 to 20.[000148] In some embodiments, the step of doping graphene oxide sheets with ion transfer mediators comprising dispersing graphene oxide in deionized water or in an organic solvent via sonicating and / or stirring, adding the ion transfer mediator(s) to the graphene oxide suspension, pouring the suspension onto a sheet to dry, and collecting the resulting material. In some embodiments, an acid or base is added to the graphene oxide suspension to achieve a desired pH. In some embodiments, the suspension is dried on a hot plate.[000149] In some embodiments, the step of mixing the doped graphene oxide sheets into a base polymer electrolyte comprises using wet chemistry methods to prepare a polymer slurry. In some embodiments, the polymer slurry is an aqueous polymer slurry.In some embodiments, the base polymer electrolyte comprises polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluorosulfonic acid (PFSA), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyethersulfone (PES), poly(methylmethacrylate) (PMMA), poly(3,4-ethylenedi oxythiophene) (PEDOT), polyurethane (PU), poly(acrylic acid) (PAA), and combinations thereof. In some embodiments, the base polymer electrolyte further comprises lithium bis(trifluoromethane)sulfonimide (LiTFSI), lithium bis(fhrorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPFe), lithium perchlorate (LiCICU), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (LiTf), and combinations and blends thereof. In some embodiments, the base polymer consists of PVDF / LiTFSI. In some embodiments, the ratio of PVDF to LiTFSI is about 1 : 1.[000150] In some embodiments, the step of mixing the doped graphene oxide sheets into a base polymer electrolyte comprises dissolving PVDF into acetone by stirring on a hot plate, adding LiTFSI into the slurry, adding the doped graphene oxide into the slurry, stirring on a hot plate, and casting the slurry on a glass sheet under electrical field.[000151] The concentration, viscosity, pH, temperature, dielectric constant, and wettability of the polymer slurry are also key parameters.[000152] In some embodiments, the weight ratio of the ion transfer mediators to the base polymer electrolyte is 0.25 to 1.[000153] In some embodiments, the suspension to solvent ratio of the polymer slurry is 0.1 g / ml to 0.2 g.ml.[000154] In some embodiments, the viscosity of the polymer slurry is 0.6 Pa- s to 0.9 Pa s. [000155] In some embodiments, the pH of the polymer slurry is 6.5 to 7.5.[000156] In some embodiments, the polymer slurry is stirred on a hot plate at 65 °C to 75°C.[000157] In some embodiments, the dielectric constant of the polymer slurry is 10 to 80.[000158] In some embodiments, the wettability of the polymer slurry is high. Turning toFIGS. 6A - 6B, in some embodiments, the step of reorienting the graphene oxide sheetscomprises exposing the polymer slurry to an electric field while the polymer slurry is still fluidal. In the electrical reorientation setup shown in FIGS. 6A- 6B, two copper foils are placed below a thin sheet. Slurry film is casted on the top of the sheet while an electrical field is applied. The sheet can be plastic, glass, or any other suitable material.[000159] In some embodiments, the strength of the electrical field is greater than 1,000 V / cm. In some embodiments, the strength of the electric field is 1,000 V / cm to 10,000 V / cm. 2,500 V / cm to 5,000 V / cm is preferred for maximining in-plane ionic conductivity. 5,000 V / cm to 10,000 V / cm is preferred for maximizing through-plane ionic conductivity.[000160] In some embodiments, the polymer slurry is electrified at 2,500V.[000161] In some embodiments, the polymer slurry is electrified between two (2) and five (5) hours.[000162] In some embodiments, the polymer slurry is covered while the electrical field is applied to allow slow drying.[000163] Turning to FIG. 7 A - 7B, in other embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to a magnetic field while the slurry is still fluidal. In the magnetic reorientation setup shown in FIGS. 7A - 7B, slurry film is casted on the top of the sheet while a magnetic field is applied. The sheet can be plastic, glass, or any other suitable material.[000164] In some embodiments, the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to an electric field and a magnetic field, while the slurry is still fluidal, sequentially or at the same time.[000165] Turning back to FIGS. 6A - 6B, in some embodiments, the electrical reorientation setup can comprise a moving doctor blade and a stationary sheet to control the thickness of the polymer slurry on the sheet and, thereby, at least partially control the drying rate of the polymer slurry. It is to be understood that the magnetic reorientation setup can alsocomprise a moving doctor blade and a stationary sheet and that other methods of controlling the thickness and / or drying rate of the polymer slurry would be known to one an ordinary skill in the art and would fall within the scope of this disclosure.[000166] Turning again to FIGS. 7A - 7B, in embodiments, the magnetic reorientation setup can comprise a stationary doctor blade and a moving sheet to control the thickness of the polymer slurry on the sheet and, thereby, at least partially control the drying rate of the polymer slurry. It is to be understood that the electrical reorientation setup can also comprise a stationary doctor blade and a moving sheet and that other methods of controlling the thickness and / or drying rate of the polymer slurry would be known to one an ordinary skill in the art and would fall within the scope of this disclosure.[000167] It is further to be understood that a moving doctor blade could also be used in combination with a moving plate and that any combination of a doctor blade, other suitable tools, a sheet, or other suitable substantially planar fixture capable of controlling the thickness of the polymer slurry could be used.[000168] Drying rate, thickness and viscosity of the polymer slurry, and temperature and humidity of the environment, are critical factors for reorienting (z.e., aligning) the doped graphene oxide sheets because the electrical and / or magnetic field(s) must be exerted while the casted polymer slurry is still fluidal.[000169] It is to be understood that other suitable methods of reorienting (z.e., aligning) graphene oxide sheets would fall within the scope of this disclosure.[000170] The inventors have discovered that by doping a base polymer with mediators anchored by graphene oxide sheets and then reorienting (z.e., aligning) the graphene oxide sheets, ionic superconductivity (ionic conductivity of 10'2S / cm or greater) can be realized.[000171] As used herein, in-plane total (ionic + electronic) conductivity and electronic conductivity can be measured using a four-point membrane cell. As used herein, in-plane ionicconductivity can be calculated by subtracting electronic conductivity from total (ionic + electronic) in-plane conductivity.[000172] As used herein, through-plane ionic conductivity and total (ionic + electronic) conductivity can be measured using a Swagelok® split cell. As used herein, electronic conductivity can be calculated by subtracting through plane ionic conductivity from the total (ionic + electronic) conductivity.[000173] As used herein, ionic and electronic conductivity of the polymer electrolyte can also be measured simultaneously using the method disclosed in Orikasa et al., Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution, Scientific Reports | 6:26382 | DOI: 10.1038 / srep26382, the entirety of which is incorporated herein by reference. In this method, one precise direct current (DC) source and two potentiostats are used. The setup is schematically illustrated in FIG. 8. The setup has to be placed in an Argon (Ar) purged glove box. After measuring the open circuit potentials of a first and second working electrode, a bias voltage is applied while the open circuit potentials are maintained by the two potentiostats. The bias is the electronic potential difference while the difference of the potentials detected using a first and second reference electrode is the ionic potential difference. Thus, using the definition of conductivity, both electronic and ionic conductivity can be evaluated simultaneously.[000174] Utilizing the above-described method of synthesizing a polymeric solid-state electrolyte, the inventors synthesized PVDF / LiTF Si-type, Nafion™-type, and PVA / H2SO4- type polymer electrolytes. Specifically, the inventors synthesized PVDF / LiTF Si-type, Nafion™-type, and PVA / FLSCL-type polymer electrolytes by using a slurry casting method and in some instances adding graphene oxide doped with ion transfer mediators and in other instances adding graphene oxide doped with ion transfer mediators and electrifying thepolymer mixture at 2,500 V / cm or 3,000 V / cm. The results are generally summarized in Table1.Table 1[000175] It can be seen that adding graphene oxide doped with ion transfer mediators improved the in-plane ionic conductivity of the PVDF / LiTFSI-type polymer electrolytes by a factor of about 20 (in-plane and Li+conductor) and that adding graphene oxide doped with ion transfer mediator and electrifying the polymer slurry at 3,000 V / cm improved the ionic conductivity of the PVDF / LiTFSI-type polymer electrolytes by a factor about 24 (in-plane) and about 2,800 (Li+conductor).[000176] Turning to FIG. 9, which is a Bode plot showing electrochemical impedance (y- axis) as a function of frequency (x-axis) for (1) a “pristine” PVDF / LiTFSI polymer electrolyte, (2) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte, and (3) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte electrified with a static electrical field of 2,500 V / cm in the in-plane direction, the average ionic conductivity is 0.0053 S / cm for the pristine PVDF / LiTFSI polymer electrolyte, 0.0124 S / cm for the PVDF / LiTFSI+SiWLi / GO polymer electrolyte, and 0.123S / cm for the electrified PVDF / LiTFSI+SiWLi / GO polymer electrolyte. Thus, the in-plane conductivity of the electrified PVDF / LiTFSI+SiWLi / GO polymer electrolyte is about 20 times greater than that of the pristine PVDF / LiTFSI polymer electrolyte.[000177] Turning next to FIG. 10, which is a Nyquist plot showing electrochemical impedance spectroscopy data for (1) a “pristine” PVDF / LiTFSI polymer electrolyte and (2) a PVDF / LiTFSI+SiWLi / GO polymer electrolyte electrified with a static electrical field of 2,500 V / cm in the in-plane direction, it can be seen that the Nyquist plots for the pristine PVDF / LiTFSI polymer electrolyte and the PVDF / LiTFSI+SiWLi / GO polymer electrolyte electrified at 2,500V are drastically different. The pristine PVDF / LiTFSI polymer electrolyte shows a large circle whereas the electrified PVDF / LiTFSI+SiWLi / GO polymer electrolyte shows a much smaller circle and equivalent series resistance (ESR). Data analyses and curve fittings yield a through-plane conductivity of 14.0 S / cm for the electrified PVDF / LiTFSI+SiWLi / GO and 0.005 S / cm for the pristine PVDF / LiTFSI. Thus, the through- plane ionic conductivity of the electrified PVDF / LiTFSI+SiWLi / GO is about 2,000 times greater than that of the pristine PVDF / LiTFSI polymer electrolyte.[000178] Turning back to Table 1, it can be seen that adding graphene oxide doped with ion transfer mediators improved the ionic conductivity of the Nafion™-type polymer electrolyte by a factor of about 5.8 and that adding graphene oxide doped with ion transfer mediator and electrifying the polymer slurry at 3,000 V / cm improved the ionic conductivity of the Nafion™-type polymer electrolyte by a factor of more than 275.[000179] The inventors also synthesized polymer electrolyte membranes using Nafion™ 117 solution and graphene oxide sheets with various additives. Specifically, 20 mg graphene oxide (single-layer graphene oxide powder, ASC Material) powder was added to 20 mL deionized water and then the mixture was sonicated for 30 minutes to obtain a well-dispersed solution. The well-dispersed solution was then vaporized at 60 °C for 12 hours to generate drygraphene oxide nanosheets. Next, the dried graphene oxide nanosheets were added to 10 mL Nation™ solution (Nation™- 117, Aldrich®, 5%) and the mixture was sonicated for 30 minutes to obtain a well-dispersed GO / Nafion™ suspension. Various additives, like SBR glue (MTI Corp.), Carboxymethyl Cellulose (CMC) (MTI Corp.), and Tungstosilicic acid hydrate (SiWH) (H4SiW12O40-26H2O, Aldrich, 99%) were selectively added to the GO / Nafion™ suspensions and stirred for 30 minutes as comparison groups. The details of the composition of the different groups are listed below in Table 2.Table 2[000180] Finally, the suspension was cast on a flat glass plate and dried on the hot plate. During the drying process, an electric field was applied to the glass plate and suspension. The output of the DC power supply was set to be 3,000 V and the electrical field was 3,000 V / cm. [000181] In order to measure area specific impedance of the resulting electrolyte membranes, the membranes were first cut into small pieces and measured. Then the samples were placed on a flat glass sheet and connected with platinum wires by 4 electrodes mode. Electrochemical impedance spectroscopy was then performed using Gamry Reference 3000.[000182] Turning to FIG. 11, the electrochemical impedance spectroscopy results are shown. It can be seen that all synthesized membranes show lower specific impedance than thecommercial Nafion™-117 membrane which was used as a baseline. Turning back to Table 2, the ionic conductivities evaluated using the area specific impedance data collected are provided. The Group #3 (electrified GO / Nafion™ + 30mg SBR + 30mg CMC) membrane had the highest ionic conductivity of 0.5456 S / cm which is more than 50 times greater than the ionic conductivity of the commercial Nafion™ 117 membrane.[000183] The inventors estimate that utilizing an electrified Nafion™ -type polymer electrolyte with doped graphene oxide in a traditional proton exchange membrane fuel cell will improve the specific power of the fuel cell by about an order of magnitude. Proton exchange membrane fuel cells have the highest specific energy among all electrochemical storage devices but typically have only about 5% of the specific power of internal combustion engines. Notably, the application of the described ultra-conductive polymer electrolytes to proton exchange membrane fuel cells will drastically shrink the gap between proton exchange membrane fuel cells and internal combustion engines.[000184] Polymer electrolyte membranes using PVA and H2SO4 (sulfuric acid) were also synthesized. Turning to FIG. 12, the electrochemical impedance spectroscopy results for these membranes are shown. It can be seen that the electrified electrolyte PVA+H2SO4+GO+HSW membrane shows substantially lower specific impedance than both the PVA+H2SO4 membrane and the non-electrified PVA+H2SO4+GO+HSW membrane.[000185] While Li-ion batteries and PEM fuel cells are two applications for the disclosed ultra-conductive polymer electrolytes, the disclosed Li-ion battery and PEM fuel cell applications are not intended to be limiting and it should be appreciated that the disclosed ultra- conductive polymer electrolytes can be used in other electrochemical storage devices, including but not limited to Na-ion batteries and Mg-ion batteries, all of which would fall within the scope of this disclosure.[000186] FIGS. 13-18 show the results of additional experimental trials. More specifically, the trials show conductivity, alignment, and periodicity in polymer samples with various chemistries and preparation.[000187] Turning first to FIG. 13, the figure presents a summary of ionic conductivity of the polymer system PVDF / LiTFSI / GO / SiWLi at various applied electrifications. More specifically, the samples comprise combinations of the constituents PVDF, LiTFSI, GO, SiWLi, and Mediator. We note that Mediator can inlclude SiWLi, among other suitable mediators.. Each sample is labeled in FIGS. 13-15 according to the following naming convention: <polymer constituents> / <applied voltage>. For example, polymer including PVDF, LiTFSI, GO, and Mediator subject to 2000V is labeled: “PVDF / LiTFSI / GO / Mediator / 2000V,” etc. Electrification voltages between 0-3000 V were applied during slurry drying of the polymer membrane. Seven samples were included in the study.[000188] As shown, the greatest ionic conductivity recorded was 684 S / cm for the PVDF / LiTFSEGO / Mediator sample electrified at 3000V (i.e., the sample labeled “PVDF / LiTFSI / GO / Mediator / 3000V”). This conductivity is quite high, certainly high enough to be considered conducting. For example, it is higher than the conductivity of carbon black. It is comparable to graphite’s conductivity.[000189] FIG. 13 also shows how high ionic conductivity can be obtained at higher electrical field in this materials system. When ionic conductivity is measured for samples with no electrical field applied during slurry drying (i.e., for sample “PVDF / LiTFSI / GO / Mediator” in FIG. 13), the ionic conductivity was 0.012 S / cm. When a field is applied corresponding to a voltage of 2000V to a sample with the same chemistry (i.e., sample “PVDF / LiTFSEGO / Mediator / 2000 V”), conductivity increases by more than a factor of threeto 0.042 S / cm. FIG. 13 also shows how the ionic conductivity increases further still to 684 S / cm when the applied voltage is increased to 3000 V (“PVDF / LiTFSI / GO / Mediator / 3000 V”). [000190] FIG. 14 presents current measured across a PVDF / LiTFSI / GO / SiWLi membrane (using the same naming convention applied above) when electrified at 3000 V during slurry drying. The ionic conductivity of this material was measured to be 684 S / cm. Conductivity was measured just after the AC measurement without changing electrode position. FIG. 14 shows results of current monitoring when a DC voltage of 0.5 V was applied between two center electrodes (not shown) for evaluating the electronic conductivity. The current measured was initially 4xl0'8A at t = 0s. After around 1 hour of testing (~ 3.5 x 103s), the current decreased to 5xl0'12A. During testing, the inter electrode voltage held at 0.5V. This corresponds to a final (end of test) electronic resistance of IxlO11ohm. The corresponds electronic conductivity was 5.88 x 10'10S / cm. This demonstrates that even when the ionic conductivity was 684 S / cm, the electronic conductivity remains small. In other words, these tests show how the polymer electrolyte’s behavior approximates that of a purely ionic conductor.[000191] FIG. 15 illustrates the effect of an applied electrical field on forming ultrahigh ionic conductive Nafion (“NF”) polymer. More specifically, the figure shows ionic conductivity as a function of the composition and electrification for Nafion based polymers cast on a glass sheet. An electrical voltage of 3500 V (indicated as “3.5 kV”) was applied during the drying process for the indicated polymer membranes.[000192] The Nafion-based samples had four principal constituents: NF, SiCh, HSW, and GO. FIG. 15 shows that the electrified sample with all four of these constituents (i.e., “NF / GO / SiO2 / HSW / 3.5kV”) exhibits the highest conductivity, specifically ultrahigh ionic conductivity. This sample had a measured conductivity in a range between 15 and 20 S / cm. All others exhibit conductivity of at least two orders of magnitude lower. This strongly suggeststhat all four NF components (NF, SiCL, HSW, and GO) should be present during electrification (in this range) for the polymer to exhibit ultrahigh ionic conductivity.[000193] FIG. 16 is a TEM micrograph at low magnification (50k*) showing domains d of 5-10 nm in size in a Nafion / SiO2 / GO / SWH / electrified at 3500V sample. FIG. 17 is another TEM micrograph of the same sample shown in FIG. 16 at an intermediate (150k*) magnification showing alignment of linear particles along the direction DI of the arrow. The figure shows semi-periodicity of linear particles. FIG. 18 is another TEM micrograph taken at an intermediate (500k*) magnification. This figure shows semi-periodicity in the two directions D2 and D3 as indicated by the arrows. Lines LI and L2 show the periodicity of the particles. While various inventive aspects, concepts, and features of the inventions have been described and illustrated herein as embodied in certain exemplary embodiments, these various aspects, concepts, and features may be used in many alternative embodiments, either individually or in various combinations and sub-combinations thereof. Unless expressly excluded herein all such combinations and sub-combinations are intended to be within the scope of the present inventions. Still further, while various alternative embodiments as to the various aspects, concepts and features of the inventions— such as alternative materials, structures, configurations, methods, circuits, devices and components, software, hardware, control logic, alternatives as to form, fit and function, and so on— may be described herein, such descriptions are not intended to be a complete or exhaustive list of available alternative embodiments, whether presently known or later developed. Those skilled in the art may readily adopt one or more of the inventive aspects, concepts or features into additional embodiments and uses within the scope of the present inventions even if such embodiments are not expressly disclosed herein. Additionally, even though some features, concepts or aspects of the inventions may be described herein as being a preferred arrangement or method, such description is not intended to suggest that such feature is required or necessary unless expressly so stated. Stillfurther, exemplary or representative values and ranges may be included to assist in understanding the present disclosure, however, such values and ranges are not to be construed in a limiting sense and are intended to be critical values or ranges only if so expressly stated. Still further, exemplary or representative values and ranges may be included to assist in understanding the present disclosure, however, such values and ranges are not to be construed in a limiting sense and are intended to be critical values or ranges only if so expressly stated. Parameters identified as “approximate” or “about” a specified value are intended to include both the specified value and values within 10% of the specified value, unless expressly stated otherwise. Further, it is to be understood that the drawings accompanying the present application may, but need not, be to scale, and therefore may be understood as teaching various ratios and proportions evident in the drawings. Moreover, while various aspects, features and concepts may be expressly identified herein as being inventive or forming part of an invention, such identification is not intended to be exclusive, but rather there may be inventive aspects, concepts and features that are fully described herein without being expressly identified as such or as part of a specific invention, the inventions instead being set forth in the appended claims. Descriptions of exemplary methods or processes are not limited to inclusion of all steps as being required in all cases, nor is the order that the steps are presented to be construed as required or necessary unless expressly so stated.

Claims

CLAIMSWhat is claimed is:

1. A polymeric electrolyte comprising: a base polymer electrolyte; graphene oxide; and an ion transfer mediator.

2. The polymeric electrolyte of claim 1, wherein the graphene oxide is in the form of a plurality of graphene oxide sheets.

3. The polymeric electrolyte of claim 2, wherein the graphene oxide sheets are substantially aligned with each other.

4. The polymeric electrolyte of claim 2, wherein the graphene oxide sheets are substantially parallel to each other.

5. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises PVDF.

6. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte is PVDF.

7. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises TFSI.

8. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises PVDF-TFSI.

9. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte is PVDF- TFSI.

10. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises Nafion™.

11. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte is Nafion™.

12. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises PVA.

13. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte is PVA.

14. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises H2SO4.

15. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises PVAand H2SO4.

16. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte consists of PVAand H2SO4.

17. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte comprises PTFE.

18. The polymeric electrolyte of claim 1, wherein the base polymer electrolyte is PTFE.

19. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises a W containing ion transfer mediator.

20. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is a W containing ion transfer mediator.

21. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises SiWLi.

22. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is SiWLi.

23. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises SiWH.

24. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises an Fe containing ion transfer mediator.

25. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is an Fe containing ion transfer mediator.

26. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprisesPrussian blue.

27. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is Prussian blue.

28. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises Turbull’s blue.

29. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is Turbull’s blue.

30. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises organic quinone.

31. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is organic quinone.

32. The polymeric electrolyte of claim 1, wherein the ion transfer mediator comprises a derivative of organic quinone.

33. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is a derivative of organic quinone.

34. The polymeric electrolyte of claim 1, wherein the ion transfer mediator is selected from the group iodine, iodides, VOSO4, V2SO4, Fe(CN)e]4“, Fe(CN)e]3“, CuCh, CuCl, C0CI2, C0CI3, FeBrs, FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetrachlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p-phenylenediamine, Phosphotungstic acid, Sulfanilic acid azo chromotrop (SA), or combinations thereof.

35. The polymeric electrolyte of claim 1, wherein the graphene oxide is doped with the ion transfer mediator.

36. The polymeric electrolyte of claim 1, further comprising SBR glue.

37. The polymeric electrolyte of claim 1, further comprising Carboxymethyl Cellulose(CMC).

38. The polymeric electrolyte of claim 1, further comprising SiWH.

39. The polymeric electrolyte of claim 1, further comprising HSW.

40. The polymeric electrolyte of claim 1, wherein the polymeric electrolyte has an ionic conductivity greater than 10'3siemens per centimeter (S / cm) at room temperature.

41. The polymeric electrolyte of claim 1, wherein the polymeric electrolyte has an ionic conductivity greater than 10'2siemens per centimeter (S / cm) at room temperature.

42. The polymeric electrolyte of claim 1, wherein the polymeric electrolyte has an ionic conductivity greater than 10'1siemens per centimeter (S / cm) at room temperature.

43. The polymeric electrolyte of claim 1, wherein the polymeric electrolyte has an ionic conductivity greater than 10 siemens per centimeter (S / cm) at room temperature.

44. The polymeric electrolyte of claim 1, wherein the weight ratio of the ion transfer mediator to graphene oxide is 5 to 20.

45. A method of synthesizing a polymeric electrolyte, the method comprising: doping one or more graphene oxide sheets with one or more ion transfer mediators; mixing the doped graphene oxide sheets into a base polymer electrolyte to form a polymer mixture; and reorienting the doped graphene oxide sheets in the polymer mixture.

46. The method of claim 45, wherein the base polymer electrolyte comprises PVDF.

47. The method of claim 45, wherein the base polymer electrolyte is PVDF.

48. The method of claim 45, wherein the base polymer electrolyte comprises TFSI.

49. The method of claim 45, wherein the base polymer electrolyte comprises PVDF-TFSI.

50. The method of claim 45, wherein the base polymer electrolyte is PVDF-TFSI.

51. The method of claim 45, wherein the base polymer electrolyte comprises Nafion™.

52. The method of claim 45, wherein the base polymer electrolyte is Nafion™.

53. The method of claim 45, wherein the base polymer electrolyte comprises PVA.

54. The method of claim 45, wherein the base polymer electrolyte is PVA.

55. The method of claim 45, wherein the base polymer electrolyte comprises H2SO4.

56. The method of claim 45, wherein the base polymer electrolyte comprises PVA andH2SO4.

57. The method of claim 45, wherein the base polymer electrolyte consists of PVA and H2SO4.

58. The method of claim 45, wherein the base polymer electrolyte comprises PTFE.

59. The method of claim 45, wherein the base polymer electrolyte is PTFE.

60. The method of claim 45, wherein the ion transfer mediators comprise W containing ion transfer mediators.

61. The method of claim 45, wherein the ion transfer mediators are W containing ion transfer mediators.

62. The method of claim 45, wherein the ion transfer mediators comprise SiWLi.

63. The method of claim 45, wherein the ion transfer mediators are SiWLi.

64. The method of claim 45, wherein the ion transfer mediators comprise SiWH.

65. The method of claim 45, wherein the ion transfer mediators are SiWH.

66. The method of claim 45, wherein the ion transfer mediators comprise Fe containing ion transfer mediators.

67. The method of claim 45, wherein the ion transfer mediators are Fe containing ion transfer mediators.

68. The method of claim 45, wherein the ion transfer mediators comprise Prussian blue.

69. The method of claim 45, wherein the ion transfer mediators are Prussian blue.

70. The method of claim 45, wherein the ion transfer mediators comprise Turbull’s blue.

71. The method of claim 45, wherein the ion transfer mediators are Turbull’s blue.

72. The method of claim 45, wherein the ion transfer mediators comprise organic quinone.

73. The method of claim 45, wherein the ion transfer mediators are organic quinone.

74. The method of claim 45, wherein the ion transfer mediators comprise a derivative of organic quinone.

75. The method of claim 45, wherein the ion transfer mediators are a derivative of organic quinone.

76. The method of claim 45, wherein the ion transfer mediator is selected from the group iodine, iodides, VOSO4, V2SO4, Fe(CN)6]4- Fe(CN)6]3- CuCl2, CuCl, CoCl2, C0CI3, FeBr3, FeBr2, [FcEIm][NTf2], l-ethyl-3-methylimidazolium bromide, methyl viologen (MV) / bromide, para-Benzoquinone (p-BQ), p-phenylenediamine (PPD), tetrachlorohydroquinone (TCHQ) and anthraquinone (AQ), hydroquinone (HQ), Ferrocene (Fc), p-phenylenediamine, Phosphotungstic acid, Sulfanilic acid azo chromotrop (SA), or combinations thereof.

77. The method of claim 45, wherein the step of doping the graphene oxide sheets with the ion transfer mediators comprises attaching the ion transfer mediators to the graphene oxide sheets using a wet chemistry method.

78. The method of claim 45, wherein the step of mixing the doped graphene oxide sheets into the base polymer electrolyte comprises using a wet chemistry method to prepare a polymer slurry.

79. The method of claim 45, further comprising adding SBR glue to the polymer mixture.

80. The method of claim 45, further comprising adding Carboxymethyl Cellulose (CMC) to the polymer mixture.

81. The method of claim 45, further comprising adding SiWH to the polymer mixture.

82. The method of claim 45, further comprising adding HSW to the polymer mixture.

83. The method of claim 45, wherein the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to an electric field.

84. The method of claim 45, wherein the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to an electric field while the polymer slurry is still fluidal.

85. The method of claim 45, wherein the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to a magnetic field.

86. The method of claim 45, wherein the step of reorienting the graphene oxide sheets comprises exposing the polymer slurry to a magnetic field while the polymer slurry is still fluidal.

87. The method of claim 45, wherein, the weight ratio of the ion transfer mediator to graphene oxide is 5 to 20.

88. The method of claim 45, wherein, the step of mixing the doped graphene oxide sheets into a base polymer electrolyte comprises dissolving PVDF into acetone by stirring on a hot plate, adding LiTFSI into the slurry, adding the doped graphene oxide into the slurry, stirring on a hot plate, and casting the slurry on a glass sheet under electrical field.

89. The method of claim 45, wherein, the weight ratio of the ion transfer mediators to the base polymer electrolyte is 0.25 to 1.

90. The method of claim 45, wherein, the suspension to solvent ratio of the polymer slurry is 0.1 g / ml to 0.2 g.ml.

91. The method of claim 45, wherein, the viscosity of the polymer slurry is 0.6 Pa s to 0.9 Pa s.

92. The method of claim 45, wherein, the pH of the polymer slurry is 6.5 to 7.5.

93. The method of claim 45, wherein, the polymer slurry is stirred on a hot plate at 65 °C to 75 °C.

94. The method of claim 45, wherein, the dielectric constant of the polymer slurry is 10 to 80.

95. The method of claim 45, wherein, the wettability of the polymer slurry is high.

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