EP4662723A1

EP4662723A1 - Rechargeable copper-zinc cell

Info

Publication number: EP4662723A1
Application number: EP24705248.3A
Authority: EP
Inventors: Nicholas Hyland KITCHIN; Darron Rolfe BRACKENBURY; Arun Tamil Selvan Vijayakumar
Original assignee: Cumulus Energy Storage Ltd
Current assignee: Cumulus Energy Storage Ltd
Priority date: 2023-02-09
Filing date: 2024-02-09
Publication date: 2025-12-17
Also published as: KR20250161552A; AU2024217972A1; WO2024166054A1

Abstract

A copper-zinc battery cell including a first pan and second pan, each of the pans forming a well for receiving an electrolyte. The battery cell may include a membrane comprising a 2D material composite which separates the respective wells of the first and second pan. The battery cell allows for scaling of a resultant battery pack for various applications.

Description

RECHARGEABLE COPPER-ZINC CELL

TECHNICAL FIELD OF THE PRESENT DISCLOSURE

[0001] The present disclosure relates to a rechargeable copper-zinc battery cell. In particular, the present disclosure relates to a copper-zinc battery cell with a pressed pan structure. The present disclosure further relates to a membrane separator for use in a battery cell.

BACKGROUND OF THE PRESENT DISCLOSURE

[0002] The electricity needs of the world are expected to grow 50% over the next 20 years, with 66% of this increase forecasted to be generated from renewable sources. Renewable sources may include, for example, wind and solar energy. However, the wind often blows and the sun often shines at times when energy needs are not high or nearly nonexistent. Additionally, the current electricity grid system is not designed to cope with variable and intermittent renewable energy generation. A buffer is needed between the generation of energy and demand so that the energy can be stored and delivered when needed. As such, there is an increasing need for grid-level energy storage to time-shift renewable energy generation, optimise transmission of energy, and manage demand for energy.

[0003] Development of a rechargeable battery using a zinc compound as a negative electrode material has been pursued. For example, an electrode has been developed by coating a mixture of zinc oxide and/or zinc powder and mercury or mercuric oxide on a current collector wherein the zinc oxide and/or zinc powder comprised from 80 to 90 wt.% of the mixture and the mercury and mercuric oxide comprised 5 to 20 wt%. However, the discharge capacity of the battery having this electrode gradually decreases if the battery is subjected to a repetitive chargedischarge operation even under the low current density of 2 to 3 mA/cm². In such an operation, it is difficult to use the battery for over 50 cycles, as the capacity is decreased to half the initial capacity. In contrast, rechargeable batteries in commercial use preferably keep more than half the initial capacity after at least the 200^th charging treatment.

[0004] Conventional cation and proton conducting membranes typically comprise a sheet of a homogeneous polymer, a laminated sheet of similar polymers, or a blend of polymers. A variety of polymers have been demonstrated to be cation conductors. An example of such a polymer is a family of perfluorosulfonic acids (PFSAs), which are solid organic super-acids, and membranes are produced as homogeneous sheets. All of these polymer materials rely on sulfonate functionalities (R-SO3-) as the stationary counter charge for the mobile cations (H+, Li+, Na+, etc.), which are generally monovalent.

SUMMARY OF THE DISCLOSURE

[0005] The present disclosure provides a copper-zinc battery cell including a first pan and second pan, each of the pans forming a well for receiving an electrolyte. The battery cell may include a membrane comprising a 2D material composite which separates the respective wells of the first and second pan.

[0006] In a first aspect of the disclosure, a pan for a battery cell is provided. The pan includes a generally continuous sidewall coupled to a base, the generally continuous sidewall and the base cooperating to define a well. A flange extends outwardly from the generally continuous sidewall. A metal covering is positioned on an interior face of the base, the metal covering being one of zinc or copper.

[0007] In a second aspect of the disclosure, a battery cell is provided. The battery cell includes a first electrode in contact with zinc; a second electrode in contact with copper; and a membrane separating the first electrode and the second electrode, the membrane comprising a 2D material composite.

[0008] In a third aspect of the disclosure, a battery cell is provided. The battery cell includes a first pan having a first base, a first sidewall extending from the first base so that the first base and the first sidewall define a first well, a first flange extending outwardly from the first base, and a zinc covering positioned on a first interior face of the first base. The battery cell further includes a second pan having a second base, a second sidewall extending form the second base so that the second base and the second sidewall define a second well, a second flange extending outwardly from the second base, and a copper covering positioned on a second interior face of the second base. The first pan and the second pan are arranged so that the zinc covering and the copper covering face each other.

[0009] In a fourth aspect of the disclosure, a battery system is provided. The battery system includes a plurality of battery packs, each battery pack having a plurality of battery cells arranged so that each battery pack includes: a first electrode in contact with zinc; a second electrode in contact with copper; and a membrane positioned between the first electrode and the second electrode. The zinc and the copper are separated from each other by the first and second electrode on one side and by the membrane on the other.

[0010] In a fifth aspect of the disclosure, a membrane is provided. The membrane includes a plurality of layers, including a first layer comprised of a 2D material and a second layer comprised of one of PVC/Silica and a proton exchange membrane.

[0011] In various aspects of the disclosure, the pan may include a port defined within the generally continuous sidewall.

[0012] In various aspects of the disclosure, the pan may define a rectangular shape.

[0013] In various aspects of the disclosure, the pan may be comprised of one of stainless steel or aluminium.

[0014] In various aspects of the disclosure, the pan may include a ridge positioned on the rim, the ridge protruding outwardly from the flange in a direction opposite of the well. The ridge may extend along the perimeter of the pan.

[0015] In various aspects of the disclosure, the flange may include a plurality of apertures.

[0016] In various aspects of the disclosure, the generally continuous sidewall may be beveled between the flange and the base.

[0017] In various aspects of the disclosure, the base may form at least one support rib.

[0018] In various aspects of the disclosure, a 2D material of the 2D material composite may comprise graphene. The graphene may comprise at least one crystal grain having a lower bound of 15 pm in diameter length. The graphene may comprise at least one crystal grain having a lower bound of 60 pm in diameter length. The graphene may include only one single crystal grain. The membrane may have a plurality of monolayers of graphene. The graphene may be polycrystalline.

[0019] In various aspects of the disclosure, the membrane may comprise a plurality of layers. The plurality of layers may include at least one layer of PVC/Silica. The plurality of layers may include at least one layer of a proton exchange membrane.

[0020] In various aspects of the disclosure, the membrane may be sans perfluoroalkyl substances and polyfluoroalkyl substances.

[0021] In various aspects of the disclosure, the first layer of the membrane may be comprised of a plurality of sublayers of monolayer graphene. [0022] In various aspects of the disclosure, the membrane may further comprise a third layer comprised of the other of PVC/Silica and the proton exchange membrane.

[0023] In various aspects of the disclosure, the plurality of layers of the membrane may include multiple layers comprised of a proton exchange membrane.

[0024] In various aspects of the disclosure, the membrane may be positioned within a fuel cell.

[0025] In various aspects of the disclosure, the membrane may be positioned within a battery.

[0026] In various aspects of the disclosure, the membrane may be positioned within a water treatment device.

[0027] In various aspects of the disclosure, the membrane may be positioned within an electrolyser.

[0028] In various aspects of the disclosure, the 2D material may be selected from a group consisting of graphene, graphyne, borophene, germanene, silicene, stanene, plumbene, phosphorene, antimonene, bismuthine, 2D alloys, 2D supracrystals, germanane, molybdenum disulphide, tungsten disulphide, and hexagonal boron nitride.

[0029] In various aspects of the disclosure, the first pan and the second pan may be physically coupled via fasteners extending through a first plurality of apertures defined by the first flange and a second plurality of apertures defined by the second rim. The battery cell may include a nylon separator positioned between each of the fasteners and the first pan and the second pan.

[0030] In various aspects of the disclosure, the first pan and the second pan may be coupled via clamps which clamp the first flange and the second flange together. The clamps may consist of a non- conductive material.

[0031] In various aspects of the disclosure, the battery cell may include a membrane positioned between the first pan and the second pan. At least one of the first pan and the second pan may include a ridge extending from one of the first flange and the second flange to facilitate clamping of the membrane between the first pan and the second pan. The membrane may comprise graphene. The membrane may be a graphene and polymer composite.

[0032] In various aspects of the disclosure, at least one of the first pan and the second pan may include a surface area enhancement.

[0033] In various aspects of the disclosure, the battery cell may include an electrolyte in each of the first well and the second well. [0034] In various aspects of the disclosure, the first pan may be an aluminium pan.

[0035] In various aspects of the disclosure, the second pan may be a stainless steel pan.

[0036] In various aspects of the disclosure, the battery cell may include an agitation mechanism positioned in at least one of the first pan and the second pan. The at least one port may be fluidly coupled to a collection container.

[0037] Additional features and advantages of the present disclosure will become apparent to those skilled in the art upon consideration of the following detailed description of the illustrative embodiments exemplifying the disclosure as presently perceived.

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The detailed description of the drawings particularly refers to the accompanying figures in which:

[0039] FIG. 1 is a perspective view of a first pan of a first embodiment of a battery cell;

[0040] FIG. 2 is a plan view of an exterior face of the first pan of FIG. 1;

[0041] FIG. 3 is a plan view of an interior face of the first pan of FIG. 1;

[0042] FIG. 4 is a side view of the first pan of FIG. 1;

[0043] FIG. 5 is a cross-sectional view of the first pan taken along line A- A of FIG. 3;

[0044] FIG. 6 is a close-up view of box B of FIG. 5;

[0045] FIG. 7 is a side view of the first embodiment of the battery cell including the first pan of FIG. 1 ;

[0046] FIG. 8A is a schematic of a first embodiment of a graphene composite membrane;

[0047] FIG. 8B is a schematic of a second embodiment of a graphene composite membrane;

[0048] FIG. 9 is a plan view of an exterior face of a first pan of a second embodiment of a battery cell;

[0049] FIG. 10 is a plan view of an interior face of the first pan of FIG. 9;

[0050] FIG. 11 is a side view of the first pan of FIG. 9;

[0051] FIG. 12 is a cross-sectional view of the first pan taken along line C-C of FIG. 9;

[0052] FIG. 13 is a cross-sectional view of the first pan taken along line D-D of FIG. 12;

[0053] FIG. 14 is a side view of a battery cell including the first pan of FIG. 9;

[0054] FIG. 15 is an end view of a battery cell including the first pan of FIG. 9; [0055] FIG. 16 is a graphical flow chart illustrating a method for creating a membrane;

[0056] FIG. 17 is a graph providing the voltage versus time plot of a six-cell series operating for over 150 continuous hours according to Example 1;

[0057] FIG. 18 is a graph providing the current profile over time according to Example 1 ;

[0058] FIG. 19A is a graph of an expanded view of five initial cycles of the potential plot of FIG. 17;

[0059] FIG. 19B is a graph of an expanded view of five final cycles of the potential plot of FIG. 17;

[0060] FIG. 20A is a graph of an expanded view of five initial cycles of the current profile of FIG. 18;

[0061] FIG. 20B is a graph of an expanded view of five final cycles of the current profile of FIG. 18;

[0062] FIG. 21 is a series of graphs providing the resulting voltage and current (mA) versus time plot for battery cells containing a variety of membranes according to Example 2; [0063] FIG. 22 is a series of graphs providing the resulting voltage and current (mA) versus time plot for battery cells containing a variety of membranes according to Example 3;

[0064] FIG. 23 is a series of graphs providing the results of a Raman Spectrometry analysis of a first area of a first composite membrane according to Example 4;

[0065] FIG. 24 is a series of graphs providing the results of a Raman Spectrometry analysis of a second area of the first composite membrane according to Example 4;

[0066] FIG. 25 is a series of graphs providing the results of a Raman Spectrometry analysis of a third area of the first composite membrane according to Example 4;

[0067] FIG. 26 is a series of graphs providing the results of a Raman Spectrometry analysis of a first area of a second composite membrane according to Example 5;

[0068] FIG. 27 is a series of graphs providing the results of a Raman Spectrometry analysis of a second area of the second composite membrane according to Example 5;

[0069] FIG. 28 is a series of graphs providing the results of a Raman Spectrometry analysis of a third area of the second composite membrane according to Example 5;

[0070] FIG. 29 is a series of graphs providing the results of a Raman Spectrometry analysis of a first area of a third composite membrane according to Example 6; [0071] FIG. 30 is a series of graphs providing the results of a Raman Spectrometry analysis of a second area of the third composite membrane according to Example 6;

[0072] FIG. 31 is a series of graphs providing the results of a Raman Spectrometry analysis of a third area of the third composite membrane according to Example 6;

[0073] FIG. 32 is a series of graphs providing the results of a Raman Spectrometry analysis of a first area of a fourth composite membrane according to Example 7;

[0074] FIG. 33 is a series of graphs providing the results of a Raman Spectrometry analysis of a second area of the fourth composite membrane according to Example 7;

[0075] FIG. 34 is a series of graphs providing the results of a Raman Spectrometry analysis of a third area of the fourth composite membrane according to Example 7;

[0076] FIG. 35 A is a first graph providing the measured potential difference across a variety of membranes including an anionic exchange membrane at a variable current density according to Example 8;

[0077] FIG. 35B is a second graph providing the measured potential difference across the variety of membranes according to Example 8 at a variable current density without results corresponding with the anionic exchange membrane of FIG. 35 A;

[0078] FIG. 36 is a graph providing the measured copper ion cross-over across a variety of membranes at a constant current density according to Example 9;

[0079] FIG. 37A is a TEM image of a first sample of a membrane including graphene according to Example 10;

[0080] FIG. 37B is a 5x zoom image of the first sample of FIG. 37A;

[0081] FIG. 37C is a 4x zoom image of a first region of the first sample of FIG. 37A;

[0082] FIG. 37D is a 2x zoom image of the first region of the first sample of FIG. 37A, including an exemplary aperture for conducting SAED;

[0083] FIG. 37E is a 1 Ox zoom image of the exemplary aperture of FIG. 37D;

[0084] FIG. 37F is an SAED image of the exemplary aperture of FIG. 37D;

[0085] FIG. 37G is a graph indicating the gray value over the distance across the measured area, corresponding to the SAED image of FIG. 37F;

[0086] FIG. 37H is an SAED image of a second area of the first region of the first sample of FIG. 37A; [0087] FIG. 371 is a graph indicating the gray value over the distance across the measured area, corresponding to the SAED image of FIG. 37H;

[0088] FIG. 38A is a 4x zoom image of a second region of the first sample of FIG. 37A;

[0089] FIG. 38B is an SAED image of the second region of the first sample of FIG. 38 A;

[0090] FIG. 39A is a TEM image of a second sample of a membrane including graphene according to Example 10;

[0091] FIG. 39B is a 2x zoom image of the second sample of FIG. 39A;

[0092] FIG. 39C is a 5x zoom image of a first region of the second sample of FIG. 39B;

[0093] FIG. 39D is an SAED image of the first region of the second sample of FIG. 39B;

[0094] FIG. 39E is a 5x zoom image of a second area of the first region of the second sample of FIG. 39B;

[0095] FIG. 39F is an aperture of the second area of the first region of the second sample of FIG. 39B;

[0096] FIG. 39G is an SAED image of the second area of the first region of the second sample of FIG. 39B;

[0097] FIG. 40A is a 5x zoom image of a second region of the second sample of FIG. 39B;

[0098] FIG. 40Bis a lOx zoom image of the second region of the second sample of FIG. 40A;

[0099] FIG. 40C is an SAED image of the second region of the second sample of FIG. 40A;

[00100] FIG. 40D is a graph indicating the gray value over the distance across the measured area, corresponding to the SAED image of FIG. 40C;

[00101] FIG. 40E is an SAED image of a second area of the second region of the second sample of FIG. 40A;

[00102] FIG. 40F is a graph indicating the gray value over the distance across the measured area, corresponding to the SAED image of FIG. 40E;

[00103] FIG. 41 A is a 5x zoom image of a third region of the second sample of FIG. 39B; [00104] FIG. 41B is an SAED image of the third region of the second sample of FIG. 41 A;

[00105] FIG. 41 C is a graph indicating the gray value over the distance across the measured area, corresponding to the SAED image of 41B;

[00106] FIG. 42A is a TEM image of a first sample of a membrane including graphene according to Example 11 and SAED images corresponding to a variety of regions of the first sample; [00107] FIG. 42B is a TEM image of a subset of regions of the first sample of FIG. 42A, including additional SAED images corresponding to a second variety of regions of the first sample of FIG. 42A;

[00108] FIG. 42C is a map of grain boundaries and crystal grains present in the first sample of FIG. 42A;

[00109] FIG. 43A is a TEM image of a second sample of a membrane including graphene according to Example 11 and SAED images corresponding to a variety of regions of the second sample;

[00110] FIG. 43B is a map of grain boundaries and crystal grains present in the second sample of FIG. 43 A;

[00111] FIG. 43 C is a TEM image indicating additional areas of a region of the second sample of FIG. 43 A subjected to SAED imaging, including SAED images corresponding to the additional areas measured;

[00112] FIG. 44A is a TEM image of a first sample of a membrane including graphene according to Example 12;

[00113] FIG. 44B is a 5x zoom image of a first region of the first sample of FIG. 44A;

[00114] FIG. 44C is an SAED image of the first region of the first sample of FIG. 44B;

[00115] FIG. 44D is a 1 Ox zoom image of a second region of the first sample of FIG. 44A;

[00116] FIG. 44E is an SAED image of the second region of the first sample of FIG. 44D;

[00117] FIG. 44F is a TEM image of a first additional area and a second additional area of the second region of the first sample of FIG. 44D subjected to SAED imaging;

[00118] FIG. 44G is a TEM image of a third additional area of the second region of the first sample of FIG. 44D subjected to SAED imaging;

[00119] FIG. 44H is an SAED image of the first additional area of the second region of the first sample of FIG. 44F;

[00120] FIG. 441 is an SAED image of the second additional area of the second region of the first sample of FIG. 44F;

[00121] FIG. 44J is an SAED image of the third additional area of the second region of the first sample of FIG. 44F;

[00122] FIG. 44K is a 1 Ox zoom image of a third region of the first sample of FIG. 44A;

[00123] FIG. 44L is an SAED image of the third region of the first sample of FIG. 44K; [00124] FIG. 44M is a 1 Ox zoom image of a fourth region of the first sample of FIG. 44A;

[00125] FIG. 44N is an SAED image of the fourth region of the first sample of FIG. 44M;

[00126] FIG. 440 is a TEM image of a first additional area and a second additional area of the fourth region of the first sample of FIG. 44M subjected to SAED imaging;

[00127] FIG. 44P is an SAED image of the first additional area of the fourth region of the first sample of FIG. 440;

[00128] FIG. 44Q is an SAED image of the second additional area of the fourth region of the first sample of FIG. 440;

[00129] FIG. 44R is a 20x zoom image of a fifth region of the first sample of FIG. 44 A;

[00130] FIG. 44S is an SAED image of the fifth region of the first sample of FIG. 44R;

[00131] FIG. 44T is a 1 Ox zoom image of a sixth region of the first sample of FIG. 44A;

[00132] FIG. 44U is an SAED image of the sixth region of the first sample of FIG. 44T;

[00133] FIG. 45A is a TEM image of a second sample of a membrane including graphene according to Example 12;

[00134] FIG. 45B is an altered image of FIG. 45 A, where the image of FIG. 45 A is taken slightly out of focus to exaggerate contrast;

[00135] FIG. 45C is a 1 Ox zoom image of a first region of the second sample of FIG. 45 A;

[00136] FIG. 45D is an SAED image of the first region of the second sample of FIG. 45C;

[00137] FIG. 45E is a 20x zoom image of a second region of the second sample of FIG. 45 A;

[00138] FIG. 45F is an SAED image of the second region of the second sample of FIG. 45E;

[00139] FIG. 45G is a 20x zoom image of a third region of the second sample of FIG. 45 A;

[00140] FIG. 45H is an SAED image of the third region of the second sample of FIG. 45G;

[00141] FIG. 451 is a 20x zoom image of a fourth region of the second sample of FIG. 45 A;

[00142] FIG. 45 J is an SAED image of the fourth region of the second sample of FIG. 451;

[00143] FIG. 45K is a 20x zoom image of a fifth region of the second sample of FIG. 45 A;

[00144] FIG. 45L is the SAED image of the fifth region of the second sample of FIG. 45K;

[00145] FIG. 45M is a 20x zoom image of a sixth region of the second sample of FIG. 45 A;

[00146] FIG. 45N is an SAED image of the sixth region of the second sample of FIG. 45M;

[00147] FIG. 450 is a 20x zoom image of a seventh region of the second sample of FIG. 45 A; [00148] FIG. 45P is an SAED image of the seventh region of the second sample of FIG. 450; [00149] FIG. 45Q is a 20x zoom image of an eighth region of the second sample of FIG. 45A; [00150] FIG. 45R is an SAED image of the eighth region of the second sample of FIG. 45Q;

[00151] FIG. 45 S is a TEM image of a first additional area and a second additional area of the eighth region of the second sample of FIG. 45Q subjected to SAED imaging;

[00152] FIG. 45T is an SAED image of the first additional area of the eighth region of the second sample of FIG. 45 S;

[00153] FIG. 45U is an SAED image of the second additional area of the eighth region o the second sample of FIG. 45 S;

[00154] FIG. 45 V is a 20x zoom image of a ninth region of the second sample of FIG. 45A;

[00155] FIG. 45 W is an SAED image of the ninth region of the second sample of FIG. 45 V;

[00156] FIG. 46A is a TEM image of a third sample of a membrane including graphene according to Example 12

[00157] FIG. 46B is an altered image of FIG. 46 A, where the image of FIG. 46A is taken slightly out of focus to exaggerate contrast;

[00158] FIG. 46C is a 20x zoom image of a first region of the third sample of FIG. 46 A;

[00159] FIG. 46D is an SAED image of the first region of the third sample of FIG. 46C;

[00160] FIG. 46E is a 1 Ox zoom image of a second region of the third sample of FIG. 46A;

[00161] FIG. 46F is an SAED image of the second region of the third sample of FIG. 46E;

[00162] FIG. 46G is a TEM image of an additional area of the second region of the third sample of FIG. 46E subjected to SAED imaging;

[00163] FIG. 46H is an SAED image of the additional area of the second region of the third sample of FIG. 46G;

[00164] FIG. 461 is a 1 Ox zoom image of a third region of the third sample of FIG. 46A;

[00165] FIG. 46J is an SAED image of the third region of the third sample of FIG. 461;

[00166] FIG. 46K is a TEM image of a first additional area and a second additional area of the third region of the third sample of FIG. 461 subjected to SAED imaging;

[00167] FIG. 46L is an SAED image of the first additional area of the third region of the third sample of FIG. 46K;

[00168] FIG. 46M is an SAED image of the second additional area of the third region of the third sample of FIG. 46K;

[00169] FIG. 46N is a 1 Ox zoom image of a fourth region of the third sample of FIG. 46 A;

[00170] FIG. 460 is an SAED image of the fourth region of the third sample of FIG. 46N; [00171] FIG. 46P is a TEM image of an additional area of the fourth region of the third sample of FIG. 46N subjected to SAED imaging;

[00172] FIG. 46Q is an SAED image of the additional area of the fourth region of the third sample of FIG. 46P;

[00173] FIG. 46R is a 20x zoom image of a fifth region of the third sample of FIG. 46A;

[00174] FIG. 46S is an SAED image of the fifth region of the third sample of FIG. 46R;

[00175] FIG. 47A is a TEM image of a fourth sample of a membrane including graphene according to Example 12;

[00176] FIG. 47B is an altered image of FIG. 47 A, where the image of FIG. 47A is taken slightly out of focus to exaggerate contrast;

[00177] FIG. 47C is a 20x zoom image of a first region of the fourth sample of FIG. 47 A;

[00178] FIG. 47D is an SAED image of the first region of the fourth sample of FIG. 47C;

[00179] FIG. 47E is a TEM image of a first additional area, a second additional area, and a third additional area of the first region of the fourth sample of FIG. 47C subjected to SAED imaging;

[00180] FIG. 47F is an SAED image of the first additional area of the first region of the fourth sample of FIG. 47E;

[00181] FIG. 47G is an SAED image of the second additional area of the first region of the fourth sample of FIG. 47E;

[00182] FIG. 47H is an SAED image of the third additional area of the first region of the fourth sample of FIG. 47E;

[00183] FIG. 471 is a 20x zoom image of a second region of the fourth sample of FIG. 47A;

[00184] FIG. 47J is an SAED image of the second region of the fourth sample of FIG. 471;

[00185] FIG. 47K is a 20x zoom image of a third region of the fourth sample of FIG. 47 A;

[00186] FIG. 47L is an SAED image of the third region of the fourth sample of FIG. 47K;

[00187] FIG. 47M is a 20x zoom image of a fourth region of the fourth sample of FIG. 47 A; and

[00188] FIG. 47N is an SAED image of the fourth region of the fourth sample of FIG. 47M.

[00189] Although the drawings represent embodiments of various features and components according to the present disclosure, the exemplification set out herein illustrates an embodiment, and such an exemplification is not to be construed as limiting the scope of the disclosure in any manner.

DETAILED DESCRIPTION OF THE DRAWINGS

[00190] Copper-zinc bateries exploit zinc corrosion and copper deposition. For such bateries to be capable of being recharged, the two electrolytes must be kept separate. If deposition of zinc is attempted in the presence of copper, copper-zinc alloys (i.e., brass) are deposited rather than pure zinc. Additionally, if copper electrolyte meets zinc, the copper automatically displaces the zinc, resulting in copper metal deposition and zinc ions in solution. The metal ions of the rechargeable battery must further have a high solubility in the electrolyte. During discharge, metallic zinc is electrochemically dissolved at the negative electrode into the electrolyte as Zn²⁺ ions, while metallic copper is electroplated onto the positive electrode. During charge, metallic copper is dissolved from the positive electrode into the electrolyte as Cu²⁺ ions, and metallic zinc is electroplated at the negative electrode. The electrode and cell reactions are further illustrated by the following equations:

Discharge

Negative electrode Zn — 2e~ > Zn²⁺

Charge

Discharge

Positive electrode Cu

< -

Charge

Cell

[00191] Generally, each batery cell involves a bipolar construction allowing generally uniform current distribution to the electrodes. Since the zinc and copper are corroding and depositing every cycle, there are no active materials other than zinc and copper that must be manufactured or maintained. This simplifies the electrode composition compared to conventional paste-based electrodes, which require conductive additives and binders. Further information related to copper-zinc batteries and their operation may be found in PCT Publication No. WO 2014/135828A1, titled RECHARGEABLE COPPER-ZINC CELL and filed February 17, 2014 with a priority date of March 4, 2013, the disclosure of which is hereby incorporated by reference in its entirety.

[00192] Referring to FIGS. 1-6, a first pan 102 of a battery cell is illustrated. The first pan 102 may have a generally continuous sidewall 104 with a first edge 112 and a second edge 114, a flange 110 extending outwardly from a first edge 112 of the sidewall 104, and a base 106 spanning the inner distance defined by the perimeter of the second edge 114 of the sidewall 104. The sidewall 104 and the base 106 may form a well 108 (FIGS. 3, 5), with the interior face 134 (FIGS. 3, 5) of the base 106 forming the bottom of the well 108. The interior face 134 of the base 106 of the first pan 102 may define an active electrode area. In various embodiments, the active electrode area may be between, and inclusive of, 13 cm² and 2000 cm². In some embodiments, the active electrode area may be about 95 cm x 20 cm.

[00193] The sidewall 104 may form a generally rectangular shape, including a square shape as illustrated. In other embodiments, the sidewall 104 may form other shapes, including circular shapes, polygons, and shapes including curved and straight lines. The sidewall 104 may be beveled or chamfered between the first edge 112 and the second edge 114, i.e., along the height of the sidewall 104 between the flange 110 and the base 106. The height of the sidewall 104 may be raised or lowered to manipulate the depth of the well 108 and the distance between the electrode and membrane 124 (FIG. 7) as described further herein. The flange 110 may have a first plurality of apertures 116 to facilitate fastening of the first pan 102 to a second pan 126 (FIG. 7) to form the battery cell as described further herein. The flange 110 may additionally have a second plurality of apertures 122 to facilitate alignment of the first pan 102 and the second pan 126 for fastening the first pan 102 to the second pan 126 and vice versa. One or more ports 119 may be formed in the sidewall 104 to introduce electrolyte into the battery cell and/or vent any produced hydrogen as described further herein.

[00194] FIG. 5 is a cross-section of the first pan 102 taken along line A- A of FIG. 3, and FIG. 6 is a close-up of flange 110 framed by box 120 (FIG. 5). As shown, a ridge 118 may be formed on the flange 110 to facilitate sandwiching of a membrane 124 (FIG. 7) between the first pan 102 and the second pan 126 (FIG. 7) as described further herein. The ridge 118 may allow for compression of the membrane 124 (FIG. 7) to facilitate clamping of the membrane 124 (FIG. 7) between the first pan 102 and the second pan 126. The ridge 118 may extend along the entire flange 110 or may be positioned in distinct positions along the perimeter of the flange 110. While the ridge 118 is illustrated as rounded, the ridge 118 may be pointed, squared, or otherwise edged in other embodiments. In other embodiments, the ridge may be replaced by a trough; that is, in some embodiments, first pan 102 may include a ridge 118 configured to mate with a corresponding trough formed in a second pan 126 to facilitate sandwiching of the membrane 124. In other embodiments, first pan 102 may include a trough configured to mate with a corresponding ridge 118 of second pan 126.

[00195] Now referring to FIG. 7, a battery cell 100 is illustrated, including first pan 102 and second pan 126. The second pan 126 has the same structure and function as the first pan 102 as described above, although first pan 102 and second pan 126 may include and/or be formed of different compositions and/or materials. To assemble the battery cell 100, the first pan 102 may be aligned with the second pan 126, with a membrane 124 positioned therebetween. Fasteners 128 may be inserted through the first plurality of apertures 116A of the first pan 102, through the membrane 124, and through the first plurality of apertures 116B of the second pan 126 to couple the first pan 102 and the second pan 126 to each other. Fasteners 128 may include bolts 130 and nuts 132 as shown. In other embodiments, other fasteners may be used, including, for example, clips or clamps. In yet other embodiments, other fastening mechanisms, including those not using fasteners, may be utilized. Polymer bushes or coatings or polymer fasteners may be utilized to prevent metal fasteners from contacting either pan 102, 126. At least one gasket may be positioned between the first pan 102 and the second pan 126 to facilitate a fluid- tight assembly. For example, in some embodiments, the battery cell 100 may include a first pan 102, a first gasket, a membrane 124, a second gasket, and a second pan 126.

[00196] The first pan 102 may be comprised of aluminium, with the interior face 134 of the base 106 of the first pan 102 being coated or otherwise covered with zinc. The second pan 126 may be comprised of stainless steel, with the interior face 134 of the base 106 of the second pan 126 being coated or otherwise covered with copper.

[00197] Once assembled, the battery cell 100 may be filled with an electrolyte via ports 119. In other words, the well 108 of each of pans 102, 126 may be filled with an electrolyte via corresponding ports 119. The holes may be capped or otherwise filled to prevent leakage or spilling of the electrolyte. Some embodiments may include ports for venting hydrogen produced during operation of the corresponding battery cell 100. Venting ports may be fluidly coupled to a collection container for collecting the produced hydrogen, rather than allowing the produced hydrogen to be vented to the ambient air.

[00198] As shown in FIGS. 8A-8B, the membrane 124 may be a layered membrane. FIG. 8 A illustrates a membrane having at least one layer 136 of one or more 2D materials sandwiched between polymer layers 138. FIG. 8B illustrates a membrane having a single polymer layer 138 sandwiched between at least two layers 136 of 2D material(s). While FIGS. 8A-8B show individual “layers”, each of the illustrated layers may include a plurality of layers of the same kind. For example, any of illustrated layers 136 of 2D material(s) may include 1, 2, 3, 4, 5, etc. layers of 2D material(s). The 2D material layer(s) of the illustrated membranes selectively prevents passage of undesirable cations to avoid creation of brass deposits as discussed above. For example, the membrane including the 2D material(s) may enable proton conductivity while preventing conductivity of Cu²⁺ and Zn²⁺. The 2D material layer(s) may continue to prevent passage of the undesirable cations through the membrane even when the membrane is rendered imperfect through use, manufacturing error, or some other event. In some embodiments, the membrane 124 may comprise or consist of an anionic exchange membrane, which allows passage of electrolyte anions, maintaining the charge balance between the copper and zinc halfcells while preventing transport of Cu²⁺ and Zn²⁺ cations, for example.

[00199] In other embodiments, the membrane 124 may comprise or consist of a proton exchange membrane (e.g., Nafion™). In some embodiments, the membrane 124 may be a layered membrane comprising a proton exchange membrane layer or layers and a 2D material layer or layers as described above. In yet other embodiments, the membrane 124 may include a layer of a spun proton exchange membrane, a layer of graphene, and/or a layer of PVC silica. In various embodiments, the membrane 124 may be without per- or polyfluoroalkyl substances. The membrane may be selected to allow proton exchange while preventing undesirable cation exchange. As described herein, the 2D material layer(s) may comprise or otherwise consist of graphene, graphyne, borophene, germanene, silicene, stanene, plumbene, phosphorene, antimonene, bismuthine, 2D alloys, 2D supracrystals, germanane, molybdenum disulphide, tungsten disulphide, hexagonal boron nitride, or other 2D materials and/or composites as known in the art.

[00200] In some embodiments, the membrane 124 may include one or more monolayers of graphene, i.e., single layers of graphene that are individually created and then, optionally, stacked as described further herein. The graphene layer(s) may include large crystal graphene, polycrystalline graphene, or single crystal graphene, selected according to the desired permeability of the application. For example, layers of poly crystalline graphene may have crystal grain boundaries which are about 15 pm or more apart, i.e., a crystal diameter of approximately 15 or more micrometers. Layers of large crystal graphene may have crystal boundaries which are about 60 pm or more apart, i.e., a crystal diameter of approximately 60 or more micrometers. Layers of single crystal graphene include a single crystal and, therefore, do not have crystal boundaries. The greater the number of crystals and the smaller the diameters of the crystals are both directly related to the crystal grain boundaries present within the membrane, which allows greater passage through the graphene layer of the membrane. In other words, the fewer the crystals within the graphene layer, the greater the selectivity of permability of the graphene layer. [00201] While the membrane is described herein as being associated with a copper zinc battery cell, it is understood that the membrane as described may have additional uses outside of such application. As described further herein and demonstrated by the provided examples, the membrane as disclosed may offer a lower resistance, higher voltaic efficiency, and higher round trip efficiency compared to conventional membranes. Additionally, crystal selection (e.g., polycrystalline, large crystal, single crystal) within the 2D material of the membrane provides a highly selective membrane which allows passage of protons while mitigating or preventing leakage of selected cations (e.g., copper and zinc). These features, and therefore the structure and design of the membrane, also has application and utility in other areas and industries for which a highly selective, efficient membrane is desired. Such applications may include, for example, fuel cells, electrolysers, and water treatment devices.

[00202] Now referring to FIGS. 9-15, another embodiment of a battery cell, battery cell 200, is provided. Battery cell 200 is similar to battery cell 100 and has similar components except as described herein.

[00203] Referring to FIGS. 9-12, a first pan 202 of battery cell 200 is illustrated. The first pan 202 may have a generally continuous sidewall 204, a flange 210 extending outwardly from a first edge 212 of the sidewall 204, and a base 206 spanning the inner distance defined by the perimeter of a second edge 214 of the sidewall 204. The sidewall 204 and the base 206 may form a well 208, with an interior face 234 of the base 206 forming the bottom of the well 208 and defining an active electrode area. The base 206 may additionally include a support rib 240 extending along a length of the first pan 202, the support rib 240 extending into the well of the first pan 202. In other embodiments, the support rib 240 may be another form of topography formed by the base 206, which increases the sturdiness of the first pan 202. While illustrated first pan 202 includes two support ribs 240, a greater or fewer number of support ribs 240 may be included as desired to increase sturdiness of the corresponding pan 202.

[00204] In some embodiments, a surface area enhancement may be attached to the pan 202 to increase the overall current density while maintaining a relatively low localized current density. The surface area enhancement may increase the surface area of the corresponding electrode as discussed above in relation to battery cell 100 and/or to move the electrode closer to the membrane 224 (FIGS. 14-15). Such enhancement may improve voltaic efficiency and, thereby, overall efficiency of the battery.

[00205] FIG. 13 is a cross-section of the first pan 202 taken along line D-D of FIG. 11. As shown, a ridge 218 may be formed on the flange 210 to facilitate sandwiching of the membrane 224 (FIG. 14-15) between the first pan 202 and the second pan 226 when battery cell 200 is assembled as discussed above. The first pan 202 may additionally include a lip 242 at the outer edge of the flange 210 which curves in a direction opposite of the base 206. Like ridge 218, the lip 242 may extend along the entire flange 210 or be positioned in distinct positions along the perimeter of the flange 110. As discussed above in relation to battery cell 100, ridge 218 may be replaced with a ridge and trough mating mechanism, wherein one of pan 202 and 226 includes a ridge 218 while the other of pan 202 and 226 includes a corresponding trough.

[00206] Now referring to FIGS. 14-15, assembled battery cell 200 is illustrated, including first pan 202 and second pan 226. The second pan 226 has the same structure and function as the first pan 202 as described above. To assembly the battery cell 200, the first pan 202 is aligned with the second pan 226, with membrane 224 positioned therebetween. First pan 202 and/or second pan 226 may include alignment apertures 246 (FIGS. 9-10) to facilitate alignment of the first pan 202 with the second pan 226. A gasket 248 may be positioned between the first pan 202 and the second pan 226 to facilitate a fluid-tight assembly. In some embodiments, a first gasket may be positioned between the first pan 202 and the membrane 224 while a second gasket may be positioned between the second pan 226 and the membrane 224 so that the battery cell structure includes first pan 202, first gasket, membrane 224, second gasket, and second pan 226. The gasket 248 may be formed of a non- conductive material which facilitates the coupling of the first pan 202 and the second pan 226 to form the battery cell 200 while keeping the first pan 202 and the second pan 226 from touching each other, i.e., the first pan 202 and the second pan 226 may be spaced apart by the gasket 248 to prevent electricity conduction between the first pan 202 and the second pan 226. The gasket 248 may be held in place by ridge 218 and lip 242. A retaining clip 250 may be used to facilitate coupling of first pan 202 and second pan 226. Ports 219 may be used for filling battery cell 200 with electrolyte and/or venting produced hydrogen as described above.

[00207] Battery cell 100, 200 may include an agitation mechanism. For example, the battery cell 100, 200 may have one or more agitators, e.g., stirrers, impellers, turbines, etc., positioned within one or both of the wells 108, 208 of first pan 102, 202 and/or second pan 126, 226 to agitate the electrolyte therein. In other embodiments, the battery cell 100, 200 may include an aeration system for introduction of microbubbles facilitating agitation of the electrolyte. In other embodiments, the battery cell 100, 200 may include a flow system for pumping the electrolyte through the battery cell 100, 200, thereby facilitating agitation of the electrolyte. In other embodiments, one or more battery cells 100, 200 may be positioned on a vibrating or shaking stand or base to agitate the electrolyte. Other structures and mechanisms for agitating battery cell(s) 100, 200 may be used.

[00208] Battery cells 100, 200 may be arranged in a multiple cell series configuration to scale a battery pack and/or battery system as desired. For example, a battery pack may have between and inclusive of 2 and 500 battery cells. A battery pack may have, for example, between and inclusive of 2 and 50 battery cells, between and inclusive of 15 and 35 battery cells, between and inclusive of 20 and 30 battery cells, between and inclusive of 50 and 150 battery cells, and/or between and inclusive of 150 and 250 battery cells. A battery pack having a greater number of battery cells may be desired to further scale a battery pack and/or battery system. A containerised battery system may have, for example, between and inclusive of 1 and 500 battery packs, between and inclusive of 100 and 400 battery packs, between and inclusive of 150 and 350 battery packs, and/or between and inclusive of 200 and 250 battery packs. A battery system, for example, may have between and inclusive of 205 and 210 battery packs. A battery system rated for 250kW/lMWh may include, for example, about 208 battery packs per system, with about 24 battery cells per battery pack. The battery packs in a battery system may be wired in a variety of configurations to match the current/voltage requirements of the bi-directional inverter. [00209] Referring now to FIG. 16, a method 300 for manufacturing an exemplary membrane 302 is illustrated. A copper foil sheet 304 and appropriate stock precursor is provided to a chemical vapour deposition system. A 2D material layer 306 (e.g., a graphene layer or another 2D material as discussed above) is grown on the copper foil sheet 304 using a chemical vapour deposition method as known in the art. For example, the copper foil sheet 304 may be positioned within a glass tube. The glass tube is heated, and the stock precursor (e.g., methane), is pumped into the glass tube and passed over the copper foil sheet 304. The methane cracks, and the resultant carbon attaches to the copper foil sheet 304. If multiple layers are provided, an additional copper foil sheet is arranged with the 2D material layer 306 opposite copper foil sheet 304, and the stacked materials are subjected to another round of chemical vapour deposition system to grow an additional 2D material layer. This process is repeated until the desired number of 2D material layers is reached.

[00210] A liquid proton exchange material (e.g., liquid Nafion™) is introduced and spun to create a spun proton exchange material layer 308 on top 2D material layer 306, or, in other embodiments, the uppermost 2D material layer. After creation of the spun proton exchange material layer 308, the copper foil sheet(s) 304 are dissolved via a wet-etch method, leaving behind the 2D material layer 306 and the spun proton exchange material layer 308. In embodiments having multiple 2D material layers, the copper foil sheets are dissolved using the same wet-etch method, leaving behind a layer group of nonintegrated 2D material layers and a spun proton exchange material layer arranged with the uppermost 2D material layer. The resultant 2D material layer group and spun proton exchange material layer are fished out of the etchant 307 using a pre-existing proton exchange material layer 310, which is arranged with the 2D material layer 306, or the bottommost 2D material layer, to form membrane 302. As discussed above in relation the membrane 124 of FIGS. 8 A, 8B, in other embodiments, membrane 302 may include layers with differing arrangements and/or additional or less layers. In yet other embodiments, the membrane 302 may be formed the layers described above using reel-to-reel production.

Methods

[00211] Raman Spectrometry is a chemical analysis technique using a light scattering technique, wherein laser light is scattered at different wavelengths depending on the chemical structure of the object being analyzed. The results are produced along a spectrum of peaks that illustrate the intensity and wavelength position of the scattered light. In determining quality of a graphene-containing membrane, Raman Spectrometry may be used. Graphene-containing membranes of preferable quality demonstrate an absence of D wavelength width peaks, narrow G wavelength width distribution (i.e., narrow G wavelength bands), and narrow 2D wavelength width distribution (i.e., narrow 2D wavelength bands). The narrow distribution of G wavelength width distribution and 2D wavelength width distribution is indicative of uniform structure and high crystallization.

Example 1

[00212] A six-cell series configuration of 10x10 cm battery cells consistent with battery cell 100 described above and using an anionic exchange membrane was run using constant potential charge and discharge cycles. The potential was set to give 70% voltaic efficiency and equated to +/- 1.4 V from the open circuit potential. Each cycle consisted of a 3660 second charge period at 1.4 V above open circuit voltage followed by 3660 second discharge period at 1.4 V below open circuit voltage. FIG. 17 provides the resulting voltage versus time plot, wherein the cycling shows the six-cell series operating for over 150 continuous hours.

[00213] FIG. 18 provides the current profile over time. As illustrated, two sets of fluctuations occurred. The first oscillation is associated with differences in temperature, similar to experienced day and night cycles. The second fluctuation trends toward lower charging and discharging currents, which is the result of cell aging. The current supported by the charge and discharge potential (1.4 V +/- open circuit voltage) is between 0.25 and 0.33 A, which is equivalent to 2.5-3.3 mA cm’².

[00214] FIG. 19A provides an expanded view of the first five cycles (hours 0-10) of the potential plot provided in FIG. 17, while FIG. 19B provides an expanded view of the last five cycles (hours 140-150) of the potential plot provided in FIG. 17. FIG. 20A provides an expanded view of the first five cycles (hours 0-10) of the current plot provided in FIG. 18, while FIG. 20B provides an expanded view of the last five cycles (hours 140-150) of the current plot provided in FIG. 18. As shown, the shape and pattern of the cycles remained the same across the entire testing period. Example 2

[00215] Battery cells consistent with battery cell 100 having a 10 cm² electrode area were run at a constant current at 1, 3, 5, 10, 15, 20, and 25 mA cm'² with a static electrolyte. Each cycle consisted of a 3660 second charge period at 1.4 V above open circuit voltage followed by 3660 second discharge period at 1.4 V below open circuit voltage. Graph 400 of FIG. 21 provides the resulting voltage 400a and Cur/mA 400b versus time plot for battery cells containing Nafion™, wherein the cycling shows the battery cells operating continuously over 96 minutes. Graph 402 of FIG. 21 provides the resulting voltage 402a and Cur/mA 402b versus time plot for battery cells containing a Nafion™-graphene-Nafion™ membrane.

[00216] Comparing graph 400 with graph 402, the presence of graphene improves the voltage driving current over time. For example, nearing the 1:12:00 time mark in each graph, the example which does not include graphene (graph 400) begins to lose consistency and stability at higher Cur/mA values (e.g., 200-250 Cur/mA), while the example including graphene (graph 402) maintains a generally consistent voltage over each cycle. The inconsistency demonstrated in the non-graphene membrane of graph 400 indicates cross-contamination of copper/zinc across the membrane, while such cross-contamination is not indicated in the example including a graphene membrane (graph 402).

Example 3

[00217] Battery cells consistent with battery cell 100 having a 10 cm² electrode area were run at a constant current at 1, 3, 5, 10, 15, 20, and 25 mA cm'² with a flowing/turbulent electrolyte. Each cycle consisted of a 3660 second charge period at 1.4 V above open circuit voltage followed by 3660 second discharge period at 1.4 V below open circuit voltage. Graph 404 of FIG. 22 provides the resulting voltage 404a and Cur/mA 404b versus time plot for battery cells containing Nafion™, wherein the cycling shows the battery cells operating continuously over 96 minutes. Graph 406 of FIG. 22 provides the resulting voltage 406a and Cur/mA 406b versus time plot for battery cells containing a Nafion™-graphene-Nafion™ membrane.

[00218] As with the graphs in Example 2 including a static electrolyte, when comparing graph 404 with graph 406, the presence of graphene improves the voltage driving current over time. Referring to the similar time stamps between each graph, the example which does not include graphene (graph 404) at least rarely demonstrates any consistency in voltage - if any - in each cycle. However, in the example which does include graphene (graph 406) tends to maintain a generally consistent voltage over each cycle. As mentioned above, the inconsistency demonstrated in the non-graphene membrane of graph 400 indicates cross-contamination of copper/zinc across the membrane, while such cross-contamination is not indicated in the example including a graphene membrane (graph 406).

Example 4

[00219] A single layer of graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. Three different areas of the resultant graphene-coated copper were then subjected to Raman Spectroscopy as discussed above. The G peak wavelength width as described herein measures the amount of indicated graphene in each square. Each measured area of the sample was split into a 64x64 arrangement, with each 1x1 section being measured for the average G peak wavelength of that section. The higher the measured G-peak wavelength, the smaller the indication of graphene in that section. Each 1x1 section measured is provided in the graphs described below, wherein the darker the square, the lower the measured G peak wavelength and the greater the indication of graphene in that section.

[00220] The results of the Raman Spectroscopy at the first area of the single-layergraphene-coated copper are illustrated by FIG. 23, wherein graph 502 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 25.4 cm’¹ with a standard deviation of 7.35 cm’¹. Graph 504 illustrates the G wavelength reflection of the scattered laser at the first area per crystallized area indicated along the X- and Y-axes.

[00221] Graph 506 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. Where the ratio of 2D wavelength wavenumbers to G wavelength wavenumbers is greater than 2, a monolayer 2D material is generally indicated. As illustrated in graph 506, the measured 2D :G wavelength ratio had an average value of 3.62 cm’¹ and a standard deviation of 1.11 cm’¹, correctly indicating a 2D monolayer material. Graph 508 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the first area. As illustrated by graph 508, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 508a and the 2D wavelength portion 508b.

[00222] The results of the Raman Spectroscopy at the second area of the single-layergraphene-coated copper are illustrated by FIG. 24, wherein graph 510 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 30.3 cm’¹ with a standard deviation of 7.8 cm’¹. Graph 512 illustrates the G wavelength reflection of the scattered laser at the second area per crystallized area indicated along the X- and Y-axes.

[00223] Graph 514 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 514, the measured 2D:G wavelength ratio had an average value of 2.87 cm’¹ and a standard deviation of 1.0 cm’¹, correctly indicating a 2D monolayer material. Graph 516 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the second area. As illustrated by graph 516, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 516a and the 2D wavelength portion 516b.

[00224] The results of the Raman Spectroscopy at the third area of the single-layer graphene-coated copper are illustrated by FIG. 25, wherein graph 518 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 18.64 cm’¹ with a standard deviation of 4.45 cm’¹. Graph 520 illustrates the G wavelength reflection of the scattered laser at the third area per crystallized area indicated along the X- and Y-axes.

[00225] Graph 522 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 522, the measured 2D:G wavelength ratio had an average value of 3.68 cm’¹ and a standard deviation of 1.0, correctly indicating a 2D monolayer material. Graph 524 illustrates the full spectrum of peaks that illustrate the intensity and wavelength position of the scattered light at the first area. As illustrated by graph 524, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 524a and the 2D wavelength portion 524b. Example 5

[00226] Three separated layers of graphene were grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. In other words, a single layer of graphene was grown on a sheet of copper foil and coated with polymethyl methacrylate (“PMMA”) before the copper foil was dissolved, leaving the single layer of graphene. The single layer of graphene with the PMMA coating was added to a second graphene layer which was grown on a sheet of copper foil, and the copper foil was dissolved, leaving a double layer of single-layer graphene. The process was repeated for a triple layer of single-layer graphene. The PMMA is further dissolved so that only the graphene layers were left behind. Three different areas of the resultant graphene- coated copper were then subjected to Raman Spectroscopy as discussed above. The G peak wavelength width as described herein measures the amount of indicated graphene in each square. Each measured area of the sample was split into a 64x64 arrangement, with each 1x1 section being measured for the average G peak wavelength of that section. The higher the measured G- peak wavelength, the smaller the indication of graphene in that section. Each 1x1 section measured is provided in the graphs described below, wherein the darker the square, the lower the measured G peak wavelength and the greater the indication of graphene in that section.

[00227] The results of the Raman Spectroscopy at the first area of the triple-layergraphene-coated copper are illustrated by FIG. 26, wherein graph 602 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 22.02 cm'¹ with a standard deviation of 3.78 cm'¹. Graph 604 illustrates the G wavelength reflection of the scattered laser at the first area per crystallized area indicated along the X- and Y-axes.

[00228] Graph 606 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. Where the ratio of 2D wavelength wavenumbers to G wavelength wavenumbers is greater than 2, a monolayer 2D material is generally indicated. As illustrated in graph 606, the measured 2D :G wavelength ratio had an average value of 3.01 cm'¹ and a standard deviation of 1.77, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 608 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the first area. As illustrated by graph 608, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 608a and the 2D wavelength portion 608b. [00229] The results of the Raman Spectroscopy at the second area of the single-layergraphene-coated copper are illustrated by FIG. 27, wherein graph 610 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 26.21 cm'¹ with a standard deviation of 2.91 cm'¹. Graph 612 illustrates the G wavelength reflection of the scattered laser at the second area per crystallized area indicated along the X- and Y-axes.

[00230] Graph 614 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 614, the measured 2D:G wavelength ratio had an average value of 3.63 cm'¹ and a standard deviation of 0.8 cm'¹, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 616 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the second area. As illustrated by graph 616, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 616a and the 2D wavelength portion 616b.

[00231] The results of the Raman Spectroscopy at the third area of the single-layer graphene- coated copper are illustrated by FIG. 28, wherein graph 618 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 18.14 cm'¹ with a standard deviation of 1.78 cm'¹. Graph 620 illustrates the G wavelength reflection of the scattered laser at the third area per crystallized area indicated along the X- and Y-axes.

[00232] Graph 622 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 622, the measured 2D:G wavelength ratio had an average value of 3.33 cm'¹ and a standard deviation of 1.08 cm'¹, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 624 illustrates the full spectrum of peaks that illustrate the intensity and wavelength position of the scattered light at the first area. As illustrated by graph 624, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 624a and the 2D wavelength portion 624b.

Example 6

[00233] A single layer of graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. Liquid Nafion™ was introduced and spun, creating a spin-coated Nafion™ layer on the single layer of graphene opposite of the copper foil. The copper foil was dissolved using a wet-etch technique, and the graphene/spin-coated Nafion™ was fished out of the etchant with a layer of polyvinyl chloride/silica nanoparticles nanocomposites (“PVC/SiO2"). Three different areas of the resultant membrane were then subjected to Raman Spectroscopy as discussed above. The G peak wavelength width as described herein measures the amount of indicated graphene in each square. Each measured area of the sample was split into a 64x64 arrangement, with each 1x1 section being measured for the average G peak wavelength of that section. The higher the measured G-peak wavelength, the smaller the indication of graphene in that section. Each 1x1 section measured is provided in the graphs described below, wherein the darker the square, the lower the measured G peak wavelength and the greater the indication of graphene in that section.

[00234] The results of the Raman Spectroscopy at the first area of the single-layergraphene-coated copper are illustrated by FIG. 29, wherein graph 702 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 25.68 cm'¹ with a standard deviation of 7.22 cm'¹. Graph 704 illustrates the G wavelength reflection of the scattered laser at the first area per crystallized area indicated along the X- and Y-axes.

[00235] Graph 706 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. Where the ratio of 2D wavelength wavenumbers to G wavelength wavenumbers is greater than 2, a monolayer 2D material is generally indicated. As illustrated in graph 706, the measured 2D :G wavelength ratio had an average value of 1.3 cm'¹ and a standard deviation of 0.64 cm'¹. It is believed that the spin-coated Nafion™ layer results in the relatively low 2D: G ratio unexpected for a monolayer 2D material. Graph 708 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the first area. [00236] The results of the Raman Spectroscopy at the second area of the single-layergraphene-coated copper are illustrated by FIG. 30, wherein graph 710 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 30.14 cm'¹ with a standard deviation of 13.8 cm'¹. Graph 712 illustrates the G wavelength reflection of the scattered laser at the second area per crystallized area indicated along the X- and Y-axes.

[00237] Graph 714 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 714, the measured 2D:G wavelength ratio had an average value of 1.01 cm'¹ and a standard deviation of 0.45 cm'¹. It is believed that the spin- coated Nafion™ layer results in the relatively low 2D: G ratio unexpected for a monolayer 2D material. Graph 716 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the second area.

[00238] The results of the Raman Spectroscopy at the third area of the single-layer graphene-coated copper are illustrated by FIG. 31, wherein graph 718 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 34.51 cm'¹ with a standard deviation of 14.07 cm'¹. Graph 720 illustrates the G wavelength reflection of the scattered laser at the third area per crystallized area indicated along the X- and Y-axes.

[00239] Graph 722 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 722, the measured 2D:G wavelength ratio had an average value of 1.02 cm'¹ and a standard deviation of 1.08 cm'¹. It is believed that the spin- coated Nafion™ layer results in the relatively low 2D: G ratio unexpected for a monolayer 2D material. Graph 724 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the third area.

Example 7 [00240] A single layer of graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. A second sheet of copper foil was introduced to the single layer of graphene opposite the first sheet of copper foil, and a second layer of graphene was grown on the second sheet of copper foil using the same method. The step was repeated until three layers of graphene were present. Liquid Nafion™ was introduced and spun, creating a spin- coated Nafion™ layer on the uppermost layer of graphene opposite of the uppermost layer of copper foil. The copper foil sheets were dissolved using a wet-etch technique, and the graphene/spin-coated Nafion™ was fished out of the etchant with a layer of PVC/SiO2. Three different areas of the resultant membrane were then subjected to Raman Spectroscopy as discussed above. The G peak wavelength width as described herein measures the amount of indicated graphene in each square. Each measured area of the sample was split into a 64x64 arrangement, with each 1x1 section being measured for the average G peak wavelength of that section. The higher the measured G-peak wavelength, the smaller the indication of graphene in that section. Each 1x1 section measured is provided in the graphs described below, wherein the darker the square, the lower the measured G peak wavelength and the greater the indication of graphene in that section.

[00241] The results of the Raman Spectroscopy at the first area of the single-layergraphene-coated copper are illustrated by FIG. 32, wherein graph 802 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 17.94 cm'¹ with a standard deviation of 3.39 cm'¹. Graph 804 illustrates the G wavelength reflection of the scattered laser at the first area per crystallized area indicated along the X- and Y-axes.

[00242] Graph 806 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. Where the ratio of 2D wavelength wavenumbers to G wavelength wavenumbers is greater than 2, a monolayer 2D material is generally indicated. As illustrated in graph 806, the measured 2D: G wavelength ratio had an average value of 4.24 and a standard deviation of 1.81 cm'¹, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 808 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the first area. As illustrated by graph 808, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 808a and the 2D wavelength portion 808b.

[00243] The results of the Raman Spectroscopy at the second area of the single-layergraphene-coated copper are illustrated by FIG. 33, wherein graph 810 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 21.73 cm'¹ with a standard deviation of 7.85 cm'¹. Graph 812 illustrates the G wavelength reflection of the scattered laser at the second area per crystallized area indicated along the X- and Y-axes.

[00244] Graph 814 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 814, the measured 2D:G wavelength ratio had an average value of 3.0 cm'¹ and a standard deviation of 1.24 cm'¹, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 816 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the second area. As illustrated by graph 816, the Raman Spectrometry analysis revealed minimum D wavelength contribution and narrow peaks at both the G wavelength portion 816a and the 2D wavelength portion 816b.

[00245] The results of the Raman Spectroscopy at the third area of the single-layer graphene-coated copper are illustrated by FIG. 34, wherein graph 818 illustrates the measured G wavelength width along the X-axis and the standard deviation along the Y-axis. As illustrated, the measured G wavelength width had an average value of 23.86 cm'¹ with a standard deviation of 5.22 cm'¹. Graph 820 illustrates the G wavelength reflection of the scattered laser at the third area per crystallized area indicated along the X- and Y-axes.

[00246] Graph 822 illustrates the ratio of measured 2D wavelength to measured G wavelength, where the measured 2D to G ratio is indicated along the X-axis and the standard deviation along the Y-axis. As illustrated in graph 822, the measured 2D:G wavelength ratio had an average value of 2.18 cm'¹ and a standard deviation of 1.01 cm'¹, indicating that the layers of 2D material are decoupled from each other, i.e., adjacent but not integrated. Graph 824 illustrates the full spectrum of peaks that indicate the intensity and wavelength position of the scattered light at the third area. Example 8

[00247] Battery cells consistent with battery cell 100 having a 10 cm² electrode area were run at a current density of 0.01 A cm'², 0.02 A cm'², 0.03 A cm'², 0.04 A cm'², 0.05 A cm'², 0.06 A cm'², 0.07 A cm'², 0.08 A cm'², 0.09 A cm'², and 0.1 A cm'². The voltage of the potential difference across the membrane in each category of tested battery was measured and plotted against the current density in FIG. 35A. Line 830 corresponds with plot points referring to battery cells tested using an anionic exchange membrane. The remaining plot points refer to battery cells tested using membranes including a proton exchange membrane and/or a PVC/silica membrane as discussed further below. As shown, the results from the anionic exchange membrane compared to the remaining results indicate a much higher resistance and therefore lower efficiency when compared to the other tested membranes. The remaining membranes are discussed in connection with FIG. 35B below.

[00248] Now referring to FIG. 35B, the remaining plot points from FIG. 35 A can be seen without reference to line 830 and the anionic exchange membrane results for clarity. Plot points A refer to battery cells tested using a Nafion™ membrane. Plot points B refer to battery cells tested using a Nafion™-Nafion™ membrane. Plot points C refer to battery cells tested using a Nafion™-single layer graphene-Nafion™ membrane. Plot points D refer to battery cells tested using a spun-coated-Nafion™-triple layer graphene-Nafion™ membrane. Plot points E refer to battery cells tested using a PVC/SiO2 membrane (i.e., Amer-Sil™ FF60). Plot points F refer to battery cells tested using a spun-coated-Nafion™-single layer graphene-PVC/SiO2 membrane. Plot points G refer to battery cells tested using a spun-coated-Nafion™-triple layer graphene- PVC/SiO2 membrane. As illustrated in FIG. 35B, membranes including PVC/SiO2 have a lower resistance than membranes including Nafion™ alone.

Example 9

[00249] Battery cells consistent with battery cell 100 having a 10 cm² electrode area were run at a current density of 25 mA/cm². Tested battery cells included a selected membrane from a group of membranes including a new spin-coated-Nafion™-triple layer graphene-PVC/SiO2 membrane; a used spin-coated-Nafion™-triple layer graphene-PVC/SiO2 membrane (this membrane is believed to have experienced a defect in which the graphene had separated from the PVC/SiO2 layer); a used spin-coated-Nafion™-single layer graphene-PVC/SiO2 membrane; a PVC/SiO2 membrane; a used spin-coated-Nafion™-single layer graphene-Nafion™ membrane; a spin-coated-Nafion™-Nafion™ membrane; and a Nafion membrane. Copper ion cross-over was measured for each membrane type and compared, as illustrated in FIG. 36; as shown, the presence of graphene within the membrane reduced copper ion cross-over in the tested batteries.

Example 10

[00250] Graphene was grown on a sheet of copper foil and supported by depositing the graphene and copper foil on a bilayer polymethyl methacrylate (“PMMA”) (3% in anisole) membrane. The copper foil was etched using APS -100 copper etchant, and the resulting graphene was mounted on a silicone nitride transmission electron microscopy (TEM) grid. Solvent was used to remove the PMMA support, and the resulting membrane was annealed (FE/Ar 450°C) prior to TEM imaging.

[00251] FIGS. 37A-37I provide the results from the TEM observations and selected area electron diffraction (SAED) observations of a first sample formed using the above method with large crystal graphene. FIG. 37A provides a TEM image of the entirety of the first sample disposed on a TEM grid. FIG. 37B provides a 5x zoom image of FIG. 37A and, specifically, area 901 of the first sample of FIG. 37A. Referring to FIG. 37B, a first region 902 and a second region 903 were subjected to SAED. FIG. 37C provides a 4x zoom image of the first region 902 of FIG. 37B. As shown in FIG. 37C, a visible line defect or ripple is visible at 904. FIG. 37D provides a 2x zoom image of the first region 902 of FIG. 37B, including a superimposed exemplary aperture 905 for conducting SAED on the first region 902. FIG. 37E provides a lOx zoom image of the exemplary aperture 905 of FIG. 37D. Now referring to FIG. 37F, an image of the SAED is provided. As highlighted by box 906, the SAED area illustrates a scattering characteristic of single monolayer graphene, despite the visible line at 904 of FIG. 37C. This conclusion is further supported by graph 907 of FIG. 37G, which plots the gray value over distance of the measured area. A second SAED image provided in FIG. 37H was taken over a second area, which also illustrates diffraction pattern characteristic of monolayer graphene, highlighted at line 908. This conclusion is further supported by graph 909 of FIG. 371, which plots the gray value over distance of the measured area.

[00252] FIGS. 38A-38B provide the results from the TEM observations and SAED observations of the second region 903 of the first sample illustrated in FIGS. 37A and 37B. FIG. 38A provides a 4x zoom image of the second region 903 of FIG. 37B; a grain boundary is indicated at line 910. FIG. 38B provides the SAED image. As highlighted by comparing the position of point 911 with the position of point 912, the SAED area illustrates a diffraction pattern having two crystal orientations, which indicates (i.e., confirms) a grain boundary within the measured region.

[00253] FIGS. 39A-39G provide the results from the TEM observations and SAED observations of a second sample formed using the above method with polycrystalline graphene. FIG. 39A provides a TEM image of the entirety of the second sample disposed on a TEM grid. FIG. 39B provides a 2x zoom image of FIG. 39A and, specifically, an area of the second sample of FIG. 39A including a first region 951 and a second region 952 subjected to SAED. FIG. 39C provides a 5x zoom image of the first region 951 of FIG. 39B. As shown in FIG. 39C, a scrolling 953 is visible across the first region 951 resulting from damage during transfer. Now referring to FIG. 39D, an SAED image is provided of the first area of first region 951 of the second sample. The circular shape of the diffraction pattern indicates several crystal structures; however, this may also be resultant of the damage (i.e., scrolling 953) described above. A second area 954 of the first region 951 was subjected to SAED (see FIGS. 39E-39F), with the results shown in FIG. 39G. As shown, the diffraction pattern remains circular, indicating multiple crystals or resulting from the damage discussed in reference to FIG. 39C.

[00254] FIGS. 40A-40F provide the results from the TEM observations and SAED observations of the second region 952 of the second sample illustrated in FIG. 39A. FIG. 40A provides a 5x zoom image of the second region 952 of FIG. 39B. FIG. 40B provides a lOx zoom image of the second region 952 of FIG. 40A, showing a typical contamination coverage (i.e., without the scrolling or other damage experienced in the first region 951 of FIG. 39C). FIG. 40C provides an SAED image. The linear shape as highlighted by box 958 of the diffraction pattern is characteristic of single crystal monolayer graphene with no grain boundaries. This conclusion is further supported by graph 955 of FIG. 40D, which plots the gray value over the distance of the observed area. A second area of the second region 952 was subjected to SAED, an image of which is provided in FIG. 40E. As with the first area (FIGS. 40C-40D), the second area indicated a diffraction pattern having a linear shape as highlighted by box 959 characteristic of single crystal bilayer (or thicker) graphene with no grain boundaries. This conclusion is further supported by graph 956 of FIG. 40F, which plots the gray value over the distance of the observed area.

[00255] FIGS. 41 A-41C provide the results from the TEM observations and SAED observations of a third region of the second sample illustrated in FIG. 39A. FIG. 41 A provides a 5x zoom image of the third region of FIG. 39A. FIG. 41B provides an SAED image. The linear shape of the diffraction pattern as highlighted by box 960 is again characteristic of a single crystal bilayer (or thicker) graphene with no grain boundaries. This conclusion is further supported by graph 957 of FIG. 41C, which plots the gray value over the distance of the observed area.

Example 11

[00256] Graphene was grown on a sheet of copper foil and supported by depositing the graphene and copper foil on a bilayer polymethyl methacrylate (“PMMA”) (3% in anisole) membrane. The copper foil was etched using APS -100 copper etchant, and the resulting graphene was mounted on a silicone nitride transmission electron microscopy (TEM) grid. Solvent was used to remove the PMMA support, and the resulting membrane was annealed (FE/Ar 450°C) prior to TEM imaging. Diffraction patterns were measured by determining the angle of the pattern(s) to the horizontal. Diffraction patterns with variances of less than 5° were considered to be within the same crystal grain to account for measurement variability and/or folds or damage occurring from transfer of the graphene to the TEM grid.

[00257] Referring to FIG. 42A, each of regions 1000 of a first sample 999 including large crystal graphene were subjected to SAED visualization, an image of which is provided for each region at corresponding image 1001. Each of the SAED images illustrate a similar orientation diffraction pattern of 33° to horizontal, except for SAED image 1001b, corresponding with region 1000b, which indicated a diffraction pattern of 4° to horizontal.

[00258] Referring to FIG. 42B, regions adjacent to region 1000b were also subjected to SAED visualization to facilitate mapping of the crystal grains. As shown, while region 1001b had a diffraction pattern indicating a single crystal grain (albeit a different pattern than the diffraction pattern visualized in the remaining regions 1000 of FIG. 42A), regions 1002a and 1002b each indicated two crystal grains - one having a diffraction pattern of 33° to horizontal, and another having a diffraction pattern of 4° to horizontal - and region 1002c indicated a single crystal grain having a diffraction pattern of 33° to horizontal. This facilitated mapping of the crystal grains across the first sample 999 as shown in FIG. 42C, including a first crystal grain at 1003 and a second crystal grain at 1004.

[00259] Referring to FIG. 43 A, each of regions 1050 of a second sample 1049 having poly crystalline graphene were subjected to SAED visualization, an image of which is provided for each region at corresponding image 1051. Each of regions 1050a and 1050b had diffraction patterns indicating a single crystal grain with a diffraction pattern of 24° to horizontal, region 1050c had a diffraction pattern indicating a single crystal grain with a diffraction pattern of 2° to horizontal, region 1050d had a diffraction pattern indicating two crystal grains - one with a diffraction pattern of 24° to horizontal and one with a diffraction pattern of 2° to horizontal, and region 1050e had a diffraction pattern indicating a single crystal grain with a diffraction pattern of 12° to horizontal. These diffraction patterns indicated three crystal grains across the second sample 1049, and facilitate mapping of the crystal grains across the second sample 1049 as shown in FIG. 43B, including a first crystal grain at 1052, a second crystal grain at 1053, and a third crystal grain at 1054.

[00260] Now referring to FIG. 43C, three areas 1055a, 1055b, and 1055c of region 1050d were subjected to SAED visualization to determine the grain boundary the crystal grains. Image 1056a of area 1055a indicates a single crystal grain with a diffraction pattern of 2° to horizontal; image 1056b of area 1055b indicates two crystal grains - one with a diffraction pattern of 2° to horizontal and one with a diffraction pattern of 24° to horizontal; and image 1056c of area 1055c indicates a single crystal grain with a diffraction pattern of 24° to horizontal. As such, it is shown that the grain boundary extends through area 1055b.

Example 12

[00261] Graphene was grown on a sheet of copper foil and supported by depositing the graphene and copper foil on a bilayer polymethyl methacrylate (“PMMA”) (3% in anisole) membrane. The copper foil was etched using APS -100 copper etchant, and the resulting graphene was mounted on a silicone nitride transmission electron microscopy (TEM) grid. Solvent was used to remove the PMMA support, and the resulting membrane was annealed (Fb/Ar 450°C) prior to TEM imaging. Diffraction patterns with variances of less than 5° were considered to be within the same crystal grain to account for measurement variability and/or folds or damage occurring from transfer of the graphene to the TEM grid.

[00262] Referring to FIG. 44A, a first sample including large crystal graphene is provided. The brighter white regions indicate that there is no graphene present in that region. Thirty-two out of the 127 regions (25%) were perforated. The dark regions shown in the image are polymer contamination, likely resulting from transfer of the film to the TEM grid. Regions 1011, 1012, 1013, 1014, 1015, and 1016 were subjected to SAED imaging, with a grain boundary observed in region 1014 and a potential grain boundary observed in region 1012 as discussed further below.

[00263] FIG. 44B provides a 5x zoom image of region 1011 of the first sample shown in FIG. 44A; FIG. 44C is the SAED image of region 1011, which indicates a single crystal grain with a diffraction pattern of 143° to horizontal. FIG. 44D provides a lOx zoom image of region 1012 of the first sample shown in FIG. 44A; FIG. 44E is the SAED image of region 1012, which includes two diffraction patterns - one diffraction pattern of 145° to horizontal as illustrated by line 1017, and another diffraction pattern of 133° to horizontal as illustrated by line 1018. Additional areas 1012a, 1012b, and 1012c of region 1012 were selected to undergo SAED imaging as shown in FIGS. 44F and 441. FIG. 44G is the SAED image of area 1012a of region 1012, which has one diffraction pattern of 145°. FIG. 44H is the SAED image of area 1012b of region 1012, which has two diffraction patterns - one diffraction pattern of 146° to horizontal and another diffraction pattern of 134° to horizontal. FIG. 44 J is the SAED image of area 1012c of region 1012, which has two diffraction patterns - one diffraction pattern of 146° to horizontal and another diffraction pattern of 134° to horizontal. No areas of region 1012 containing only the 134° grain were discovered, which may indicate a unique grain or a fold in the graphene film.

[00264] FIG. 44K provides a lOx zoom image of region 1013 of the first sample shown in FIG. 44A; FIG. 44L is the SAED image of region 1013, which indicates a single crystal grain with a diffraction pattern of 146° to the horizontal as shown by line 1019. FIG. 44M provides a lOx zoom image of region 1014 of the first sample shown in FIG. 44A; FIG. 44N is the SAED image of region 1014, which indicates two crystal grains - one with a diffraction pattern of 147° to the horizontal as shown by line 1020a, and one with a diffraction pattern of 129° to the horizontal as shown by line 1020b. Two additional areas 1014a and 1014b of region 1014 underwent SAED imaging as shown in FIG. 440. FIG. 44P provides the SAED image of area 1014a, indicating a single crystal grain with a diffraction pattern of 129° to horizontal, and FIG. 44Q provides the SAED image of area 1014b, indicating a single crystal grain with a diffraction pattern of 146° to horizontal. As such, the grain boundary laid between area 1014a and 1014b.

[00265] FIG. 44R provides a 20x zoom image of region 1015 of the first sample shown in FIG. 44A; FIG. 44S is the SAED image of region 1015, which indicates a single crystal grain with a diffraction pattern of 146° to the horizontal. FIG. 44T provides a lOx zoom image of region 1016; FIG. 44U is the SAED image of region 1016, which indicates a single crystal grain with a diffraction pattern of 147° to the horizontal. In view of the results of the sample illustrated in FIGS. 44A-44U, the sample included two crystal grains as observed in region 1014, with a potential anomaly in the form of a fold in region 1012.

[00266] Referring to FIGS. 45A-45B, a second sample including large crystal graphene is provided. FIG. 45B is an altered image of 45A, where the image is taken slightly out of focus to exaggerate contrast. The brighter regions indicate the presence of graphene in that region. Seventy-eight of 127 regions (61%) were perforated. Regions 1021, 1022, 1023, 1024, 1025, 1026, 1027, 1028, and 1029, as labeled in FIG. 45 A, were subjected to SAED imaging and included the same diffraction pattern, with a grain boundary also observed in regions 1027 and 1028.

[00267] FIG. 45 C provides a lOx zoom image of region 1021 of the second sample shown in FIGS. 45A-45B; FIG. 45D is the SAED image of region 1021, which indicates a single crystal grain with a diffraction pattern of 152° to the horizontal as shown by line 1030. FIG. 45E provides a 20x zoom image of region 1022 of the second sample shown in FIGS. 45A-45B; FIG. 45F is the SAED image of region 1022, which indicates a single crystal grain with a diffraction pattern of 153° to the horizontal as shown by line 1040. FIG. 45G provides a 20x zoom image of region 1023 of the second sample shown in FIGS. 45A-45B; FIG. 45H is the SAED image of region 1023, which indicates a single crystal grain with a diffraction pattern of 153° to the horizontal as shown by line 1060. FIG. 451 provides a 20x zoom image of region 1024 of the second sample shown in FIGS. 45A-45B; FIG. 45 J is the SAED image of region 1024, which indicates a single crystal grain with a diffraction pattern of 154° to the horizontal as shown by line 1061. FIG. 45K provides a 20x zoom image of region 1025 of the second sample shown in FIGS. 45A-45B; FIG. 45L is the SAED image of region 1025, which indicates a single crystal grain with a diffraction pattern of 154° to the horizontal as shown by line 1062. [00268] FIG. 45M provides a 20x zoom image of region 1026 of the second sample shown in FIGS. 45A-45B; FIG. 45N is the SAED image of region 1026, which indicates a single crystal grain with a diffraction pattern of 153° to the horizontal as shown by line 1063. FIG. 450 provides a 20x zoom image of region 1027 of the second sample shown in FIGS. 45A-45B; FIG. 45P is the SAED image of region 1027, which indicates two crystal grains - one with a diffraction pattern of 153° to the horizontal as shown by line 1064a and one with a diffraction pattern of 120° to the horizontal as shown by line 1064b.

[00269] FIG. 45 Q provides a 20x zoom image of region 1028 of the second sample shown in FIGS. 45A-45B; FIG. 45R is the SAED image of region 1028, which indicates three crystal grains - one with a diffraction pattern of 154° to the horizontal as shown by line 1065a, one with a diffraction pattern of 139° to the horizontal as shown by line 1065b, and one with a diffraction pattern of 135° to the horizontal. The third crystal grain having a diffraction pattern of 135° to the horizontal is not highlighted in the large image of FIG. 45R but can be seen in the “zoomed region”. Two additional areas 1028a and 1028b of region 1028 underwent SAED imaging as shown in FIG. 45S. FIG. 45T provides the SAED image of area 1028a, indicating a single crystal grain with a diffraction pattern of 153° to the horizontal as shown by line 1066, and FIG. 45U provides the SAED image of area 1028b, indicating three crystal grains - one with a diffraction pattern of 153° to the horizontal as shown by line 1067a, one with a diffraction pattern of 140° to the horizontal as shown by line 1067b, and one with a diffraction pattern of 125° to the horizontal as shown by 1067c.

[00270] FIG. 45 V provides a 20x zoom image of region 1029 of the second sample shown in FIGS. 45A-45B; FIG. 45W is the SAED image of region 1029, which indicates a single crystal grain with a diffraction pattern of 153° to the horizontal as shown by line 1068.

[00271] Referring to FIGS. 46A-46B, a third sample including poly crystalline graphene is provided. FIG. 46B is an altered image of 46A, where the image is taken slightly out of focus to exaggerate contrast. The brightness of the regions indicate the presence of graphene in that region. Thirty -two of 37 regions (86%) were perforated. Only two films remained fully intact. Regions 1031, 1032, 1033, 1034, and 1035, as labeled in FIG. 46A, were subjected to SAED imaging and included the same diffraction pattern. Additional crystal grains were observed in regions 1032, 1033, and 1034. [00272] FIG. 46C provides a 20x zoom image of region 1031 of the third sample shown in FIGS. 46A-46B; FIG. 46D is the SAED image of region 1031, which indicates a single crystal grain with a diffraction pattern of -1° to the horizontal as shown by line 1069. FIG. 46E provides a lOx zoom image of region 1032 of the third sample shown in FIGS. 46A-46B; FIG. 46F is the SAED image of region 1032, which indicates two crystal grains - one with a diffraction pattern of 1° to the horizontal as shown by line 1070a and one with a diffraction pattern of 10° to the horizontal as shown by line 1070b. An additional area of region 1032 underwent SAED imaging as shown in FIG. 46G. FIG. 46H provides the SAED image of area 1032a, indicating a single crystal grain with a diffraction pattern of 10° to the horizontal as shown by line 1071. This indicates a grain boundary is present in region 1032.

[00273] FIG. 461 provides a lOx zoom image of region 1033 of the third sample shown in FIGS. 46A-46B; FIG. 46J is the SAED image of region 1033, which indicates multiple single crystal grains, including one with a diffraction pattern of -1° to the horizontal as shown by line 1072. Two additional areas 1033a and 1033b of region 1033 underwent SAED imaging as shown in FIG. 46K. FIG. 46L provides the SAED image of area 1033 a, indicating several crystal grains with varying diffraction patterns, but no crystal grain having a diffraction pattern of -1° to the horizontal. FIG. 46M provides the SAED image of area 1033b, indicating a single crystal grain of -1° to the horizontal as shown by line 1073. This indicates at least one grain boundary is present in region 1033.

[00274] FIG. 46N provides a lOx zoom image of region 1034 of the third sample shown in FIGS. 46A-46B; FIG. 460 is the SAED image of area 1034a (FIG. 46N) of region 1034, which indicates a single crystal grain with a diffraction pattern of 12° to the horizontal as shown by line 1074. An additional area 1034b of region 1034 underwent SAED imaging as shown in FIG. 46P. FIG. 46Q provides the SAED image of area 1034b, indicating several crystal grains with varying diffraction patterns, including at least one crystal grain with a diffraction pattern of 2° to the horizontal as shown by line 1075, but no crystal grains with a diffraction pattern of 12° to the horizontal, indicating at least one, if not multiple, grain boundaries within region 1034.

[00275] FIG. 46R provides a 20x zoom image of region 1035 of the third sample shown in FIGS. 46A-46B; FIG. 46S is the SAED image of area 1035a (FIG. 46R) of region 1035, which indicates several crystal grains with varying diffraction patterns, including at least one crystal grain with a diffraction pattern of 2° to the horizontal as shown by line 1076, but no crystal grains with a diffraction pattern of 12° to the horizontal.

[00276] Referring to FIGS. 47A-47B, a fourth sample including poly crystalline graphene is provided. FIG. 47B is an altered image of 47A, where the image is taken slightly out of focus to exaggerate contrast. The brightness of the regions indicate the presence of graphene in that region. Thirty-three of 37 regions (89%) were perforated. Only two films remained fully intact. Regions 1041, 1042, 1043, and 1044, as labeled in FIG. 47A, were subjected to SAED imaging. Regions 1041 and 1042 each contained the same crystal grain diffraction pattern. Regions 1043 and 1044 each contained a different crystal grain diffraction pattern from regions 1041 and 1042. The crystal grain patterns in regions 1043 and 1044, as discussed further below, varied from each other by 5°, which may indicate a common crystal grain pattern twisted during transfer or separate crystal grains.

[00277] FIG. 47C provides a 20x zoom image of region 1041 of the fourth sample shown in FIGS. 47A-47B; FIG. 47D is the SAED image of region 1041, which indicates two crystal grains - one with a diffraction pattern of -3° to horizontal as shown by line 1077a and one with a diffraction pattern of 10° to horizontal as shown by line 1077b. Three additional areas 1041a, 1041b, and 1041c, of region 1041 underwent SAED imaging as shown in FIG. 47E. FIG. 47F provides the SAED image of area 1041a, indicating a single crystal grain with a diffraction pattern of 10° to horizontal. FIG. 47G provides the SAED image of area 1041b, indicating two crystal grains - one with a diffraction pattern of -3° to horizontal as shown by line 1078a and one with a diffraction pattern of 10° to horizontal as shown by line 1078b. FIG. 47H provides the SAED image of area 1041c, indicating a single crystal grain with a diffraction pattern of 10° to horizontal as shown by line 1079. The similar crystal grain patterns at both sides of the boundary (i.e., areas 1041a and 1041c) indicates that the potential boundary within area 1041b is actually a fold within the sample rather than a grain boundary.

[00278] FIG. 471 provides a 20x zoom image of region 1042 of the fourth sample shown in FIGS. 47A-47B; FIG. 47J is the SAED image of region 1042, which indicates a single crystal grain with a diffraction pattern of 10° to horizontal as shown by line 1080. FIG. 47K provides a 20x zoom image of region 1043 of the fourth sample shown in FIGS. 47A-47B; FIG. 47L is the SAED image of area 1043 a (FIG. 47K) of region 1043, which indicates a single crystal grain with a diffraction pattern of 28° to horizontal as shown by line 1081. FIG. 47M provides a 20x zoom image of region 1044 of the fourth sample shown in FIGS. 47A-47B; FIG. 47N is the S AED image of area 1044a of region 1044, which indicates a single crystal grain with a diffraction pattern of 23° to horizontal as shown by line 1082.

[00279] The results of the SAED and TEM imaging indicate that large crystal graphene has four times the crystal grain size as polycrystalline graphene, and also indicates the success of stacking multiple layers, and at least three layers, of monolayer graphene. For example, the grain boundaries in the large crystal graphene samples are near the edge of the samples, indicating a lower bound of ~ 60 pm in diameter length, while the grain boundaries in the poly crystalline graphene samples are nearer the centre of the samples, indicating a lower bound of ~ 15 pm in diameter length. The number of visible crystal grains per sample, and the diameter of the available area to be measured per sample, are provided below in Table 1

[00280] Damaged occurred less frequently during transfer of the large crystal graphene samples when compared to damage occurring during transfer of the polycrystalline graphene samples

Example 13

[00281] A layer of polycrystalline graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. In other words, a single layer of poly crystalline graphene was grown on a sheet of copper foil and coated with polymethyl methacrylate (“PMMA”) before the copper foil was dissolved, leaving the single layer of poly crystalline graphene. The poly crystalline graphene layer was applied to a layer of PCV/silica and a layer of Nafion™ to create a polycrystalline graphene membrane.

[00282] A layer of large crystal graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. In other words, a single layer of large graphene was grown on a sheet of copper foil and coated with polymethyl methacrylate (“PMMA”) before the copper foil was dissolved, leaving the single layer of large crystal graphene. The large crystal graphene layer was applied to a layer of PCV/silica and a layer of Nafion™ to create a large crystal graphene membrane.

[00283] The potential difference, or conductivity, across several sample membranes was measured in voltage over the experienced current density (A cm’²), with the averages provided in FIG. 48. The PVC/silica membrane results are provided at “A”. The polycrystalline graphene membrane results (“B”) were averaged after twelve runs using four samples. The large crystal graphene membrane results (“C”) were averaged after six runs using two samples. The PVC/silica and Nafion™ membrane (without a graphene layer) results (“D”) were averaged after six runs using two samples.

[00284] As shown, the membranes containing graphene (A, B) experienced greater potential difference across the membrane, indicating higher resistance when compared to membranes which did not contain graphene. However, referring again to FIG. 35A of Example 8, the graphene membranes continued to experience a significantly lower resistance than previously measured for an anionic exchange membrane. Furthermore, the higher resistance of the graphene membrane is generally offset by the high selectivity the graphene layer provides to the membrane as discussed further herein.

Example 14

[00285] A layer of large crystal graphene was grown on a sheet of copper foil using a batch, horizontal, warm-walled, quartz-based, low-pressure chemical vapour deposition system including methane as a stock precursor. In other words, a single layer of large graphene was grown on a sheet of copper foil and coated with polymethyl methacrylate (“PMMA”) before the copper foil was dissolved, leaving the single layer of large crystal graphene. The large crystal graphene layer was applied to a layer of PCV/silica and a layer of Nafion™ to create a large crystal graphene membrane.

[00286] The large crystal graphene membrane was subjected to a membrane leakage test using a static standard copper ion solution (1000 mg/L) and current density of 25 mA cm’², which resulted in leakage of 0.11 mM/hr per cm². In previous iterations of similar tests, a PVC/silica membrane experienced leakage of 1.1 mM/hr per cm²; a single-layer poly crystalline graphene plus PVC/silica membrane post-conductivity testing experienced leakage of 0.16 mM/hr per cm²; a triple-layer polycrystalline graphene plus PVC/silica membrane postconductivity testing experienced leakage of 0.98 mM/hr per cm²; and a triple-layer polycrystalline graphene plus PVC/silica membrane without conductivity testing experienced leakage of 0.20 mM/hr per cm². These results indicate that membranes including graphene experience less leakage than non-graphene membranes and further indicate that large crystal graphene membranes experience about 40% less leakage than polycrystalline graphene membranes. As crystal size within the membrane increases, the less grain boundaries are present within the membrane, which results in less leakage across the membrane and, therefore, higher selectivity. As such, the trend of the results indicates that including single crystal graphene in the membrane will result in minimal to no leakage.

[00287] While the system and methods herein have been described by reference to various specific embodiments it should be understood that numerous changes may be made within the spirit and scope of the concepts described, accordingly, it is intended that the invention not be limited to the described embodiments but will have full scope defined by the language of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A pan for a batery cell, the pan comprising: a generally continuous sidewall coupled to a base, the generally continuous sidewall and the base cooperating to define a well; a flange extending outwardly from the generally continuous sidewall; and a metal covering positioned on an interior face of the base, the metal covering being one of zinc or copper.

2. The pan of claim 1 , further comprising a port defined within the generally continuous sidewall.

3. The pan of any one of claims 1-2, wherein the pan defines a rectangular shape.

4. The pan of any one of claims 1-3, wherein the pan is comprised of one of stainless steel or aluminium.

5. The pan of any one of claims 1-4, further comprising a ridge positioned on the rim, the ridge protruding outwardly from the flange in a direction opposite of the well.

6. The pan of claim 5, wherein the ridge extends along the perimeter of the pan.

7. The pan of any one of claims 1-6, wherein the flange includes a plurality of apertures.

8. The pan of any one of claims 1-7, wherein the generally continuous sidewall is beveled between the flange and the base.

9. The pan of any one of claims 1-8, wherein the base forms at least one support rib.

10. A batery cell comprising: a first electrode in contact with zinc;

44

SUBSTITUTE SHEET (RULE 26) a second electrode in contact with copper; and a membrane separating the first electrode and the second electrode, the membrane comprising a 2D material composite.

11. The battery cell of claim 10, wherein a 2D material of the 2D material composite comprises graphene.

12. The battery cell of claim 11, wherein the graphene comprises at least one crystal grain having a lower bound of 15 pm in diameter length.

13. The battery cell of claim 12, wherein the graphene comprises at least one crystal grain having a lower bound of 60 pm in diameter length.

14. The battery cell of claim 11, wherein the graphene includes only one single crystal grain.

15. The battery cell of claim 11, wherein the membrane has a single layer of graphene.

16. The battery cell of any one of claims 10-15, wherein the membrane comprises a plurality of layers.

17. The battery cell of claim 16, wherein the membrane has a plurality of monolayers of graphene.

18. The battery cell of any one of claims 16-17, wherein the plurality of layers includes at least one layer of PVC/Silica.

19. The battery cell of any one of claims 16-18, wherein the plurality of layers includes at least one layer of a proton exchange membrane.

45

SUBSTITUTE SHEET (RULE 26)

20. The battery cell of any one of claims 10-19, wherein the membrane is sans perfluoroalkyl substances and polyfluoroalkyl substances.

21. A battery cell comprising: a first pan having a first base, a first sidewall extending from the first base so that the first base and the first sidewall define a first well, a first flange extending outwardly from the first base, and a zinc covering positioned on a first interior face of the first base; and a second pan having a second base, a second sidewall extending from the second base so that the second base and the second sidewall define a second well, a second flange extending outwardly from the second base, and a copper covering positioned on a second interior face of the second base; wherein the first pan and the second pan are arranged so that the zinc covering and the copper covering face each other.

22. The battery cell of claim 21, wherein the first pan and the second pan are physically coupled via fasteners extending through a first plurality of apertures defined by the first flange and a second plurality of apertures defined by the second rim.

23. The battery cell of claim 21, further comprising a nylon separator positioned between each of the fasteners and the first pan and the second pan.

24. The battery cell of claim 21 , wherein the first pan and the second pan are coupled via clamps which clamp the first flange and the second flange together.

25. The battery cell of claim 24, wherein the clamps consist of a non-conductive material.

26. The battery cell of any one of claims 21-25, further comprising a membrane positioned between the first pan and the second pan.

46

SUBSTITUTE SHEET (RULE 26)

27. The battery cell of claim 26, wherein at least one of the first pan and the second pan includes a ridge extending from one of the first flange and the second flange to facilitate clamping of the membrane between the first pan and the second pan.

28. The battery cell of any one of claims 26-27, wherein the membrane comprises graphene.

29. The battery cell of any one of claims 26-28, wherein the membrane is a graphene and polymer composite.

30. The battery cell of any one of claims 21-29, wherein at least one of the first pan and the second pan includes a surface area enhancement.

31. The battery cell of any one of claims 21-30, further comprising an electrolyte in each of the first well and the second well.

32. The battery cell of any one of claims 21-31, wherein the first pan is an aluminium pan.

33. The battery cell of any one of claims 21-32, wherein the second pan is a stainless steel pan.

34. The battery cell of any one of claims 21-33, further comprising an agitation mechanism positioned in at least one of the first pan and the second pan.

35. The battery cell of any one of claims 21-34, further comprising at least one port defined by the sidewall of at least one of the first pan and the second pan.

36. The battery cell of claim 35, wherein the at least one port is fluidly coupled to a collection container.

37. A battery system, comprising:

47

SUBSTITUTE SHEET (RULE 26) a plurality of battery packs, each battery pack having a plurality of battery cells arranged so that each battery pack includes: a first electrode in contact with zinc; a second electrode in contact with copper; and a membrane positioned between the first electrode and the second electrode; wherein the zinc and the copper are separated from each other by the first and second electrode on one side and by the membrane on the other.

38. A membrane, comprising: a plurality of layers, including: a first layer comprised of a 2D material; and a second layer comprised of one of:

PVC/Silica; and a proton exchange membrane.

39. The membrane of claim 38, wherein the 2D material is graphene.

40. The membrane of claim 39, wherein the graphene comprises at least one crystal grain having a lower bound of 15 pm in diameter length.

41. The membrane of claim 40, wherein the graphene comprises at least one crystal grain having a lower bound of 60 pm in diameter length.

42. The membrane of claim 39, wherein the graphene includes only one single crystal grain.

43. The membrane of claim 39, wherein the graphene is poly crystalline.

44. The membrane of claim 38, wherein the first layer is comprised of a plurality of sublayers of monolayer graphene.

48

SUBSTITUTE SHEET (RULE 26)

45. The membrane of any one of claims 38-43, wherein the membrane is sans perfluoroalkyl substances and polyfluoroalkyl substances.

46. The membrane of any one of claims 38-44, further comprising a third layer comprised of the other of PVC/Silica and the proton exchange membrane.

47. The membrane of any one of claims 38-45, wherein the plurality of layers includes multiple layers comprised of a proton exchange membrane.

48. The membrane of any one of claims 38-46, wherein the membrane is positioned within a fuel cell.

49. The membrane of any one of claims 38-46, wherein the membrane is positioned within a battery.

50. The membrane of any one of claims 38-46, wherein the membrane is positioned within a water treatment device.

51. The membrane of any one of claims 38-46, wherein the membrane is positioned within an electrolyser.

52. The membrane of claim 38, wherein the 2D material is selected from a group consisting of graphene, graphyne, borophene, germanene, silicene, stanene, plumbene, phosphorene, antimonene, bismuthine, 2D alloys, 2D supracrystals, germanane, molybdenum disulphide, tungsten disulphide, and hexagonal boron nitride.

49

SUBSTITUTE SHEET (RULE 26)