Polymer electrolyte for a flexible battery

Abstract

The present disclosure generally relates to a non-aqueous polymer electrolyte precursor. In particular, the non-aqueous polymer electrolyte precursor of the present disclosure comprises a liquid electrolyte and a solvated polymer matrix. The present disclosure also relates to a non- aqueous polymer electrolyte obtained from the non-aqueous polymer electrolyte precursor. The present disclosure also relates to methods for preparing a non-aqueous polymer electrolyte and a non-aqueous polymer electrolyte, and the use of these in electrochemical cells.

Description

POLYMER ELECTROLYTE FOR A FLEXIBLE BATTERYTECHNICAL FIELD[1] The present disclosure relates generally to a polymer electrolyte precursor and to polymer electrolytes. In particular, the present disclosure relates to a polymer electrolyte precursor which can be used to obtain polymer electrolytes for the production of electrochemical cells, particularly flexible electrochemical cells. The present disclosure also relates to processes for preparing a polymer electrolyte precursor, and processes for preparing an electrochemical cell comprising the polymer electrolyte. The present disclosure also relates to electrochemical cells comprising the polymer electrolyte.BACKGROUND[2] The rapid advancement of wearable devices and flexible displays has highlighted a need for improvements in battery technology. Batteries are required not only to provide sufficient energy and power outputs, but must also be thin and mechanically deformable to facilitate integration with small electronics, such as wearable electronics, rollable displays, and flexible sensors.[3] Zinc-manganese dioxide (Zn-Mn02) and zinc-silver oxide (Zn-Ag20) chemistries have been widely adopted for commercialised flexible batteries. Flexible batteries may employ polymer electrolytes (PEs). Polymer electrolytes are inherently flexible and can conform to different shapes and sizes, making them suitable for use in flexible batteries.[4] To date, the majority of the polymer electrolytes are aqueous-based, such as those based on potassium hydroxide, this is primarily due to their low material cost. However, these electrolytes pose certain challenges, including a narrow thermodynamic voltage window of up to 1.23 V, and Zn corrosion and / or dendritic growth. The aforementioned issues may reduce battery voltage and cyclability, ultimately restricting energy density and cycling lifetime.[5] Ionic liquids have also been incorporated into electrolytes as solvents, see for example US 2014 / 0302373 Al and US 2014 / 0017557 Al. While electrolytes containing ionic liquids may exhibit a wide electrochemical stability window, high thermal stability, and negligible vapor pressure they have notable disadvantages including their relatively high cost compared to traditional electrolyte solvents and higher viscosity which can limit ion mobility. Ionic liquids may also raise environmental concerns due to their synthesis and disposal processes.[6] CN 11864528 A provides a solid composite electrolyte membrane, which is composed of a solid polymer electrolyte layer and gel polymer electrolyte layer prepared from a polymer electrolyte composition containing a polymer, a plastic crystal and an electrolyte salt dissolved in a solvent, such as acetone, acetonitrile, dichloromethane, with acetonitrile exemplified.[7] Another challenge associated with the incorporation of polymer electrolytes into electrochemical cells is the ability to manufacture cells on a commercial scale. Each electrochemical cell requires precise assembly to guarantee proper electrode alignment and electrical connection. Uniformity and consistency of the polymer electrolyte within the electrochemical cell is also required, as variations in its composition can lead to inconsistencies in performance. Any imperfections in the polymer electrolyte layer or the cell structure may compromise performance and even pose safety hazards.SUMMARY[8] The present disclosure provides a non-aqueous polymer electrolyte (PE) precursor. The present disclosure also provides a non-aqueous polymer electrolyte. The present disclosure also provides a non-aqueous polymer electrolyte obtained from the non-aqueous polymer electrolyte precursor described herein. The present disclosure also provides a method for preparing a nonaqueous polymer electrolyte precursor. The present disclosure also provides a method for preparing a non-aqueous polymer electrolyte. The non-aqueous polymer electrolyte described herein and obtained from the process described herein may be used in electrochemical cells.[9] In a first aspect, the present disclosure provides for a non-aqueous polymer electrolyte precursor comprising: a liquid electrolyte comprising: an organic solvent, and a metal salt; a solvated polymer matrix; and a filler.

[0010] In some embodiments, the non-aqueous polymer electrolyte precursor comprises: a liquid electrolyte comprising: a non-ionic organic solvent, and a metal salt; a solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt%; wherein the amount of solvated polymer matrix (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt% wherein the amount of filler (as a weight % of polymer electrolyte precursor) is between about 0.1 wt% to about 20 wt%.

[0011] In some embodiments, the non-ionic organic solvent is selected from N,N- dimethylformamide, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0012] In some embodiments, the metal salt includes a cation selected from lithium, zinc, and combinations thereof.

[0013] In another aspect, the present disclosure provides for a non-aqueous polymer electrolyte film comprising: a liquid electrolyte comprising an organic solvent, and a metal salt; a polymer matrix; and a filler.

[0014] In some embodiments, the non-aqueous polymer electrolyte film comprises: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte film) is between about 40 wt% to about 90 wt%; wherein the amount of polymer matrix (as a weight % of polymer electrolyte film) is between about 10 wt% to about 50 wt% wherein the amount of filler (as a weight % of polymer electrolyte film) is between about 0.1 wt% to about 20 wt%.

[0015] In another aspect, the present disclosure provides for a printable gel non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising an organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler.

[0016] In some embodiments, the printable gel non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, anda metal salt; a partially solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 10 wt% to about 60 wt%; wherein the amount of partially solvated polymer matrix (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 30 wt% to about 90 wt% wherein the amount of filler (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 0.1 wt% to about 20 wt%.

[0017] In another aspect, the present disclosure provides for a method of preparing a nonaqueous polymer electrolyte precursor comprising:(i) obtaining a liquid electrolyte comprising a non-ionic organic solvent and a metal salt;(ii) obtaining a polymer matrix comprising a polymer and polymer solvent;(iii) obtaining a filler; and(iv) mixing the liquid electrolyte, the polymer matrix and the filler to form the nonaqueous polymer electrolyte precursor.

[0018] In a fifth aspect, the present disclosure provides for a method of preparing an optionally printable non-aqueous polymer electrolyte comprising:(i) obtaining a liquid electrolyte comprising a non-ionic organic solvent and a metal salt;(ii) obtaining a polymer matrix comprising a polymer and polymer solvent;(iii) obtaining a filler;(iv) mixing the liquid electrolyte, the polymer matrix and the filler to form a nonaqueous polymer electrolyte precursor; and(v) heating the non-aqueous polymer electrolyte precursor to remove at least a portion of polymer solvent to form the non-aqueous polymer electrolyte.

[0019] The method of the fourth or fifth aspect, wherein the method further comprises (vi) casting the non-aqueous polymer electrolyte precursor or non-aqueous polymer electrolyte to form a non-aqueous polymer electrolyte film.

[0020] In another aspect, the present disclosure provides for a non-aqueous polymer electrolyte precursor obtained from the method of the fourth aspect or a non-aqueous polymer electrolyte obtained from the method of the fifth aspect.

[0021] In another aspect, the present disclosure provides for the use of the non-aqueous polymer electrolyte precursor of the first aspect or that obtained from the method of the fourth aspect in the manufacture of an electrochemical cell and / or use of a non-aqueous polymerelectrolyte as defined by the second or third aspects or obtained from the method of the fifth aspect, in the manufacture of an electrochemical cell.

[0022] In another aspect, the present disclosure provides for an electrochemical cell comprising: a negative electrode; a positive electrode; a non-aqueous polymer electrolyte of the second or third aspects or as obtained by the sixth or seventh aspects.

[0023] After extensive research and development, the present inventors have surprisingly discovered a non-aqueous polymer electrolyte precursor which can be used to produce nonaqueous polymer electrolytes for electrochemical cells. The non-aqueous polymer electrolytes described herein may provide a flexible and robust alternative to existing electrolytes and may be incorporated into electrochemical cells by a variety of manufacturing methods. Advantageously, the non-aqueous polymer electrolytes or electrolytes derived from the non-aqueous polymer electrolyte precursor described herein are suitable for ambient operation, thus overcoming issues associated with water-based solvents. Furthermore, the non-aqueous polymer electrolytes or electrolytes derived from the non-aqueous polymer electrolyte precursor described herein may offer cost advantages over ionic liquid electrolyte solvents. Thus, the non-aqueous polymer electrolyte of the present disclosure may provide a cost-effective pathway for producing electrochemical cells, particularly for use in flexible batteries, including zinc batteries.BRIEF DESCRIPTION OF DRAWINGS

[0024] Whilst it will be appreciated that a variety of embodiments disclosed herein may be utilised, described herein are a number of examples with reference to the following drawings:

[0025] Figure 1 : Schematic illustration outlining the synthetic route for a non-aqueous polymer electrolyte, printable gel polymer electrolyte, and free-standing polymer electrolyte film for printed batteries according to some embodiments of the present disclosure;

[0026] Figure 2: (a) Schematic illustration of the screen-printing process; (b) layer-by-layer component demonstration; (c) photos of screen-printed PE, Zn anode, MnCb cathode and current collector; (d) photos of assembled screen-printed batteries;

[0027] Figure 3: (a) Apparent viscosity of polymer electrolyte; (b) shear stress of PE under different temperature conditions; (c) printed PE on top of the electrode layers;

[0028] Figure 4: (left) PE under tensile testing via Instron electro-mechanical loadframe; (right) Stress-strain curves of the Zn anode on Cu CC, MnCb cathode on Al-C CC, and PE (CC: current collector);

[0029] Figure 5: Electrochemical impedance spectroscopy (EIS) spectra of (a) dry polymer electrolyte film; (b) polymer electrolyte film soaked in liquid electrolyte sandwiched between two stainless steel blocking electrodes under different testing temperatures; (c) temperature dependence of ionic conductivity of the dry and soaked polymer electrolyte films;

[0030] Figure 6: Symmetric Zn|Zn plating / stripping test under 0.5 mA cm'2when incorporated with liquid electrolyte and non-aqueous polymer electrolyte;

[0031] Figure 7: (a) Electrochemical impedance spectra of the full cells, with a printed area of 0.25 and 0.5 cm2, respectively; (b) Change of a full cell’s open circuit voltage during a three- point bending test, where the flexure displacement varied from 0 to 9 mm; (c) discharge profiles under different current densities; (d) areal capacity and coulombic efficiency of a printed battery in long term cycling; and

[0032] Figure 8: SEM images of (a) cross-sectional view of PE; (b) top view of polymer electrolyte printed on the Zn anode surface; (c) top view of polymer electrolyte printed on the MnCb cathode surface.DETAILED DESCRIPTION

[0033] The present disclosure describes the following various non-limiting embodiments, processes, methods compositions and / or articles.General terms

[0034] In the following description, reference is made to the accompanying drawings which form a part hereof, and which is shown, by way of illustration, several embodiments. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure.

[0035] With regards to the definitions provided herein, unless stated otherwise, or implicit from context, the defined terms and phrases include the provided meanings. Unless explicitly stated otherwise, or apparent from context, the terms and phrases below do not exclude the meaning that the term or phrase has acquired by a person skilled in the relevant art. The definitions are provided to aid in describing particular embodiments, and are not intended to limit the claimed invention, because the scope of the invention is limited only by the claims. Furthermore, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0036] All publications discussed and / or referenced herein are incorporated herein in their entirety.

[0037] Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present disclosure. It is not to be taken as an admission that any or all of these matters form partof the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each claim of this application.

[0038] Throughout this disclosure, unless specifically stated otherwise or the context requires otherwise, reference to a single step, composition of matter, group of steps or group of compositions of matter shall be taken to encompass one and a plurality (i.e., one or more) of those steps, compositions of matter, groups of steps or groups of compositions of matter. Thus, as used herein, the singular forms “a”, “an” and “the” include plural aspects unless the context clearly dictates otherwise. For example, reference to “a” includes a single as well as two or more; reference to “an” includes a single as well as two or more; reference to “the” includes a single as well as two or more and so forth.

[0039] Those skilled in the art will appreciate that the disclosure herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all of the examples, steps, features, methods, compositions, coatings, processes, and coated substrates, referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features.

[0040] The term “and / or”, e.g., “X and / or Y” shall be understood to mean either “X and Y” or “X or Y” and shall be taken to provide explicit support for both meanings or for either meaning.

[0041] As used herein, the phrase “at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the list may be needed. The item may be a particular object, thing, or category. In other words, “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required. In some cases, “at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.

[0042] As used herein, the term “about”, unless stated to the contrary, typically refers to + / - 10%, for example + / - 5%, of the designated value.

[0043] It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.

[0044] Throughout the present specification, various aspects and components of the invention can be presented in a range format. The range format is included for convenience and should not be interpreted as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range, unless specifically indicated. For example, description of a range such as from 1 to 5 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 5, from 3 to 5 etc., as well as individual and partial numbers within the recited range, for example, 1, 1.5, 2, 2.2, 3, 4, 4.6, and 5, unless where integers are required or implicit from context. This applies regardless of the breadth of the disclosed range. Where specific values are required, these will be indicated in the specification.

[0045] Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0046] The reference to “substantially free” generally refers to the absence of that compound or component in the composition other than any trace amounts or impurities that may be present, for example this may be an amount by weight % in the total composition of less than about 3%, 2% 1%, 0.1%, 0.01%, 0.001%, or 0.0001%.

[0047] Herein “weight %” may be abbreviated to “wt%”.

[0048] In the following description, reference is made to the accompanying drawings which form a part hereof, and which is shown, by way of illustration, several embodiments. It is understood that other embodiments may be utilised and structural changes or adaptions to one or more methods or processes, may be made without departing from the scope of the present disclosure.Non-aqueous polymer electrolyte precursor

[0049] The non-aqueous polymer electrolyte precursor described herein provides for distinct advantages in forming a polymer electrolyte for use in flexible batteries. The non-aqueous polymer electrolyte precursor of the disclosure comprises only minor or trace amounts of water or, preferably, substantially no water content. The use of a non-aqueous polymer electrolyte precursor allows the approach herein to be suitable for ambient operation, thus overcoming issues associated with water-based solvents. It may also provide for cost-savings in comparison with an ionic liquid-based approach. Further, it may provide for benefits in extending the working voltage window of the electrochemical cell incorporating the formed polymer electrolyte in comparison with a similar polymer electrolyte precursor which does contain water. The non-aqueous polymer electrolyte precursor of the present disclosure may provide an inexpensive base composition to obtain a polymer electrolyte for use in flexible batteries. In one aspect, the non-aqueous polymer electrolyte precursor comprises a liquid electrolyte as describedherein and a solvated polymer matrix as described herein. In some aspects or embodiments, the non-aqueous polymer electrolyte precursor further comprises a filler as described herein.

[0050] Advantageously, the non-aqueous polymer electrolyte precursor may be modified to obtain electrolytes with a wide range of properties including, but not limited to, ionic conductivity, thermal stability, and / or viscosity. Further, the precursor composition may be used to obtain free-standing polymer electrolyte films and printable polymer electrolyte gels. Achieving both free-standing polymer electrolyte films and printable polymer electrolyte gels from the same base non-aqueous polymer electrolyte precursor is a significant advantage as it tackles the current challenge of transitioning laboratory research into large-scale production for flexible batteries. This customisation potentially allows for the optimisation of non-aqueous polymer electrolytes as described herein for specific battery applications, including those that require flexibility. The non-aqueous polymer electrolyte of the present disclosure may be used with a wide range of electrode materials, including various metals, metal oxides, and conductive polymers, making it versatile for different battery chemistries.

[0051] In one aspect of the present disclosure, there is provided a non-aqueous polymer electrolyte precursor comprising: a liquid electrolyte comprising: an organic solvent, and a metal salt; a solvated polymer matrix; and a filler.

[0052] In some embodiments, the non-aqueous polymer electrolyte precursor comprises: a liquid electrolyte comprising: a non-ionic organic solvent, and a metal salt; a solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt%; wherein the amount of solvated polymer matrix (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt% wherein the amount of filler (as a weight % of polymer electrolyte precursor) is between about 0.1 wt% to about 20 wt%.

[0053] In some embodiments, the non-aqueous polymer electrolyte precursor comprises: a liquid electrolyte comprising:a non-ionic organic solvent, and a metal salt; a solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte precursor) is between about 5 wt% to about 50 wt%; wherein the amount of solvated polymer matrix (as a weight % of polymer electrolyte precursor) is between about 10 wt% to about 90 wt% wherein the amount of filler (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 20 wt%.

[0054] The inventors of the present disclosure have surprisingly found that various embodiments of polymer electrolytes of the present disclosure obtained from this precursor composition may have one or more advantageous properties including, but not limited to, printability via, for example, screen printing or roll-to-roll processing; the ability to be simply formed into free standing films; and reduced cost compared to other electrolytes such as, for example, ionic liquid-based electrolytes.Non-aqueous

[0055] The person skilled in the art would understand ‘non-aqueous’ to mean that the nonaqueous polymer electrolyte precursor of the present disclosure is distinguished from those polymer electrolytes that utilise liquid water as at least a component of a solvent in the preparation thereof. In some embodiments, the non-aqueous polymer electrolyte precursor comprises only trace amounts of water. In some embodiments, the non-aqueous polymer electrolyte precursor is substantially free of liquid water. In some embodiments, the non-aqueous polymer electrolyte precursor is substantially anhydrous or substantially only comprises water as a hydrate of a chemical component or trace amounts which may be absorbed from the atmosphere. In some embodiments, the non-aqueous polymer electrolyte precursor is formed without the addition of liquid water or of an aqueous solution / component. The absence of water in the non-aqueous polymer electrolyte precursor may be advantageous in extending the working voltage window above 1.23 V when using electrolytes derived from the precursor composition. Further, the non-aqueous polymer electrolyte of the present disclosure derived from the precursor may extend the electrochemical window beyond water splitting range.

[0056] In some embodiments, the non-aqueous polymer electrolyte precursor comprises less than 5% w / w water, preferably less than 4% w / w water, more preferably less than 3% w / w water, even more preferably less than 2% w / w water, still more preferably less than 1% w / w water, and yet still more preferably less than 0.75% w / w water. Reference here to “water” is toliquid water added to the precursor and does not include any water of hydration of the chemical components of the precursor.

[0057] In some embodiments relating to the non-aqueous polymer electrolyte precursor the term “trace amount(s)” of water refers to less than 0.7% w / w, less than 0.6% w / w, less than 0.5% w / w, less than 0.4% w / w, less than 0.3% w / w or less than 0.25% w / w of water. Reference here to “water” is to liquid water added to the precursor and does not include any water of hydration of the chemical components of the precursor.

[0058] In some embodiments relating to the non-aqueous polymer electrolyte precursor the term “substantially free” of water refers to less than 0.2% w / w, less than 0.1% w / w or less than 0.05% w / w of water. Reference here to “water” is to liquid water added to the precursor and does not include any water of hydration of the chemical components of the precursor.

[0059] In some embodiments, there is provided a non-aqueous polymer electrolyte precursor comprising: a liquid electrolyte comprising: a non-ionic organic solvent, and a metal salt; a solvated polymer matrix; and a filler, wherein the precursor comprises less than 5% w / w of water, or less than 3% w / w water, or less than 1% w / w water.Liquid electrolyte

[0060] The non-aqueous polymer electrolyte precursor comprises a liquid electrolyte. The liquid electrolyte comprises a non-ionic organic solvent and a metal salt.

[0061] In some embodiments, the liquid electrolyte comprises no more than trace amounts of water.

[0062] In some embodiments, the liquid electrolyte consists or consists essentially of one or more non-ionic organic solvents and one or more metal salts.Non-ionic organic solvent

[0063] The person skilled in the art would understand that a suitable organic solvent may be selected from a wide range of available organic solvents for use in the liquid electrolyte. The organic solvent will be selected to ensure sufficient solubility of the appropriate metal salt to achieve the desired ionic conductivity in a polymer electrolyte derived from the non-aqueous polymer electrolyte precursor.

[0064] In some embodiments, the organic solvent is a non-ionic organic solvent.

[0065] In some embodiments, the non-ionic organic solvent is selected from alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, l-methoxy-2-propanol, tetrahydrofurfuryl alcohol (THFA), cyclohexanol, cyclopentanol, terpineol; lactones such as butyl lactone; polyethers; ketones, including diketones and cyclic ketones, such as cyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, acetone, benzophenone, acetyl acetone, acetophenone, cyclopropanone, isophorone, methyl ethyl ketone; esters such ethyl acetate, dimethyl adipate, proplyene glycol monomethyl ether acetate, dimethyl glutarate, dimethyl succinate, glycerol acetate, carboxylates; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycol ether, glycol ether acetate; carbonates such as propylene carbonate; glycerol and other polyols and polymeric polyols or glycols such as glycerol, diol, triol, tetraol, pentaol, ethylene glycol, 1,4-butanediol,1.2-butanediol, 2,3-butanediol, 1,3 -propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol,1.2-propanediol, 1,3 -butanediol, 1,2-pentanediol, etohexadiol, p-menthane-3,8-diol, 2-methyl- 2,4-pentanediol; tetramethyl urea, N-methylpyrrolidone (NMP), acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO), thionyl chloride, sulfuryl chloride, and combinations thereof.

[0066] In some embodiments, the non-ionic organic solvent is selected from isopropyl alcohol, diethylene glycol, glycerol, ethylene glycol, ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, vinylene carbonate, dimethyl ether, 1,3 -di oxolane, l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1 -butyl-3 -methylimidazolium bis(trifluoromethylsulfonyl)imide, 1 -ethyl- 1 -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N,N-dimethylformamide, acetonitrile, dimethyl sulfoxide, tetramethylene sulfone, and combinations thereof.

[0067] In some embodiments, the organic solvent is selected from N,N-dimethylformamide, acetonitrile, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0068] In some embodiments, the organic solvent is selected from N,N-dimethylformamide, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0069] In some embodiments, the organic solvent comprises one or more hydroxyl groups.

[0070] In some embodiments, the organic solvent is selected from ethylene glycol, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0071] In some embodiments, the organic solvent is ethylene glycol.

[0072] In some embodiments, the non-ionic organic solvent is selected from N,N- dimethylformamide, acetonitrile, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0073] In some embodiments, the non-ionic organic solvent is selected from N,N- dimethylformamide, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0074] In some embodiments, the non-ionic organic solvent comprises one or more hydroxyl groups.

[0075] In some embodiments, the non-ionic organic solvent is selected from ethylene glycol, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

[0076] In some embodiments, the non-ionic organic solvent is ethylene glycol.Metal salt

[0077] It will be appreciated by the person skilled in the art that the metal salt may be selected from any salt suitable to be incorporated into a polymer electrolyte. The metal salt may be selected from any metal salt which can be dissolved in a non-ionic organic solvent and which can function in the polymeric electrolyte system. In some embodiments, the metal salt can include a cation selected from lithium, zinc, nickel, aluminum, cobalt, and combinations thereof.

[0078] In some embodiments, the metal salt can include a cation selected from lithium, zinc, and combinations thereof.

[0079] In some embodiments, the metal salt can include an anion selected from tris(pentafluoroethyl)trifluorophosphate, trifluorom ethanesulfonate, hexafluorophosphate, tetrafluorob orate, ethyl sulfate, dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate, triflate, tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl) phosphinate, iodide, chloride, bromide, nitrate, methanesulfonate, methyl sulfate, acetate, and fluoroacetate, and combinations thereof.

[0080] In some embodiments, the metal salt is selected from zinc tetrafluoroborate hydrate, zinc sulfate heptahydrate, zinc sulfate monohydrate, zinc trifluoromethanesulfonate, zinc di[bis(trifluoromethylsulfonyl)imide], zinc chloride, zinc perchlorate hexahydrate, zinc nitrate hexahydrate, lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, and combinations thereof.

[0081] In some embodiments, the metal salt is a zinc salt.

[0082] In some embodiments, the metal salt is selected from zinc tetrafluoroborate hydrate, zinc sulfate heptahydrate, zinc sulfate monohydrate, zinc trifluoromethanesulfonate, zinc di[bis(trifluoromethylsulfonyl)imide], zinc chloride, zinc perchlorate hexahydrate, zinc nitrate hexahydrate, and combinations thereof.

[0083] In some embodiments, the metal salt is selected from zinc tetrafluoroborate, zinc trifluoromethanesulfonate, zinc sulfate, and combinations thereof.

[0084] In some embodiments, the metal salt is zinc tetrafluorob orate.

[0085] The metal salt may be provided at any concentration suitable to provide the desired ionic conductivity of the liquid electrolyte. In some embodiments, the concentration (molality, m) of the metal salt (mol / kg of non-ionic organic solvent) in the liquid electrolyte is about, or greater than about: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 13,3, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, the concentration of the metal salt (mol / kg of non-ionic organic solvent) in the liquid electrolyte is less than about: 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The metai salt may be in a concentration (molality, m) range provided by any two of these upper and / or lower values, for example between about 0.1 and about 20, between about 1 and about 15, or between about 5 and about 15.

[0086] In some embodiments, the metal salt is provided at or about the saturation concentration in the liquid electrolyte.

[0087] In some embodiments, the non-ionic organic solvent is ethylene glycol, the metal salt is zinc tetrafluorob orate or a hydrate thereof and is provided in a concentration (mol / kg of non- ionic organic solvent) of between about 1 and about 20 in the liquid electrolyte.

[0088] In some embodiments, the non-ionic organic solvent is ethylene glycol, the metal salt is zinc tetrafluorob orate or a hydrate thereof and is provided at or about the saturation concentration in the liquid electrolyte.Solvated polymer matrix

[0089] The non-aqueous polymer electrolyte precursor comprises a solvated polymer matrix. In some embodiments, the solvated polymer matrix comprises a polymer, which forms the polymer framework of the polymer electrolyte, and a polymer solvent. In some embodiments, the solvated polymer matrix comprises a polymer and a polymer solvent. The inclusion of a suitable amount of the solvated polymer matrix in the non-aqueous polymer electrolyte precursor may provide the non-aqueous polymer electrolyte precursor with one or more desirable properties, for example, but not limited to, a desired viscosity and / or adhesiveness. Based on the particular application required and the present disclosure, it would be within the level of ordinary skill ofthe person of skill in the art to select an appropriate solvated polymer matrix and to determine the relative amount required.

[0090] In some embodiments, the solvated polymer matrix comprises no more than trace amounts of water.

[0091] In some embodiments, the solvated polymer matrix consists or consists essentially of one or more polymers and one or more non-aqueous polymer solvents.Polymer

[0092] The person skilled in the art would appreciate that any of a wide range of suitable polymers may be selected for inclusion in the solvated polymer matrix. In some embodiments, the polymer is selected from polyvinyl pyrrolidone, polyvinyl alcohol, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), polyvinylidene fluoride-trifluoroethylene, polytetrafluoroethylene, polydimethylsiloxane, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethylene glycolhexafluoropropylene, polyethylene, polyvinylalcogel, polyvinylpyrrolidone, polyvinyl chloride, polyvinyl butyral; polyimide polymers and copolymers (including aliphatic, aromatic and semi-aromatic polyimides) such as polyamide, polyaramides, polyacrylamide; acrylate and (meth)acrylate polymers and copolymers such as polymethylmethacrylate, polyacrylonitrile, acrylonitrile butadiene styrene, allylmethacrylate, polyvinylcaprolactam, polystyrene, polybutadiene, polybutylene terephthalate, polycarbonate, polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin; saccharides and polysaccharides such as guar gum, xanthan gum, starch, butyl rubber, agarose, pectin; celluloses and modified celluloses such as hydroxy methylcellulose, methylcellulose, ethyl cellulose, propyl methylcellulose, methoxy cellulose, methoxy methylcellulose, methoxy propyl methylcellulose, hydroxy propyl methylcellulose, carboxy methylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose, cellulose ether, cellulose ethyl ether; chitosan, and combinations thereof.

[0093] In some embodiments, the polymer is selected from polyvinyl alcohol, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), polyethylene oxide, polypropylene oxide, polyimide polymers and copolymers, polyacrylamide; acrylate and (meth)acrylate polymers and copolymers; saccharides and polysaccharides such as guar gum, xanthan gum, starch, butyl rubber, agarose, pectin; celluloses and modified celluloses such as hydroxy methylcellulose, methylcellulose, ethyl cellulose, propyl methylcellulose, methoxy cellulose, methoxy methylcellulose, methoxy propyl methylcellulose, hydroxy propyl methylcellulose, carboxy methylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose, cellulose ether, cellulose ethyl ether, and combinations thereof.

[0094] In some embodiments, the polymer is selected from polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), and combinations thereof. In some embodiments, the polymer is poly(vinylidene fluoride-co-hexafluoropropylene). In some embodiments, the polymer is polyvinylidene fluoride.Polymer solvent

[0095] The person skilled in the art would appreciate that any suitable non-aqueous solvent may be selected for inclusion in the solvated polymer matrix. The term “polymer solvent” does not imply that the solvent in any way has polymeric character but merely that it is suitable for preparation of the polymer matrix with the polymer of choice. It will be further appreciated that the polymer solvent may be selected for compatibility with the polymer. The polymer solvent is selected from methanol, ethanol, propanol, butanol, pentanol , hexanol, octanol, l-methoxy-2- propanol, tetrahydrofurfuryl alcohol (THFA), cyclohexanol, cyclopentanol, terpineol; lactones such as butyl lactone; gamma-butyrolactone (oxolan-2-one); gamma-valerolactone (5- methyloxolan-2-one); cyrene (dihydrolevoglucosenone, (lR,5S)-7,8-dioxabicyclo[3.2.1]octan-2- one); ethers such as, ethyl propyl ether, and polyethers; ketones, including diketones and cyclic ketones, such as cyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, , benzophenone, acetylacetone, acetophenone, cyclopropanone, isophorone, methyl ethyl ketone; esters such ethyl acetate, dimethyl adipate, proplyene glycol monomethyl ether acetate, dimethyl glutarate, dimethyl succinate, glycerol acetate, carboxylates; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycol ether, glycol ether acetate; carbonates such as propylene carbonate; glycerols and other polyols and polymeric polyols or glycols such as glycerol, diol, triol, tetraol, pentaol, ethylene glycol, 1,4-butanediol,1.2-butanediol, 2,3-butanediol, 1,3 -propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol,1.2-propanediol, 1,3 -butanediol, 1,2-pentanediol, etohexadiol, p-menthane-3,8-diol, 2-methyl- 2,4-pentanediol; tetramethyl urea, N-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO); thionyl chloride; sulfuryl chloride; and combinations thereof.

[0096] In some embodiments, the polymer solvent is selected from acetone, esters such as ethyl acetate, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycol ether, glycol ether acetate, N-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO), gamma-butyrolactone, gamma-valerolactone, cyrene, and combinations thereof.

[0097] In some embodiments, the polymer solvent is selected from acetone, ethyl acetate, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropyleneglycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, N-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO), gamma-butyrolactone, gammavalerolactone, cyrene, and combinations thereof.

[0098] In some embodiments, the polymer solvent is selected from N-methylpyrrolidone, dimethyl formamide, dimethyl sulfoxide, gamma-butyrolactone, gamma-valerolactone, cyrene, and combinations thereof.

[0099] In some embodiments, the polymer solvent is N-methylpyrrolidone.

[0100] In some embodiments, the polymer solvent is different from the organic solvent. In some embodiments, the polymer solvent is different from the non-ionic organic solvent. Compositions

[0101] In some embodiments, the amount of polymer in the solvated polymer matrix (% w / w) based on the total weight of the solvated polymer matrix is about, or greater than about: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, or 50. In some embodiments, the amount of polymer in the solvated polymer matrix (% w / w) based on the total weight of the solvated polymer matrix is less than about: 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The amount of polymer in the solvated polymer matrix (%w / w) based on the total weight of the solvated polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 1 to about 50, between about 2 to about 20, or between about 5 to about 15.

[0102] In some embodiments, the amount of polymer solvent in the solvated polymer matrix (% w / w) based on the total weight of the solvated polymer matrix is about, or greater than about: 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99. In some embodiments, the amount of polymer in the solvated polymer matrix (% w / w) based on the total weight of the solvated polymer matrix is less than about: 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 85, 80, 75, 70, 65, 60, 55, or 50. The amount of polymer solvent in the solvated polymer matrix (%w / w) based on the total weight of the solvated polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 50 to about 99, between about 80 to about 98, or between about 85 to about 95.Filler

[0103] The filler may be selected from any appropriate material known in the art. In some embodiments, the filler may be selected from substantially non-conductive or otherwise electrically insulating materials. In some embodiments, the filler is selected from glass, metal oxides, aluminium oxide, polystyrene, melamine, organic materials, natural materials, and combinations thereof. In some embodiments, the filler is selected from glass, metal oxides, aluminium oxide, and combinations thereof.

[0104] In some embodiments, the filler functions as a Lewis acid. Advantageously, when the filler functions as a Lewis acid it may compete with the metal ion of the metal salt for coordination sites in the polymer matrix thereby increasing the amount of metal ion which is free to diffuse in the electrolyte and enhance ionic conductivity.

[0105] In some embodiments, the filler is selected from aluminium oxide (AI2O3), titanium dioxide (TiCh), zinc oxide (ZnO), silicon dioxide (SiCh), and combinations thereof.

[0106] In some embodiments, the filler is aluminium oxide (AI2O3).

[0107] In one embodiment, the filler has a particle size (in nm) of between about 1 to about 2000. In one embodiment, the filler has a particle size (in nm) of at least about 1, 2, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 300, 400, 500, 750, 1000, 1250, 1500, 1750, or 2000. In one embodiment, the filler has a particle size (in nm) of less than about 2000, 1750, 1500, 1250, 1000, 750 500, 400, 300, 200, 150, 100, 75, 50, 25, 20, 15, 10, 5, 2 or 1. The filler particle size (nm) may be a range provided by any two of these upper and / or lower values, for example between about 1 to about 2000, between about 5 to about 1000, between about 10 to about 500, or between about 20 to about 100, or between about 25 to about 75. In one embodiment, the filler has a particle size (in nm) of about 50.Composition of non-aqueous polymer electrolyte precursor

[0108] The liquid electrolyte comprising a non-ionic organic solvent and a metal salt may be provided at any suitable amount such that the non-aqueous polymer electrolyte precursor described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or ionic conductivity. In some embodiments, the amount of liquid electrolyte in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor is about, or greater than about: 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90. In some embodiments, the amount of liquid electrolyte in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor is less than about: 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, or 1. The amount of liquid electrolyte in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor may be in a range provided by any two of these upper and / or lower values, for example between about 1 to about 90, between about 5 to about 50, between about 10 to about 30, or between about 15 to about 25.

[0109] In some embodiments, the amount of liquid electrolyte (as a weight % of polymer electrolyte precursor) is about 1 wt% to about 90 wt%, preferably between about 20 wt% to about 30 wt%.

[0110] The solvated polymer matrix comprising a polymer and a polymer solvent may be provided at any suitable amount such that the non-aqueous polymer electrolyte precursor described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or strength. In some embodiments, the amount of solvated polymer matrix in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the nonaqueous polymer electrolyte precursor is about, or greater than about: 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90. In some embodiments, the amount of solvated polymer matrix in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor is less than about: 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, or 1. The amount of solvated polymer matrix in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor may be in a range provided by any two of these upper and / or lower values, for example between about 1 and about 90, between about 10 to about 90, between about 25 to about 90, between to 40 to about 80, or between about 50 to about 90, or between about 70 to about 90.

[0111] In some embodiments, the amount of polymer matrix (as a weight % of polymer electrolyte precursor) is about 10 wt% to about 90 wt%, preferably between about 9 wt% to about 12 wt%.

[0112] The filler may be provided at any suitable amount such that the non-aqueous polymer electrolyte precursor described herein may possess one or more desirable properties, for example, but not limited to, a desired ionic conductivity. In some embodiments, the amount of filler in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor is about, or greater than about: 0.1, 0.2, 0.3, 0.4 , 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, the amount of filler in the non-aqueous polymer electrolyte precursor (% w / w) based on the total weight of the non-aqueous polymer electrolyte precursor is less than about: 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1. The amount of filler in the v (% w / w) based on the total weight of the non-aqueous polymer electrolyte may be in a rangeprovided by any two of these upper and / or lower values, for example between about 0.1 to about 20, between about 1 to about 20, between about 2 to about 18, or between about 4 to about 10.Non-aqueous polymer electrolyte

[0113] The inventors have surprisingly found that by processing of the non-aqueous polymer electrolyte precursor to remove at least a portion of the polymer solvent from the compositions, non-aqueous polymer electrolytes may be obtained with advantageous properties as demonstrated in the examples.

[0114] In another aspect of the present disclosure there is provided a non-aqueous polymer electrolyte obtained from the non-aqueous polymer electrolyte precursor described herein.Printable gel non-aqueous polymer electrolyte

[0115] In another aspect of the present disclosure there is provided a printable gel non-aqueous polymer electrolyte. In some embodiments there is provided a printable gel non-aqueous polymer electrolyte comprising a liquid electrolyte comprising: an organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler.

[0116] In another aspect of the present disclosure there is provided a printable gel non-aqueous polymer electrolyte. In some embodiments there is provided a printable gel non-aqueous polymer electrolyte comprising a liquid electrolyte comprising: a non-ionic organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler.

[0117] A printable gel non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 10 wt% to about 60 wt%; wherein the amount of partially solvated polymer matrix (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 30 wt% to about 90 wt% wherein the amount of filler (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 0.1 wt% to about 20 wt%.

[0118] In another aspect of the present disclosure there is provided a printable gel non-aqueous polymer electrolyte obtained from the non-aqueous polymer electrolyte precursor described herein.

[0119] A non-aqueous polymer electrolyte in the form of a printable gel may be advantageous in that it is a core component of a printed battery. The printable gel non-aqueous polymerelectrolyte described herein may be used in a variety of printing methods. For example, the printable gel non-aqueous polymer electrolyte described herein may be used in screen-printing and / or roll-to-roll processing. Advantageously, this allows for high-volume manufacturing. The process would be known to a person of skill in the art and, briefly, involves screen-printing conductive inks onto a substrate material, layer by layer with precise control of the patterns. This approach enables the consistent production of batteries, comprising the non-aqueous polymer electrolyte described herein, that meet particular device geometries and requirements, thus effectively addressing the need for battery flexibility, practicality, and scalability.Partially solvated polymer matrixComposition of partially solvated polymer matrix

[0120] In some embodiments, the amount of polymer in the partially solvated polymer matrix (% w / w) based on the total weight of the partially solvated polymer matrix is about, or greater than about: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75. In some embodiments, the amount of polymer in the partially solvated polymer matrix (% w / w) based on the total weight of the partially solvated polymer matrix is less than about: 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5. The amount of polymer in the partially solvated polymer matrix (%w / w) based on the total weight of the partially solvated polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 5 and about 75, or between about 10 and about 50.

[0121] In some embodiments, the amount of polymer solvent in the partially solvated polymer matrix (% w / w) based on the total weight of the partially solvated polymer matrix is about, or greater than about: 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95. In some embodiments, the amount of polymer in the partially solvated polymer matrix (% w / w) based on the total weight of the partially solvated polymer matrix is less than about: 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25. The amount of polymer solvent in the partially solvated polymer matrix (%w / w) based on the total weight of the partially solvated polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 5 and about 75, or between about 50 and about 90.Composition of printable gel non-aqueous polymer electrolyte

[0122] The liquid electrolyte comprising a non-ionic organic solvent and a metal salt may be provided at any suitable amount such that the printable gel non-aqueous polymer electrolyte described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or ionic conductivity. In some embodiments, the amount of liquid electrolyte in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is about, or greater than about: 10,15, 20, 25, 30, 35, 40, 45, 50, 55, or 60. In some embodiments, the amount of liquid electrolyte in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is less than about: 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10. The amount of liquid electrolyte in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte may be in a range provided by any two of these upper and / or lower values, for example between about 10 and about 60, or between about 15 and about 45.

[0123] The partially solvated polymer matrix comprising a polymer and a polymer solvent may be provided at any suitable amount such that the printable gel non-aqueous polymer electrolyte described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or strength. In some embodiments, the amount of partially solvated polymer matrix in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is about, or greater than about: 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90. In some embodiments, the amount of partially solvated polymer matrix in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is less than about: 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, or 30. The amount of partially solvated polymer matrix in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte may be in a range provided by any two of these upper and / or lower values, for example between about 30 and about 90, or between about 40 and about 80.

[0124] The filler may be provided at any suitable amount such that the printable gel nonaqueous polymer electrolyte described herein may possess one or more desirable properties, for example, but not limited to, a desired ionic conductivity. In some embodiments, the amount of filler in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is about, or greater than about: 0.1, 0.2, 0.3, 0.4 , 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, the amount of filler in the printable gel non-aqueous polymer electrolyte (% w / w) based on the total weight of the printable gel non-aqueous polymer electrolyte is less than about: 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1. The amount of filler in the v (% w / w) based on the total weight of the non-aqueous polymer electrolyte may be in a range provided by any two of these upper and / or lower values, for example between about 0.1 and about 20, between about 1 and about 20, between about 2 and about 18, or between about 2 and about 10.Non-aqueous polymer electrolyte film

[0125] In another aspect of the present disclosure there is provided a non-aqueous polymer electrolyte film comprising: a liquid electrolyte comprising an organic solvent, and a metal salt; a polymer matrix; and a filler.

[0126] In another aspect of the present disclosure there is provided a non-aqueous polymer electrolyte film comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler.

[0127] A non-aqueous polymer electrolyte film comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte film) is between about 40 wt% to about 90 wt%; wherein the amount of polymer matrix (as a weight % of polymer electrolyte film) is between about 10 wt% to about 50 wt% wherein the amount of filler (as a weight % of polymer electrolyte film) is between about 0.1 wt% to about 20 wt%.

[0128] In another aspect of the present disclosure there is provided a non-aqueous polymer electrolyte film obtained from the non-aqueous polymer electrolyte precursor described herein.

[0129] In some embodiments, the non-aqueous polymer electrolyte film may be obtained from the non-aqueous polymer electrolyte precursor by a heating step.

[0130] In some embodiments, the non-aqueous polymer electrolyte film may be obtained from the non-aqueous polymer electrolyte precursor by removal of at least a portion of the polymer solvent.

[0131] In some embodiments, the non-aqueous polymer electrolyte of the present disclosure may be a free-standing non-aqueous polymer electrolyte film. Advantageously, once incorporated into a flexible electrochemical cell the non-aqueous polymer electrolyte film described herein may be capable of providing mechanical support and stability to the flexible electrochemical cell, potential enhancing the resistance to physical stress, bending, and vibrations.Thickness

[0132] The non-aqueous polymer electrolyte film of the present disclosure may be provided in any thickness suitable for incorporation into an electrochemical cell. In one embodiment, thenon-aqueous polymer electrolyte film has a thickness (in pm) of at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 200, 250, 300, 400, or 500. In one embodiment, the non-aqueous polymer electrolyte film has a thickness (in pm) of less than about 500, 400, 300, 250, 200, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10. The non-aqueous polymer electrolyte film thickness (in pm) may be a range provided by any two of these upper and / or lower values, for example between about 10 to about 500, between about 10 to about 400, between about 10 to about 300, between about 10 to about 200, between about 70 to about 300, between about 70 to about 200, or between about 90 to about 120.Polymer matrixComposition of polymer matrix

[0133] In some embodiments, the amount of polymer solvent in the polymer matrix (% w / w) based on the total weight of the polymer matrix is about, or greater than about: 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the amount of polymer solvent in the polymer matrix (% w / w) based on the total weight of the polymer matrix is less than about: 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001. The amount of polymer solvent in the polymer matrix (%w / w) based on the total weight of the polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 0.001 and about 10, between about 0.01 and about 5, or between about 0.1 and about 5.

[0134] In some embodiments, the amount of polymer in the polymer matrix (% w / w) based on the total weight of the polymer matrix is about, or greater than about: 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99, 99.5, 99.9, 99.95, 99.99, 99.995, or 99.999. In some embodiments, the amount of polymer in the polymer matrix (% w / w) based on the total weight of the polymer matrix is less than about: 99.999, 99.995, 99.99, 99.95, 99.9, 99.5, 99, 98, 97, 96, 95, 94, 93, 92, 91, or 90. The amount of polymer in the polymer matrix (%w / w) based on the total weight of the polymer matrix may be in a range provided by any two of these upper and / or lower values, for example between about 90 and about 99.999, between about 95 and about 99.99, or between about 95 and about 99.9.Composition of non-aqueous polymer electrolyte film

[0135] The liquid electrolyte comprising a non-ionic organic solvent and a metal salt may be provided at any suitable amount such that the non-aqueous polymer electrolyte film described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or ionic conductivity. In some embodiments, the amount of liquid electrolyte in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is about, or greater than about: 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90. In some embodiments, the amount of liquid electrolyte in the non-aqueous polymerelectrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is less than about: 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40. The amount of liquid electrolyte in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film may be in a range provided by any two of these upper and / or lower values, for example between about 40 and about 90, or between about 45 and about 70, or between about 50 and about 65.

[0136] The polymer matrix comprising a polymer and a polymer solvent may be provided at any suitable amount such that the non-aqueous polymer electrolyte film described herein may possess one or more desirable properties, for example, but not limited to, a desired viscosity and / or strength. In some embodiments, the amount of polymer matrix in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is about, or greater than about: 10, 15, 20, 25, 30, 35, 40, 45, or 50. In some embodiments, the amount of polymer matrix in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is less than about: 50, 45, 40, 35, 30, 25, 20, 15, or 10. The amount of polymer matrix in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film may be in a range provided by any two of these upper and / or lower values, for example between about 10 and about 50, or between about 20 and about 40.

[0137] The filler may be provided at any suitable amount such that the non-aqueous polymer electrolyte film described herein may possess one or more desirable properties, for example, but not limited to, a desired ionic conductivity. In some embodiments, the amount of filler in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is about, or greater than about: 0.1, 0.2, 0.3, 0.4 , 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, the amount of filler in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte film is less than about: 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1. The amount of filler in the non-aqueous polymer electrolyte film (% w / w) based on the total weight of the non-aqueous polymer electrolyte may be in a range provided by any two of these upper and / or lower values, for example between about 0.1 and about 20, between about 2 and about 18, or between about 8 and about 14.Preparation Process

[0138] In another aspect of the present disclosure, there is provided a method of preparing a non-aqueous polymer electrolyte precursor comprising: (i) obtaining a liquid electrolyte comprising an organic solvent and a metal salt; (ii) obtaining a polymer matrix comprising apolymer and polymer solvent; (iii) obtaining a filler; and (iv) mixing the liquid electrolyte, the polymer matrix and the filler to form the non-aqueous polymer electrolyte precursor.

[0139] In some embodiments of the present disclosure, there is provided a method of preparing a non-aqueous polymer electrolyte precursor comprising: (i) obtaining a liquid electrolyte comprising a non-ionic organic solvent and a metal salt; (ii) obtaining a polymer matrix comprising a polymer and polymer solvent; (iii) obtaining a filler; and (iv) mixing the liquid electrolyte, the polymer matrix and the filler to form the non-aqueous polymer electrolyte precursor.

[0140] In some embodiments, to provide the non-aqueous polymer electrolyte, the method further comprises (v) removing at least a portion of the polymer solvent to form a printable gel non-aqueous polymer electrolyte. It will be appreciated that steps (iv) and (v) may be carried out consecutively or concurrently, as required.

[0141] In some embodiments, step (v) may be a step of heating the non-aqueous polymer electrolyte precursor to remove at least a portion of the polymer solvent.

[0142] In some embodiments, the method comprises (vi) casting the non-aqueous polymer electrolyte precursor or printable gel non-aqueous polymer electrolyte to form a non-aqueous polymer electrolyte film.(iv) process conditions

[0143] The person skilled in the art would appreciate that the mixing in (iv) may be performed for any time period sufficient to effectively mix the components of the non-aqueous polymer electrolyte. In some embodiments, the mixing in (iv) is performed for a time effective to form a homogeneous mixture. In some embodiments, the mixing in (iv) is performed for a time effective to form a homogeneous gel-like mixture. In some embodiments, the mixing in (iv) is performed for a period of time of at least about 1, 2, 3, 4, 5, 6, 8, 10, 12, 18, 20, 24, 36 or 48 hours. In some embodiments, the mixing in (iv) is performed for a period of time for a period of time of less than about 48, 36, 24, 20, 18, 12, 10, 8, 6, 5, 4, 3, 2, or 1 hours. The time period that the mixing in (iv) is performed may be in a range provided by any two or more of the upper and / or lower amounts, for example, the mixing in (iv) may be for a period of time of between about 1 hours to 48 hours, between about 6 hours to 36 hours or between about 18 hours to 24 hours.

[0144] The person skilled in the art would appreciate that the mixing in (iv) may be performed at any temperature to effectively allow the components of the non-aqueous polymer electrolyte to mix. In some embodiments, the mixing in (iv) is performed at a temperature effective to form a homogeneous mixture. In some embodiments, the mixing in (iv) is performed at a temperature effective to form a homogeneous gel-like mixture. In some embodiments, the mixing in (iv) maybe performed at a temperature of at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 °C. In some embodiments, the mixing in (iv) may be performed at a temperature of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20°C. The temperature at which the mixing in (iv) is performed may be in a range provided by any two or more of the upper and / or lower amounts, for example, the mixing in (iv) may be performed at a temperature of between about 20°C to 95 °C, or about 50°C to 90°C.

[0145] It will be appreciated that combinations of any two or more of the above mixing temperatures and times are also possible, for example the mixing in (iv) may be performed for a period of time of between about 12 hours to 36 hours and at a temperature of between about 50°C to 90°C.

[0146] The person skilled in the art would appreciate that the mixing in (iv) may be facilitated through stirring. The person skilled in the art will appreciate that the rotation speed required may depend on a number of factors including, but not limited to, the components of the non-aqueous polymer electrolyte, the temperature at which mixing is performed, and / or the time period for which mixing is performed. In some embodiments, the mixing at (iv) comprises stirring the liquid electrolyte, the polymer matrix and the filler. In some embodiments, the stirring is performed at a speed (rpm) of about, or greater than about: 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700 750, 800, 850, 900, 950 or 1000. In some embodiments the stirring is performed at a speed (rpm) of less than about: 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, or 50. The speed at which the stirring is performed (rpm) may be in a range provided by any two or more of the upper and / or lower amounts, for example between about 50 and about 1000, between about 50 to 750, between about 250 and 750, or between about 150 and 450. In one embodiment, the stirring is performed at a speed (rpm) of about 300.(v) process conditions

[0147] The removal of at least a portion of the polymer solvent may be achieved by a number of methods known in the art such as heating or exposure to a vacuum or other pressure change, and the like. A heating step may be preferred, with optional stirring. The person skilled in the art would appreciate that the heating in (v) may be performed for any time period sufficient to effectively evaporate at least a portion of polymer solvent to form a printable gel polymer electrolyte. The heating in step (v) may effectively perform the function of the heating discussed for step (iv). That is, separate heating steps may not be required. In some embodiments, the heating in (v) is performed for a period of time of at least about 1, 2, 3, 4, 5, 6, 8, 10, 12, 18, 20, 24, 36 or 48 hours. In some embodiments, the heating in (v) is performed for a period of time for a period of time of less than about 48, 36, 24, 20, 18, 12, 10, 8, 6, 5, 4, 3, 2, or 1 hours. The timeperiod that the heating in (v) is performed may be in a range provided by any two or more of the upper and / or lower amounts, for example, the heating in (v) may be performed for a period of time of between about 1 hour to 48 hours, between about 6 hours to 36 hours or between about 18 hours to 24 hours.

[0148] The person skilled in the art would appreciate that the heating in (v) may be performed at any temperature to effectively to evaporate at least a portion of one or more components of the non-aqueous polymer electrolyte. In some embodiments, the heating in (v) is performed at a temperature effective to form evaporate at least a portion of the polymer solvent to form a printable gel polymer electrolyte. In some embodiments, the heating in (v) may be performed at a temperature of at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95°C. In some embodiments, the heating in (v) may be performed at a temperature of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20°C. The temperature at which the heating in (v) is performed may be in a range provided by any two or more of the upper and / or lower amounts, for example, the heating in (v) may be performed at a temperature of between about 20°C to 95 °C, or about 50°C to 90°C.

[0149] In some embodiments, the mixing of (iv) and the heating of (v) are performed simultaneously.(vi) process conditions

[0150] The person skilled in the art would appreciate that the casting in (vi) may be performed for any time period sufficient to effectively to form a polymer electrolyte film. In some embodiments, the casting in (vi) is performed for a period of time of at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180 minutes. In some embodiments, the casting in (vi) is performed for a period of time for a period of time of less than about 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 minutes. The time period that the casting in (vi) is performed may be in a range provided by any two or more of the upper and / or lower amounts, for example, the casting in (vi) may be performed for a period of time of between about 10 minutes to about 180 minutes, between about 30 minutes to about 150 minutes or between about 60 minutes to about 120 minutes.

[0151] In some embodiments, the casting in (vi) is performed at a temperature effective to evaporate at least a portion of the polymer solvent to form a polymer electrolyte film. In some embodiments, the casting in (vi) may be performed at a temperature of at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95°C. In some embodiments, the casting in (vi) may be performed at a temperature of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20°C. The temperature at which the casting in (vi) is performed may be in arange provided by any two or more of the upper and / or lower amounts, for example, the casting in (vi) may be performed at a temperature of between about 20°C to 95°C, or about 35°C to °C.Electrochemical cell

[0152] In another aspect of the present disclosure, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; and a non-aqueous polymer electrolyte as described herein.

[0153] In another aspect of the present disclosure, there is provided an electrochemical cell comprising: an anode; a cathode; and a non-aqueous polymer electrolyte as described herein.

[0154] In another aspect of the present disclosure, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; and a non-aqueous polymer electrolyte obtained from the non-aqueous polymer electrolyte precursor as described herein.

[0155] In another aspect of the present disclosure, there is provided an electrochemical cell comprising: an anode; a cathode; and a non-aqueous polymer electrolyte obtained from the nonaqueous polymer electrolyte precursor as described herein.

[0156] In some embodiments, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; and a printed gel non-aqueous polymer electrolyte as described herein.

[0157] In some embodiments, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; a non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler.

[0158] In some embodiments, there is provided an electrochemical cell comprising: an anode; a cathode; and a printed gel non-aqueous polymer electrolyte as described herein.

[0159] In some embodiments, there is provided an electrochemical cell comprising: an anode; a cathode; and a non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a partially solvated polymer matrix; and a filler.

[0160] In some embodiments, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; and a non-aqueous polymer electrolyte film as described herein.

[0161] In some embodiments, there is provided an electrochemical cell comprising: a negative electrode; a positive electrode; a non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler.

[0162] In some embodiments, there is provided an electrochemical cell comprising: an anode; a cathode; and a non-aqueous polymer electrolyte film as described herein.

[0163] In some embodiments, there is provided an electrochemical cell comprising: an anode; a cathode; and a non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler.

[0164] The inventors of the present application have surprisingly found that various embodiments of the electrochemical cell described herein may have one or more advantageous properties including an areal capacity of, for example above 2 mAh / cm2, above 3 mAh / cm2, or above 4 mAh / cm2at 0.5 mA / cm2; or an increased voltage, for example up to 1.5 V, or up to 2 V when compared to electrochemical cells comprising aqueous-based electrolytes which may suffer from water splitting at lower voltages.

[0165] In some embodiments, the electrochemical cell is an energy storage device. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a secondary battery. The electrochemical cell may be suitable for any type of battery. In some embodiments, the electrochemical cell is a printed electrochemical cell. In some embodiments, the printing technique is selected from direct ink writing, inkjet printing, and 3D printing. In some embodiments, the electrochemical cell is a flexible electrochemical cell.

[0166] It will be understood by the person skilled in the art that during a discharge cycle of the electrochemical cell described herein the positive electrode is the cathode. In some embodiments, the cathode active material may be selected from lithium cobalt oxide (LiCoCh), lithium manganese oxide (LiMmC ), lithium iron phosphate (LiFePC ), lithium manganese iron phosphate (LiMmFei-xPC , where x<l), lithium nickel cobalt manganese oxide (LiNixMnyCoi-x- yCh, where x+y<l), lithium nickel cobalt aluminum oxide (LiNixAlyCoi-x-yCh, where x+y<l), sodium cobalt oxide (NaCoCh), sodium manganese oxide (NaMnCh), sodium iron phosphate (NaFePC ), potassium cobalt oxide (KCOO2), nickel cobalt aluminum oxides, copper oxide (CU2O, CuO), cobalt oxide (CO3O4), manganese dioxide (MnCh), manganese oxide (M Ch), manganese hexacyanoferrate (Prussian Blue), iron oxide (Fe2Ch, FesC ), vanadium Oxide (V2O5), chromium oxide (CnCh), tin oxide (SnO2), magnesium vanadium oxide (MgXhCh), and combinations thereof. In some embodiments, the cathode active component comprises at least one of silver(I) oxide (Ag2O), a silver(I,III) oxide (AgO), manganese(IV) oxide (Mn02), nickel oxyhydroxide (NiOOH), and silver nickel oxide (AgNiO2). In some embodiments, the cathode active material is comprises at least one of manganese(IV) oxide (MnCh), silver(I) oxide (Ag2O), and combinations thereof. In some embodiments, the cathode active material is comprises at least one of manganese(IV) oxide (MnCh). In some embodiments, the cathode active material is comprises at least one of silver(I) oxide (Ag2O).

[0167] In some embodiments, the cathode may comprise an organic component selected from the group consisting of polyaniline, polypyrrole, polythiophene, poly(p-phenylene), polyindole, aquinone, an acromatic imide, an anhydride imide, an imine, a nitronyl nitroxide, an organosulfur polymer, and triphenylamine.

[0168] It will be understood by the person skilled in the art that during a discharge cycle of the electrochemical cell described herein the negative electrode is the anode. In some embodiments, the anode comprises at least one of zinc, cadmium, iron, nickel, aluminium, a metal hydrate, and hydrogen. In some embodiments, the anode comprises at least one of zinc and lithium. In some embodiments, the anode comprises zinc. In some embodiments, the anode comprises lithium.

[0169] In some embodiments, the electrochemical cell is a zinc battery. In some embodiments, the electrochemical cell is a zinc-ion battery. In some embodiments, the electrochemical cell is a zinc-manganese(IV) oxide (Zn-MnCb) battery. In some embodiments, the electrochemical cell is a zinc-silver(I) oxide (Zn-Ag2O) battery.

[0170] In some embodiments, the electrochemical cell is a lithium battery. In some embodiments, the electrochemical cell is a lithium-ion battery.

[0171] It will be appreciated that the non-aqueous polymer electrolyte, in a printed, film, or other form, within the electrochemical cell is one which has been formed from the non-aqueous polymer electrolyte precursor as described herein.Products and use

[0172] In a further aspect of the present disclosure, there is provided a non-aqueous polymer electrolyte precursor obtained by the method described herein and / or a printable gel non-aqueous polymer electrolyte obtained by the method described herein and / or a non-aqueous polymer electrolyte film obtained by the method described herein.

[0173] In a further aspect of the present disclosure, there is provided the use of a non-aqueous polymer electrolyte precursor as described herein or obtained from the method as described herein in the manufacture of an electrochemical cell and / or use of a non-aqueous polymer electrolyte film as described herein or obtained from the method as described herein in the manufacture of an electrochemical cell and / or use of a printable gel non-aqueous polymer electrolyte film as described herein or obtained from the method as described herein in the manufacture of an electrochemical cell.EXAMPLESExample 1: Electrolyte and electrochemical cell preparation

[0174] Raw Materials: Zinc powder (7.5 pm, 98.8%) was purchased from Goodfellow. MnCb (99.9%) was purchased from HAOXI. Zn(BF4)2, ethylene glycol (EG), N-methyl-2-pyrrolidone (NMP), zinc oxide (ZnO), bismuth(III) oxide EfeCh), aluminium oxide (AI2O3) (nanopowder, < 50 nm) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) were purchasedfrom Sigma- Aldrich. Acetylene carbon black (AC carbon, 100% compressed) was purchased from Strem Chemicals.

[0175] The liquid electrolyte (LE) was prepared by dissolving Zn(BF4)2 in EG with a molality concentration of 13.3 m and stirring until a clear solution was obtained.

[0176] As depicted in Figure 1, the non-aqueous polymer electrolyte was prepared by mixing PVDF-co-HFP, NMP, AI2O3, and the liquid electrolyte in the amounts shown in Table 1 at 75 °C and stirring at 300 rpm for at least 20 hours until a homogenous, gel-like mixture was acquired.Table 1 : Non-aqueous polymer electrolyte precursor composition

[0177] To form polymer electrolyte films, the non-aqueous polymer electrolyte was transferred on a petri dish and heated at 55°C for 90 minutes to allow a portion of the solvent to evaporate. The resulting film was a stand-alone polymer electrolyte film with an average thickness of 110 pm. Polymer electrolyte films were stored in a vacuum desiccator to provide dry polymer electrolyte films, or soaked in the liquid electrolyte to provide soaked polymer electrolyte films.

[0178] A Zn slurry was prepared with 62.1 wt.% Zn powder, 3.4 wt.% ZnO, 2 wt.% EfoCh, and the remaining a binder solution containing 1.9 wt.% carboxymethyl cellulose (CMC), 1.9 wt.% styrene-butadiene (SBR) and 96.2 wt.% deionised (DI) water. ZnO and Bi2O3 were included to suppress hydrogen gas evolution and reduce the Zn anode corrosion rate.

[0179] The resultant ink was then screen printed onto Cu current collector and dried at 85 °C for 12 hours in a vacuum oven to form a zinc anode. A Mn02 slurry was prepared by mixing CMC, DI water, SBR binder, AC carbon and 8-MnCb in a mass ratio of 1 :50: 1 : 1 : 17 using a homogenizer until a homogenous texture was obtained.

[0180] The resultant ink was then screen printed onto Al current collector and dried at 85 °C for 12 hours in a vacuum oven. The thickness of the printed MnCb cathode was approximately 170 pm.

[0181] Screen-printing was used to deposit the Zn anode, MnCb cathode, and PE onto a silvercarbon current collector substrate. A diagram illustrating this process is shown in Figure 2a, while Figure 2b provides a detailed representation of each component's layer-by-layer arrangement. Figure 2c shows the printed anode and cathode. Subsequently, they were stackedtogether and encapsulated with laminating sheets and Kapton tapes. The resulting configuration of the printed battery is depicted in Figure 2d on the left.Example 2: Rheology Measurements

[0182] Shear rheology measurements were carried out on the Haake Mars III rheometer (Thermo Scientific) with 35 mm diameter parallel plate geometry. To prevent slip, these plates are roughened by sandblasting to a roughness of 1.8 pm. Temperature was controlled using the Haake Mars Peltier element. The gap between the plates was set at 0.8 mm. The edge of the sample was coated with low viscosity silicone oil to prevent drying on the exposed surface. Step shear measurements were used from 1 to 1000 Pa in 24 steps at a maximum of 10s per point.

[0183] An adequate level of viscosity is essential for enabling the ink to flow through the mesh and adhere to the substrate without excessive spreading. The PE ink displays Newtonian behaviour as depicted in the linear relationships between the viscosity and shear rate (Figure 3a, and between the shear stress and shear rate (Figure 3b). Figure 3c illustrates that PE did not spread during the printing procedure. Based on the rheological analysis, it can be concluded that the polymer electrolyte of the present disclosure can be viable for large-scale screen-printing applications.Example 3: Mechanical Testing

[0184] All electrode and polymer electrolyte samples were cut into rectangular strips of 10 x 60 mm and thicknesses were measured. The tensile tests were carried out using an Instron 5584 loadframe (Figure 4a) with a 100 N load cell and pneumatic grips; and set up using the Bluehill Universal Software. The samples were tested under a crosshead speed of 1 mm / min for the metal substrates and 10 mm / min for the PE samples. Sample dimensions and operation conditions were taken from literature. Stresses and strains were computed by the software. On the one hand, stresses were obtained by dividing the tensile load P with the initial cross-sectional area A as o= P / A. On the other hand, an Advanced Video Extensometer (AVE) camera was used for strain measurements, which measured the initial length L and axial displacement AL to compute the tensile strain as 8=AL / L.

[0185] The stress-strain curve shows an initial linear region in which the PE or the electrode behaves elastically (Figure 4b). The yield strength is the maximum stress that the sample can withstand before plastic deformation occurs. During battery operation, the yield strength should not be exceeded. The anode and cathode samples were made of Zn casted on Cu foils (denoted as Zn on Cu CC) and Mn02 casted on carbon-coated Al foils (denoted as MnCb on C-Al CC) respectively. These metal-based foils exhibited similar linear regions however differed slightly on the tensile strength and elongation at break. Compared to the two electrodes, the polymer electrolyte has a reasonable yield strength, with a high strain to failure. Such higher strainsuggests a higher degree of flexibility, making the battery more deformable to be incorporated into flexible electronics, as it exhibits the ability to return to its original shape.Example 4: Electrochemical Testing

[0186] Electrochemical impedance analysis for internal resistance was measured with two parallel, stainless steel blocking electrodes (0 = 15.2 mm), and a stand-alone polymer film (dry or soaked) contained between. The cell was rested in an oven with a set temperature (25, 40, 60 and 80°C). Each measurement was taken 1.5 hours after the set temperature was reached, to allow the cell to fully equilibrate. Measurements were performed with a Bio-Logic electrochemical workstation by applying a frequency range from 100 kHz to 0.1 Hz. The ionic conductivity was calculated using the below equation, o=l / (RxA) where I, R and A are the thickness of the polymer electrolyte film (= 1.1 x 10-4 cm), bulk resistance (Q), the area of the stainless steel blocking electrode (cm2), respectively. The electrode thickness used for each cell was 100 pm with an electrode area of 0.7 cm2.

[0187] Galvanostatic Charge / Discharge and Cell Cycling Performance were collected by a LAND battery testing system. Each battery component was stacked layer-by-layer. The stacked multilayer battery was subsequently encapsulated using Kapton tape. All batteries were charged and discharged between 0.6 and 2.0 V.

[0188] Initially, the electrochemical stability window of the liquid electrolyte (LE) containing different concentrations (4, 7, 10, 13.3 m) of zinc tetrafluoroborate (Zn(BF4)2) salt in ethylene glycol (EG) solvent was examined to ensure safe operational voltages for the battery. No significant variation in the electrochemical stability window was observed across different salt concentrations. Based on these results, galvanostatic charge / discharge was carried out between 0.6 - 2.0 V for all LE cells. Increasing the Zn(BF4)2 concentration resulted in a higher output voltage and capacity, while maintaining a comparable longevity.

[0189] Electrochemical impedance spectroscopy (EIS) was performed to determine the bulk resistance and to calculate the ionic conductivity of the non-aqueous polymer electrolyte films. As depicted in Figure 5a and 5b, the ionic conductivity of the dry, and soaked polymer electrolyte films at 298 K (25 °C) was 9.67 x 10'3and 1.50 x 10'2mS cm'1, respectively and ionic conductivity increases as temperature increases (Figure 5c). Without being bound by theory, the inventors speculate that the addition of inorganic aluminium oxide (AI2O3) filler function as a Lewis acid and compete with Zn2+ions to interact the coordination sites in the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) polymer matrix, thereby releasing more free Zn2+ions for enhanced ionic conductivity.

[0190] Symmetric cells were constructed to compare the Zn metal plating / stripping behaviours in the liquid electrolyte and polymer electrolyte. The experimental setup involved sandwiching (1) a glass fibre that was fully immersed with liquid electrolyte and (2) a free-standing polymer electrolyte film, between two Zn metal electrodes, denoted as Zn|LE|Zn and Zn|PE|Zn, respectively. The applied current density was 0.5 mA cm'2with an areal capacity of 0.5 mAh cm'2. As shown in Figure 6, the Zn|LE|Zn cell experienced a serious voltage fluctuation after 25 hours, signalling severe Zn corrosion and dendrite accumulation. In contrast, the Zn|PE|Zn, cell effectively suppressed these unwanted side reactions, as evidenced by a much more stable plating / stripping voltage profile over 400 hours. Without being bound by theory, the inventors speculate that this is attributable to the stronger physical contact at the Zn-electrolyte interfaces within the Zn|PE|Zn, cell, which leads to a more uniform electric field distribution, in comparison to cells using a liquid electrolyte.

[0191] To investigate the internal losses in the full cells, electrochemical impedance spectroscopy (EIS) was employed (Figure 7a). The resulting impedance spectra data were fitted with an equivalent circuit model to identify and quantify individual loss components. At the high-frequency region where the spectrum intersects the real impedance axis (Z1), the ohmic resistance (denoted as Rohm) was determined. This resistance characterizes the overall bulk resistance contributed by the electrodes and electrolyte, reflecting the resistance within the bulk electrolyte and the electrical contact resistances. When the battery area was increased from 0.25 to 0.5 cm2, the Rohm value remained relatively constant at around 20 cm2. This observation suggests a minimal change in the resistance at the bulk PE and electrode interfaces.

[0192] The open circuit voltage (OCV) of the printed battery was first evaluated under bending conditions. When gradually increasing the flexure displacement from 0 to 9 mm, the OCV remained stable at approximately 1.35 V (Figure 7b). Following this, the batteries were subjected to testing at various current densities. It was observed that an increase in the current density corresponded to a reduction in the overall capacity of the battery (refer to Figure 7c). The cell charged at 0.5 mA cm'2showed a high areal capacity of nearly 4 mAh cm'2. However, the cyclability was found improved with larger currents. At 2 mA cm'2, the battery had a cycling life of over 65 cycles, with a stable areal capacity and high CE (> 90%), as shown in Figure 7d.Example 5: Scanning electron microscopy

[0193] The sample morphology was characterized by a field-emission scanning electron microscopy (FESEM) a hot (Schottky) electron gun (JEOL JSM-7100F). All electrodes were stored in a sealed container prior to the characterization. Figure 8a shows the cross-sectional view of the PE, which reveals its porous nature. This high porosity offers a larger surface area, allowing for more ion diffusion pathways and consequently leading to higher ionic conductivityof the PE. Such a uniform and distributed porous structure can be attributed to the incorporation of AI2O3 nanoparticles into the polymer matrix.

[0194] Upon screen-printing the polymer electrolyte directly on the Zn and MnCh electrode surface (as depicted in Figure 8b and 8c, respectively), the surface morphologies of both electrodes were almost identical, indicating complete coverage by the polymer electrolyte. This effectively prevented electrode permeation and exposure, thus avoiding short-circuiting of the printed battery.

[0195] There is strong interfacial adhesion between the polymer electrolyte and the Zn anode. The compact and continuous interlayer contact can be attributed to the melted PVDF-co-HFP, which has an affinity towards the binder in the electrodes. Accordingly, the polymer electrolyte could diffuse and seep through the electrodes, creating favorable interfacial conditions and reducing the overall internal resistances of the printed battery.

[0196] Following battery cycling, the battery was disassembled and the cycled printed electrodes, Zn anode and MnCb cathode, were imaged. The Zn particles in the cycled Zn anode appeared flattened, which is attributed to the compression used to construct the battery. There is no evidence of dendrite formation in the Zn anode of the cycled polymer electrolyte battery. The MnCb cathode exhibited no discernible differences in morphology after cycling. This indicated an absence of dissolution issues that has been commonly reported in liquid-based electrolyte environments. Hence, the cycled polymer electrolyte battery showed no evidence of Zn dendrite growth or MnCb cathode dissolution due to reduced liquid volume.

[0197] It will be appreciated by persons skilled in the art that numerous variations and / or modifications may be made to the above-described embodiments, without departing from the broad general scope of the present disclosure. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.

Claims

CLAIMS1. A non-aqueous polymer electrolyte precursor comprising: a liquid electrolyte comprising: a non-ionic organic solvent, and a metal salt; a solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt%; wherein the amount of solvated polymer matrix (as a weight % of polymer electrolyte precursor) is between about 1 wt% to about 90 wt% wherein the amount of filler (as a weight % of polymer electrolyte precursor) is between about 0.1 wt% to about 20 wt%.

2. The non-aqueous polymer electrolyte precursor of claim 1, wherein the non-ionic organic solvent is selected from N,N-dimethylformamide, ethyl methyl carbonate, dimethyl sulfoxide, dimethyl carbonate, tetramethylene sulfone, ethylene glycol, propylene carbonate, isopropyl alcohol, diethylene glycol, glycerol, and combinations thereof.

3. The non-aqueous polymer electrolyte precursor of claim 1 or claim 2, wherein the metal salt can include a cation selected from lithium, zinc, and combinations thereof.

4. The non-aqueous polymer electrolyte precursor of any one of the preceding claims, wherein the metal salt is a zinc salt; preferably zinc sulfate, zinc trifluoromethanesulfonate, zinc tetrafluoroborate, and combinations thereof; more preferably zinc tetrafluoroborate.

5. The non-aqueous polymer electrolyte precursor of any one of the preceding claims, wherein the solvated polymer matrix comprises a polymer and a polymer solvent.

6. The non-aqueous polymer electrolyte precursor of claim 5, wherein the polymer is selected from polyvinyl alcohol, polyvinylidene fluoride, poly(vinylidene fluoride-co- hexafluoropropylene), polyethylene oxide, polypropylene oxide, polyimide polymers and copolymers, polyacrylamide; acrylate and (meth)acrylate polymers and copolymers; saccharides and polysaccharides such as guar gum, xanthan gum, starch, butyl rubber, agarose, pectin; celluloses and modified celluloses such as hydroxy methylcellulose, methylcellulose, ethyl cellulose, propyl methylcellulose, methoxy cellulose, methoxy methylcellulose, methoxy propyl methylcellulose, hydroxy propyl methylcellulose, carboxy methylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose, cellulose ether, cellulose ethyl ether; and combinations thereof; preferably wherein the polymer is polyvinylidene fluoride and / or poly(vinylidene fluoride-co-hexafluoropropylene).

7. The non-aqueous polymer electrolyte precursor of claim 5 or claim 6, wherein the polymer solvent is selected from acetone, esters such as ethyl acetate, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycol ether, glycol ether acetate, N-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO), gammabutyrolactone, gamma-valerolactone, cyrene, and combinations thereof; preferably wherein the polymer solvent is N-methylpyrrolidone.

8. The non-aqueous polymer electrolyte precursor of any one of the preceding claims, wherein the filler is selected from glass, metal oxides, aluminium oxide, polystyrene, melamine, organic materials, natural materials, and combinations thereof; preferably aluminium oxide (AI2O3), titanium dioxide (TiCh), zinc oxide (ZnO), silicon dioxide (SiCh), and combinations thereof.

9. The non-aqueous polymer electrolyte precursor of any one of the preceding claims, wherein the metal salt has a concentration of between about 1 m to about 20 m in the liquid electrolyte, preferably the metal salt is provided at the saturation limit in the liquid electrolyte relative to the amount of non-ionic organic solvent.

10. A non-aqueous polymer electrolyte film comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt; a polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of polymer electrolyte film) is between about 40 wt% to about 90 wt%; wherein the amount of polymer matrix (as a weight % of polymer electrolyte film) is between about 10 wt% to about 50 wt% wherein the amount of filler (as a weight % of polymer electrolyte film) is between about 0.1 wt% to about 20 wt%.

11. The non-aqueous polymer electrolyte film of claim 10, wherein the polymer electrolyte film has a thickness of between about 10 pm to about 300 pm, preferably between about 90 pm to about 120 pm.

12. A printable gel non-aqueous polymer electrolyte comprising: a liquid electrolyte comprising a non-ionic organic solvent, and a metal salt;a partially solvated polymer matrix; and a filler, wherein the amount of liquid electrolyte (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 10 wt% to about 60 wt%; wherein the amount of partially solvated polymer matrix (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 30 wt% to about 90 wt% wherein the amount of filler (as a weight % of printable gel non-aqueous polymer electrolyte) is between about 0.1 wt% to about 20 wt%.

13. A method of preparing a non-aqueous polymer electrolyte precursor comprising:(i) obtaining a liquid electrolyte comprising a non-ionic organic solvent and a metal salt;(ii) obtaining a polymer matrix comprising a polymer and polymer solvent;(iii) obtaining a filler; and(iv) mixing the liquid electrolyte, the polymer matrix and the filler to form the nonaqueous polymer electrolyte precursor.

14. A method of preparing an optionally printable non-aqueous polymer electrolyte comprising:(i) obtaining a liquid electrolyte comprising a non-ionic organic solvent and a metal salt;(ii) obtaining a polymer matrix comprising a polymer and polymer solvent;(iii) obtaining a filler;(iv) mixing the liquid electrolyte, the polymer matrix and the filler to form a nonaqueous polymer electrolyte precursor; and(v) heating the non-aqueous polymer electrolyte precursor to remove at least a portion of polymer solvent to form the non-aqueous polymer electrolyte.

15. The method of claim 13 or claim 14, wherein the method further comprises (vi) casting the non-aqueous polymer electrolyte precursor or non-aqueous polymer electrolyte to form a non-aqueous polymer electrolyte film.

16. Use of a non-aqueous polymer electrolyte precursor as defined by any one of claims 1 to 9 or obtained from the method of claim 13 in the manufacture of an electrochemical cell and / or use of a non-aqueous polymer electrolyte as defined by any one of claims 10 to 12 or obtained from the method of claim 14 or claim 15 in the manufacture of an electrochemical cell.

17. An electrochemical cell comprising: a negative electrode; a positive electrode; a non-aqueous polymer electrolyte as defined by any one of claims 13 to 16 or as obtained by any of claim 18 to claim 20.

18. The electrochemical cell of claim 17, wherein the electrochemical cell is an energy storage device, preferably a battery, more preferably a secondary battery.

19. The electrochemical cell of claim 17 or claim 18, wherein the electrochemical cell is a flexible electrochemical cell, optionally wherein the electrochemical cell is a printed electrochemical cell.

20. The electrochemical cell of any one of claims 17 to 19, wherein the electrochemical cell is a zinc battery, preferably selected from a zinc-manganese(IV) oxide (Zn-MnCh) battery or a zinc-silver(I) oxide (Zn-Ag2O) battery.

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