JP7510240B2 - Solid ionically conductive polymer materials - Google Patents

Description

Statement regarding federally funded research and development (not applicable)

FIELD OF THEINVENTION The present invention relates generally to polymer chemistry, and more particularly to solid polymer electrolytes and methods for their synthesis.

2. Background of the Invention The history of batteries is one of slow progress and incremental improvements. Battery performance, cost, and safety have historically had conflicting goals, resulting in conflicting outcomes that limit the viability of end uses such as grid-level storage and mobile power. The demand for transformative batteries has reached national interest, driving extensive efforts to provide higher energy density and low-cost, safe electrochemical energy storage.

Alessandro Volta invented the first true battery, which became known as the "Voltaic pile". This consisted of a pair of zinc and copper plates stacked on top of each other, separated from each other by a layer of cloth or paperboard soaked in salt water as the electrolyte. Although this discovery was not practical, it advanced the understanding of electrochemical cells and the role of electrolytes.

Since Volta, inventors have improved upon liquid electrolytes based on porous separators filled with concentrated solutions of salts, alkalis, or acids in water or organic solvents. These liquid electrolytes are generally corrosive and/or flammable, and in many cases are thermodynamically unstable with respect to the electrode materials, resulting in performance limitations and safety issues. These challenges make solid-state electrolytes highly attractive for battery development. Solid-state electrolytes can offer substantial advantages, such as no electrolyte leakage, more flexible geometry, higher energy density electrodes, and improved safety.

Ceramics and glasses were the first solid-state materials found and developed to have ionic conductivity. Further materials followed, but all of these materials have the property that sufficiently high ionic conductivity is only available at very high temperatures. For example, Toyota in Japan has developed a new "crystalline superionic crystal", _the glassy ceramic _{Li10GeP2S12 .}
The company has announced research and development using "superionic crystal" for its battery electrodes. However, this material only has high conductivity above 140°C, and ceramics suffer from the usual problems of manufacturing and brittleness. The manufacturing challenges with ceramics in particular preclude the inclusion of the material in battery electrodes.

Initial interest in polymer electrolytes was sparked in 1975 by Professor Peter V. Wright's discovery that complexes of polyethylene oxide (PEO) could conduct metal ions. Shortly thereafter, Professor Michael Armand recognized the potential use of PEO-lithium salt complexes for battery applications. Combinations of PEO and lithium salts have been developed over the years. One example of this material is the P(EO) _n LiBETI complex. Over the past 30 years, polyethylene oxide (PEO) has been used as a conductive material for many applications.
There have _been many attempts to _improve the conductivity of _P
In EO-based materials, cation mobility is dominated by the segmental motion of the polymer. This segmental motion of PEO is an effectively liquid-like mechanism, although chain entanglements and partial crystallinity may give the electrolyte some solid bulk properties. However, segmental motion is essential for PEO to be ionically conductive.

Plasticized polymer-salt complexes are prepared by adding a liquid plasticizer to PEO to achieve a compromise between the solid polymer and the liquid electrolyte. The magnitude of this environmental conductivity is substantially enhanced due to increased segmental motion, but at the expense of a deterioration of the mechanical integrity of the film as well as an increased corrosive reactivity of the polymer electrolyte towards the metal electrode.

Gel electrolytes are achieved by incorporating a large amount of liquid solvent(s)/liquid plasticizer into a polymer matrix, where the solvent/plasticizer is capable of forming a gel with the polymer host structure. The liquid solvent becomes trapped by the polymer in the matrix, forming a liquid conductive pathway through the otherwise non-conductive solid polymer. Gel electrolytes can provide high ambient conductivity, but suffer from similar drawbacks as those mentioned for plasticized polymer electrolytes.

Rubber-like electrolytes are actually polymer-in-salt systems as opposed to salt-in-polymer, where a large amount of salt is mixed with a small amount of polymer, namely poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), etc. The glass transition temperatures of these materials are low and they can remain rubber-like or viscoelastic at room temperature, which in turn provides high conductivity due to enhanced segmental motion. However, the complexed/dissolved salts are prone to crystallization, thus preventing their use in practical electrochemical devices.

Composite polymer electrolytes are prepared by simply dispersing a small fraction of micro/nano-sized inorganic (ceramic)/organic filler particles into a conventional polymer host. The polymer acts as the first phase, while the filler material is dispersed in the second phase. As a result of the dispersion, ionic conductivity, mechanical stability and interfacial activity can be enhanced. Ionic conductivity is attributed to a decrease in the crystallization level of the polymer in the presence of the filler, and a corresponding increase in segmental motion.

Polyelectrolytes contain charged groups covalently attached to the polymer backbone, which make the oppositely charged ions highly mobile. The charged groups are flexible through the segmental motions required for cationic diffusion.

Other polymer electrolytes include Rod-Coil Block polyimide (NASA Research) and various polymer/liquid blends (ionic liquid/PVDF-HFP). Unfortunately, the low conductivity at room temperature precludes all of these known polymer electrolytes from practical applications, since segmental motion of the polymer is necessary to enable ionic conductivity. Because the ionic conductivity of typical polymer electrolytes depends on segmental motion above the glass transition temperature (Tg) of the material, all attempts to create useful solid polymer electrolytes have focused on suppressing the crystalline phase and/or lowering the glass phase transition temperature to a state where segmental motion is possible (i.e., viscoelastic or rubbery).

In polymer-salt complexes where both crystalline and amorphous phases exist, ion transport occurs in the amorphous phase. The Vogel-Tamman-Fulcher (VTF) equation describes the behavior of ion diffusion through polymers. The VTF equation is based on the assumption that ions are transported by the semi-random motion of short polymer segments. The occurrence of such segmental motion occurs when the temperature is raised above the glass transition temperature, Tg, and becomes more rapid at higher temperatures in the viscoelastic state. Segmental motion is thought to facilitate ion motion both by disrupting the solvation of the multiple coordination sites corresponding to the ions on the polymer and by providing space or free volume through which the ions can diffuse. The fact that segmental motion of the polymer is necessary for ion transport has generally forced such complexes to focus on amorphous materials with low glass transition temperatures.

SUMMARY OF THE DISCLOSURE According to one aspect, there is provided a solid, ionically conductive polymeric material comprising a crystallinity greater than 30%; a melting temperature; a glassy state; and at least one both cationic and anionic diffusing ion, wherein the diffusing ion is mobile in the glassy state. The material may further comprise a plurality of charge transfer complexes, and a plurality of monomers, wherein each charge transfer complex is located on a monomer.

The material may further comprise an area specific resistance of less than 1.0×10 ⁵ ohms cm ² at room temperature.

In one aspect, a solid semi-crystalline ionically conducting polymeric material is provided having a plurality of monomers; a plurality of charge transfer complexes, each charge transfer complex located on a monomer, and the material has a resistance per unit area of less than 1.0×10 ^ohms cm ² at room temperature. The material can have a crystallinity greater than 30%; a glassy state that exists at a temperature below the melting temperature of the material; and both cationic and anionic diffusing ions, whereby each diffusing ion is mobile in the glassy state.

According to further aspects of the solid, ionically conductive polymer material, the material aspects can include one or more of the following:
A charge transfer complex is formed by reaction of the polymer with an electron acceptor;
the material has a glassy state and at least one cationic and at least one anionic diffusing ion, where each diffusing ion is mobile in the glassy state;
The material has at least three diffusing ions;
The material contains more than one anionic diffusing ion;
The melting temperature of the material is greater than 250°C;
The ionic conductivity of the material is greater than 1.0×10 ⁻⁵ S/cm at room temperature;
the material comprises a single cationic diffusing ion, wherein the diffusivity of the cationic diffusing ion is greater than 1.0×10 ⁻¹² m ² /s at room temperature;
the material comprises a single anionic diffusing ion, wherein the diffusivity of the anionic diffusing ion is greater than 1.0×10 ⁻¹² m ² /s at room temperature;
a material in which at least one cationic diffusing ion comprises an alkali metal, an alkaline earth metal, a transition metal, or a post-transition metal;
The material comprises at least one anionic diffusing ion per monomer;
The material comprises at least one cationic diffusing ion per monomer;
the material comprises at least 1 mole of cationic diffusing ion per liter of material;
A charge transfer complex of the material is formed by reaction of a polymer, an electron acceptor and an ionic compound, where each cationic and anionic diffusing ion is a reaction product of the ionic compound;
the material is formed from at least one ionic compound, where the ionic compound comprises cationic and anionic diffusing ions, respectively;
the material is a thermoplastic;
The cationic diffusing ion of the material comprises lithium;
At least one cationic and anionic diffusive ion of the material has a diffusivity, where the cationic diffusivity is greater than the anionic diffusivity;
The material has a material cation transference number greater than 0.5 and less than 1.0;
The concentration of cationic diffusing ions in the material is greater than 3 moles of cations per liter of material;
The cationic diffusing ion of the material comprises lithium;
The diffusing cation of the material is monovalent;
The valence of the diffusing cation is greater than 1;
The material contains more than one diffusing anion per monomer;
The diffusing anion of the material is a hydroxyl ion;
The diffusing anion of the material is monovalent;
The diffusing anions and diffusing cations of the material are monovalent;
At least one cationic and anionic diffusive ion of the material has a diffusivity, where the anionic diffusivity is greater than the cationic diffusivity;
The material has a material cation transport number of less than or equal to 0.5 and greater than zero;
At least the cationic diffusing ions of the material have a diffusivity greater than 1.0×10 ⁻¹² m ² /s;
one of the at least one anionic diffusing ions of the material has a diffusivity greater than 1.0×10 ⁻¹² m ² /s;
At least one anionic diffusing ion and at least one cationic diffusing ion of the material has a diffusivity greater than 1.0×10 ⁻¹² m ² /s;
Each monomer of the material comprises an aromatic or heterocyclic ring structure located on the backbone of the monomer;
the material further comprises a heteroatom located on the backbone either contained in the ring structure or adjacent to the ring structure;
The material contains heteroatoms selected from the group consisting of sulfur, oxygen, or nitrogen;
The heteroatoms of the material are located on the backbone of the monomer adjacent to the ring structure;
The heteroatom of the material is sulfur;
The material is pi-conjugated;
at least one anionic diffusing ion of the material per monomer, and wherein at least one monomer comprises a lithium ion;
the material comprises a plurality of monomers, wherein the molecular weight of the monomers is greater than 100 grams/mole;
The material is hydrophilic;
The ionic conductivity of the material is isotropic;
The material has an ionic conductivity greater than 1×10 ⁻⁴ S/cm at room temperature;
The material has an ionic conductivity of greater than 1×10 ⁻³ S/cm at 80° C.;
The material has an ionic conductivity of greater than 1×10 ⁻⁵ S/cm at −40° C.;
the cationic diffusing ion of the material comprises lithium, and wherein the diffusivity of the lithium ion is greater than 1.0×10 ⁻¹³ m ² /s at room temperature;
The material is non-flammable;
The material is non-reactive when mixed with a second material, where the second material is selected from the group comprising electrochemically active materials, electrically conductive materials, rheology modifying materials and stabilizing materials;
The material is in the form of a film;
The Young's modulus of the material is 3.0 MPa or more;
The material becomes ionically conductive after being doped with an electron acceptor;
The material becomes ionically conductive after being doped with an electron acceptor in the presence of an ionic compound that either contains both cationic and anionic diffusing ions or is convertible to both cationic and anionic diffusing ions via oxidation by an electron acceptor;
The material is formed from a reaction product of a base polymer, an electron acceptor, and an ionic compound;
The base polymer of the material is a conjugated polymer;
The base polymer of the material is PPS or liquid crystal polymer;
The ionic compound reactant of the material is an oxide, chloride, hydroxide or salt;
A charge transfer complex of the material is formed by reaction of an electron acceptor with a polymer; and the reactant electron acceptor of the material is a quinone or oxygen.

In one aspect, a solid, ionically conducting macromolecule and a material comprising the macromolecule are provided, which include:
A plurality of monomers, each monomer comprising an aromatic or heterocyclic ring structure;
Any heteroatom included in or adjacent to the ring structure;
cationic and anionic diffusing ions, both of which are incorporated into the structure of the polymer;
It consists of:
where both cationic and anionic species can diffuse along the polymer;
Here, there is no segmental motion in the polymeric material as cationic or anionic molecules diffuse along the polymer.

Further aspects of this may include one or more of the following:
The material has an ionic conductivity greater than 1×10 ⁻⁴ S/cm;
The molecular weight of each monomer is greater than 100 grams per mole;
At least one cationic diffusing ion of the material comprises an alkali metal, an alkaline earth metal, a transition metal, or a post-transition metal;
In one aspect, a method of making a solid, ionically conducting polymer material comprises the steps of: mixing a base polymer of a plurality of monomers, an electron acceptor, and an ionic compound to form a first mixture; and heating the first mixture to form the solid, ionically conducting polymer material.

A further aspect is a method of making a solid, ionically conductive polymer material, comprising: mixing a polymer of a plurality of monomers and a compound comprising ions to form a first mixture; doping the first mixture with an electron acceptor to form a second mixture; and heating the second mixture.

A further aspect is a method of making a solid, ionically conductive polymer material, comprising: mixing a polymer of a plurality of monomers and an electron acceptor to form a first mixture; heating the first mixture to form an intermediate material comprising a charge transfer complex; and mixing the intermediate material with a compound comprising ions to form the solid, ionically conductive polymer material.

Further aspects of the method of making the solid, ionically conducting polymer material can include one or more of the following:
an annealing step, where the annealing step increases the crystallinity of the base polymer;
the substrate polymer comprises a plurality of monomers, and wherein the molar ratio of monomer to electron acceptor is 1:1 or greater;
the base polymer has a glass transition temperature, and where the glass transition temperature of the base polymer is greater than 80° C.;
The weight ratio of the base polymer and the ionic compound in the mixing step is less than 5:1;
During the heating step, positive pressure is applied to the mixture;
During the heating process, the mixture changes color;
During the heating step, a charge transfer complex is formed;
an additional mixing step of mixing the solid, ionically conductive polymer material with a second material;
an extrusion step in which the solid, ionically conductive polymer material is extruded; and an ionically conductive step in which the solid, ionically conductive polymer material transports at least one ion.

Further aspects include: an electrochemically active material composite comprising the material of the previous aspect and an electrochemically active material;
an electrode comprising the material of the above aspect;
A battery comprising the material of the above aspects;
A fuel cell comprising the material of the above aspect;
an electrolyte comprising the material of the preceding aspect;
A device for ion conduction comprising a material of the above aspect;
A method for conducting ions comprising the material of the previous aspect; and A method for separating ions comprising the material of the previous aspect.

In a further aspect, the novel ion conduction mechanism allows for ion conduction in both the crystalline phase and the amorphous glassy state of the polymer, which allows for solid polymer materials with the conductivity of liquids at room temperature;
and enabling the creation of composite anodes and cathodes containing polymers and electrochemically active compounds for increased capacity and lifetime;
Allows the use of abundant and inexpensive active materials; and Allows novel battery manufacturing methods using low-cost, high-volume extrusion and other plastic processing techniques.

These and other aspects, features, advantages and objects will be further understood and appreciated by those skilled in the art with reference to the following specification, claims and accompanying drawings.

In the drawing:
1 is a plot of cycle testing of a lithium ion battery using a LCO cathode including a solid ionically conductive polymer material. 2A, B and C are x-ray diffraction plots as described in Example 9. 1 is a DSC plot described in Example 10. 1 is a plot of measured conductivity versus temperature as described in Comparative Example 13. 1 is a plot of measured conductivity versus temperature as described in Comparative Example 13. 1 is a plot of the conductivity measured for material samples described in Example 14. 13 is a plot of measured diffusivity versus temperature for material samples described in Example 16. 13 is an NMR diffusivity plot for the comparative material described in Example 17. 1 is an NMR spectrum of the base polymer reactant described in Example 18. NMR spectrum of the material described in Example 18. NMR spectrum of the material described in Example 18. 1 is an NMR spectrum of the electron acceptor described in Example 18. 13A is an NMR spectrum of the material described in Example 18. 13B is an NMR spectrum of the material described in Example 18. NMR spectrum of the material described in Example 19. 1 is an illustration of a battery using materials described in Example 19. 13 is a discharge curve for three batteries as described in Example 20. 2 is a discharge curve for the battery as described in Example 21. 2 is a discharge curve of a battery as described in Example 22.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS This patent application claims priority to U.S. Provisional Patent Application No. 62/158,841, filed May 8, 2015, the disclosure of which is incorporated herein by reference in its entirety.

The following explanations of terms are provided to more fully describe the aspects, aspects and objects described in this section. Unless otherwise explained or specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. To facilitate review of the various disclosed aspects, the following explanations of specific terms are provided:
A depolarizer is synonymous with an electrochemically active substance, i.e., a substance that changes oxidation state or participates in the formation or breaking of chemical bonds during the charge transfer step of an electrochemical reaction and in an electrochemically active material. When an electrode has more than one electroactive substance, they can be called codepolarizers.

Thermoplasticity is the property of a plastic substance or polymer to become pliable or plastic above a certain temperature, often at or near its melting temperature, and to harden upon cooling.

Solid electrolytes include solvent-free polymers, and ceramic compounds (crystals and glasses).

A "solid" is characterized by its ability to maintain its shape indefinitely, and is distinct from and different from liquid-phase materials. The atomic structure of a solid can be either crystalline or amorphous. A solid can be mixed with or be a component of a composite structure. However, for purposes of this application and claims, a solid material is required such that the material is ionically conductive through the solid, but not through any of the solvent, gel, or liquid phases, unless otherwise specified. For purposes of this application and claims, gelled (or wet) polymers and other materials that rely on liquids for ionic conductivity are not defined as solid electrolytes in that they rely on the liquid phase for their ionic conductivity.

Polymers are generally organic and composed of carbon-based macromolecules, each of which has one or more types of repeating units or monomers. They are light, ductile, usually non-conductive, and melt at relatively low temperatures. They can be made into products by injection, blowing and other molding methods, extrusion, pressing, stamping, three-dimensional printing, machining, and other plastic processes. Polymers generally have a glassy state at temperatures below the glass transition temperature Tg. This glass temperature is a function of chain flexibility, which occurs when there is enough vibrational (thermal) energy in the system to create enough free volume to allow a series of segments of the polymer macromolecule to move as a unit. However, in the glassy state of the polymer, segmental motion of the polymer does not occur.

Polymers are distinct from ceramics, which are inorganic, non-metallic materials, generally defined as compounds consisting of metals covalently bonded to oxygen, nitrogen, or carbon, that are brittle, strong, and non-conductive.

The glass transition, which occurs in some polymers, is the midpoint temperature between the supercooled liquid state and the glassy state when the polymeric material is cooled. Thermodynamic measurements of the glass transition are made by measuring the physical properties of the polymer, such as volume, enthalpy or entropy, and other derivative properties as a function of temperature. The glass transition temperature is observed from a plot of the selected property (volume vs enthalpy) as a break or change in slope (heat capacity or coefficient of thermal expansion) at the transition temperature. When a polymer is cooled from above Tg to below Tg, the mobility of the polymer molecules slowly decreases until the polymer reaches its glassy state.

Because a polymer can comprise both amorphous and crystalline phases, the crystallinity of a polymer is the amount of this crystalline phase relative to the amount of polymer and is expressed as a percentage. The percentage of crystallinity can be calculated via X-ray diffraction of the polymer by analysis of the relative areas of amorphous and crystalline phases.

A polymer film is generally described as a thin piece of polymer, but should be considered to be less than 300 micrometers thick.

It is important to note that ionic conductivity is different from electrical conductivity. Ionic conductivity depends on the diffusivity of ions, and the properties are related by the Nernst-Einstein equation. Ionic conductivity and ionic diffusivity are both measures of the mobility of an ion. An ion is mobile in a material if its diffusivity in the material is positive (greater than zero), i.e., the ion contributes to a positive conductivity. All such ionic mobility measurements are performed at room temperature (about 21° C.) unless otherwise noted. Ionic mobility is affected by temperature, making it difficult to detect at low temperatures. The detection limit of the instrument may be a factor in measuring small amounts of mobility. Mobility can be considered an ionic diffusivity of at least 1×10 ⁻¹⁴ m ² /s, and preferably at least 1×10 ⁻¹³ m ² /s, both of which convey that an ion is mobile in the material.

A solid polymeric ionically conductive material is a solid that comprises a polymer and that conducts ions as further described.

Aspects of the invention include a method for synthesizing a solid, ionically conductive polymer material from at least three separate components: a polymer, a dopant, and an ionic compound. The components and synthesis method are selected for a particular application of the material. The selection of the polymer, dopant, and ionic compound can also vary based on the desired performance of the material. For example, the desired components and synthesis method can be determined by optimizing a desired physical property (e.g., ionic conductivity).

Synthesis The synthesis method can also vary depending on the particular components and the desired form of the final material (e.g., film, particles, etc.). However, the method includes the basic steps of mixing at least two components first, adding a third component in an optional second mixing step, and heating the components/reactants to synthesize the solid, ionically conductive polymer material in a heating step. In one embodiment of the invention, the resulting mixture can be optionally formed into a film of the desired size. If a dopant was not present in the mixture produced in the first step, the dopant can be subsequently added to the mixture under heating and optionally pressure (positive or negative). All three components can be present and mixed and heated to complete the synthesis of the solid, ionically conductive polymer material in a single step. However, this heating step can be done at a step separate from any mixing or can be completed while mixing is taking place. The heating step can be done regardless of the form of the mixture (e.g., film or particles, etc.). In an embodiment of the synthesis method, all three components are mixed and then extruded into a film. The film is heated to complete the synthesis.

When the solid, ionically conductive polymer material is synthesized, a color change occurs that can be visually observed because the reactants are relatively light in color and the solid, ionically conductive polymer material is relatively dark or black in color. This color change is believed to occur when charge transfer complexes are formed and may occur gradually or rapidly depending on the synthesis method.

An embodiment of the synthesis method is to mix the base polymer, ionic compound and dopant together and heat the mixture in a second step. The heating step can be done in the presence of the dopant since the dopant can be in the gas phase. The mixing step can be done in an extruder, blender, mill or other common plastics processing equipment. The heating step can last for several hours (e.g. 24 hours) and the color change is a reliable indication that the synthesis is complete or partially complete. Additional heating after the synthesis is complete does not appear to have any adverse effect on the material.

In an embodiment of the synthesis method, the base polymer and ionic compound can be mixed first. The dopant is then mixed with the polymer-ionic compound mixture and heated. Heat can be applied to the mixture during the second mixing step or subsequent to the mixing step.

In another synthesis embodiment, the base polymer and dopant are first mixed and then heated. This heating step can be applied after or during mixing and results in the formation of a charge transfer complex and a color change indicating a reaction between the dopant and the base polymer. An ionic compound is then mixed with the reacted polymer dopant material to complete the formation of the solid ionically conductive polymer material.

Common methods of doping are known to those skilled in the art and can include vapor doping of films containing polymers and ionic compounds, as well as other doping methods known to those skilled in the art. It is believed that doping of solid polymeric materials makes them ionically conductive, and that the doping acts to activate the ionic components of the solid polymeric material so that they become diffusible ions.

Other non-reactive ingredients can be added to the mixture during the initial mixing step, the second mixing step, or during a mixing step subsequent to heating. Such other ingredients include, but are not limited to, depolarizers or electrochemically active materials, such as anode or cathode active materials, conductive materials such as carbon, rheological agents such as binders or extrusion aids (e.g., ethylene propylene diene monomer "EPDM"), catalysts, and other ingredients useful for achieving desired physical properties of the mixture.

Polymers useful as reactants in the synthesis of solid, ionically conductive polymeric materials are those that can be oxidized by an electron donor or electron acceptor. Semi-crystalline polymers with a crystallinity index greater than 30% and greater than 50% are suitable reactant polymers. Totally crystalline polymeric materials, such as liquid crystal polymers ("LCPs"), are also useful reactant polymers. LCPs are completely crystalline and therefore their crystallinity index is hereby defined as 100%. Undoped conjugated polymers and polymers such as polyphenylene sulfide ("PPS") are also suitable polymeric reactants.

Polymers are generally not electrically conductive. For example, virgin PPS has a conductivity ^{of 10-20} S.
cm ⁻¹ Non-conducting polymers are suitable reactant polymers.

In one embodiment, polymers useful as reactants have aromatic or heterocyclic moieties in the backbone of each repeating monomer group, and heteroatoms either contained in the ring or located along the backbone adjacent to an aromatic ring. The heteroatoms can be located directly on the backbone or can be bonded to a carbon atom located directly on the backbone. In both cases where the heteroatom is located on the backbone or bonded to a carbon atom located on the backbone, the backbone atom is located on the backbone adjacent to an aromatic ring. Non-limiting examples of polymers used in this embodiment of the invention can be selected from the group including PPS, poly(p-phenylene oxide) ("PPO"), LCPs, polyetheretherketone ("PEEK"), polyphthalamide ("PPA"), polypyrrole, polyaniline, and polysulfone. Copolymers containing monomers of the listed polymers and mixtures of these polymers can also be used. For example, copolymers of p-hydroxybenzoic acid can be suitable liquid crystal polymer substrate polymers. Table 1 details non-limiting examples of reactant polymers useful in the present invention, along with monomer structures and some physical property information, but these should also be considered non-limiting since polymers can take many forms that can affect their physical properties.

Dopants useful as reactants in the synthesis of solid, ionically conductive polymer materials are electron acceptors or oxides. The dopants are believed to release ions for ion transport and migration, and are believed to create sites similar to charge transfer complexes or sites within the polymer for ionic conductivity. Non-limiting examples of useful dopants include quinones, such as: 2,3-dicyano-5,6-dichlorodicyanoquinone (C ₈ Cl _{2 )} , also known as "DDQ";
Dopants _that are _{useful are tetrachloro-1,4-benzoquinone (C 6 Cl 4 O 2 ), also known as chloranil, tetracyanoethylene (C 6 N 4 ) , also} known as TCNE, sulfur trioxide ("SO ₃ "), ozone (trioxygen or O ₃ ), oxygen (O ₂ , including air), transition metal oxides including manganese dioxide ("MnO ₂ "), or suitable electron acceptors, and the like, and combinations thereof. Dopants that are useful are those that are temperature stable at the temperatures of the heating step of the synthesis, and quinones and other dopants that are both temperature stable and strong oxidizing quinones are most useful. Table 2 provides a non-limiting list of dopants along with their chemical diagrams.

Ionic compounds useful as reactants in the synthesis of solid, ionically conductive polymeric materials are compounds that release the desired ions during the synthesis of the solid, ionically conductive polymeric material. Ionic compounds differ from dopants in that they require both an ionic compound and a dopant. Non-limiting examples include _Li2O , _LiOH , ZnO, _TiO2 , _Al3O2 , NaOH, KOH, _LiNO3
, Na ₂ O, MgO, CaCl ₂ , MgCl ₂ , AlCl ₃ , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiFSI (lithium bis(fluorosulfonyl)imide), lithium bis(oxalato)borate (LiB(C ₂ O ₄ ) ₂ "Li
Examples of suitable ionic compounds include lithium salts such as tetrahydrofuran (BOB"), as well as other lithium salts and combinations thereof. Hydrated forms of these compounds (e.g., monohydrides) can be used to make the compounds easier to handle. Inorganic oxides, chlorides and hydroxides are suitable ionic compounds in that they dissociate during synthesis to produce at least one anionic and cationic diffusing ion. Any such ionic compound that dissociates to produce at least one anionic and cationic diffusing ion is useful as well. Numerous ionic compounds can be useful, so many anionic and cationic diffusing ions may be suitable. The particular ionic compounds included in the synthesis will depend on the desired use of the material. For example, in applications where it is desired to have a lithium cation, lithium and Lithium hydroxide or lithium oxide, which can be converted to hydroxide ion, would be suitable. Any lithium-containing compound that releases both a lithium positive electrode and a diffusing anion during synthesis would be suitable. A non-limiting group of such lithium ion compounds includes those that are used as lithium salts in organic solvents. Similarly, if aluminum or other specific cations are desired, aluminum or other specific ion compounds react to release the specific desired ion and diffusing anion during synthesis in such systems. As further shown, ionic compounds containing alkali metals, alkaline earth metals, transition metals and post-transition metals in a form capable of producing both the desired cation and anion diffusing species are suitable as ionic compounds of the synthesis reactants.

The purity of the materials is potentially important to prevent any unintended side reactions and maximize the efficiency of the synthesis reaction to produce highly conductive materials. Generally, substantially pure reactants including high purity dopants, base polymers and ionic compounds are preferred, with purities greater than 98% being more preferred, but even higher purities are most preferred, e.g. LiOH: 99.6%, DDQ: >98%, and chloranil: >99%.

To further illustrate the versatility of applications of the solid, ionically conductive polymer materials and the above-described synthesis methods for the solid, ionically conductive polymer materials of the present invention, several solid, ionically conductive polymer materials that are useful in many electrochemical applications and are distinguished by their applications are described:

Lithium Ion Battery In this embodiment, the reacting or base polymer is characterized as being semi-crystalline or fully crystalline and having a crystallinity between 30% and 100%, and preferably between 50% and 100%. The base polymer has a glass transition temperature above 80°C, and preferably above 120°C, and more preferably above 150°C, and most preferably above 200°C. The base polymer has a melting temperature above 250°C, and preferably above 280°C, and more preferably above 320°C. The molecular weight of the monomer units of the base polymer of the present invention ranges from 100 to 200 gm/mol, and can be higher than 200 gm/mol. Common materials that can be used for the base polymer include liquid crystal polymers and polyphenylene sulfide, also known as PPS, or semi-crystalline polymers with a crystallinity index higher than 30%, and preferably higher than 50%.

In this embodiment, the dopant is an electron acceptor, such as DDQ, TCNE, chloranil, and sulfur trioxide (SO3). The electron acceptor can be "premixed" with all other ingredients and extruded without post-treatment, or alternatively, using a doping procedure such as vapor doping, the electron acceptor can be added to the composition after the other ingredients have been mixed, such as in an extruder, and formed into a film.

Common compounds _that comprise ion sources or "ionic compounds" for use in this aspect of the invention include, but are not limited to, _Li2O , LiOH, ZnO, _TiO2 , _Al3O2 , LiTFSI, and other lithium ion compounds and combinations thereof. Ionic compounds contain the appropriate ions in a stable form that is modified to release the ions during synthesis of the solid, ionically conducting polymer material.

Example 1
PPS and chloranil powders are mixed in a 4.2:1 molar ratio (base polymer monomer:dopant ratio greater than 1:1). The mixture is then heated in argon or air at elevated temperatures (up to 350° C.) for 24 hours at atmospheric pressure. A color change is observed to confirm the formation of a charge transfer complex in the polymer-dopant reaction mixture. The reaction mixture is then re-ground to a small average particle size of 1-40 micrometers. LiTFSI is then mixed with the reaction mixture to produce the synthesized solid, ionically conductive polymer material.

Example 2
Lithium cobalt oxide ( _LiCoO2 ) containing material synthesized from Example 1 ("LC
A 3000-.O″) cathode was prepared. The cathode mixed with solid ionically conductive polymer material and conductive carbon used a high LCO loading of 70 wt %. The cell was prepared using a lithium metal anode, a porous polypropylene separator and a standard Li-ionic liquid electrolyte consisting of LiPF6 salt and carbon-based solvent. The cell was assembled in a dry glove box and cycle tested.

The capacity is shown in Figure 1 in terms of the weight in grams of LCO used in these cells. It can be seen that the capacity was stable when charged at 4.3 V, and the target 0.5 equivalents of Li transferred from the cathode remained constant during charging. The cells were also cycled at a higher charge voltage of 4.5 V, which utilized a higher percentage of lithium from the cathode and produced high capacity >140 mAh/g. The slight decrease in capacity with cycle number observed in the 4.5 V charge test is consistent with decomposition (i.e., instability) of the liquid electrolyte at this higher voltage. Overall the performance of the LCO cathodes containing the materials of the present invention is favorable and comparable to the slurry-coated LCO cathodes.

Alkaline Batteries The base polymer of the solid, ionically conductive polymer material with hydroxyl ion mobility is preferably a crystalline or semi-crystalline polymer, which generally has a crystallinity greater than 30% and including up to 100%, and preferably between 50% and 100%. The base polymer of this aspect of the invention has a glass transition temperature greater than 80°C, and preferably greater than 120°C, and more preferably greater than 150°C, and most preferably greater than 200°C. The base polymer has a melting temperature greater than 250°C, and preferably greater than 280°C, and more preferably greater than 300°C.

Dopants in solid, ionically conductive polymer materials with hydroxyl ion mobility are electron acceptors or oxidants. Common dopants for use in this aspect of the invention are DDQ, chloranil, TCNE, _SO3 , oxygen (including air), _MnO2 and other metal oxides, etc.

Compounds that contain ion sources for the solid, ionically conductive polymer material that have hydroxyl ion mobility include salts, hydroxides, oxides, or other materials that contain hydroxyl ions or can be converted to such materials, including, but not limited to, LiOH, NaOH, KOH, _Li2O , _LiNO3 , and the like.

Example 3
PPS polymer was mixed with the ionic compound LiOH monohydrate in the ratio of 67% to 33% (by weight), respectively, and mixed using a jet mill. DDQ dopant was added to the resulting mixture via vapor doping in the amount of 1 mole of DDQ per 4.2 moles of PPS monomer. The mixture was heated at 190-200°C for 30 minutes under medium pressure (500-1000 P).
SI) and heat treated.

Composite MnO2 Cathode In this aspect of the invention relating to the preparation of a solid ionically conductive polymer material-MnO2 composite cathode, the base polymer can be a semi-crystalline, or fully crystalline polymer with a crystallization index greater than 30%, and can be selected from the group consisting of conjugated polymers or polymers that can be easily oxidized with a selected dopant. Non-limiting examples of base polymers used in this aspect of the invention include PPS, PPO, PEEK, PPA, etc.

In this embodiment, the dopant is an electron acceptor or oxidant. Non-limiting examples of dopants include DDQ, chloranil, tetracyanoethylene also known as TCNE, SO3, ozone, oxygen, air, transition metal oxides including MnO2, or any suitable electron acceptor.

In this embodiment, the compound containing the ion source is a salt, hydroxide, oxide, or other material that contains hydroxyl ions, or is convertible to such materials, including, but not limited to, LiOH, NaOH, KOH, Li2O, LiNO3, etc.

Example 4
PPS polymer and LiOH monohydrate were added together in a ratio of 67% to 33% (by weight), respectively, and mixed using a jet mill. Additional alkaline battery cathode components were added and further mixed: _MnO2 , _Bi2O3 , and conductive carbon. The _MnO2 content varied from 50% to _{80% by weight, Bi2O3 ranged} from 0 to 30% by weight, the carbon _black amount was 3-25% by weight, and the polymer/LiOH content was 10-30% by weight.

The mixture was heated to synthesize an alkaline battery cathode comprising a solid, ionically conductive polymer material useful in typical zinc-manganese dioxide alkaline batteries.

Example 5
A zinc-manganese dioxide alkaline battery was fabricated using the positive electrode of Example 4 and a commercial non-woven separator (NKK), a Zn foil negative electrode, and 6M LiOH solution as the electrolyte.

The cells were discharged under constant current conditions of 0.5mA/cm2 using a Bio-Logic VSP 15 test system. The specific capacity of MnO2 was found to be 303mAh/g, i.e. close to the theoretical 1e-discharge.

In this embodiment, the solid, ionically conductive polymer material is used in a metal-air battery and comprises a base polymer, a compound comprising an ion source, and a dopant. The polymer can be selected from the group of PPS, LCP, polypyrrole, polyaniline, and polysulfone and other base polymers.

The dopant may be an electron acceptor or a compound containing a functional electron acceptor capable of initiating an oxidation reaction with the polymer. Common dopants are DDQ, chloranil, TCNE, SO3, ozone, and transition metal oxides including MnO2. The material containing the ion source may be in the form of a salt, hydroxide, oxide, or other material that contains hydroxyl ions or that can be converted to such materials, including but not limited to LiOH, NaOH, KOH, Li2O, LiNO3, etc.

Example 6
Using the material synthesized in Example 3, air electrodes were prepared by mixing the solid, ionically conductive polymer material with various carbons, specifically: TIMCAL SUPER C45 conductive carbon black (C45), Timcal SFG6 (synthetic graphite), A5303 carbon black from Ashbury, and natural vein graphite nano (N99) from Ashbury. The carbon content was varied from 15 to 25 wt%.

The positive electrode was cut to fit a 2032 coin cell. Zinc foil was used as the negative electrode. The non-woven separator was immersed in 40% KOH aqueous solution. Two holes were drilled into the top surface of the coin facing the positive electrode. The cell was discharged at room temperature using an MTI coin cell tester at a constant current of 0.5 mA.

The cathode parameters and test results are summarized in Table 3. The discharge curves are shown in Figure 2. The cell with the air cathode of this example using the material of the present invention shows typical discharge behavior for Zn-air cells without any traditional catalyst (transition metal substrate) added to the mixture. In addition to conducting hydroxyl ions from the air cathode to the anode, the material acts to catalyze the formation of hydroxyl ions from oxygen present on the cathode surface. As shown in this example, the material of the present invention has catalytic functionality.

Other Ionic Compounds Numerous anions and cations can be conducted by the materials of the present invention. The ionic compounds used in the synthesis can be selected so that the desired diffusing ions are included in the synthesized material.

Example 7
Material samples were prepared by mixing LCP polymer [SRT900?] and ionic compounds in various ratios. DDQ was used as the dopant. The monomer to dopant molar ratio of the polymer was 4.2:1 and is listed in Table 4. The mixtures were heat treated at 190-200C for 30 minutes at medium pressure (500-1000 psi).

The samples were sandwiched between stainless steel electrodes and placed in the test fixture. AC impedance was recorded in the range of 800 KHz to 100 Hz using a Bio-Logic VSP test system to measure the electrolyte conductivity.

The results are shown in Table 3 below. The high ionic conductivity observed indicates that the solid polymer material is capable of conducting many ions, including lithium Li ⁺ , potassium K ⁺ , sodium Na ⁺ , calcium Ca2 ⁺ , magnesium Mg2 ⁺ , aluminum Al3 ⁺ , hydroxyl ^OH- , and chloride ^Cl- ions.

Any ionic compound that can be dissociated by a dopant can be used as long as the dissociated ions are desirable for the applicable electrochemical application in which the material is used. The anions and cations derived from the ionic compound are thus rendered ionically conductive by the material. Ionic compounds include oxides, chlorides, hydroxides, and other salts. In this example, a metal (or other cation) oxide gives rise to a metal (or other cation) cation and a hydroxyl ion.

The ability to conduct multiple ions in addition to lithium cations opens new avenues of application for the materials of the present invention. Sodium- and potassium-based energy storage systems are considered as alternatives to Li-ions, driven primarily by low cost and relatively abundant raw materials. The conductivity of calcium, magnesium and aluminum is necessary for multivalent intercalation systems that can potentially increase energy density beyond the capabilities of Li-ion batteries. Such materials can also be used to create power sources with metallic anodes that are more stable, safer and less expensive than lithium.

Example 8
Additional solid, ionically conductive polymer materials, once prepared using the synthesis method of Example 1, are listed in Table 5 along with their reactants and associated ionic conductivities (EIS method).

Additional solid, ionically conductive polymer materials prepared using the synthesis method of Example 3 are listed in Table 6 along with their reactants and associated ionic conductivities (EIS method).

The LCPs listed in Table 6 are supplied by Solvay under the trademark Xydar and are LCP grades with different melting temperatures.

Physical properties of the solid ionically conductive polymer material:
The physical properties of the solid, ionically conductive polymer material can vary based on the reactants used. The specific ion mobilities and anion and cation diffusing ions are derived from the synthesis of the material, but other physical properties do not appear to change significantly for the reactant polymers.

Example 9
Crystallinity The reactants PPS, DDQ and LiOH from Example 3 were used to compare the relative physical properties of the reactant polymers and the synthesized solid, ionically conductive polymer material.

In the first step, the PPS reactant and LiOH monohydride were mixed and analyzed via x-ray diffraction ("XRD"). In Figure 2A , the XRD of this amorphous polymer mixture shows a peak between 30 and 34 degrees that corresponds to LiOH monohydride. Otherwise, the XRD shows that the polymer is amorphous and lacks any significant crystallinity.

The mixture is extruded and drawn into a film. Heating the PPS polymer through the extruder in this process anneals the amorphous PPS material (heating and maintaining at a suitable temperature below the melting point followed by slow cooling) while simultaneously extruding the material into a film, thereby creating or increasing crystallinity. Figure 2B shows a significant crystalline polymer peak, which can also be used to quantify the crystallinity of the PPS material at about 60%. A LiOH monohydride peak also remains.

The film mixture was then subjected to vapor doping of DDQ dopant to produce the solid, ionically conductive polymer material of the present invention, and the corresponding XRD is shown in FIG. 2C . A color change is observed during doping as the material turns black after doping. This color change indicates that an ionic charge transfer complex is formed, indicating that the polymer and dopant reactants have reacted in the presence of the ionic compound, and that the material has been activated to become ionically conductive. The polymer peak remains, indicating that the degree of crystallinity of the material remains at about 60%, thus unchanged. However, the LiOH monohydride peak disappears and is not replaced by any other peak. The conclusion drawn is that the ionic compound has dissociated into its component cations and anions, and these ions are now part of the material structure.

Glass Transition and Melting Temperatures Example 10
While many techniques exist for measuring the melting temperature and Tg of bulk and thin film polymer samples, differential scanning calorimetry ("DSC" and described in ASTM D7426 (2013)) provides a rapid test method for measuring the change in specific heat capacity of a polymeric material. The glass transition temperature appears as a step change in the specific heat capacity.

Referring to Figure 3 , a DSC plot for the material synthesized from Example 1 is shown. The melting point of the material [PPS-chloranil-LiTFSI] is derived from DSC and determined to be not different from the reactant polymer PPS: Tm of about 300C. The glass transition temperature Tg of this base polymer is between 80-100C, but no Tg inflection is observed in the DSC plot, and it is believed that upon synthesis the solid ionically conductive polymer material lost its viscoelastic state, which is evident in the PPS base polymer, where the glassy state extends into the lower temperature range below the melting temperature of the material. The sudden drop in the plot at 130C is believed to be an artifact of ionic compounds.

Ionic Conductivity The ionic conductivity of the solid, ionically conductive polymer material of the present invention is measured and compared to related conventional electrolytes. The material of the present invention was found to be ionically conductive at ambient conditions, while in the glassy state the reactant polymer was ionically disconnected. Since the material is in the glassy state, there can be no relevant segmental motion, and thus diffusion of lithium cations and anions must be possible via a different ionic conduction mechanism where segmental motion is not necessary.

Specifically, films of the solid, ionically conductive polymer material of the present invention described in Example 1 are extruded in thicknesses ranging from 0.0003 inches (7.6 micrometers) up. The ionic surface conductivity of the films is measured using a standard test of AC-electrochemical impedance spectroscopy (EIS) known to those skilled in the art. A sample of the solid, ionically conductive polymer material film is sandwiched between stainless steel blocking electrodes and placed in the test fixture. AC-impedance was recorded using a Bio-Logic VSP test system in the range of 800 KHz to 100 Hz to measure the ionic conductivity of the material. The in-plane and through-plane ionic conductivity was measured using Bio-Logic by placing the material film in an appropriate jig. The cross-plane conductivity was measured at 3.1×10 ⁻⁴ S/cm and the through-plane conductivity was measured at 3.5×10 ⁻⁴ S/cm. The measurements were similar enough to consider the isotropic relative ion conductivity of the material.

A film approximately 150 micrometers thick was made using the material of Example 1. The conductivity was measured directly via a constant potential experiment. The film was placed between stainless steel blocking electrodes and a voltage of 0.25 V was held between the electrodes. The current was measured at 180 nanoamps, resulting in a conductivity of 2.3 x 10 ⁶ ohms cm ² at room temperature. This conductivity (resistance per unit area) is low, less than 1.0 x 10 ⁵ ohms cm ² at room temperature, which is sufficient for an electrolyte.

Thermogravimetric analysis of the material of Example 1 was performed to measure the moisture content of the material. After storing the material in a glove box in a dry environment, thermogravimetric analysis was performed and showed that the material contained <5 ppm water. Certain salts used as reactants in the solid ionically conductive polymer material (e.g. LiOH as an ionic compound) can attract atmospheric water, which makes the material hydrophilic.

Example 12
The modulus of the material synthesized in Example 3 was tested. The Young's modulus range of electrolytes made from this particular solid polymer material is 3.3-4.0 GPa. However, the range of Young's modulus of the materials listed in this application is much larger and spans from 3.0 MPa to 4 GPa. The synthesized material remains thermoplastic and can be reformed by plastic processing techniques. The material of Example 3 was heated above its melting point and cooled. The material was then reformed into a film. Thus, the material is shown to have both a high modulus and to be thermoplastic.

Comparative Example 13
The results of the ionic conductivity measurements reported in Example 1 are illustrated in Figures 4 and 5. The conductivity of a solid, ionically conductive polymer material film according to the present invention (Δ) is compared to that of trifluoromethanesulfonate PEO (□) and an electrolyte made from a Li salt solute and ethylene carbonate-propylene carbonate "EC:PC" solvent combination using a Celgard separator (O).

FIG. 4 shows the measured conductivity of the solid polymer ionically conductive material as a function of temperature. It also shows the measured ionic conductivity of the liquid electrolyte EC:PC with LiPF6 salt and PEO-LiTFSI electrolyte with Celgard separator. The conductivity of the solid ionically conductive polymer material at room temperature is about 2.5 orders of magnitude higher than that of the PEO-LiTFSI electrolyte and is comparable to the conductivity of the conventional liquid electrolyte/separator system measured under similar conditions. The temperature dependence of the conductivity of the solid ionically conductive polymer material does not show a sharp rise above its glass transition temperature accompanied by chain migration as described by the temperature activated Vogel Tamman-Fulcher behavior. Thus, segmental motion as an ionic conduction mechanism of the polymer electrolyte material is not occurring since the material shows significant ionic conductivity in its glassy state. This further proves that the inventive polymer material has a similar level of ionic conductivity to the liquid electrolyte.

In Figure 5 , the ionic conductivity of the solid, ionically conductive polymer material is compared to a conventional liquid electrolyte, a comparative example, lithium oxynitride phosphorus acid "LIOPN," and to the associated DOE targets for both conductivity and temperature. With reference to Figure 4B , the ionic conductivity of the solid, ionically conductive polymer material is greater than 1x10-04 S/cm at room temperature (about 21°C) and is greater than ^1x10-04 S/cm at about -30°C.
x 10 ^-04 S/cm (and greater than 1 x 10 ^-05 S/cm, and greater than 1 x 10 ^-03 S/cm at about 80°C.

Example 14
Ionic conductivity can be optimized by adjusting the formulation of the material. Figure 6 shows the improvement and optimization of ionic conductivity, which was brought about by adjusting the formulation of the polymer material, for example, by changing the base polymer, dopant or ionic compound.

Diffusivity In addition to ionic conductivity, diffusivity is an important intrinsic property of any electrolyte and ionically conductive material.

Example 15
Diffusion measurements were performed on the material prepared in Example 3.

Basic NMR techniques were used to unambiguously identify Li+ as a free-flowing ion in the solid, ionically conductive polymer material. NMR is element specific (e.g., H, Li, C, F, P, and Co) and sensitive to small changes in local structure.

Specifically, the diffusivity of lithium and hydroxyl ions was evaluated by pulsed gradient spin echo ("PGSE") lithium NMR. The PGSE-NMR measurements were performed using a Varian-S Direct Drive 300 (7.1T) spectrometer. Magic angle spinning was used to average the chemical shift anisotropy and dipolar interactions. A pulsed gradient spin stimulated echo pulse sequence was used for the self-diffusion (diffusivity) measurements. Self-diffusion coefficient measurements for cations and anions in each material sample were made using ^1H and ^7Li nuclei, respectively. The NMR-determined self-diffusion coefficient is a measure of random thermally induced translational motion similar to Brownian motion, where there is no external driving force. However, self-diffusion is closely related to ionic mobility and ionic conductivity via the Nernst-Einstein equation and is therefore an important parameter to measure when characterizing battery electrolytes. With both ionic conductivity and diffusivity data, it is possible to ascertain the presence of ion pairing or higher aggregation effects that limit the performance of the electrolyte. Such testing concludes that the solid polymer ionically conductive material has a Li ⁺ diffusivity of 5.7× ¹⁰⁻¹¹ m2/s at room temperature and 1.5×10−11 m2/ ^s at 90°C.
0/LiTFSI and at least an order of magnitude higher _{than Li10GeP2S12} (measured at high temperatures). Thus, the solid, _ionically conductive polymer material can act as a new solid electrolyte with the unique ability to conduct many ions that can diffuse and become mobile, and provide ionic conductivity at room temperature that is high enough for batteries and other applications.

The diffusivity of OH ^- ions was 4.1×10 ⁻¹¹ m ² /s at room temperature. Thus, the solid, ionically conductive polymer material has a very high diffusivity for solid OH ^- conductors.
The corresponding cation transport number (defined in equation (1) below) is 0.58, which is also significantly higher and different from prior art solid electrolytes.

Example 16
Diffusivity measurements were performed on the material [PPS-DDQ-LiTFSI] prepared in Example 1. Self-diffusion was measured using the technique described in Example 15. The material had a cation diffusivity D( ⁷ Li) of 0.23×10 ⁻⁹ m ² /s at room temperature, and an anion diffusivity D( ¹ H) of 0.45×10 ⁻⁹ m ² /s at room temperature.

To determine the degree of ionic association that reduces the conductivity of the material, the conductivity of the material was calculated using diffusion measurements measured via the Nernst-Einstein equation, and the associated calculated conductivity was determined to be much greater than the measured conductivity. This difference was on average at least an order of magnitude (i.e., 10x). It is therefore believed that conductivity can be improved by improving ionic dissociation, and the calculated conductivity can be considered to be within this range of conductivity.

The cation transport number can be predicted from the diffusion coefficient data via equation (1) as follows:
t ⁺ ∼D ⁺ /(D ⁺ +D ^- ) (1)
where D ⁺ and D ^- refer to the diffusion coefficients of the Li cation and TFSI anion, respectively. From the above data, we obtain a t ⁺ value of about 0.7 for the solid ionically conductive polymer material, compared to a t ⁺ value of about 0.2 for the corresponding PEO electrolyte (liquid carbonate electrolyte also has a t ⁺ value of about 0.2). This property of high cation transport number has important implications for battery performance. Ideally, a t ⁺ value of 1.0 would be preferred, meaning that Li ions carry all the current. Anion mobility creates electrode polarization effects that can limit battery performance. In materials where both ions can be mobile, t ⁺ values of 0.5 or higher are highly desired but very rarely achieved. The calculated transport number of 0.7 is not believed to have been observed in any liquid or PEO-based electrolyte. Although ion association may affect the calculation, electrochemical results confirm a range of transport numbers between 0.65 and 0.75.

We believe that t ⁺ is dependent on the anion diffusion since the diffusion of lithium cations is high. If the cation diffusion is larger than the corresponding anion diffusion, the cation transport number must always be higher than 0.5, and if the anion is mobile, the cation transport number must also be less than 1.0. We believe that the investigation of lithium salts as ionic compounds yields this range of cation transport numbers higher than 0.5 and less than 1.0. As a comparative example, some ceramics have been reported to have high diffusion numbers, but such ceramics only transport a single ion, and therefore the cation transport number falls to 1.0 when D- is zero.

Although the transport numbers are calculated from NMR derived diffusion measurements, another means of calculating the transport numbers is by direct methods such as the Bruce and Vincent method.
The method of G. and Vincent was used to calculate the transport numbers of the solid, ionically conductive polymer materials and was found to correlate well with NMR-derived measurements.

With reference to FIG. 7 , the results of diffusion measurements of the solid ionically conductive polymer material over a wide temperature range are shown and compared to PEO with LiTFSI as the ion source. The most important conclusions are: (i) at temperatures where both compounds can be measured, the diffusion of Li is nearly two orders of magnitude higher for the solid polymer ionically conductive material than the PEO LiTFSI polymer electrolyte; (ii) the diffusion coefficient of the solid polymer ionically conductive material is measurable down to at least −45° C., a very low temperature for Li diffusion measured in a solid material, specifically a lithium ion diffusivity of greater than 1×10 ⁻¹³ m ² /s. This superior ion conductivity performance of the solid ionically conductive polymer material at low temperatures surpasses that of common liquid battery electrolytes. It is also noteworthy that the temperature dependence of the NMR spectrum suggests that the ion motion is not due to segmental motion of the polymer, but is instead decoupled from the polymer in that its glassy state allows significant ion diffusion. Thus, the existence of a solid, ionically conductive polymer material is demonstrated that has greater than 30% crystallinity; a glassy state; and at least one both cationic and anionic diffusing ion, where at least one (in this embodiment both diffusing ions) diffusing ion is mobile in the glassy state.

Comparative Example 17
The cation diffusion rate of LiPON was investigated in "Structural characterization and Li dynamics in new Li _{3 PS4} ceramic ion conductor by solid-state and pulsed magnetic field gradient NMR" (Sang et _al ., 2003).
(LiD-state and pulsed-field gradient NMR)" Mallory Govet, Steve Greenbaum, Chengdu Liang and Gayari Saju, Chemistry of Metals (2014). The experimental method used was similar to that described in Examples 15 and 16, and the diffusion curve is described in Figure 8. LiPON has a diffusion coefficient of 0.54 x ^{10-12 m2} /s at 100°C.
This diffusivity is about 80 times smaller than that of the material of the present invention at ambient temperature ( ²¹ ° C.).

Chemical Structure of the Material Experiments are performed to measure information about the chemical structure of the solid, ionically conductive polymer material.

Example 18
In this example, the material synthesized in Example 3 was run with its reactants PPS and DDQ and LiOH monohydride.

The reactant or base polymer PPS was analyzed first, and in FIG. 9 , the proton ( ¹ H) NMR spectrum of PPS was compared against a spectroscopic standard of tetramethylsilane ("TMS") at 60° C.
The PPS polymer is characterized by a single peak centered at 0.8 ppm, which is a clear indication of aromatic hydrogen as expected from the polymer structure. The proton solid-state MAS NMR spectrum of this PPS polymer was taken on a 300 MHz instrument. The asterisk indicates a spinning sideband, and the inset shows a larger resolution image.

With reference to FIG. 10 , ¹ H NMR spectra of the solid ionically conductive polymer material (top), including the spectral deconvolution into OH-type protons (middle), and aromatic protons (bottom).
R spectrum. This spectrum confirms aromatic hydrogens and hydroxides. The solid-state MAS NMR spectrum of the protons of the material was taken on a 500 MHz instrument. The asterisks indicate spinning sidebands, and the inset shows a magnified resolution view. Deconvolution of the spectrum to ^OH- and base polymer protons is shown in the inset as an additional experimental spectrum. Since NMR spectroscopy is quantitative (as long as care is taken not to saturate the signal), direct integration of the spectral peaks gives the percentage of nuclei in a particular phase. The result of this integration shows that the material has more than one mobile OH ion per aromatic repeat group: and contains about two LiOH molecules per repeat unit (monomer) of the polymer, which is a very high ion concentration. The narrow OH signal indicates high mobility of the OH ion.

Additional structural information can be obtained by carbon-13 solid-state MAS NMR, made possible by ^13C at a natural abundance of .about.1%. Cross polarization (CP) is used, whereby nearby protons are made to resonate simultaneously with the ^13C nuclei, as in transfer nuclear magnetization to "rear" spins to enhance detection sensitivity. In FIG. 11 , the PPS polymer spectrum is represented in both direct polarization (bottom), where all carbons participate in the signal, and in CP (top), where only those directly bonded to hydrogen participate. The difference spectrum (middle) corresponds to the carbons that are bonded to sulfur, i.e.

In Figure 12 , the ^13C spectrum of the electron acceptor compound taken on a 500 MHz instrument with direct polarization is shown, along with the proposed spectral assignment of the electron acceptor DDQ. Since there is no hydrogen in this molecule, the spectrum was obtained under direct detection. Due to the very long spin-lattice relaxation time (such as more than 1 minute), the signal to noise ratio is rather low. The assignments for the various peaks are shown in Figure 12. The appearance of six different peaks instead of the expected four (corresponding to the four chemically non-equivalent carbons) suggests the possible presence of isomers.

The ^13C solid-state MAS NMR spectrum of the solid ionically conductive polymer material taken on a 500 MHz instrument by direct polarization is shown in Figure 13A and shows a shift in the main peak (dominated by aromatic carbons) from PPS into the ionically conductive material. The CP spectrum in the center of the inset suggests that the PPS polymer interacts strongly with the OH groups of LiOH.
The expanded spectra of both the material and the DDQ electron acceptor are compared in FIG. 13B and indicate that there is a chemical reaction in the material that obscures the original spectroscopic signature of the reactants.

This NMR analysis clearly shows that three different reactants react to form the solid, ionically conductive polymer material of the present invention. A new material has been formed that is not simply a mixture of the components. There is a reaction between the three components, and the solid polymeric, ionically conductive material is the reaction product. In particular, there is a shift in the ^13C NMR peaks between the base polymer and the synthesized material. Furthermore, the effect of simultaneous illumination of the ^1H and ^13C resonances of the hydrogen associated with OH indicates that ions have been incorporated into the structure, and thus all three separate components have reacted and are part of the new synthesized material.

Example 19
Quantification of the cation (e.g., lithium ion) concentration in the material of Example 3 can be completed by inserting the material into an inner coaxial tube and surrounding it with an external reference solution of a shift reagent complex such as lithium dysprosium polyphosphate (Dy). Referring to FIG. 14 , a shift in the Li cation resonance is induced by the paramagnetic Dy allowing for quantification of lithium in the sample. In the measured sample, the lithium cation concentration was found to be approximately 3 moles per liter of material ([Li] ∼ 3 moles/liter). This high concentration of cations allows the solid ionically conductive polymer material to have very high ionic conductivity at room temperature and over a wide temperature range.

Material Stability Liquid electrolytes and other polymer electrolytes address the issue of lithium stability. Their interaction with lithium results in reactions between lithium and the electrolyte that are detrimental to the battery's life. The electrolyte also needs to be compatible and non-reactive when used with other battery components such as electrochemically active materials, including intercalation materials, conductive additives, rheological agents, and other additives. Furthermore, at voltages above 4.0 volts, typical electrolytes may simply decompose, again resulting in poor battery life. Thus, lithium "stability" becomes a requirement for polymer electrolytes. Specifically, polymer electrolytes are non-reactive and do not decompose, while at the same time transporting lithium metal at voltages above 4.0V, 4.5V, and 5.0V.

Referring to FIG. 15 , a thin film battery structure 10 is depicted. The negative electrode is composed of lithium metal 10 with associated current collectors (not shown), i.e., anode intercalation materials typical of lithium ion batteries. Once an intercalation material is selected, a solid, ionically conductive polymer material is mixed therewith. The positive electrode 30 is composed of a cathode collector (not shown) and an electrochemically active material or intercalation material. Again, a solid, ionically conductive polymer material is mixed therewith along with an electrically conductive material. A film of the solid, ionically conductive polymer material is used as the separator/electrolyte 40 and is sandwiched between the negative and positive electrodes.

Example 20
The solid ionically conductive polymer material demonstrates compatibility with a wide variety of current lithium ion chemistries. Referring to Figure 16 , the performance of a battery constructed according to Figure 15 and labeled according to the associated positive electrode electrochemically active material. Specifically, the battery was constructed using _LiFePO4
, _LiMn2O4 , and _LiCoO2 positive _electrodes and lithium metal negative electrodes. Batteries constructed with the materials of the present invention mixed in the positive electrode with the electrochemically active material use the electrolyte to conduct lithium ions to and from the negative and positive electrodes and exhibit adequate discharge performance.

By using this solid polymer material as the electrolyte in all battery structures or in one structure (negative electrode, positive electrode, separator and electrolyte), new levels of performance can be achieved without the use of any liquid electrolyte. The material can be mixed with the electrochemically active material or intercalation material in at least one electrode. The ions required for the electrochemical reaction of the battery are conducted through the electrolyte. The material can be in the form of granules, slurry, film or other suitable application for the battery. As a film, the material can be sandwiched between electrodes or between an electrode and a current collector, placed to encapsulate a current collector or electrode, or placed where ionic conductivity is required. All three major components of the battery can be made using solid polymer materials as described in FIG. 15. In the embodiment shown in FIG . 15 , the film-form electrodes and the sandwiched separator or electrolyte can be free-standing structures or can be secured together by heat welding or other means for holding thermoplastic films together.

Example 21
A positive electrode was fabricated using LCO encapsulation with the material from Example 1. The positive electrode was paired with a lithium metal negative electrode, and a film of the material was sandwiched between the negative and positive electrodes as described in the configuration of Figure 15. The assembled battery was then charged and discharged for multiple cycles. Figure 17 shows the resulting discharge curve over a number of cycles.

The charge-discharge curves show little polarization and the efficiency is at least 99%. This result demonstrates the functionality of the polymer as an ion transport medium in the positive electrode and also its ability to serve as an electrolyte in a solid-state battery. Also important is the voltage stability of the electrolyte during operation from 4 (4.0) volts to 4.3 V and 5.0 V, the stability of the lithium metal, and the stability of transporting lithium at rates exceeding 100 mAh/g (specifically at least: 133.5 mAh/g lithium).

Example 22
A LiS battery is constructed containing a lithium metal anode and a sulfur cathode made in the configuration described in Figure 15. The materials from Example 1 are used in the construction of the battery. In general, lithium-sulfur systems have struggled to overcome poor cycle life caused by the dissociation of intermediates in the sulfur reaction chemistry in the liquid electrolyte typical of such batteries.

The solid polymer material acts to limit this dissociation of the reaction intermediates by trapping them in a solid system, allowing the Li-S system. The solid polymer material allows lithium ions to be transported while blocking polysulfide ions from reaching the negative electrode. The solid polymer material limits the solubility of the sulfur particles and the transport of sulfides, thereby allowing more sulfur to participate in the reaction and improving the capacity of the positive electrode. This improved capacity is shown in FIG. 18 relative to a battery comprising a standard positive electrode containing only sulfur and carbon. Again, it is important to note that this data was taken at room temperature. The solid polymer material does not allow for "indiscriminate diffusion," typical of liquid electrolytes and some common polymer electrolytes, but instead only allows the diffusion of ions incorporated into the material during synthesis. Thus, sulfides cannot diffuse and are instead non-ionically conductive just like other ions other than the diffusing anion(s) and cation(s), i.e. the material can act as an ion separation membrane that can be engineered to allow ion movement only for selected ions.

Solid Polymer Electrolyte As described, the solid, ionically conductive polymer material acts as a solid electrolyte. As a solid electrolyte, it obviates the need for a separator, although many of the same separator properties are required for a solid electrolyte.

A separator is an ion-permeable membrane placed between the negative and positive electrodes of a battery. The separator's main function is to keep the two electrodes apart, preventing short circuits, while also allowing the transport of ionic charge carriers that are necessary to close the circuit during the passage of electrical current in an electrochemical cell. This separation and ion transport operation is necessary for all batteries.

The solid electrolyte must also be chemically stable towards the electrode materials in the aggressively reactive environment when the battery is repeatedly fully charged and discharged. The separator should not decompose during normal and abnormal use of the battery. Of particular importance is voltage stability over the range of voltages encountered during charging and discharging.

The solid electrolyte must be thin to facilitate the energy and power density of the battery. However, it must act as a separator and cannot be too thin to balance mechanical strength and safety. The thickness should be uniform to support many charging cycles. Approximately 25.4 μm- (1.0 mil) and less than 30 micrometers are generally standard widths. The thickness of the solid electrolyte is determined by the Technical Association of the Pulp and Paper Industry.
The thickness of the extruded polymer can be measured using the T411 om-83 method by the Pulp and Paper Industry and was extruded to a thickness of 5 to 150 micrometers.

Polymer separators generally increase the resistance of the electrolyte by a factor of four to five, and deviations from uniform permeability result in non-uniform current density distribution, which can lead to the formation of dendrites. Both problems can be eliminated by the use of solid electrolytes, which produce and have uniform, isotropic ionic conductivity.

The solid electrolyte must be strong enough to withstand any flexing operations during battery assembly, or the bending and other abuse of the battery. Mechanical strength is generally defined in terms of tensile strength in both the machine (flexing) and cross directions, tear resistance and puncture strength. These parameters are defined in terms of Young's modulus, which is the ratio of stress to strain. The Young's modulus range for electrolytes made from solid polymeric materials is 3.0 MPa-4.0 GPa, and can be engineered higher if necessary by using additives such as glass or carbon fibers.

The solid electrolyte must lay completely flat without curling or puckering and be stable over a wide temperature range. The ionic transport properties of the solid electrolyte of the present invention vary with temperature, but the structural integrity remains stable even when exposed to excessive heat, as described more fully below.

Thus, the solid ionically conductive polymer material meets the requirements of a separator and solid electrolyte, as it achieves each of the requirements listed above. Specifically, the solid polymer electrolyte has a Young's modulus greater than 3.0 MPa, a thickness less than 50 micrometers, isotropic ionic conductivity, diffusivity of many ions at temperatures as low as -45°C, stability (non-reactivity) with lithium metal, electrochemically active materials and conductive additives at high voltages, thermoplasticity and moldability.

Example 23
The solid polymeric materials were tested for flammability according to the parameters of the UL 94-V0 flammability test. The solid polymeric materials were found to be virtually non-flammable - self-extinguishing in 2 seconds. Per the UL 94-V0 standard, a material must self-extinguish within 10 seconds to be considered non-flammable.

This application and this detailed description incorporate herein the entire specifications of the following applications, including the claims, abstracts and drawings: U.S. Provisional Patent Application No. 62/158,841, filed May 8, 2015; U.S. Provisional Patent Application No. 14/559,430, filed December 3, 2014; U.S. Provisional Patent Application No. 61/911,049, filed December 3, 2013; U.S. Provisional Patent Application No. 13/861,170, filed April 11, 2013; and U.S. Provisional Patent Application No. 61/622,705, filed April 11, 2012.

Although the present invention has been described in detail herein in connection with certain preferred embodiments, numerous modifications and variations therein may be made by those skilled in the art without departing from the spirit of the invention. We therefore intend to be limited only by the scope of the appended claims, and not in any way by the details and instrumentalities of the embodiments described herein.

It is understood that various modifications and improvements can be made to the structure described above without departing from the concepts of the invention, and further understood that such concepts are intended to be covered by the following claims, even if not specifically stated otherwise.

Claims (71)

A solid semi-crystalline ionically conducting polymeric material having a plurality of repeating units, a glassy state, and at least one cationic and anionic diffusing ion, wherein at least one diffusing ion is mobile in the glassy state;
the material has a resistance per unit area of less ^than 1.0×10 ^ohm cm at room temperature;
At least one of the at least one anionic diffusing ion is a hydroxyl ion;
at least one of the at least one cationic diffusing ion is an alkali metal, an alkaline earth metal, a transition metal or a post-transition metal;
However, the melting temperature of the material is higher than 250° C.
The material is
A method in which the base polymer and dopant are first mixed and then heated, where a heating step is applied after or during mixing to produce a color change indicative of a reaction between the dopant and the base polymer, and then an ionic compound is mixed with the reacted polymer dopant material to complete the formation of the solid ionically conductive polymer material.
where :
the base polymer is selected from the group consisting of polyphenylene sulfide (PPS), poly(p-phenylene oxide) (PPO), liquid crystal polymers (LCPs), polyether ether ketone (PEEK), polyphthalamide (PPA), polypyrrole, polyaniline, polysulfone, copolymers containing repeating units of the polymers mentioned, mixtures of these polymers, polyaniline poly-phenylamine [C ₆ H ₄ NH] _n , poly-paraphenylene terephthalamide [-CO-C ₆ H ₄ -CO-NH-C ₆ H ₄ -NH-] _n , polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), and polyethylene (PE);
the ionic compound is selected from _the group consisting of _Li2O , LiOH, ZnO, _TiO2 , _Al2O3 , NaOH, KOH, _LiNO3 , _Na2O , MgO, _CaCl2 , _MgCl2 , _AlCl3 , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiFSI (lithium bis(fluorosulfonyl)imide), lithium bis(oxalato)borate ( _{LiB(C2O4 ) 2} , LiBOB), other lithium salts, and combinations thereof;
The dopant is selected from the group consisting of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (C ₈ Cl ₂ N ₂ O ₂ ), tetrachloro-1,4-benzoquinone (chloranil) (C ₆ Cl ₄ O ₂ ), tetracyanoethylene (C ₆ N ₄ ), sulfur trioxide (SO ₃ ), ozone (trioxygen or O ₃ ), oxygen (O ₂ , including air), transition metal oxides, and combinations thereof, with the proviso that
The dopant is an electron acceptor;
Each cationic diffusing ion and anionic diffusing ion is a reaction product of said ionic compounds;
A solid semi-crystalline ionically conducting polymer material. 2. The material of claim 1, wherein the material has a resistance per unit area of less than 1.0 x 10 ^ohm cm ² at room temperature. a solid semi-crystalline ionically conductive polymer material having a plurality of repeating units, said material having a resistance per unit area of less ^than 1.0×10 ^ohms cm at room temperature;
However, the material
A method in which the base polymer and dopant are first mixed and then heated, where a heating step is applied after or during mixing to produce a color change indicative of a reaction between the dopant and the base polymer, and then an ionic compound is mixed with the reacted polymer dopant material to complete the formation of the solid ionically conductive polymer material.
where :
the base polymer is selected from the group consisting of polyphenylene sulfide (PPS), poly(p-phenylene oxide) (PPO), liquid crystal polymers (LCPs), polyether ether ketone (PEEK), polyphthalamide (PPA), polypyrrole, polyaniline, polysulfone, copolymers containing repeating units of the polymers mentioned, mixtures of these polymers, polyaniline poly-phenylamine [C ₆ H ₄ NH] _n , poly-paraphenylene terephthalamide [-CO-C ₆ H ₄ -CO-NH-C ₆ H ₄ -NH-] _n , polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), and polyethylene (PE);
the ionic compound is selected from _the group consisting of _Li2O , LiOH, ZnO, _TiO2 , _Al2O3 , NaOH, KOH, _LiNO3 , _Na2O , MgO, _CaCl2 , _MgCl2 , _AlCl3 , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiFSI (lithium bis(fluorosulfonyl)imide), lithium bis(oxalato)borate ( _{LiB(C2O4 ) 2} , LiBOB), other lithium salts, and combinations thereof;
The dopant is selected from the group consisting of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (C ₈ Cl ₂ N ₂ O ₂ ), tetrachloro-1,4-benzoquinone (chloranil) (C ₆ Cl ₄ O ₂ ), tetracyanoethylene (C ₆ N ₄ ), sulfur trioxide (SO ₃ ), ozone (trioxygen or O ₃ ), oxygen (O ₂ , including air), transition metal oxides, and combinations thereof, with the proviso that
The dopant is an electron acceptor.
A solid semi-crystalline ionically conducting polymer material. The material according to claim 3, wherein the crystallinity of the material is greater than 30%. The material according to claim 1 or 3, in which the glassy state exists at a temperature below the melting temperature of the material. The material further comprises both cationic and anionic diffusing ions, whereby each diffusing ion is mobile in the glassy state, with the proviso that:
At least one of the anionic diffusing ions is a hydroxyl ion;
at least one of the cationic diffusing ions is an alkali metal, an alkaline earth metal, a transition metal, or a post-transition metal;
Each cationic diffusing ion and anionic diffusing ion is a reaction product of said ionic compounds; and
4. The material of claim 3, wherein the crystallinity of the material is greater than 30%. The material has a glassy state and includes at least one cationic diffusing ion and at least one anionic diffusing ion, each diffusing ion being mobile in the glassy state, with the proviso that:
At least one of the anionic diffusing ions is a hydroxyl ion;
at least one of the cationic diffusing ions is an alkali metal, an alkaline earth metal, a transition metal, or a post-transition metal;
4. The material of claim 3, wherein each cationic diffusing ion and anionic diffusing ion is a reaction product of said ionic compounds. The material according to claim 1 or 7 having at least three diffusing ions. The material of claim 1 or 7 having more than one anionic diffusing ion. The material according to claim 3, wherein the melting temperature of the material is greater than 250°C. The material of claim 1 or 3, wherein the ionic conductivity of the material is greater than 1.0×10 ⁻⁵ S/cm at room temperature. 8. The material of claim 1 or 7, wherein the material comprises a single cationic diffusing ion, the diffusivity of the cationic diffusing ion being greater than 1.0×10 ⁻¹² m ² /s at room temperature. 8. The material of claim 1 or 7, wherein the material comprises a single anionic diffusing ion, the diffusivity of the anionic diffusing ion being greater than 1.0×10 ⁻¹² m ² /s at room temperature. The material of claim 7, wherein there is at least one anionic diffusing ion per repeat unit. The material of claim 7, wherein there is at least one cationic diffusing ion per repeat unit. The material of claims 1 or 7, wherein there is at least 1 mole of cationic diffusing ions per liter of material. The material of claim 1 or 7, wherein the material is formed from at least one ionic compound, each of which comprises a cationic and anionic diffusing ion. The material according to claim 1 or 3, wherein the material is a thermoplastic material. The material according to claim 1 or 7, wherein the cationic diffusing ion comprises lithium. The material of claim 1 or 7, wherein at least one cationic and one anionic diffusive ion each has a diffusivity, the cationic diffusivity being greater than the anionic diffusivity. The material according to claim 1 or 7, wherein the cationic transport number of the material is greater than 0.5 and less than 1.0. The material of claim 19, wherein the concentration of lithium is greater than 3 moles of lithium per liter of material. The material according to claim 20 or 21, wherein the cationic diffusing ion comprises lithium. The material according to claim 1 or 7, wherein the cationic diffusing ion is monovalent. The material according to claim 1 or 7, in which the valence of the cationic diffusing ion is greater than 1. The material of claim 7, wherein the material contains more than one anionic diffusing ion per repeat unit. The material according to claim 1 or 7, wherein the anionic diffusing ion is a hydroxyl ion. The material according to claim 1 or 7, wherein the anionic diffusing ion is monovalent. The material according to claim 1 or 7, wherein both the anionic diffusing ion and the cationic diffusing ion are monovalent. The material according to claim 1 or 7, wherein at least one cationic diffusing ion and at least one anionic diffusing ion each have a diffusivity, and the diffusivity of the anionic diffusing ion is greater than the diffusivity of the cationic diffusing ion. The material according to claim 1 or 7, wherein the cationic transport number of the material is 0.5 or less and greater than zero. 10. The material of claim 1 or 7, wherein at least one of the cationic diffusing ions has a diffusivity greater than 1.0×10 ⁻¹² m ² /s. 10. The material of claim 1 or 7, wherein one of the at least one anionic diffusing ion has a diffusivity greater than 1.0×10 ⁻¹² m ² /s. 10. The material of claim 1 or 7, wherein one of both the at least one anionic diffusing ion and the at least one cationic diffusing ion has a diffusivity greater than 1.0 x ^{10-12 m2} /s. The material of claim 3, wherein each repeat unit comprises an aromatic or heterocyclic ring structure located in the backbone of the repeat unit. The material of claim 35, wherein the material further comprises a heteroatom located on the backbone that is included in the ring structure or adjacent to the ring structure. The material of claim 36, wherein the heteroatom is selected from the group consisting of sulfur, oxygen, or nitrogen. The material of claim 37, wherein the heteroatom is located on the backbone of the repeating unit adjacent to the ring structure. The material of claim 38, wherein the heteroatom is sulfur. The material according to claim 1 or 3, wherein the material is pi-conjugated. The material of claim 35, wherein there is at least one anionic diffusing ion per repeat unit, and at least one repeat unit comprises a lithium ion. The material of claim 1 or 3, wherein the polymer comprises a plurality of repeating units, and the molecular weight of the repeating units is greater than 100 grams/mole. The material according to claim 1 or 3, wherein the material is hydrophilic. The material according to claim 1 or 3, wherein the ionic conductivity of the material is isotropic. 4. The material of claim 1 or 3 having an ionic conductivity of greater than 1×10 ⁻⁴ S/cm at room temperature. 4. The material of claim 1 or 3 having an ionic conductivity of greater than 1×10 ⁻³ S/cm at 80° C. The material according to claim 1 or 3, having an ionic conductivity of greater than 1×10 ⁻⁵ S/cm at −40° C. 10. The material of claim 1 or 7, wherein the cationic diffusing ion comprises lithium and the diffusivity of lithium ions is greater than 1.0×10 ⁻¹³ m ² /s at room temperature. The material according to claim 1 or 3, which is non-flammable. The material of claim 1 or 3, wherein the material is non-reactive when mixed with a second material, the second material comprising an electrochemically active material, an electrically conductive material, a rheology modifying material, and a stabilizing material. The material according to claim 1 or 3, wherein the material is in the form of a film. The material according to claim 1 or 3, wherein the Young's modulus of the material is 3.0 MPa or more. The material of claim 1 or 3, which becomes ionically conductive after the material is doped with an electron acceptor. The material according to claim 1 or 7, wherein the material becomes ionically conductive after being doped with an electron acceptor in the presence of either an ionic compound containing both cationic and anionic diffusing ions or an ionic compound that can be converted to both cationic and anionic diffusing ions via oxidation by an electron acceptor. The material according to claim 1 or 3, wherein the base polymer is a conjugated polymer. 1. A method of making a solid, ionically conducting polymer material comprising the steps of: a base polymer and a dopant are first mixed and then heated, where the heating step is applied after or during mixing; and then an ionic compound is mixed with the reacted polymer dopant material to complete the formation of the solid, ionically conducting polymer material, wherein
the base polymer is selected from the group consisting of polyphenylene sulfide (PPS), poly(p-phenylene oxide) (PPO), liquid crystal polymers (LCPs), polyether ether ketone (PEEK), polyphthalamide (PPA), polypyrrole, polyaniline, polysulfone, copolymers containing repeating units of the polymers mentioned, mixtures of these polymers, polyaniline poly-phenylamine [C ₆ H ₄ NH] _n , poly-paraphenylene terephthalamide [-CO-C ₆ H ₄ -CO-NH-C ₆ H ₄ -NH-] _n , polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), and polyethylene (PE);
the ionic compound is selected from _the group consisting of _Li2O , LiOH, ZnO, _TiO2 , _Al2O3 , NaOH, KOH, _LiNO3 , _Na2O , MgO, _CaCl2 , _MgCl2 , _AlCl3 , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiFSI (lithium bis(fluorosulfonyl)imide), lithium bis(oxalato)borate ( _{LiB(C2O4 ) 2} , LiBOB), other lithium salts, and combinations thereof;
The dopant is selected from the group consisting of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (C ₈ Cl ₂ N ₂ O ₂ ), tetrachloro-1,4-benzoquinone (chloranil) (C ₆ Cl ₄ O ₂ ), tetracyanoethylene (C ₆ N ₄ ), sulfur trioxide (SO ₃ ), ozone (trioxygen or O ₃ ), oxygen (O ₂ , including air), transition metal oxides, and combinations thereof, with the proviso that
The dopant is an electron acceptor.
The above-mentioned production method. The method of claim 56, further comprising an annealing step, wherein the annealing step increases the crystallinity of the base polymer. 57. The method of claim 56, wherein the base polymer comprises a plurality of repeat units and the molar ratio of repeat units to electron acceptors is 1:1 or greater. The method of claim 56, wherein the base polymer has a glass transition temperature, and the glass transition temperature of the base polymer is greater than 80°C. The method of claim 56, wherein the weight ratio of the base polymer and the ionic compound in the mixing step is less than 5:1. The method of claim 56, wherein positive pressure is applied to the mixture during the heating step. The method of claim 56, wherein the mixture changes color during the heating step. 57. The method of claim 56, further comprising an additional mixing step of mixing the solid, ionically conductive polymer material with a second material. 57. The method of claim 56, further comprising an extrusion step in which the solid, ionically conductive polymer material is extruded. The method of claim 56, further comprising an ion conducting step in which the solid, ionically conductive polymer material transports at least one ion. An electrochemically active material composite comprising the material according to claim 1 or 3 and an electrochemically active material. An electrode comprising the material of claim 1 or 3 or the electrochemically active material composite of claim 66. A battery comprising the material of claim 1 or 3 or the electrochemically active material composite of claim 66. A fuel cell comprising the material of claim 1 or 3 or the electrochemically active material composite of claim 66. An electrolyte comprising the material of claim 1 or 3 or the electrochemically active material composite of claim 66. A device for conducting ions comprising the material of claim 1 or 3 or the electrochemically active material composite of claim 66.

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