CN108028406A - Solid ion conductive polymeric material - Google Patents

Abstract

The present invention relates to a solid ion-conducting polymer material having: greater than 30% crystallinity; a glassy state; and at least one cation diffusing ion and at least one anion diffusing ion, wherein each diffusing ion is in the glassy state The following is transferable.

Description

Solid Ion Conducting Polymer Materials

Statement Regarding Federal Funding for Research or Development (Not Applicable)

technical field

The present invention relates generally to polymer chemistry, and in particular to solid polymer electrolytes and methods for their synthesis.

Background technique

The history of batteries is one of slow progress and incremental improvements. Historically, battery performance, cost, and safety have been conflicting goals requiring trade-offs, limiting the viability of end applications such as grid-level storage and mobile power. The demand for conversion batteries has reached the level of national interest, driving great efforts to provide safe electrochemical energy storage with higher energy density and lower cost.

Alessandro Volta invented what became the first true battery known as the "voltaic pile". It consists of pairs of zinc and copper disks stacked one on top of the other, separated by a layer of cloth or cardboard soaked in brine as electrolyte. The discovery, while impractical, has led to an understanding of the role of electrochemical cells and electrolytes.

Since Volta, inventors have made improvements in liquid electrolytes based on porous membranes filled with concentrated solutions of salts, bases or acids in water or organic solvents. These liquid electrolytes are often corrosive and/or flammable and, in many cases, thermodynamically unstable with electrode materials, leading to performance limitations and safety concerns. These challenges make solid-state electrolytes extremely attractive for battery development. Solid electrolytes can offer significant benefits such as impermeable electrolytes, more flexible geometries, higher energy density electrodes, and improved safety.

Ceramics and glasses were the first solid materials discovered and developed to possess ionic conductivity. There are other materials to follow, but all of these have the characteristic that sufficiently high ionic conductivities are only achievable at very high temperatures. For example, Toyota of Japan has announced development work using a new "crystalline superionic crystal", which is a glassy ceramic Li ₁₀ GeP ₂ S ₁₂ . However, this material has high electrical conductivity only above 140 °C, while ceramics suffer from common problems of manufacturability and brittleness. The fabrication challenges of ceramics can be particularly daunting for incorporating materials into battery electrodes.

The initial interest in polymer electrolytes arose from the discovery in 1975 by Professor Peter V. Wright that complexes of polyethylene oxide (PEO) could conduct metal ions. Not long after, Prof. Michel Armand recognized the potential use of PEO lithium salt complexes in battery applications. The combination of PEO and lithium salts has been developed over the years. An example of such a material is the P(EO) _nLiBETI complex. In the past three decades, there have been many attempts to improve the conductivity of polyethylene oxide (PEO) _- ( _CH2CH2O ) _n- . In these PEO-based materials, cation mobility is dominated by polymer segment motion. This segmental motion of PEO is actually a liquid-like mechanism, but chain entanglement and partial crystallization can give the electrolyte some of the bulk properties of a solid. However, segmental motion is essential for PEO to become ionically conductive.

Plasticized polymer-salt complexes are prepared by adding a liquid plasticizer to PEO in such a way that there is a compromise between solid polymer and liquid electrolyte. Due to the increased segmental motion, the value of ambient conductivity is greatly improved, but this is at the expense of the degradation of the mechanical integrity of the membrane and the presence of increased corrosion reactivity of the polymer electrolyte to the metal electrode.

Gel electrolytes are obtained by incorporating a large amount of liquid solvent/liquid plasticizer into a polymer matrix capable of forming a gel with a polymer host structure. The liquid solvent remains in the polymer matrix and forms a liquid conductive path through the otherwise non-conductive solid polymer. Gel electrolytes can offer high room-temperature conductivity, but suffer from similar drawbacks to those mentioned for plasticized polymer electrolytes.

The rubbery electrolyte is actually a "polymer-in-salt" system; unlike "salt-in-polymer", the "salt-in-polymer" system has a large amount of salt combined with a small amount of polymer substances (ie polyethylene oxide (PEO), polypropylene oxide (PPO), etc.) mixed. The glass transition temperature of these materials can be lower to maintain a rubbery or viscoelastic state at room temperature, which in turn provides high electrical conductivity through enhanced segmental motion. However, complexed/dissolved salts may have a tendency to crystallize, thus hampering their use in practical electrochemical devices.

Composite polymer electrolytes are prepared simply by dispersing a 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 improved. The ionic conductivity is attributed to the reduced level of polymer crystallinity and the corresponding increase in segmental motion in the presence of fillers.

Polyelectrolytes contain charged groups covalently bonded to the polymer backbone, which makes the migration of oppositely charged ions very easy. Charged groups are made flexible by segmental motion required for cation diffusivity.

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 excludes all these known polymer electrolytes from practical applications because they require segmental motion to achieve ionic conductivity. Since typical polymer electrolyte ionic conductivity relies on segmental motion above the glass transition temperature (T _g ) of the material, all attempts to produce usable solid polymer electrolytes have focused on suppressing the crystalline phase and/or reducing The temperature at which the glass transitions to a state capable of segmental motion (ie, a viscoelastic or rubbery state).

In polymer-salt complexes where crystalline and amorphous phases exist, ion transport occurs in the amorphous phase. The Vogel-Tamman-Fulcher (VTF) equation describes the behavior of ions diffusing through polymers. The VTF equation is based on the assumption that ions are transported by semi-random motion of short polymer chain segments. The onset of this segmental motion occurs with increasing temperature above the glass transition temperature, _Tg , and becomes faster as temperature increases in the viscoelastic regime. Segmental motion is believed to facilitate ion motion by disrupting the solvation of ion-relative multiple coordination sites on the polymer and providing space or free volume into which ions may diffuse. The fact that polymer segment motion is necessary for ion transport generally requires that such complexes be concentrated on amorphous materials with low glass transition temperatures.

Contents of the invention

According to one aspect, there is provided a solid ionically conductive polymer material having a crystallinity greater than 30%; a melting temperature; a glassy state; and at least one cation-diffusing ion and at least one anion-diffusing ion ( both at least one cationic and anionic diffusing ion), wherein each diffusing ion is mobile in the glassy state. The material may further comprise a plurality of charge transfer complexes, and

A plurality of (a plurality of) monomers, wherein each charge transfer complex is located on the monomer.

The material may also have an area specific resistance of less than 1.0×10 ⁵ Ω·cm ² at room temperature.

In one aspect, there is provided a solid semicrystalline ionically conductive polymer material having: a plurality of monomers; a plurality of charge transfer complexes, wherein each charge transfer complex is located on the monomer; and wherein the The area specific resistance of the above material is less than 1.0×10 ⁵ Ω·cm ² at room temperature. The material may have a crystallinity of greater than 30%; a glassy state existing at a temperature below the melting temperature of the material; and cation-diffusing ions and anion-diffusing ions, whereby each diffusing ion is mobile in the glassy state.

According to other aspects of the solid ion-conducting polymer material, other aspects of the material may include one or more of the following features:

Charge transfer complexes are formed by the reaction of polymers and electron acceptors;

The material has a glassy state and comprises at least one cation diffusing ion and at least one anion diffusing ion, wherein each diffusing ion is mobile in said glassy state;

The material contains at least three diffuse ions;

The material contains more than one anion diffusing ion;

The melting temperature of the material is greater than 250°C;

The ionic conductivity of the material is greater than 1.0x10 ^-5 S/cm at room temperature;

The material comprises a single cation-diffusing ion, wherein the diffusivity of the cation-diffusing ion is greater than 1.0×10 ⁻¹² m ² /s at room temperature;

The material comprises a single anion-diffusing ion, wherein the anion-diffusing ion has a diffusivity at room temperature greater than 1.0×10 ⁻¹² m ² /s;

The material, wherein at least one of the cation-diffusing ions comprises an alkali metal, alkaline earth metal, transition metal, or post transition metal;

The material comprises at least one anion diffusing ion/monomer;

The material comprises at least one cation-diffusing ion/monomer;

The material contains at least 1 mole of cation diffusing ions per liter of material;

A charge transfer complex of the material is formed by the reaction of a polymer, an electron acceptor, and an ionic compound, wherein each of the cation-diffusing ions and the anion-diffusing ions is a reaction product of the ionic compound;

the material is formed from at least one ionic compound, wherein the ionic compound comprises respective cation-diffusing ions and anion-diffusing ions;

the material is thermoplastic;

The cation-diffusing ions of the material include lithium;

at least one cation-diffusing ion and at least one anion-diffusing ion of the material have a diffusivity, wherein the cation diffusivity is greater than the anion diffusivity;

The material has a cation transfer number greater than 0.5 and less than 1.0;

The material has a cation-diffusing ion concentration greater than 3 moles of cations per liter of material;

The cation-diffusing ions of the material include lithium;

The diffuse cations of the material are monovalent;

The valence of the diffuse cation is greater than 1;

The material contains more than 1 diffusing anion/monomer;

The diffusing anions of the material are hydroxide ions;

The diffuse anions of the material are monovalent;

The diffuse anions and diffuse cations of the material are monovalent;

at least one cation-diffusing ion and at least one anion-diffusing ion of the material have a diffusivity, wherein the anion diffusivity is greater than the cation diffusivity;

The material has a cation transport number equal to or less than 0.5 and greater than zero;

The material has a diffusivity of at least one cation-diffusing ion greater than 1.0x10 ^-12 m ² /s;

The material has a diffusivity of at least one anion diffusing ion greater than 1.0x10 ^-12 m ² /s;

The material has a diffusivity of at least one anion-diffusing ion and at least one cation-diffusing ion greater than 1.0 x 10 ⁻¹² m ² /s;

Each monomer of the material comprises an aromatic ring structure or a heterocyclic structure in the skeleton of the monomer;

The material further comprises a heteroatom incorporated into said ring structure or located on the backbone adjacent to said ring structure;

The material comprises heteroatoms selected from sulfur, oxygen or nitrogen;

The heteroatom of the material is located on the backbone of the monomer adjacent to the ring structure;

The heteroatom of this material is sulfur.

The material is π-conjugated;

at least one anion of the material diffuses ions/monomers, and wherein at least one monomer comprises lithium ions;

The material comprises a plurality of monomers, wherein the monomers have a molecular weight greater than 100 g/mole;

the material is hydrophilic;

The ionic conductivity of the material is isotropic;

The material has an ionic conductivity greater than 1x10 ^-4 S/cm at room temperature;

The ionic conductivity of the material at 80°C is greater than 1x10 ^-3 S/cm;

The ionic conductivity of the material at -40°C is greater than 1x10 ^-5 S/cm;

The cation-diffusing ions of the material comprise lithium, and wherein the diffusivity of the lithium ions is greater than 1.0 x 10 ⁻¹³ m ² /s at room temperature;

the material is non-flammable;

The material is non-reactive when mixed with the second material, wherein the second material is selected from the group consisting of 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 equal to or greater than 3.0MPa;

The material becomes ionically conductive when doped with electron acceptors;

The material becomes ionically conductive after doping electron acceptors in the presence of ionic compounds comprising cation-diffusing ions and anion-diffusing ions, or can be converted to cation-diffusing ions by oxidation of said electron acceptors and anion diffusing ions;

The material is formed from the 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 the reaction of the electron acceptor and the polymer; and

The reactant electron acceptor for this material is quinone or oxygen.

In one aspect, solid ion-conducting macromolecules and materials comprising the macromolecules are provided, comprising:

A plurality of monomers, wherein each monomer comprises an aromatic ring structure or a heterocyclic structure;

a heteroatom incorporated into or positioned adjacent to said ring structure;

cation-diffusing ions and anion-diffusing ions, wherein both the cation-diffusing ions and the anion-diffusing ions are incorporated into the structure of the macromolecule;

wherein both the cation-diffusing ions and the anion-diffusing ions can diffuse along the macromolecules;

Wherein there is no segmental motion in the polymer material as cation-diffusing ions or anion-diffusing ions diffuse along said macromolecule.

Additionally, this aspect can include one or more of the following features:

The ionic conductivity of the material is greater than 1x10 ^-4 S/cm;

The molecular weight of each monomer is greater than 100 g/mol;

The at least one cation-diffusing ion of the material includes an alkali metal, alkaline earth metal, transition metal, or post-transition metal.

One aspect is a method of making a solid ion-conducting polymer material, comprising the steps of: mixing a base polymer comprising a plurality of monomers, an electron acceptor, and an ionic compound to produce a first mixture; heating the first mixture to produce the solid ion-conducting polymer material.

Another aspect is a method of preparing a solid ion-conducting polymer material, comprising the steps of: mixing a polymer comprising a plurality of monomers and an ion-containing compound to produce a first mixture; doping the resulting polymer with an electron acceptor said first mixture to produce a second mixture; and heating said second mixture.

Another aspect is a method of preparing a solid ion-conducting polymer material, comprising the steps of: mixing a polymer comprising a plurality of monomers and an electron acceptor to produce a first mixture; heating the first mixture to produce an intermediate material comprising a charge transfer complex; mixing the intermediate material with an ion-containing compound to produce the solid ion-conducting polymer material.

Other aspects of the method of making a solid ion-conducting polymer material can include one or more of the following features:

an annealing step, wherein the crystallinity of the base polymer is increased during said annealing step;

The base polymer comprises a plurality of monomers, and wherein the molar ratio of monomers to electron acceptors is equal to or greater than 1:1;

The base polymer has a glass transition temperature, and wherein the glass transition temperature of the base polymer is greater than 80°C;

The weight ratio of the base polymer to the ionic compound during the mixing step is less than 5:1;

applying a positive pressure to the mixture during the heating step;

The mixture undergoes a color change during the heating step;

Formation of a charge transfer complex during the heating step;

an additional mixing step of mixing the solid ion-conducting polymer material with the second material;

an extrusion step, wherein the solid ion-conducting polymer material is extruded; and

The ion conducting step, wherein the solid ion-conducting polymer material transports at least one ion.

Additional aspects include: an electrochemically active material composite comprising the material of the preceding aspects and an electrochemically active material;

An electrode comprising a material of the preceding aspect;

A battery comprising a material of the preceding aspect;

A fuel cell comprising a material of the preceding aspect;

An electrolyte comprising a material of the preceding aspect;

A device for conducting ions comprising a material of the preceding aspect;

A method for conducting ions comprising a material of the preceding aspect; and

A method for separating ions comprising a material of the preceding aspect;

In another aspect, a novel ion conduction mechanism is provided that enables ion conduction in both the crystalline phase and the amorphous glassy state of the polymer, which enables solid polymers with the conductivity of liquids at room temperature Material;

Ability to produce composite anodes and cathodes comprising the polymer and an electrochemically active compound to enhance capacity and cycle life;

Enables the use of plentiful and low-cost active materials; and

New battery fabrication methods using low-cost, high-volume extrusion and other plastic processing techniques can be implemented.

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

Description of drawings

In the attached picture:

Figure 1 is a graph of cycling tests of lithium-ion batteries using LCO cathodes comprising solid ion-conducting polymer materials;

Fig. 2 is the discharge curve figure of embodiment 6;

3A, 3B and 3C are X-ray diffraction patterns described in Example 9;

Fig. 4 is the DSC curve described in embodiment 10;

Figure 5 is a graph of measured conductivity versus temperature as described in Comparative Example 13;

Figure 6 is a graph of measured conductivity versus temperature as described in Comparative Example 13;

Figure 7 is a graph of the measured conductivity of samples of the material described in Example 14;

Figure 8 is a graph of measured diffusivity versus temperature for samples of the material described in Example 16;

Figure 9 is a graph of NMR diffusivity curves for comparative materials described in Example 17;

FIG. 10 is an NMR spectrum of the base polymer reactant described in Example 18. FIG.

FIG. 11 is an NMR spectrum of the material described in Example 18. FIG.

FIG. 12 is an NMR spectrum of the material described in Example 18. FIG.

FIG. 13 is an NMR spectrum of the electron acceptor described in Example 18. FIG.

FIG. 14A is an NMR spectrum of the material described in Example 18. FIG.

FIG. 14B is an NMR spectrum of the material described in Example 18. FIG.

Figure 15 is an NMR spectrum of the material described in Example 19.

FIG. 16 is an illustration of a battery using materials as described in Example 19. FIG.

FIG. 17 is the discharge curves of the three cells described in Example 20. FIG.

FIG. 18 is a discharge curve of the battery described in Example 21. FIG.

FIG. 19 is a discharge curve of the battery described in Example 22. FIG.

Detailed ways

This patent application claims priority to U.S. Provisional Patent Application No. 62/158,841, filed May 8, 2015, the entire disclosure of which is incorporated herein by reference.

The following explanations of terms are provided to better detail the aspects, embodiments and objects that will be set forth in this section. Unless otherwise explained or defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. To facilitate reading of the various embodiments of the present disclosure, the following explanations of certain terms are provided:

Depolarizer is a synonym for electrochemically active species, that is, a substance that changes its oxidation state, or participates in the formation or breaking of chemical bonds, during electrochemical reactions and charge transfer steps of electrochemically active species. When electrodes have more than one electroactive species, they can be referred to as codepolarizers.

Thermoplasticity is the characteristic of a plastic material or polymer that becomes pliable or moldable above a certain temperature (often at or near its melting temperature) and solidifies when cooled.

Solid electrolytes include solvent-free polymers and ceramic compounds (crystalline and glassy).

A "solid" is characterized by its ability to retain its shape for an indefinite period of time and is distinct and distinct from liquid phase materials. The atomic structure of a solid can be crystalline or amorphous. Solids may be mixed with or be components of the composite structure. However, for the purposes of this application and its claims, unless otherwise stated, a solid material requires that the material be ionically conductive through the solid and not through any solvent, gel or liquid phase. For the purposes of this application and its claims, gel (or wet) polymers and other materials that rely on liquids for their ionic conductivity are defined as not being solid electrolytes because they rely on a liquid phase for their ionic conductivity.

Polymers are generally organic and composed of carbon-based macromolecules, each of which has one or more repeating units or monomers. Polymers are lightweight, malleable, generally nonconductive, and melt at relatively low temperatures. Polymers can be made into products by injection molding, blow molding and other shaping processes, extrusion, pressing, stamping, 3D printing, machining and other plastic processes. Polymers generally have a glassy state at temperatures below the glass transition temperature Tg. This glass transition temperature is a function of chain flexibility; and occurs when there is sufficient vibrational (thermal) energy in the system to create sufficient free volume so that the chain segment sequence of the polymer macromolecule can Move together as a unit. However, in the glassy state of the polymer, there is no segmental motion of the polymer.

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

The glass transition that occurs in some polymers is the midpoint temperature between the supercooled liquid state and the glass state when the polymer material is cooled. Thermodynamic measurements of glass transitions are accomplished by measuring physical properties of the polymer (eg, volume, enthalpy or entropy, and other derived properties) as a function of temperature. The glass transition temperature is observed on such a curve as a breakdown of a selected property (volume of enthalpy) or as a change in slope (heat capacity or coefficient of thermal expansion) at the transition temperature. As the polymer is cooled from above Tg to below Tg, the rate of migration of the polymer molecules slows until the polymer reaches its glassy state.

Since polymers may contain both amorphous and crystalline phases, polymer crystallinity is the amount of this crystalline phase relative to the amount of polymer and is expressed as a percentage. The percent crystallinity can be calculated by analyzing the relative areas of the amorphous and crystalline phases via X-ray diffraction of the polymer.

A polymer film is generally described as a thin section of polymer, but is understood to be equal to or less than 300 microns thick.

It is important to note that ionic conductivity is not the same as electrical conductivity. Ionic conductivity depends on ion diffusivity, and these two properties are related by the Nerst Einstein equation. Both ionic conductivity and ionic diffusivity are measures of ion mobility. Ions are mobile in a material if their diffusivity in the material is positive (greater than zero), or if they contribute to positive conductivity. All these ion mobility measurements were performed at room temperature (approximately 21° C.) unless otherwise stated. Since ion mobility is temperature dependent, it can be difficult to detect at low temperatures. The device detection limit may be a factor in determining the amount of small mobility. Mobility is understood to mean an ion diffusivity of at least 1x10 ^-14 m ² /s, preferably at least 1x10 ^-13 m ² /s, both of which render the ions mobile in the material.

A solid polymeric ion-conducting material is a solid that comprises a polymer and conducts ions, as described further below.

One aspect of the invention includes a method of synthesizing a solid ion-conducting polymer material from at least three different components: a polymer, a dopant, and an ionic compound. Components and methods of synthesis are selected for specific applications of materials. The choice of polymers, dopants, and ionic compounds can also vary based on the desired properties of the material. For example, desired synthetic components and methods can be determined by optimizing desired physical properties such as ionic conductivity.

synthesis:

Synthetic methods can also vary depending on the specific components and desired form of the final material (eg, films, particles, etc.). However, the method comprises the basic steps of first mixing at least two of the components, adding a third component in an optional second mixing step, and heating the components/reactants to synthesize solid ions in the heating step conductive polymer material. In one aspect of the invention, the resulting mixture can optionally be formed into a film of desired dimensions. If no dopant is present in the mixture resulting from the first step, it can then be added to the mixture with heat and optionally the application of pressure (positive pressure or vacuum). All three components can be present and mixed and heated for one-step synthesis of solid ion-conducting polymer materials. However, this heating step can be done in a separate step from any mixing, or it can be done while mixing is taking place. The heating step can be carried out regardless of the form of the mixture (eg film, granule, etc.). In one aspect of the method of synthesis, all three components are mixed and then extruded into a film. The film is heated to complete the synthesis.

When synthesizing a solid ion-conducting polymer material, a visually observable color change occurs because the reactant color is a relatively light color and the solid ion-conducting polymer material is a relatively dark color or black. This color change is believed to occur when the charge transfer complex is being formed; and may occur gradually or rapidly depending on the method of synthesis.

One aspect of the synthesis method involves mixing the base polymer, ionic compound and dopant together and heating the mixture in a second step. Since the dopant can be in the gas phase, the heating step can be performed in the presence of the dopant. The mixing step can be carried out in extruders, mixers, mills or other equipment typical of plastics processing. The heating step can last for several hours (eg, twenty-four (24) hours), and the color change is a reliable indicator of complete or partial completion of the synthesis. Additional heating after synthesis does not appear to negatively affect the material.

In one aspect of the method of synthesis, the base polymer and the ionic compound can first be mixed. The dopant is then mixed with the polymer-ionic compound mixture and heated. The mixture may be heated during the second mixing step or after the mixing step.

In another aspect of the method of synthesis, the base polymer and dopant are first mixed and then heated. This heating step can be applied after or during mixing and produces a color change indicating the formation of a charge transfer complex and the reaction between the dopant and the base polymer. The ionic compound is then mixed into the reacted polymer dopant material to complete the formation of the solid ion-conducting polymer material.

Typical methods of adding dopants are known to those skilled in the art and may include vapor doping of thin films containing polymers and ionic compounds, as well as other doping methods known to those skilled in the art. Upon doping, the solid polymer material becomes ionically conductive; it is believed that the doping acts to activate the ionic components of the solid polymer material so that they are diffusive ions.

Other non-reactive components may be added to the above mixture during the initial mixing step, the second mixing step, or the post-heating mixing step. Such other components 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 mono body "EPDM"), catalysts and other components that may be used to achieve the desired physical properties of the mixture.

Polymers useful as reactants in the synthesis of solid ion-conducting polymer materials are electron donors or polymers that can be oxidized by electron acceptors. Semi-crystalline polymers having a crystallinity index greater than 30% and greater than 50% are suitable reactant polymers. Fully crystalline polymeric materials such as liquid crystal polymers ("LCPs") can also be used as reactant polymers. LCP is completely crystalline, so its crystallinity index is defined as 100%. Undoped conjugated polymers and polymers such as polyphenylene sulfide ("PPS") are also suitable polymer reactants.

Polymers generally do not conduct electricity. For example, native PPS has a conductivity of ^10-20 S cm ^-1 . Non-conductive polymers are suitable reactant polymers.

In one aspect, polymers useful as reactants may have an aromatic or heterocyclic component in the backbone of each repeating monomeric group, and be incorporated into the heterocycle or positioned along the backbone with A heteroatom at a position adjacent to an aromatic ring. Heteroatoms may be located directly on the backbone or bonded to carbon atoms located directly on the backbone. In both cases where the heteroatom is on the backbone or is bonded to a backbone carbon atom, the backbone atom is on the backbone adjacent to the aromatic ring. Non-limiting examples of polymers useful in this aspect of the invention may be selected from PPS, poly-p-phenylene ether ("PPO"), LCP, polyether ether ketone ("PEEK"), polyphthalamide ("PPA"), polypyrrole, polyaniline and polysulfone. Copolymers of monomers comprising the listed polymers and mixtures of these polymers may also be used. For example, copolymers of p-hydroxybenzoic acid may be suitable liquid crystal polymer base polymers. Table 1 details non-limiting examples of reactant polymers that can be used in the present invention along with monomer structure and some physical property information, which should be considered non-limiting because the polymers can take forms that can affect their physical properties. of various forms.

Table 1

Dopants useful as reactants in the synthesis of solid ion-conducting polymer materials are electron acceptors or oxidizing agents. The dopant is believed to function to release ions for ion transport and mobility, and is believed to function to create sites similar to charge transfer complexes or sites within the polymer that allow ionic conductivity. Non-limiting examples of useful dopants are: quinones such as 2,3-dicyano-5,6-dichlorodicyanoquinone (C ₈ Cl ₂ N ₂ O ₂ ) also known as “DDQ” and 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 (trioxide or O ₃ ); oxygen (O ₂ , including air); transition metal oxides (including manganese dioxide (“MnO ₂ ”)); or any suitable electron acceptor, etc.; and their combination. Those dopants that are temperature stable at the temperature of the synthesis heating step are useful, and temperature stable quinones and other dopants and strong oxidant quinones are most useful. Table 2 provides a non-limiting list of dopants along with their chemical diagrams.

Table 2

Ionic compounds useful as reactants in the synthesis of solid ion-conducting polymer materials are compounds that release desired ions during the synthesis of solid ion-conducting polymer materials. Ionic compounds differ from dopants in that both ionic compounds and dopants are required. Non-limiting examples include _Li2O , _LiOH , ZnO, _TiO2 , _Al3O2 , _NaOH , KOH, _LiNO3 , Na2O, MgO, _CaCl2 , _MgCl2 , AlCl3, _LiTFSI (bistrifluoromethanesulfonate Lithium imide), LiFSI (lithium bis(fluorosulfonyl)imide), bis(oxalato)boronic acid (LiB(C ₂ O ₄ ) ₂ “LiBOB”) and other lithium salts and combinations thereof. Hydrated forms of these compounds (eg, monhydrates) are useful to simplify handling of the compounds. Inorganic oxides, chlorides and hydroxides are suitable ionic compounds because they dissociate during synthesis to produce at least one of anion-diffusing ions and cation-diffusing ions. Any such ionic compound that dissociates to produce at least one anion-diffusing ion and a cation-diffusing ion is likewise suitable. A variety of ionic compounds may also be available, resulting in a variety of anion-diffusing ions and cation-diffusing ions may be preferred. The specific ionic compound included in the synthesis depends on the desired use of the material. For example, in applications where lithium cations are desired, lithium hydroxide or lithium oxide, which can be converted to lithium ions and hydroxide ions, would be suitable. Any lithium-containing compound that releases a lithium cathode and diffuses anions during synthesis would also be suitable. Non-limiting examples of such lithium ion compounds include those used as lithium salts in organic solvents. Similarly, in those systems where aluminum or other specific cations are desired, the aluminum or other specific ionic compounds react during synthesis to release the specific desired ions and diffusive anions. As will be further demonstrated, ionic compounds including alkali metals, alkaline earth metals, transition metals, and late transition metals in a form that yields the desired cation-diffusing species and anion-diffusing species are suitable as synthetic reactant ionic compounds.

The purity of the material is potentially important to prevent any undesired side reactions and to maximize the effectiveness of the synthesis reactions to produce high conductivity materials. Substantially pure reactants with generally high purity of dopant, base polymer and ionic compound are preferred, and more preferably greater than 98% pure, most preferably even higher, e.g. LiOH: 99.6%, DDQ: > 98%, Chloranil: >99%.

To further describe the utility of solid ion-conducting polymer materials and the generality of the methods described above for the synthesis of solid ion-conducting polymer materials of the present invention, several classes of solids are described that can be used in multiple electrochemical applications and differentiated by their applications. Ion-conducting polymer materials:

Lithium Ion Battery

In this aspect, the reaction or base polymer is characterized as semi-crystalline or fully crystalline and has a crystallinity value of from 30% to 100%, preferably from 50% to 100%. The glass transition temperature of the base polymer is above 80°C, preferably above 120°C, more preferably above 150°C, most preferably above 200°C. The melting temperature of the base polymer is above 250°C, preferably above 280°C, more preferably above 320°C. The molecular weight of the monomer units of the base polymer of the present invention is in the range of 100 to 200 gm/mol and may be greater than 200 gm/mol. Typical 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 greater than 30%, preferably greater than 50%.

In this aspect, the dopant is an electron acceptor such as DDQ, TCNE, _chloranil , and sulfur trioxide (SO3). The electron acceptor can be "pre-mixed" with all other ingredients and extruded without post-processing, or a doping process such as gas phase doping can be used to mix the other ingredients (e.g. in an extruder) and form The electron acceptor is added to the composition after the film.

Typical compounds comprising 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 . The ionic compound contains a suitable stable form of the ion, which is modified to release the ion during the synthesis of the solid ion-conducting polymer material.

Example 1

PPS and chloranil powder were mixed in a molar ratio of 4.2:1 (the ratio of base polymer monomer to dopant was greater than 1:1). The mixture was then heated under argon or air at elevated temperature (up to 350°C) at atmospheric pressure for 24 hours. A color change was observed, confirming the generation of a charge transfer complex in the polymer-dopant reaction mixture. The reaction mixture is then reground to a small average particle size of 1-40 microns. LiTFSI was then mixed with the reaction mixture to produce a synthesized solid ion-conducting polymer material.

Example 2

A lithium cobaltate (LiCoO ₂ ) (“LCO”) cathode containing the synthesized material from Example 1 was prepared. The cathode used a high loading of 70 wt% LCO mixed with solid ion-conducting polymer material and conductive carbon. Cells were fabricated using a lithium metal anode, a porous polypropylene separator, and a standard Li-ionic liquid electrolyte composed of LiPF6 salt and carbonate _- based solvent. The cells were assembled and cycle tested in a dry glove box.

The capacity in grams of weight of the LCO used in these batteries is shown in FIG. 1 . It can be seen that when charged to 4.3 V, the capacity is stable and consistent with the target of 0.5 equivalent Li removed from the cathode during charging. The cell was also cycled to a higher charge voltage of 4.5V, which utilizes a higher percentage of lithium from the cathode; and resulted in a high capacity of >140mAh/g. The slight drop in capacity with cycle number observed in the 4.5 V charge test is consistent with the decomposition (ie, instability) of the liquid electrolyte at this high voltage. Overall, the performance of LCO cathodes containing the materials of the present invention is advantageously comparable to that of slurry-coated LCO cathodes.

alkaline battery

The base polymer of the solid ion-conducting polymer material with hydroxide ion mobility is preferably a crystalline or semi-crystalline polymer having a crystallinity value generally above 30% and up to and including 100%, preferably 50% to 100%. The base polymer of this aspect of the invention has a glass transition temperature above 80°C, preferably above 120°C, more preferably above 150°C, most preferably above 200°C. The melting temperature of the base polymer is above 250°C, preferably above 280°C, more preferably above 300°C.

Dopants for solid ion-conducting polymer materials with hydroxide ion mobility are electron acceptors or oxidants. Typical dopants for use in this aspect of the invention are DDQ, _chloranil , TCNE, SO3, oxygen (including air), _MnO2 and other metal oxides and the like.

Compounds comprising a source of ions comprising a solid ion-conducting polymer material having hydroxide ion mobility include salts, hydroxides, oxides, or other materials containing hydroxide ions or convertible to such materials, including but not Limited to LiOH, NaOH, KOH, _Li2O , _LiNO3 , etc.

Example 3

The PPS polymer was mixed with the ionic compound LiOH monohydrate at a ratio of 67% to 33% by weight, respectively, and mixed using jet milling. A DDQ dopant was added to the resulting mixture by vapor phase doping in an amount of 1 mole DDQ/4.2 moles PPS monomer. The mixture was heat treated at 190-200° C. for 30 minutes under moderate pressure (500-1000 PSI).

Composite _MnO2 cathode

In this aspect of the invention involving the preparation of a solid ion-conducting polymer material- _MnO2 composite cathode, the base polymer may be a semi-crystalline or fully crystalline polymer with a crystallinity index greater than 30%, and may be selected from conjugated polymeric compounds or polymers that can be readily oxidized with selected dopants. Non-limiting examples of base polymers useful in this aspect of the invention include PPS, PPO, PEEK, PPA, and the like.

In this aspect, the dopant is an electron acceptor or an oxidizing agent. Non-limiting examples of dopants are DDQ, chloranil, tetracyanoethylene (also known as _TCNE ), SO3, ozone, oxygen, air, transition metal oxides (including _MnO2 ), or any suitable electron acceptor body etc.

In this aspect, the compound comprising the ion source is a salt, hydroxide, oxide, or other material containing hydroxide ions or which can be converted to such a material, including but not limited to LiOH, NaOH, KOH, _Li2O , LiNO ₃ etc.

Example 4

The PPS polymer and LiOH monohydrate were added together at a ratio of 67% to 33% by weight, respectively, and mixed using a jet mill. Additional alkaline battery cathode components were additionally mixed: MnO ₂ , Bi ₂ O ₃ and conductive carbon. The content of MnO ₂ is 50-80% by weight, the content of Bi ₂ O ₃ is 0-30% by weight, the content of carbon black is 3-25% by weight, and the content of polymer/LiOH is 10-30% by weight.

The mixture is heated to synthesize an alkaline battery cathode comprising a solid ion-conducting polymer material, which can be used in a conventional zinc-manganese dioxide alkaline battery.

Example 5

A zinc-manganese dioxide alkaline battery was prepared by using the cathode of Example 4 and a commercially available non-woven separator (NKK), a Zn foil anode and 6M LiOH solution as electrolyte.

Using a Bio-Logic VSP 15 test system, the battery was discharged under a constant current condition of 0.5 mA/cm ² . The specific capacity of _MnO2 was found to be 303mAh/g or close to the theoretical 1e-discharge.

metal air battery

In this aspect, a solid ion-conducting polymer material is used in a metal-air battery and comprises a base polymer, a compound containing an ion source, and a dopant. The polymer may be selected from PPS, LCP, polypyrrole, polyaniline and polysulfone, among other base polymers.

The dopant may be an electron acceptor or a compound containing a functional electron acceptor group capable of initiating an oxidation reaction with the polymer. Typical dopants are DDQ, _chloranil , TCNE, SO3, ozone and transition metal oxides including _MnO2 . The material comprising the ion source may be in the form of a salt, hydroxide, oxide, or other material containing hydroxide ions or which can be converted to such a material, including but not limited to LiOH, NaOH, KOH, _Li2O , _LiNO3 Wait.

Example 6

The material synthesized in Example 3 was used to prepare an air electrode by mixing a solid ion-conducting polymer material with various carbons, specifically: TIMCAL SUPER C45 conductive carbon black (C45) from Ashbury, Timcal SFG6 (synthetic graphite), A5303 carbon black, and natural vein graphite Nano 99 (N99) from Ashbury. The carbon content varies between 15 and 25% by weight.

Punch the cathode to fit a 2032 coin cell. Zinc foil was used as the anode. The nonwoven separator was impregnated with 40% KOH aqueous solution. Drill two holes in the top of the button facing the cathode. The battery was discharged at a constant current of 0.5mA at room temperature by using an MTI coin cell tester.

Table 3 summarizes the cathode parameters and test results. The discharge curve is shown in Figure 2. The cell with the air cathode of this example using the inventive material exhibited the typical discharge behavior of a Zn-air cell without any traditional catalyst (transition metal based) added to the mixture. In addition to conducting hydroxide ions from the air cathode to the anode, the material also acts to catalyze the formation of hydroxide ions from the oxygen present at the cathode surface. As shown in this example, the materials of the present invention are catalytically functional.

table 3.

other ionic compounds

Many anions and cations can be conducted through the materials of the invention. The ionic compounds used in the synthesis can be chosen such that the desired diffusing ions are included in the synthesized material.

Example 7

The material sample is made by adding LCP polymer [SRT900? ] Ionic compounds are made by mixing them in various proportions. DDQ was used as a dopant. The molar ratio of polymer monomer to dopant was 4.2:1. The results are listed in Table 4. The mixture was heat treated at 190-200° C. for 30 minutes under moderate pressure (500-1000 psi).

The sample is sandwiched between stainless steel electrodes and placed in the test fixture. By using the Bio-Logic VSP test system, record the AC impedance in the range of 800KHz ~ 100Hz to determine the electrolyte conductivity.

The results are shown in Table 3 below. The observed high ionic conductivity indicates that the solid polymer material can conduct a variety of ions, including lithium ions Li ⁺ , potassium ions K ⁺ , sodium ions Na ⁺ , calcium ions Ca ²⁺ , magnesium ions Mg ²⁺ , aluminum ions Al ^{3 +} , hydroxide OH ^- and chloride ion Cl ^- .

Table 4

Any ionic compound that can be dissociated by the dopant can be used as long as the dissociated ions are desired in the applicable electrochemical application in which the material is used. Anions and cations derived from ionic compounds are thereby ionically conducted by the material. Ionic compounds include oxides, chlorides, hydroxides and other salts. In this embodiment, the metal (or other cation) oxide produces metal cations (or other cations) and hydroxide ions.

The ability to conduct multiple ions other than lithium cations provides new applications for the materials of the present invention. Sodium-based and potassium-based energy storage systems are considered as Li-ion alternatives, which are mainly driven by low-cost and relatively abundant raw materials. Calcium, magnesium and aluminum conductivity are required for multivalent intercalation systems, potentially enabling increased energy density beyond the performance of Li-ion batteries. It is also possible to use this material to make power sources with metal anodes, which are more stable, safer and less expensive than lithium.

Embodiment 8:

Additional solid ion-conducting polymer materials prepared by using the synthesis method of Example 1 are listed in Table 5 along with their reactants and associated ionic conductivities (EIS method).

table 5

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

Table 6

The LCPs listed in Table 6 are from Solvay, and the trade name is Xydar, which are LCP varieties with different melting temperatures.

Physical properties of solid ion-conducting polymer materials:

The physical properties of solid ion-conducting polymer materials can vary based on the reactants used. The specific ion mobilities as well as anion-diffusing ions and cation-diffusing ions are derived from material synthesis; however, other physical properties do not appear to change significantly relative to 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 polymer and the synthesized solid ion-conducting polymer material.

In the first step, the PPS reactant and LiOH monohydrate were mixed and analyzed by X-ray diffraction ("XRD"). In Figure 3A, the XRD of the amorphous polymer mixture shows a peak between 30-34 degrees corresponding to LiOH monohydrate. Otherwise, XRD showed that the polymer was amorphous without any significant crystallinity.

The mixture is extruded and drawn into a film. In this step, heating the PPS polymer through the extruder anneals (heats and holds at a suitable temperature below the melting point, then slowly cools) the amorphous PPS material while extruding the material into a film, thereby creating or increasing crystallization Spend. In Figure 3B, a distinct crystalline polymer peak is shown, which can also be used to quantify the crystallinity of the PPS material to be about 60%. The peak for LiOH monohydrate remains.

The thin film mixture was then gas-phase doped with DDQ dopant to produce the solid ion-conducting polymer material of the present invention, and the corresponding XRD is shown in Figure 3C. 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 being formed, 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 remained, indicating that the crystallinity of the material remained at about 60% and thus was unchanged. However, the LiOH monohydrate peak has disappeared and is not replaced by any other peak. It was concluded that the ionic compound had been dissociated into its component cations and anions and that these ions were now part of the material structure.

Glass Transition and Melting Point Temperature

Example 10

Although many techniques exist for determining the melting temperature and Tg of bulk or thin-film polymer samples, Differential Scanning Calorimetry ("DSC", described in ASTM D7426 (2013)) provides a method for determining the melting temperature and Tg of polymer samples. A rapid test method for the change in specific heat capacity of materials. The glass transition temperature appears as a step change in the specific heat capacity.

Referring to FIG. 4 , a DSC graph of the synthesized material from Example 1 is shown. The melting point of the material [PPS-chloranil-LiTFSI] was obtained by DSC and confirmed to be no different from the reactant polymer PPS: Tm was about 300°C. The glass transition temperature Tg of the base polymer is 80-100°C, however no Tg inflection point appears in the DSC curve; it is believed that upon synthesis, the solid ion-conducting polymer material loses its apparent viscoelastic state in the PPS base polymer , and the glassy state extends below the temperature range below the melting temperature of the material. It is believed that the dip in the graph at 130°C is an artifact of the ionic compound.

Ionic conductivity

The ionic conductivity of the solid ion-conducting polymer materials of the present invention was measured and compared against conventional electrolytes. The material of the present invention was found to be ionically conductive at ambient conditions in the glassy state, whereas the reactant polymer was ionically insulating. Since the material is in the glassy state, there cannot be any associated segmental motion, so the diffusion of lithium cations and anions must be achieved through a different ion conduction mechanism in which no segmental motion is required.

Specifically, thin films of the inventive solid ion-conducting polymer material described in Example 1 were extruded at a thickness of 0.0003 inches (7.6 microns) or greater. The ionic surface conductivity of the films was measured by a standard test using AC electrochemical impedance spectroscopy (EIS) known to those of ordinary skill in the art. A sample of a thin film of solid ion-conducting polymer material was sandwiched between stainless steel blocking electrodes and placed in the test fixture. By using the Bio-Logic VSP test system, the AC impedance was recorded in the range of 800KHz-100Hz to determine the ionic conductivity of the material. In-plane and through-plane ionic conductivities were measured by placing thin films of material in suitable fixtures using Bio-Logic. The measured through-surface conductivity is 3.1x10 ^-4 S/cm, and the in-plane conductivity is 3.5x10 ^-4 S/cm. These measurements were similar enough to consider the material to be isotropic in ion conductivity.

Films with a thickness of approximately 150 microns were prepared using the material from Example 1. Electronic conductivity is directly measured by potentiostatic experiments. The membrane was placed between stainless steel blocking electrodes and a voltage of 0.25 V was maintained between the electrodes. The current was measured at a current of 180 nanoamperes, resulting in an electronic conductivity of 2.3× ^{10 6} Ω·cm ² at room temperature. The electron conductivity (area specific resistance) is low, below 1.0× ^{10 5} Ω·cm ² at room temperature, which is sufficient for an electrolyte.

Thermogravimetric analysis was performed on the material from Example 1 to determine the moisture content of the material. After storage of the material in a dry atmosphere glove box, thermogravimetric analysis was performed, showing that the material contained <5 ppm of water. Certain salts used as reactants for solid ion-conducting polymer materials, such as LiOH as an ionic compound, absorb atmospheric moisture and thus can render the material hydrophilic.

Example 12

The modulus of the synthetic material of Example 3 was tested. The Young's modulus of the electrolyte made of this particular solid polymer material ranges from 3.3 to 4.0 GPa. However, the range of Young's moduli for the materials listed in this application is much wider, ranging from 3.0 MPa to 4 GPa. Synthetic materials remain thermoplastic and can be reformed using plastics processing techniques. The material of Example 3 was heated above its melting point and then cooled. The material is then reformed into a thin film. Therefore, the material appears to have high modulus and thermoplasticity.

Comparative Example 13

The results of the ionic conductivity measurements reported in Example 1 are shown in FIGS. 5 and 6 . The electrical conductivity (Δ) of the solid ion-conductive polymer material film of the present invention is compared with the electrical conductivity (□) of triflate PEO, and is determined by the Li salt solute and ethylene carbonate-propylene carbonate "EC: The conductivity (O) of a liquid electrolyte (using a Celgard separator) composed of a PC" combined solvent was compared.

See Figure 5, which shows the measured conductivity of a solid polymeric ion-conducting material as a function of temperature. Also shown are the measured ionic conductivity of the liquid electrolyte EC:PC+LiPF ₆ salt and the measured ionic conductivity of the PEO-LiTFSI electrolyte with a Celgard separator. The conductivity of the solid ion-conducting polymer material at room temperature is about 2.5 orders of magnitude higher than that of the PEO-LiTFSI electrolyte and comparable to that of conventional liquid electrolyte/separator systems measured under similar conditions. The temperature dependence of the conductivity of solid ion-conducting polymer materials does not show a sharp increase above its glass transition temperature, as described by the temperature-activated Vogel-Tamman-Fulcher behavior, which is related to chain mobility. Therefore, segmental motion, which is the mechanism of ion conduction in polymer electrolyte materials, does not occur because the material exhibits significant ionic conductivity when in its glassy state. Furthermore, this indicates that the polymeric material of the present invention has a similar level of ionic conductivity to liquid electrolytes.

In FIG. 6 , the ionic conductivity of the solid ion-conducting polymer material is compared with that of a conventional liquid electrolyte, a comparative example lithium phosphorus oxynitride "LIPON" and related DOE targets. Referring to Figure 5B, the ionic conductivity of the solid ion-conducting polymer material is greater than ^1x10-04 S/cm at room temperature (about 21°C), greater than ^1x10-04 S/cm (and greater than ^1x10-05 S/cm), greater than 1x10 ^-03 S/cm at about 80°C.

Example 14

Ionic conductivity can be optimized by tuning the material formulation. Figure 7 shows the improvement and optimization of the ionic conductivity obtained by tuning the polymeric material formulation (eg changing the base polymer, dopant or ionic compound).

Diffusion rate

In addition to ionic conductivity, diffusivity is an important inherent quality of any electrolyte and ion-conducting material.

Example 15

Diffusion rate measurements were performed on the material produced in Example 3.

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

Specifically, the diffusivity of lithium and hydroxide ions was evaluated by pulsed gradient spin echo ("PGSE") lithium NMR method. PGSE-NMR measurements were performed using a Varian-S Direct Drive 300 (7.1T) spectrometer. Use magic angle rotation technique to average chemical shift anisotropy and dipole interactions. A pulsed gradient spin stimulated echo pulse sequence was used for self-diffusion (diffusion rate) measurements. The self-diffusion coefficients of cations and anions in the respective material samples were measured by using ¹ H and ⁷ Li nuclei, respectively. The NMR-determined self-diffusion coefficient is a measure of random thermally induced translational motion similar to Brownian motion, in which there is no external directional driving force. However, self-diffusion is closely related to ion mobility and ion conductivity through the Nerst Einstein equation and is therefore an important measurement parameter when characterizing battery electrolytes. When both ionic conductivity and diffusion data are available, the presence of ion pairing or higher aggregation effects that limit the performance of the electrolyte can be determined. These tests concluded that the solid polymer ion-conducting material has a Li ⁺ diffusivity of ^5.7x10-11 m ² /s at room temperature, making it higher than PEO/LiTFSI at 90°C and better than Li ₁₀ GeP ₂ S ₁₂ (measured at high temperature) is at least an order of magnitude higher. Therefore, solid ion-conducting polymer materials can be used as new solid electrolytes with the unique ability to conduct a wide variety of ions that can diffuse, Can be migrated.

The diffusivity of OH ^- ions at room temperature is 4.1x10 ^-11 m ² /s. Therefore, solid ion-conducting polymer materials have very high diffusion rates 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 produced in Example 1 [PPS-DDQ-LiTFSI]. Self-diffusion was measured using the technique set forth in Example 15. The cation diffusivity D( ⁷ Li) of the material at room temperature is 0.23x10 ^-9 m ² /s, and the anion diffusivity D( ¹ H) at room temperature is 0.45x10 ^-9 m ² /s.

To determine the degree of ion association that would reduce the conductivity of the material, the conductivity of the material was calculated by using the measured diffusion measurements via the Nernst-Einstein equation, and it was determined that the associated calculated conductivity was much greater than the measured conductivity. The difference is on average at least an order of magnitude (or 10-fold). Therefore, it is believed that the conductivity can be enhanced by improving ion dissociation, and the calculated conductivity can be considered to be within the conductivity range.

The number of cation transfers can be estimated from the diffusion coefficient data by equation (1):

t+～D+/(D++D-) (1)

where D+ and D- refer to the diffusivity of Li cations and TFSI anions, respectively. From the above data, a t+ value of about 0.7 is obtained in the solid ion-conducting polymer material compared to about 0.2 in the corresponding PEO electrolyte (liquid carbonate electrolyte also has a t+ value of about 0.2). The property of high cation transfer number has an important impact on battery performance. Ideally, a t+ value of 1.0 is preferred, which means the Li ions carry the full current. Anion mobility leads to electrode polarization effects that can limit battery performance. In materials where both ions are mobile, t+ values above 0.5 are highly sought, although rarely available. A calculated transfer number of 0.7 is not believed to have been observed in any liquid or PEO based electrolyte. Although ionic associations may affect the calculations, electrochemical results confirm that the shift number ranges from 0.65 to 0.75.

It is believed that t+ is dependent on anion diffusion due to the higher lithium cation diffusion. Since the cation diffusion is greater than the corresponding anion diffusion, the cation transport number is always above 0.5; and since the anions are mobile, the cation transport number must also be less than 1.0. It is believed that investigation of lithium salts as ionic compounds will yield a range of cation transport numbers greater than 0.5 and less than 1.0. As a comparative example, some ceramics have been reported to have a high diffusion number, but such ceramics only transport a single ion, so when D− is zero, the cation transport number decreases to 1.0.

While migration numbers are calculated from NMR-derived diffusivity measurements, alternative methods of calculating migration can be achieved by direct methods such as the method of Bruce and Vincent. The method of Bruce and Vincent was used to calculate the transport number for solid ion-conducting polymer materials and was found to correlate well with NMR-derived measurements.

See Figure 8, which shows the results of diffusion measurements on a solid ion-conducting polymer material over a broad temperature range, compared to PEO containing LiTFSI as an ion source. The most important conclusions are: (i) Li diffusion in solid polymer ion-conducting materials is almost two orders of magnitude higher than in PEO LiTFSI polymer electrolytes at temperatures where both compounds can be measured; (ii) solid polymer ion-conducting Diffusion coefficients in solid materials are measurable down to at least -45°C, a very low temperature for lithium diffusion measured in any solid material; specifically, lithium ion diffusivities greater than 1x10 ^-13 m ² /s. This excellent ion-conducting performance at low temperatures of solid ion-conducting polymer materials exceeds that of typical liquid battery electrolytes. It is also worth noting that the temperature dependence of the NMR spectrum indicates that the ion motion is independent of the polymer, as it does not depend on the motion of the polymer segment, but rather achieves significant ion diffusion in its glassy state. Thus, the existence of solid ion-conducting polymer materials having greater than 30% crystallinity, a glassy state, and at least one cation diffusing ion and at least one anion diffusing ion, wherein at least one diffusing ion (in this aspect, two diffusing ions) are mobile in the glassy state.

Comparative Example 17

The cation diffusivity of LiPON was taken from "Structural Characterization and Li dynamics in new Li ₃ PS ₄ ceramic ion conductor by solid-state and pulsed-field gradient NMR", Mallory Govet, Steve Greenbaum, Chengdu Liang and Gayari Saju, Chemistry of Metals (2014). An experimental method similar to that presented in Examples 15 and 16 was used and the diffusivity curves are shown in FIG. 9 . The 100°C cation diffusivity D( ⁷ Li) of LiPON was determined to be 0.54x10 ^-12 m ² /s. This diffusivity is about 80 times smaller than that of the inventive material at ambient temperature (21°C).

chemical structure of the material

Experiments were performed to determine information about the chemical structure of the solid ion-conducting polymer material.

Example 18

In this example, the material synthesized in Example 3 and its reactant components PPS, DDQ and LiOH monohydrate were investigated.

The reactant or base polymer PPS was first analyzed: Referring to Figure 10, the proton ( ^1H ) NMR spectrum of PPS is characterized by a single peak centered at 6.8 ppm relative to a tetramethylsilane ("TMS") spectral standard. This is a clear indication of aromatic hydrogens, as expected from the polymer structure. Proton solid-state MAS NMR spectra of PPS polymers were acquired on a 300 MHz instrument. Asterisks indicate spin sidebands and insets show expanded resolution.

See FIG. 11 , ¹ H NMR spectrum (top) of a solid ion-conducting polymer material, where the spectrum is deconvoluted into OH-type protons (middle) and aromatic protons (bottom). Spectra confirmed aromatic hydrogens and hydroxides. Proton solid-state MASNMR spectra of the material were acquired on a 500 MHz instrument. Asterisks indicate spin sidebands and insets show expanded resolution. Spectra deconvoluted into OH- and base polymer protons are shown in the inset as additional experimental spectra. Since NMR spectra are quantitative (as long as care is taken not to saturate the signal), direct integration of the spectral peaks gives the proportion of nuclei in a particular phase. The results of this integration show that the material has more than one mobile OH ion per repeating aromatic group and contains about two LiOH molecules per polymer repeating unit (monomer), which is very high ion concentration. The narrow OH signal shows the high mobility of OH ions.

Additional structural information is available by carbon 13 solid-state MAS NMR enabled by -1% natural abundance ^of13C . Using cross-polarization (CP), whereby nearby protons resonate simultaneously with ^the13C nucleus, transfers the nuclear magnetization to "rare" spins to increase detection sensitivity. In Figure 12, the PPS polymer spectrum is depicted under two direct polarizations: CP where all carbons participate in the signal (bottom), and CP where only those carbons directly bonded to hydrogen participate (top). Thus, the difference spectrum (middle) corresponds to carbon bonded to sulfur.

See Figure 13, which shows the ¹³ C spectrum MAS NMR spectrum of the electron acceptor compound obtained by direct polarization on a 500 MHz instrument with the proposed spectral assignment of electron acceptor DDQ. Due to the absence of hydrogen in this molecule, the spectrum was obtained under direct detection. The signal-to-noise ratio is rather low due to the very long spin-lattice relaxation time (possibly exceeding 1 min). The assignments for the individual peaks are shown in FIG. 3 . Instead of the expected four peaks (corresponding to four chemically non-equivalent carbons), the presence of six distinct peaks indicates the possible presence of isomers.

The ¹³ C solid-state MASNMR spectrum of the solid ion-conducting polymer material acquired by direct polarization on a 500 MHz instrument is shown in Figure 14A, which shows that the main peak (dominated by aromatic carbon) shifts from PPS to the ion-conducting material. The CP spectrum in the middle of the inset indicates that the PPS polymer strongly interacts with the OH groups of LiOH. The scaled-up spectra of this material and the DDQ electron acceptor are compared in Figure 14B, indicating that there is a chemical reaction in the material that obscures the original spectral signature of the reactants.

The NMR analysis clearly shows that three different reactants have reacted to form the solid ion-conducting polymer material of the present invention. New materials have been formed that are not merely mixtures of their constituent parts. There is a reaction between these three components, and the solid polymer ion-conducting material is the product of the reaction. In particular, there is a shift in ^the13C NMR peaks between the base polymer and the synthetic material. Furthermore, the effect of simultaneous radiation of the ¹ H resonance and ¹³ C resonance of hydrogen associated with OH indicated that the ions had been incorporated into the structure so that all three different components had reacted and were part of the newly synthesized material.

Example 19

Quantification of the concentration of cations (e.g., lithium ions) in the material of Example 3 can be achieved by inserting the material into an internal coaxial tube and displacing it with a displacement reagent complex (e.g., lithium Dysprosium polyphosphate (Dy, lithium Dysprosiumpolyphosphate)). Surrounded by an external reference solution. Referring to Figure 15, the shift in the lithium cation resonance is caused by the paramagnetic Dy that quantifies the lithium in the sample. In the measured samples, the concentration of lithium cations was found to be about 3 mol /liter of material ([Li]˜3 mol/liter). This large concentration of cations enables solid ion-conducting materials to have very high ionic conductivity at room temperature and over a wide temperature range.

material stability

Liquid electrolytes and other polymer electrolytes can suffer from lithium stability issues. Their interaction with lithium leads to a reaction between lithium and the electrolyte, which is detrimental to battery 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. Additionally, at high voltages above 4.0 volts, typical electrolytes can simply decompose, which in turn leads to poor battery life. Thus, lithium "stability" is a requirement for polymer electrolytes. Specifically, the polymer electrolyte is nonreactive and does not decompose when transporting Li metal at voltages above 4.0 V, 4.5 V, and 5.0 V.

Referring to Figure 16, a thin film battery structure 10 is shown. The anode comprises a lithium metal 10 or typical anode intercalation material for a lithium ion battery with an associated current collector (not shown). If an intercalation material is chosen, a solid ion-conducting polymer material is mixed with it. Cathode 30 includes a cathode current collector (not shown) and an electrochemically active material or intercalation material. Again the solid ionically conductive polymer material is mixed with the conductive material. A thin film of solid ion-conducting polymer material is used as the separator/electrolyte 40 and is interposed between the anode and cathode.

Example 20

Solid ion-conducting polymer materials exhibit compatibility with various current Li-ion chemistries. See Figure 17, which shows the performance of a cell constructed as shown in Figure 16 and labeled according to the associated cathode electrochemically active material. Specifically, the battery consists of LiFePO ₄ , LiMn ₂ O ₄ and LiCoO ₂ cathodes and a lithium metal anode. A battery composed of the inventive material mixed with an electrochemically active material in the cathode, where the inventive material is used as an electrolyte for introducing/exporting lithium ions into/from the anode and cathode, exhibits suitable discharge performance.

By using solid polymer materials as electrolytes in all battery structures or in one of such structures (anode, cathode, separator, and electrolyte), new levels of performance can be achieved without the use of any liquid electrolyte. The material may be mixed with an electrochemically active material or an intercalation material in at least one of the electrodes. The ions required in the electrochemical reactions of the battery are conducted through the electrolyte. The material may be in the form of particles, slurries, films or other forms suitable for use in batteries. As a thin film, the material can be inserted between electrodes or between an electrode and a current collector, placed to encapsulate current collectors or electrodes, or placed wherever ionic conductivity is desired. As shown in Figure 16, all three major components of the battery can be made using solid polymer materials. In the aspect shown in Figure 16, the film-like electrodes and intervening separator or electrolyte can be separate structures, or can be attached to each other by heat welding or otherwise integrating thermoplastic films.

Example 21

A cathode was prepared from LCO encapsulated with the material of Example 1. A cathode was paired with a lithium metal anode, and a thin film of material was inserted between the anode and cathode, as depicted in the structure of FIG. 16 . The assembled battery is then charged and discharged through multiple cycles. Figure 18 shows the resulting discharge curves for multiple cycles.

The charge-discharge curves showed little polarization with an efficiency of at least 99%. This result demonstrates the functionality of the polymer as an ion-transport medium within the cathode and its ability to serve as an electrolyte in solid-state batteries. Also important is the voltage stability of the electrolyte when operating at voltages from four (4.0) volts to 4.3 volts and to 5.0 volts, and the stability of lithium metal, and the Lithium) rate transport lithium stability.

Example 22

A LiS cell was constructed to include a lithium metal anode and a sulfur cathode prepared in the configuration depicted in FIG. 16 . The material of Example 1 was used in the preparation of batteries. Traditionally, lithium-sulfur systems have struggled to overcome the low cycle life caused by the dissolution of chemical intermediates in the sulfidation reaction in the liquid electrolytes typical of such batteries.

The solid polymer material plays a role in realizing the Li-S system by trapping the reaction intermediates in the solid system to limit the dissolution of the reaction intermediates. The solid polymer material can transport lithium ions while preventing polysulfide ions from reaching the anode. The solid polymer material restricts the dissolution of sulfur particles and the transport of sulfide ions, thereby allowing more sulfur to participate in the reaction and increasing the capacity of the cathode. This improved capacity is shown in Figure 19 relative to a cell containing a standard cathode containing only sulfur and carbon. It is also important to note that this data was obtained at room temperature. Solid polymer materials cannot achieve the typical "indifferential diffusion" of liquid electrolytes and some common polymer electrolytes, but only enable the diffusion of ions incorporated into the material during synthesis. Thus, sulfides cannot diffuse, but are rather ionically non-conductive much like any other ion except diffusing anions and diffusing cations. Thus, the material can act as an ion barrier because it can be designed to enable ion migration only for selected ions.

solid polymer electrolyte

As described, a solid ion-conducting polymer material is used as the solid electrolyte. As a solid electrolyte, it does not require a separator, but solid electrolytes require many of the same separator properties.

The separator is an ion-permeable membrane placed between the anode and cathode of the battery. The main function of the separator is to keep the two electrodes apart to prevent electrical shorts, while also being able to transport the ionic charge carriers needed to close the circuit during the passage of electrical current in the electrochemical cell. All batteries require this separation and ion transport to operate.

When the battery is repeatedly fully charged and discharged, the solid electrolyte must also be chemically stable to the electrode material in the highly reactive environment. The separator should not be degraded during normal and abnormal use of the battery. Of particular importance is voltage stability over the range of voltages encountered during charging and discharging.

Solid electrolytes must be thin to facilitate the energy density and power density of the battery. However, the solid electrolyte must work as a separator and not be so thin that it compromises mechanical strength and safety. Thickness should be consistent to support multiple charge cycles. Standard widths are typically about 25.4 μm-(1.0 mil) and less than 30 μm. The thickness of the solid electrolyte can be measured by the T411om-83 method of the Pulp and Paper Industry Technical Association. And, it has been extruded at a thickness of 5-150 microns.

The polymer separator typically increases the electrical resistance of the electrolyte by a factor of four to five, and deviations from uniform permeability create an inhomogeneous current density distribution, which leads to the formation of dendrites. Both of these problems can be eliminated by using solid electrolytes that create uniformity in ionic conductivity and have isotropic ionic conductivity.

The solid electrolyte must be strong enough to withstand the strain of any winding manipulation during battery assembly, or bending or other mishandling of the battery. Mechanical strength is usually defined in terms of tensile strength in the machine (winding) and transverse directions, and 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 of electrolytes made of solid polymer materials ranges from 3.0 MPa to 4.0 GPa, and it can be engineered higher by using additives such as glass fibers or carbon fibers if necessary.

A solid electrolyte must remain stable over a wide temperature range without curling or wrinkling, and lay perfectly flat. While the ion transport properties of the solid electrolytes of the present invention vary with temperature, the structural integrity remains stable even when exposed to extreme heat, as will be described more fully below.

Therefore, the solid ion-conducting polymer material satisfies the requirements of a separator and a solid polymer electrolyte by satisfying the requirements listed above. Specifically, the solid polymer electrolyte has the following properties: Young's modulus greater than 3.0 MPa, thickness less than 50 micrometers, isotropic ionic conductivity, diffusivity of various ions at temperatures as low as -45 °C , stability (non-reactive), thermoplasticity and moldability at high voltages with lithium metal, electrochemically active materials and conductive additives.

Example 23

The flammability of solid polymer materials is tested according to the parameters of the UL94-V0 flammability test. The solid polymer material was found to be virtually non-flammable, self-extinguishing within two seconds. According to the UL94-V0 standard, in order to be considered non-flammable, a material needs to self-extinguish in less than ten seconds.

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

Although the invention has been described in detail according to certain preferred embodiments thereof, many modifications and changes therein can be made by those skilled in the art without departing from the spirit of the invention. Accordingly, it is the applicant's intention to be limited only by the scope of the appended claims and not by the details and instrumentalities of the described embodiments shown herein.

It is to be understood that changes and modifications may be made to the structures described above without departing from the concepts of the present invention, and it is to be understood that these concepts are intended to be covered by the appended claims unless expressly stated otherwise in those claims Regulation.

Claims (92)

1. A solid ion-conducting polymer material having: Greater than 30% crystallinity; melting temperature; glassy state; and at least one cation diffusing ion and at least one anion diffusing ion, wherein at least one diffusing ion is mobile in said glass state. 2. The material of claim 1, further comprising a plurality of charge transfer complexes. 3. The material of claim 2, wherein the material comprises a plurality of monomers, and wherein each charge transfer complex is located on a monomer. 4. The material according to claim 1 or 3, wherein the material has an area specific resistance of less than 1.0×10 ⁵ Ω·cm ² at room temperature. 5. A solid semicrystalline ion-conducting polymer material having: multiple monomers; a plurality of charge transfer complexes, wherein each charge transfer complex is located on a monomer; Wherein the area specific resistance of the material is less than 1.0×10 ⁵ Ω.cm ² at room temperature. 6. The material of claim 5, wherein the crystallinity of the material is greater than 30%. 7. A material as claimed in claim 1 or 5, wherein the glassy state exists at a temperature below the melting temperature of the material. 8. The material of claim 5, wherein the material further comprises cation diffusing ions and anion diffusing ions, each diffusing ion being mobile in the glassy state, and wherein the material has a degree of crystallinity greater than 30%. 9. The material of claim 2 or 5, wherein the charge transfer complex is formed by the reaction of a polymer and an electron acceptor. 10. The material of claim 5, wherein the material has a glassy state and has at least one cation diffusing ion and at least one anion diffusing ion, wherein each diffusing ion is mobile in the glassy state. 11. A material as claimed in claim 1 or 10 having at least three kinds of diffuse ions. 12. A material as claimed in claim 1 or 10 having more than one anion diffusing ion. 13. The material of claim 1 or 5, wherein the melting temperature of the material is greater than 250°C. 14. The material of claim 1 or 5, wherein the ionic conductivity of the material is greater than 1.0 x ^10-5 S ^/ cm at room temperature. 15. The material of claim 1 or 10, wherein the material comprises a single cation-diffusing ion, wherein the diffusivity of the cation-diffusing ion is greater than 1.0×10 ⁻¹² m ² /s at room temperature. 16. The material of claim 1 or 10, wherein the material comprises a single anion diffusing ion, wherein the diffusivity of the anion diffusing ion is greater than 1.0 x 10~ ^{12 m2} /s at room temperature. 17. The material of claim 1 or 10, wherein at least one cation-diffusing ion comprises an alkali metal, alkaline earth metal, transition metal, or late transition metal. 18. A material as claimed in claim 3 or 10, wherein at least one anion diffusing ion is present on each monomer. 19. A material as claimed in claim 3 or 10, wherein at least one cation diffusing ion is present on each monomer. 20. A material as claimed in claim 1 or 10, wherein at least 1 mole of cation diffusing ions is present per liter of material. 21. The material of claim 2 or 5, wherein the charge transfer complex is formed by the reaction of a polymer, an electron acceptor, and an ionic compound, wherein each cation diffusing ion and anion diffusing ion is the ionic compound reaction product. 22. The material of claim 1 or 10, wherein the material is formed from at least one ionic compound, wherein the ionic compound comprises respective cation-diffusing ions and anion-diffusing ions. 23. The material of claim 1 or 5, wherein the material is thermoplastic. 24. The material of claim 1 or 10, wherein the cation diffusing ions comprise lithium. 25. The material of claim 1 or 10, wherein at least one cation-diffusing ion and at least one anion-diffusing ion each have a diffusivity, wherein the cation diffusivity is greater than the anion diffusivity. 26. The material of claim 1 or 10, wherein the material has a cation transport number greater than 0.5 and less than 1.0. 27. The material of claim 24, wherein the concentration of lithium is greater than 3 moles of lithium per liter of material. 28. A material as claimed in claim 25 or 26, wherein the cation diffusing ions comprise lithium. 29. The material of claim 1 or 10, wherein the diffusing cations are monovalent. 30. The material of claim 1 or 10, wherein the diffusive cations have a valence greater than one. 31. The material of claim 3 or 10, wherein the material comprises more than 1 diffusing anion/monomer. 32. The material of claim 1 or 10, wherein the diffusive anions are hydroxide ions. 33. The material of claim 1 or 10, wherein the diffusive anions are monovalent. 34. The material of claim 1 or 10, wherein the diffusing anions and the diffusing cations are both monovalent. 35. The material of claim 1 or 10, wherein at least one cation-diffusing ion and at least one anion-diffusing ion each have a diffusivity, wherein the anion diffusivity is greater than the cation diffusivity. 36. The material of claim 1 or 10, wherein the material has a cation transport number equal to or less than 0.5 and greater than zero. 37. The material of claim 1 or 10, wherein the diffusivity of one of the at least one cation-diffusing ions is greater than 1.0 x ^{10-12 m2} /s. 38. The material of claim 1 or 10, wherein the diffusivity of one of the at least one anion-diffusing ions is greater than 1.0 x ^{10-12 m2} /s. 39. The material of claim 1 or 10, wherein the diffusivity of one of the at least one anion-diffusing ion and the at least one cation-diffusing ion is greater than 1.0 x ^{10-12 m2} /s. 40. The material of claim 3 or 5, wherein each monomer comprises an aromatic ring structure or a heterocyclic structure within the backbone of the monomer. 41. The material of claim 40, wherein the material further comprises a heteroatom incorporated into the ring structure or located on the backbone adjacent to the ring structure. 42. The material of claim 41, wherein the heteroatom is selected from sulfur, oxygen or nitrogen. 43. The material of claim 42, wherein the heteroatom is located on the backbone of the monomer adjacent to the ring structure. 44. The material of claim 43, wherein the heteroatom is sulfur. 45. The material of claim 1 or 5, wherein the material is pi-conjugated. 46. The material of claim 40, wherein at least one anion diffusing ion is present on each monomer, and wherein at least one monomer comprises lithium ions. 47. The material of claim 1 or 5, wherein the polymer comprises a plurality of monomers, wherein the monomers have a molecular weight greater than 100 g/mole. 48. The material of claim 1 or 5, wherein the material is hydrophilic. 49. The material of claim 1 or 5, wherein the ionic conductivity of the material is isotropic. 50. The material of claim 1 or 5, which has an ionic conductivity greater than 1 x ^10-4 S/cm at room temperature. 51. The material of claim 1 or 5, which has an ionic conductivity at 80°C of greater than 1 x ^10-3 S/cm. 52. The material of claim 1 or 5, which has an ionic conductivity greater than 1 x ^10-5 S/cm at -40°C. 53. The material of claim 1 or 10, wherein the cation-diffusing ions comprise lithium, and wherein the diffusion rate of lithium ions is greater than 1.0 x ^{10-13 m2} /s at room temperature. 54. The material of claim 1 or 5, wherein the material is non-flammable. 55. The material of claim 1 or 5, wherein said material is non-reactive when mixed with a second material selected from the group consisting of electrochemically active materials, conductive materials, rheological Modified and stabilized materials. 56. The material of claim 1 or 5, wherein the material is in the form of a film. 57. The material of claim 1 or 5, wherein the material has a Young's modulus equal to or greater than 3.0 MPa. 58. A solid ion-conducting macromolecule comprising: A plurality of monomers, wherein each monomer comprises an aromatic ring structure or a heterocyclic structure; a heteroatom incorporated into or positioned adjacent to said ring structure; cation-diffusing ions and anion-diffusing ions, wherein both the cation-diffusing ions and the anion-diffusing ions are incorporated into the structure of the macromolecule; wherein both the cation-diffusing ions and the anion-diffusing ions can diffuse along the macromolecules; Wherein, when the cation-diffusing ions or anion-diffusing ions diffuse along the macromolecule, there is no segmental movement in the polymer material. 59. A material comprising the macromolecule of claim 58. 60. The material of claim 59, wherein the ionic conductivity of the material is greater than 1 x ^10-4 S/cm. 61. The material of claim 59, wherein each monomer has a molecular weight greater than 100 g/mole. 62. The material of claim 59, wherein at least one cation-diffusing ion comprises an alkali metal, alkaline earth metal, transition metal, or post-transition metal. 63. The material of claim 1 or 5, wherein the material becomes ionically conductive upon doping with electron acceptors. 64. The material of claim 1 or 10, wherein the material becomes ionically conductive upon doping electron acceptors in the presence of an ionic compound comprising cation-diffusing ions and anion-diffusing ions , or can be converted into cation-diffusing ions and anion-diffusing ions by oxidation of the electron acceptor. 65. The material of claim 1 or 5, wherein the material is formed from the reaction product of a base polymer, an electron acceptor, and an ionic compound. 66. The material of claim 65, wherein the base polymer is a conjugated polymer. 67. The material of claim 65, wherein the base polymer is PPS or a liquid crystal polymer. 68. The material of claim 65, wherein the ionic compound is an oxide, chloride, hydroxide or salt. 69. The material of claim 2 or 5, wherein the charge transfer complex is formed by the reaction of an electron acceptor and a polymer. 70. The material of claim 65, wherein the electron acceptor is quinone or oxygen. 71. A method of preparing a solid ion-conducting polymer material, comprising the steps of: mixing a base polymer comprising a plurality of monomers, an electron acceptor, and an ionic compound to produce a first mixture; heating the first mixture to produce The solid ion-conducting polymer material. 72. A method of preparing a solid ion-conducting polymer material comprising the steps of: mixing a polymer comprising a plurality of monomers and an ion-containing compound to produce a first mixture; doping the first mixture with an electron acceptor to produce a second mixture; and heating the second mixture. 73. A method of preparing a solid ion-conducting polymer material, comprising the steps of: mixing a polymer comprising a plurality of monomers and an electron acceptor to produce a first mixture; heating the first mixture to produce a charge-transfer complex comprising an intermediate material of a compound; mixing the intermediate material with an ion-containing compound to produce the solid ion-conducting polymer material. 74. The method of any one of claims 71-73, further comprising an annealing step, wherein the crystallinity of the base polymer increases during the annealing step. 75. The method of any one of claims 71-73, wherein the base polymer comprises a plurality of monomers, and wherein the molar ratio of monomers to electron acceptors is equal to or greater than 1:1. 76. The method of any one of claims 71-73, wherein the base polymer has a glass transition temperature, and wherein the glass transition temperature of the base polymer is greater than 80°C. 77. The method of any one of claims 71-73, wherein the weight ratio of the base polymer to the ionic compound during the mixing step is less than 5:1. 78. The method of any one of claims 71-73, wherein a positive pressure is applied to the mixture during the heating step. 79. The method of any one of claims 71-73, wherein the mixture undergoes a color change during the heating step. 80. The method of any one of claims 71-73, wherein a charge transfer complex is formed during the heating step. 81. The method of any one of claims 71-73, further comprising the additional mixing step of mixing the solid ion-conducting polymer material with a second material. 82. The method of any one of claims 71-73, further comprising the step of extruding, wherein the solid ion-conducting polymer material is extruded. 83. The method of any one of claims 71-73, further comprising an ion conducting step, wherein the solid ion conducting polymer material transports at least one ion. 84. A material produced by the method of any one of claims 71-73. 85. An electrochemically active material composite comprising the material of claim 1 , 5, 59 or 85 and an electrochemically active material. 86. An electrode comprising the material of claim 1 , 5, 59, or 85. 87. A battery comprising the material of claim 1, 5, 59, or 85. 88. A fuel cell comprising the material of claim 1, 5, 59, or 85. 89. An electrolyte comprising the material of claim 1, 5, 59, or 85. 90. A device for conducting ions comprising the material of claim 1 , 5, 59 or 85. 91. A method for conducting ions comprising the material of claim 1 , 5, 59 or 85. 92. A method for separating ions comprising the material of claim 1, 5, 59 or 85.