JP2019517712A - Electrochemical cell with solid ion conducting polymeric material - Google Patents

Abstract

The present invention relates to an electrochemical cell having a negative electrode and a positive electrode, at least one of the negative electrode and the positive electrode comprising a solid ion conducting polymeric material capable of ionically conducting hydroxyl ions. [Selected figure] Figure 1

Description

  The present invention relates to an electrochemical cell having a negative electrode and a positive electrode, at least one of the negative electrode and the positive electrode comprising a solid ion conducting polymeric material capable of ionically conducting hydroxyl ions.

Federally funded research and development statement (not applicable)

BACKGROUND OF THE INVENTION Batteries are becoming increasingly important in the modern society both in supplying power to a large number of portable electronic devices and in being an important component in new environmental protection technologies. These new technologies are committed to removing reliance on current energy sources such as coal, petroleum products and natural gas that contribute to the generation of by-products, greenhouse gases. Furthermore, the ability of energy storage in both fixed and mobile applications is critical for the success of new energy sources and appears to rapidly increase the demand for advanced batteries of all sizes. Especially in the case of batteries for large applications, the low base cost of the battery will be important for the introduction and overall success of these applications.

  However, conventional batteries have limitations. For example, lithium ion and other batteries generally use liquid electrolytes, which are dangerous to humans and the environment, and can be the cause of fires or explosions. Liquid electrolyte cells are sealed in steel or other strong packaging material, which adds to the weight and bulk of the packaged cells. Conventional liquid electrolytes suffer from the deposition of a solid interface layer at the electrode / electrolyte interface, which results in damage to the cell. Normal lithium ion batteries also show slow charge times and suffer from a limited number of recharges, which reach completion of the chemical reactions in the battery and can be recharged because of corrosion and dendritic formation It is because it limits sex. Liquid electrolytes also limit the maximum energy density, which begins to decline at about 4.2 volts, but new industrial applications often require voltages of 4.8 volts and higher. Conventional lithium ion batteries minimize liquid electrolyte separators to allow the flow of ions but block the flow of electrons, vents to relieve pressure in the housing, and even potentially dangerous over currents and temperatures. Need safety circuit components to

With respect to alkaline cells relying on transport of OH ^- ions for electrical conduction, at some point the electrolyte saturates with ions (eg zincate ions during discharge of Zn / MnO ₂ cells) and as a result the negative electrode is water Are exhausted. In rechargeable alkaline cells, the reaction is reversed during charging. However, the formation of the same ion saturated electrolyte can prevent discharge. The positive electrode reaction results in the release of OH ^- ions. However generation of soluble low-valent species (e.g. Zn / MnO ₂ cell Mn species during discharge) may adversely affect the utilization of the active material. MnO ₂ theoretically undergoes two-electron reduction and can have a theoretical capacity of 616 mAh / g, but in practice no specific capacity close to the theoretical two-electron discharge was shown. Crystal structure rearrangement with the formation of the inactive phase and out diffusion of the soluble product limits the positive electrode capacity.

U.S. Pat. No. 5,959,015 describes the use of pentavalent bismuth metal oxides to enhance the overall discharge performance of alkaline batteries. A positive electrode containing 10% AgBiO ₃ and 90% electrolyte MnO ₂ has a discharge rate of 10 mA / g as compared to 287 mAh / g for 100% MnO ₂ and 200 mAh / g for 100% AgBiO ₃ Have been shown to deliver 351 mAh / g to a 0.8 V cut-off voltage. The specific capacity of 351 mAh / g corresponds to the 1.13 electron discharge of MnO ₂ and corresponds to the highest specific capacity delivered in the practically useful discharge rate and voltage range. It was claimed that the bismuth- or lead-modified MnO ₂ materials disclosed in US Pat. In the literature [Non Patent Literature 1, Non Patent Literature 2, Non Patent Literature 3], bismuth or lead cations can stabilize the crystal structure of MnO ₂ during discharge and / or soluble Mn ²⁺ species It is theorized that it allows two-electron reduction to proceed via a heterogeneous mechanism involving Containing the Mn ²⁺ species appears to be important to obtain high MnO ₂ availability and reversibility. In the high carbon content (30-70%) cathodes according to U.S. Pat. However, there is no data to suggest that a complete battery utilizing these positive electrodes was constructed or that it worked with the Zn negative electrode.

Thus, 1) polyelectrolytes that interfere with the dissolution of ions that would otherwise saturate the electrolyte and 2) the dissolution and transport of low valent species improve the utilization and recharging of alkaline cells. I will. Furthermore, it has been suggested that the insertion of Li stabilizes the MnO ₂ structure upon reduction, allowing for recharging. Polymers engineered to conduct Li ⁺ and OH ⁻ ions open the possibility to tune the MnO ₂ discharge mechanism in favor of proton or lithium insertion, which is to improve the life cycle It can act as an additional tool.

In addition, the battery technology for many advanced applications is lithium ion (Li ^- ion), but the energy density per volume (Wh / L) for portable devices and for electric vehicles and other large applications The increased demand for higher energy density in both points of energy density per weight (Wh / kg) has shown the need to approach technologies well beyond the current possibilities of Li ^- ion batteries. One such promising technology is Li / sulfur batteries. Sulfur-based positive electrodes are attractive because of their high theoretical energy density (1672 mAh / g), which is about 10 times better than current Li ^- ion metal oxide positive electrode active materials. Sulfur Many current Li ^- ion battery materials, for example, LiCoO ₂ which differ from it very rich, low cost, it is also attractive because it is environmentally friendly materials.

  In recent years, there has been a lot of activity in Li / Sulfur battery research, and there have been advances in the capacity and cycle life of rechargeable Li / Sulfur batteries. The activities included modifications to the positive electrode, the negative electrode, the electrolyte and the separator, all aimed at reducing polysulfide shuttle and thereby improving cell performance. The application of this study to sulfur cathodes involves two major areas: 1) Use of materials designed to enclose and contain sulfur and soluble lithiation products, eg: see US Pat. 2.) Concentrated on the use of conducting polymers to react with sulfur to give "sulfurized" composite cathode materials. Examples of "sulfided polymers" include the reaction product from high temperature exposure of sulfur with polyacrylonitrile (PAN) [see Non-Patent Document 5 and Non-Patent Document 6]. Other conductive polymer systems used in sulfur cathodes include polyvinyl pyrrolidone (PVP) [see non-patent document 7] and polypyrrole (PPY) [see non-patent document 8]. While these methods have experienced varying degrees of success in the limitations of the polysulfide shuttle mechanism, they all rely on the use of expensive materials that are not well suited to large scale production.

U.S. Patent No. 7,972,726 U.S. Pat. No. 5,156,934 U.S. Patent No. 5,660,953 US Patent Application No. 2013/0065128

Y. F. Yao, N. Gupta, H. et al. S. Wroblowa, J. Electroanal. Chem. , 223, 107, 1987 H. S. Wroblowa, N .; Gupta, J. Electroanal. Chem. , 238, 93, 1987 D. Y. Qu, L. et al. Bai, C.I. G. Castledine, B .; E. Conway, J. Electroanal. Chem. , 365, 247, 1994 M. Minakshi, P .; Singh, J. Solid State Elecrochem. 16, 1487, 2012 Jeddi, K. , Et al. , J. Power Sources 245, 656- 662, 2014 Li, L .; , Et al. , J. Power Sources 252, 107-112, 2014 Zheng, G. et al. , Et al. , Nano Lett. , 13, 1265-1270, 2013 Ma, G., et al. , Et al. , J. Power Sources 254, 353-359, 2014

  Provided is a solid ion conducting polymeric material having very high ion diffusivity and conductivity at room temperature and over a wide temperature range. Solid ionic polymeric materials are useful as solid electrolytes for alkaline batteries and also as parts for the manufacture of electrodes for alkaline batteries. The materials are not limited to battery applications, but are more widely applicable for other purposes such as alkaline fuel cells, electric double layer capacitors (supercapacitors), electrochromic devices, sensors and the like. The polymeric materials are flame retardant and self-extinguishing, which is particularly attractive for applications that may otherwise be flammable. In addition, the materials are mechanically strong and may be manufactured using high volume polymer processing methods and equipment that are themselves known in the art.

In one aspect of the invention, the solid ion conducting polymeric material acts as an electrolyte for the transmission of OH ^- ions in alkaline cells. Alkaline batteries include Zn / MnO ₂ , Zn / Ni, FE / NI, Zn / air, Ni / metal hydride, silver oxide, metal oxide / air and others known in the art including but not limited to others Can include battery chemistries. The chemistry of zinc / manganese oxide (Zn / MnNO ₂ ) is most widely used for household alkaline batteries.

  A solid ionic polyelectrolyte for a lithium ion battery comprising a solid ion conducting polymeric material is disclosed in co-pending US patent application Ser. No. 13 / 861,170, filed Apr. 11, 2013. , Assigned to the same assignee as the present invention.

  In another aspect of the invention, a solid ion conducting polymeric material is used to form the positive electrode, the electrolyte and the negative electrode of an alkaline battery. The three layers of the cell are solid and may be coextruded to effectively form the cell structure. The individual layers can be extruded separately or otherwise formed and layered together to form the cell structure, or alternatively.

The solid ion conducting polymeric material comprises at least one compound comprising a base polymer, a dopant and an ion source. Dopants include electron donors, electron acceptors or oxidants. OH ^- In one embodiment for the cells using chemical, basic polymers polyphenylene sulfide, sometimes known polyetheretherketone or liquid crystal polymer as PEEK. In this embodiment, the dopant is an electron acceptor such as, by way of non-limiting example, 2,3, dichloro-5,6-dicyano-1,4-benzoquinone, TCNE, sulfur trioxide or chloranil. Other dopants may be used that contain functional groups capable of acting as electron acceptors or capable of accepting electrons. Compounds that include an ion source include, but are not limited to, compounds containing hydroxyl ions, or hydroxides, oxides, salts or mixtures thereof that are chemically convertible to compounds containing hydroxyl ions Materials and more particularly Li ₂ O, Na ₂ O, MgO, CaO, ZnO, LiOH, KOH, NaOH, CaCl ₂ , AlCl ₃ , MgCl ₂ , LiTFSI (lithium bis trifluoromethane sulfone imide), LiBOB (lithium bis (Oxalate) borate) or a mixture of the above two components.

The solid ion conducting polymeric material exhibits ¹³ C NMR (detected at 500 MHz) chemical shift peaks at about 172.5 ppm, 143.6 ppm, 127.7 ppm and 115.3 ppm. Similar ¹³ C NMR scans of the electron acceptor show chemical shift peaks at about 195 ppm and 107.6 ppm, as well as chemical shift peaks at about 172.5 ppm, 143.6 ppm, 127.7 ppm and 115.3 ppm. In other words, the reaction between the base polymer and the electron acceptor appears to remove chemical shift peaks at about 195 ppm and 107.6 ppm. In addition, there is a movement of the main peak (dominated by aromatic carbon) of the ¹³ C NMR spectrum of the solid ion conducting polymer on transfer from the base polymer to the solid ion conducting polymer. The chemical shift of the dominant peak in the solid ion conducting polymer is greater than the chemical shift of the dominant peak in the base polymer.

  The material has a crystallinity of at least about 30% or more.

  The compound containing the ion source is present in the range of 10% by weight to 60% by weight.

  The dopant molar ratio is in the range of about 1-16.

The material has an ionic conductivity of at least 1 × 10 ⁻⁴ S / cm at room temperature of 20 ° C. to 26 ° C.

  The material has a tensile strength in the range of 5 to 100 MPa, a modulus in the range of 0.5 to 3.0 GPa and an elongation in the range of 0.5 to 30%.

The material has an OH ^- diffusivity greater than 10 ^-11 cm ² / S at room temperature between 20 ° C. and 26 ° C.

OH ^- battery having a chemical if rechargeable, or may not be rechargeable.

  In another aspect, the invention provides a rechargeable alkaline battery comprising a negative electrode; a positive electrode; and an electrolyte; wherein at least one of the negative electrode, the positive electrode and the electrolyte comprises a solid ion conducting polymeric material.

In one embodiment of the battery, the battery comprises a negative electrode; a positive electrode; and wherein at least one of the negative electrode and the positive electrode comprises a solid ion conducting polymeric material. The battery may be a rechargeable battery or a primary battery. The battery further comprises an electrolyte, which may comprise a solid ion conducting polymeric material. The battery may alternatively or additionally additionally contain an electrolyte, and the electrolyte may be alkaline. A solid ion conducting polymer may conduct multiple OH ^- ions at temperatures in the range of 20 ° C to 26 ° C and has an OH ^- diffusivity greater than 10 ^-11 cm ² / s, so it is an alkaline battery It is particularly well suited for use on the electrode.

  The solid ion conducting polymeric material is formed from a reactant product comprising a basic polymer, an electron acceptor and a compound comprising an ion source. In some cases, a solid ion conductive polymer material is used as an electrolyte in the negative electrode or the positive electrode. When used in a battery, the positive electrode of the battery is a ferrate, iron oxide, cuprous oxide, iodate, cupric oxide, mercury (II) oxide, cobaltous oxide, manganese oxide, lead dioxide, oxidized Silver, oxygen, nickel oxyhydroxide, nickel dioxide, silver peroxide, permanganate, bromate, silver vanadium oxide, carbon monofluoride, iron disulfide, iodine, vanadium oxide, copper sulfide, sulfur or carbon and There may be active materials selected from the group comprising combinations thereof. The negative electrode of the cell comprises lithium, magnesium, aluminum, zinc, chromium, iron, nickel, tin, lead, hydrogen, copper, silver, palladium, mercury, platinum or gold and combinations thereof and their alloyed materials May comprise an active material selected from the group consisting of

In alkaline batteries, where the positive electrode contains manganese dioxide and the negative electrode contains zinc. Manganese dioxide is β-MnO ₂ (pyroleite), ramsdellite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ , electrolytic manganese dioxide (EMD) and chemical manganese dioxide (CMD) form may be taken as well as combinations of the above forms. Furthermore, at least one of the negative electrode and the positive electrode may comprise particles of active material, and the solid ion conducting polymeric material may encapsulate all of the particles of active material or all of the active material. Such positive electrodes exhibited specific capacities greater than 400 mAh / g, 450 mAh / g and 500 mAh / g.

Alternatively, the battery may include an electrically conductive additive and / or a functional additive in the negative electrode or the positive electrode. The electrically conductive additive may be selected from the group comprising carbon black, natural graphite, synthetic graphite, graphene, conductive polymers, metal particles, and a combination of at least two of the foregoing components. The functional additive may be selected from the group comprising bismuth, ZnO, MgO, CaO, SnO ₂ , Na ₂ SnO ₃ and ZnSO ₄ .

The battery electrode (negative electrode or positive electrode) may have a composite structure that may be molded by methods such as injection molding, tube extrusion and compression molding. In one aspect of the preparation of solid ion conducting polymeric materials, the base polymer is oxidatively doped in the presence of an ion source. The ion source is a compound containing at least one hydroxyl group or a compound convertible to a compound containing at least one hydroxyl group, or alternatively selected from the group consisting of LiOH, Li ₂ O or a mixture of the two components mentioned above Compound. The basic polymer is selected from the group comprising liquid crystal polymers, polyetheretherketone (PEEK) and polyphenylene sulfide (PPS) or semi-crystalline polymers having a degree of crystallinity greater than 30%, and combinations thereof. The electron acceptor reacting with the base polymer in the presence of the ion source comprises 2,3, dichloro-5, 6-dicyano-1, 4-benzoquinone, TCNE, sulfur trioxide or chloranil and combinations thereof It may be selected from the group. The method may further include a heating step to promote the reaction. The electrochemically active material can be added to the mixing stage, and if so added, it is encapsulated by the reacted ion conducting polymer. Such a cell having a MnO ₂ positive electrode, a zinc negative electrode and an alkaline electrolyte, characterized in that the alkaline cell has a flat discharge curve higher than 1 V and a voltage drop below 0.3 V at 5 to 95% depth of discharge.

  Because the solid ion conducting polymeric material is electrically nonconductive and ionically conductive, it may also be useful as a separator film. Thus, a solid ion conducting polymeric material, cast or otherwise rendered as a film, may be used as a separator placed between the negative and positive electrodes. In addition, solid ion conducting polymeric materials may be coated on the electrodes to function as separators or to isolate the electrodes or electrode components from other battery components such as aqueous electrolytes. The solid ion conducting polymeric material allows ionic communication between such isolated components, regardless of whether they are physically separated and electrically separated from the remaining battery components. Do. The material may also include agglomerated or cast agglomerates of small particles of solid ion conducting polymeric material. Such aggregates may take any form, but may be designed and include porosity while retaining the designed surface area. Fillers such as hydrophobic materials may be mixed into the material to provide desirable physical properties such as low effective aqueous porosity. A catalyst may be added to the solid ion conducting polymeric material to allow for the combination of catalysis and ion conductivity as required in air electrodes for metal / air batteries. Thus, the solid ion conducting polymeric material may include low or very high surface area and low or very high porosity. Shapes such as rings or other castable forms with the desired physical properties having the ionic conductivity of the solid ion conducting polymeric material can be designed, which is made possible by the present invention.

  According to one aspect, an electrochemical cell comprises a solid ion conducting polymeric material, which is used at its negative electrode or positive electrode or both.

  In one aspect, an electrochemical cell produces electrical energy through an electrochemical reaction that includes a negative electrode and a positive electrode; wherein the solid ion conducting polymeric material is capable of ionically conducting hydroxyl ions, thereby solidifying The ion conducting polymeric material can conduct hydroxyl ions during the electrochemical reaction.

Further aspects of the electrochemical cell may include one or more of the following individually or in combination;
The positive electrode may provide hydroxyl ions during the electrochemical reaction.

  The solid ion conducting polymeric material has a crystallinity of at least about 30% or more.

The solid ion conducting polymeric material comprises at least one hydroxyl ion and has an OH ^- diffusivity greater than 10 ^{-11 at} a temperature in the range of 20 ° C to 26 ° C.

  The positive electrode contains an active material that produces hydroxyl ions during the electrochemical reaction.

  The negative electrode comprises a solid ion conducting polymeric material and further comprises a negative electrode electrochemical active material, wherein the solid ion conducting polymeric material and the negative electrode electrochemical active material are mixed, whereby the solid ion conducting polymer The material is capable of ionically conducting hydroxyl ions to the negative electrode electrochemically active material.

The positive electrode comprises a solid ion conducting polymeric material and further comprises a positive electrode electrochemical active material, wherein the solid ion conducting polymeric material and the positive electrode electrochemical active material are mixed, whereby the solid ion conducting polymer The material is capable of ionically conducting hydroxyl ions to the positive electrode electrochemically active material.

  Here, at least a portion of the solid ion conducting polymeric material is in contact with the negative electrode electrochemically active material.

  Here, at least a portion of the solid ion conducting polymeric material is in contact with the positive electrode electrochemically active material.

  The positive electrode comprises manganese dioxide, wherein the cell has a specific capacity of greater than 308 mAh / g of manganese dioxide.

  The solid ion conducting polymeric material is positioned between the negative electrode and the positive electrode, whereby the solid ion conducting polymeric material conducts hydroxyl ions between the negative electrode and the positive electrode.

  The positive electrode comprises a solid ion conducting polymeric material, wherein the amount of solid ion conducting polymeric material is in the range of 1 to 40 weight percent of the positive electrode.

  The cell is rechargeable, wherein the positive electrode comprises manganese dioxide, and wherein the amount of manganese dioxide is in the range of 20 to 90 weight percent of the positive electrode.

  The cell is a primary cell, wherein the positive electrode comprises manganese dioxide, and wherein the amount of manganese dioxide is in the range of 50 to 95 weight percent of the positive electrode.

  The cell further comprises a liquid electrolyte, wherein the liquid electrolyte comprises hydroxyl ions.

  Both the negative and positive electrodes contain a solid ion conducting polymeric material, where the battery is in the solid state and does not contain any liquid electrolyte, whereby the ion conductivity of the cell is a solid ion conducting polymeric material It becomes possible through.

  The negative electrode comprises zinc and the positive electrode comprises manganese dioxide, wherein the battery is a primary battery.

  The negative electrode comprises zinc and the positive electrode comprises manganese dioxide, wherein the battery is a secondary battery.

  The negative electrode comprises aluminum and the positive electrode comprises manganese dioxide, wherein the battery is a primary battery.

  The negative electrode comprises zinc and the positive electrode is fluidly connected with oxygen or is simply exposed to oxygen, where the oxygen acts as the positive electrode electrochemically active material.

Exemplarily shows the formula obtained for the crystalline polymer of the present invention; Exemplarily shows a dynamic scanning colorimeter curve of a semicrystalline polymer; Exemplarily shows the formulations studied for use in the present invention; Shows a schematic representation of amorphous and crystalline polymers; Illustratively show the chemical diagram of 2,3-dicyano-5,6-dichlorodicyanoquinone (DDQ) as a typical electron acceptor dopant for use in the present invention; Figure exemplarily shows a plot of the conductivity of the ion conducting polymer according to the invention in comparison with liquid electrolytes and polyethylene oxide lithium salt compounds; Exemplarily shows the mechanical properties of the ion conducting film according to the invention; Exemplarily shows a possible mechanism of conduction of the solid electrolyte polymer according to the present invention; Exemplarily shows a UL 94 combustion test carried out on a polymer according to the invention; Fig. 8 exemplarily shows a plot of volt vs. current of the ion conducting polymer according to the invention against lithium metal; Exemplarily shows a schematic view of an extruded ion conducting electrolyte and an electrode part according to the invention; Fig. 3 exemplarily shows a solid-state battery according to the invention in which the electrodes and the electrolyte are glued together; Exemplarily shows the final solid state battery according to the invention having a novel and flexible form; Illustratively show the method of the present invention including the steps for producing a solid state battery using the extruded polymer; Exemplarily shows the extrusion process according to the invention; Fig. 6 exemplarily shows a diagram of an embodiment according to the invention Fig. 3 exemplarily shows an alkaline battery with three layers according to the invention; An exemplary comparison of the process steps for standard Li-ion positive electrode production with the process steps for extrusion of the composite polymer-sulfur positive electrode of the present invention; Exemplarily shows the OH-diffusivity at room temperature in the solid polymer electrolyte of the invention; Exemplarily shows the lithium diffusion rate at room temperature in the solid polymer electrolyte of the present invention; The voltage distribution of the cells of the present invention according to Example 2 as a function of the specific capacity of the MnO ₂ in the discharge rate of 0.5 mA / cm ² exemplarily shows; 3 exemplarily shows the voltage distribution of the cell of the invention according to Example 3 as a function of the specific capacity of MnO ₂ at C / 9 rate (C / 9 rate) (35 mA / g); 7 exemplarily shows the specific capacity of MnO ₂ as a function of the number of cycles in the cell of the invention according to Example 4; Fig. 7 exemplarily shows the discharge curve of the coin cells of the invention according to Example 5 as a function of test time; Fig. 8 exemplarily shows the voltage distribution of the cell of the invention according to Example 6 as a function of test time; Fig. 8 exemplarily shows the discharge curve of the button cell of the invention according to Example 7 as a function of discharge capacity; The exemplary potentiodynamic scan at 1 mV / s of the inventive negative electrode (curve A) and the reference Al foil (curve B) in a ZnSO ₄ electrolyte is shown. Using Zn foil as counter electrode; Shows the specific capacity of Duracell Coppertop AA cells under various constant current discharge rates; Fig. 6 shows the discharge curve for an alkaline button cell at a rate of 10 mA / g according to the prior art; Exemplarily illustrates the voltage distribution of the cell of the invention according to Comparative Example 12 at a constant current discharge of 35 mA / g as a function of the specific capacity of MnO ₂ ; 13 exemplarily shows the voltage distribution of the cell of the invention according to Example 13 as a function of the specific capacity of MnO ₂ ; 13 exemplarily shows the voltage distribution of the cell of the invention according to Example 14 as a function of the specific capacity of MnO ₂ in comparison with the Duracell Coppertop cell; 13 exemplarily shows the voltage distribution of the cell of the invention according to Example 15 as a function of the specific capacity of MnO ₂ in comparison with the Duracell Coppertop cell; Exemplarily shows a first discharge voltage curve for the Li / ionic polymer-sulfur cell of the invention; Exemplarily shows a discharge capacity curve plotted as a function of cycle number for the Li / ionic polymer-sulfur cell of the invention; An exemplary comparison of the first discharge with respect to Li / Sulfur-CMK-3 of the literature example and the first discharge with respect to the Li / ionic polymer-sulfur according to the invention; Figure 7 shows charge / discharge voltage curves for Li / sulfur-poly (pyridinopyridine) cells from the prior art; Shows rate profiles of button cells; Show positive capacity with respect to battery energy density; Indicates button cell discharge capacity with respect to discharge current; and FIG. 6 shows a plot of voltage over time for one battery embodiment.

  This application is a continuation-in-part of US patent application Ser. No. 14 / 559,430, filed Dec. 3, 2014. US Provisional Patent Application No. 62 / 342,432, filed May 27, 2016, is hereby incorporated by reference for all purposes.

  The present invention comprises a solid ion conducting polymeric material comprising at least one compound comprising a basic polymer, a dopant and an ion source. The polymeric material has a capacity for ion conduction over a wide temperature range, including room temperature. Ion "hopping" is believed to occur from high density atomic sites. Thus, the polymeric material can function as a means for the supply of ions and has significant material strength.

  For the purpose of the present application, the term "polymer" refers to a polymer having a crystalline or semi-crystalline structure. In some applications, the solid ion conducting polymeric material may be formed into a form that can be folded back on itself, allowing for new physical formats depending on the application. Do. The base polymer is chosen depending on the desired properties of the composition related to the desired application.

  For the purpose of the present application, the term "dopant" refers to an electron acceptor or oxidant or an electron donor. The dopant is chosen depending on the desired properties of the composition related to the desired application.

  Similarly, the compound containing the ion source is chosen depending on the desired properties of the composition related to the desired application.

I. In one aspect of the chemistry of Li ⁺ , the present invention relates to solid polymer electrolytes comprising solid ion conducting polymer materials in lithium ion batteries.

In this aspect, the base polymer is characterized as having a crystallinity value of 30% to 100%, and preferably 50% to 100%. The base polymer has a glass transition temperature above 80 ° C., preferably above 120 ° C., more preferably above 150 ° C., most preferably above 200 ° C. The base polymer has a melting temperature above 250 ° C., preferably above 280 ° C., more preferably above 320 ° C. The molecular weight of the monomer units of the basic polymer of the present invention is in the range of 100 to 200 gm / mole and may be greater than 200 gm / mole. FIG. 1 shows the molecular structure of a typical base polymer, wherein the monomer units of the base polymer have a molecular weight of 108.16 g / mol. FIG. 2 exemplarily shows a dynamic scanning calorimeter curve of a typical semicrystalline basic polymer. FIG. 3 shows a representative formulation for a solid ion conducting polymeric material in this aspect of the invention where DDQ is a dopant. Typical materials that can be used as the base polymer include liquid crystal polymers and polyphenylene sulfide, also known as PPS, or semi-crystalline polymers having a crystallinity of more than 30%, preferably more than 50%. In one embodiment, the present invention uses the "crystalline or semi-crystalline polymers" exemplarily shown in FIG. 4, which typically have crystallinity values above 30% and above 200.degree. C. It has a glass transition temperature and a melting temperature higher than 250 ° C.

In this aspect the dopant is 2,3-dicyano-5,6-dichlorodicyanoquinone (C ₈ Cl ₂ N ₂ O ₂ ), also known as DDQ as a non-limiting example, tetracyanoethylene (C ₆ N ₄ ) and electron acceptors such as sulfur trioxide (SO ₃ ). The preferred dopant is DDQ. FIG. 5 gives the structural formula of this preferred dopant. The purpose of the electron acceptor appears to be dual: releasing ions for transport mobility and creating polar high density sites within the polymer to allow for ionic conductivity. The electron acceptor may be "premixed" with the initial components and extruded without post treatment, or alternatively, the electron acceptor may be added to the composition after the material is made using a doping method such as vapor doping. is there.

Exemplary compounds that include an ion source for use in this aspect of the invention include, but are not limited to, Li ₂ O, LiOH, ZnO, TiO ₂ , Al ₂ O _{3, and the} like. Compounds containing suitable ions in stable form may be modified after preparation of the solid polyelectrolyte film.

  Other additives such as carbon particle nanotubes and the like can be added to the solid polymer electrolyte comprising solid ion conducting material to further enhance the conductivity or current density.

  The novel solid polymer electrolytes allow lighter weight and much safer construction by eliminating the need for heavy and bulky metal hermetic packaging and protective circuitry. Novel solid polymer batteries containing solid polymer electrolytes may be of smaller size, lighter weight and higher energy density than liquid electrolyte batteries of the same volume. The novel solid polymer cell also benefits from less complex manufacturing methods, lower cost and less safety issues as the electrolyte material is flame retardant. The novel solid polymer cells are capable of cell voltages higher than 4.2 volts and are stable to higher and lower voltages. The novel solid polyelectrolytes may be formed into various shapes by extrusion (and co-extrusion), molding and other methods to provide various form factors to the cell. Certain shapes may be made to fit within variously shaped enclosures in a powered device or facility. Furthermore, the novel solid polymer battery does not require a separator between the electrolyte and the electrode as in the case of a liquid electrolyte battery. The weight of the novel solid polymer cell is substantially lighter than cells of conventional construction with similar capacity. In some embodiments, the weight of the novel solid polymer battery may be less than half of the weight of a conventional battery.

  In another aspect of the invention, a solid polymer electrolyte comprising a solid ion conducting polymeric material is in the form of an ionic polymer film. An electrode material is applied directly to each surface of the ionic polymer film and a foil charge collector or terminal is applied on each electrode surface. A light weight protective polymer covering may be applied over the terminals to complete the film based structure. The film based structure forms a thin film battery that is flexible and can be rolled or folded into the intended shape to meet the requirements of installation.

  In yet another aspect of the invention, a solid polymer electrolyte comprising a solid ion conducting polymeric material is in the form of an ionic polymer hollow monofilament. Electrode materials and charge collectors are applied directly to each surface of the solid ion conducting polymeric material (co-extrusion) and terminals are applied to each electrode surface. A light weight protective polymer cover may be applied over the terminals to complete the structure. The structure is thin, flexible and forms a battery that can be coiled into the intended shape to meet installation requirements including very small applications.

  In yet another aspect of the invention, a solid polyelectrolyte comprising a solid ion conducting polymeric material has a desired shaped shape. The negative and positive electrode materials are placed on the facing surfaces of the solid polymer electrolyte to form a cell unit. Electrical terminals can be provided on the negative and positive electrodes of each battery unit for interconnection with other battery units to provide multi cell batteries or for connection to a utilization device.

  In aspects of the invention relating to batteries, the electrode materials (positive and negative electrodes) can be combined with some form of novel solid ion conducting polymeric material to further facilitate the movement of ions between the two electrodes. This is similar to a conventional liquid electrolyte which dips into each electrode material in a conventional lithium ion battery.

  A film of the solid ion conducting polymeric material of the present invention was extruded with a thickness ranging upward from .0003 inches. The ionic surface conductivity of the films was measured using standard tests of AC-Electrochemical Impedance Spectroscopy (EIS) known to the person skilled in the art. A sample of the solid ion conducting polymeric material film was sandwiched between stainless steel blocking electrodes and placed in the test fixture. AC-impedance was recorded in the range of 800 KHz to 100 KHz using a Biologic VSP test system to determine electrolyte conductivity. The results of the surface conductivity measurement are shown in FIG. The conductivity (Δ) of the solid ion conducting polymer material film according to the present invention is a conductivity of trifluoromethanesulfonate PEO (□) and a liquid electrolyte composed of Li salt solute and EC: PC combined solvent using a Celgard separator Compare to conductivity (O). The conductivity of the solid ion conducting polymer material film according to the present invention tracks the conductivity of the liquid electrolyte and far outperforms the conductivity of trifluoromethanesulfonate PEO at relatively low temperatures. Furthermore, unlike the PEO electrolyte, the temperature dependence of the conductivity for the polymeric material of the present invention is related to its glass transition associated with chain mobility described by temperature activated Vogel-Tamman-Fulcher behavior It shows no sharp improvement above temperature. Therefore, segmental movement as an ion conduction mechanism in the polymer material of the present invention is unlikely. Furthermore, this indicates that the polymeric material of the present invention has an ionic conductivity similar to that of the liquid electrolyte.

  FIG. 7 shows the mechanical properties of the solid ion conducting polymeric material film of the present invention. The mechanical properties were evaluated using the Institute for Interconnection and Packaging Electronic Circuits IPC-TM-650 Test Methods Manual 2.4.18.3. In the tensile strength vs. elongation curve of FIG. 7, the “ductile fracture” appearance indicates that the material can be very robust.

The solid ion conducting polymeric material of the present invention offers three important advantages in its polymeric performance properties: (1) It has a wide temperature range. In laboratory scale tests, crystalline polymers exhibited high ionic conductivity both at room temperature and over a wide temperature range. (2
) It is flame retardant. The polymer is self-extinguishing and passes the UL-V0 burn test. The ability to operate at room temperature and the flame retardant properties show a transformative safety improvement, which eliminates expensive heat treatment systems. (3) It gives low cost mass production. Rather than spraying the polymer onto the electrode, the polymeric material can be extruded into a thin film via the roll-to-roll method, which is the industry standard for plastic production. After extruding the film, it is coated with electrodes and charge collector material to build a "from the inside out" cell. This allows for a thin flexible form factor without the need for hermetic packaging, leading to easy incorporation into vehicle and storage applications at low cost.

  The solid ion conducting polymer material of the present invention creates a new ion conduction mechanism, which gives higher density of sites for ion transport, without the risk of thermal runaway or damage to the ion transport site from eg lithiation It is believed that the conductive material allows to hold higher voltages. This property allows the solid ion conducting polymeric material to be durable for negative electrode materials and thin film applications of higher voltage positive electrodes, and higher energy for batteries that can be used for vehicle and fixed storage applications Produce a density. The ability to hold high voltages within solid ion conducting polymeric materials that are mechanically robust over a wide range of temperatures as well as room temperature, resistant to chemicals and humidity, and are flame retardant today Allows integration with high performance electrodes without the expensive heat and safety mechanisms used by the industry.

  A battery using a solid polymer electrolyte comprising the solid ion conducting polymer material of the present invention is -40.degree. C. to 150.degree. Is characterized by the performance range of Solid polyelectrolytes can be extruded by the method of producing 6 micron thick polymers, which enables thin film formats under commercial production conditions on a batch scale. In addition, such extrusion methods allow high throughput, low cost production lines for the production of solid polymer electrolytes, and the methods can be incorporated into a variety of production lines including lithium and zinc battery production. Battery cost can be reduced by up to 50%.

  Furthermore, solid ion conducting polymeric materials are not limited to use in batteries, and may be used in any device or composition that includes an electrolyte material. For example, the novel solid ion conducting polymeric materials can be used in electrochromic devices, electrochemical sensors, electric double layer capacitors and fuel cells. FIG. 8 shows a possible mechanism of conduction of the solid ion conducting polymer material on the side of the solid polymer electrolyte of the present invention. Charge carrier complexes are set up in the polymer as a result of the doping process.

  The flammability of a solid polymer electrolyte comprising the solid ion conducting polymer material of the present invention was tested using the UL 94 burn test. For a polymer to be rated UL94-V0, it must "self-extinguish" within 10 seconds and "not drip". The solid polyelectrolyte was tested for this property and it was determined that it self-extinguished and did not drip in 2 seconds and therefore easily passed the V0 rating. FIG. 9 shows a picture of the result.

In addition to ion conductivity, flame resistance, high temperature behavior and excellent mechanical properties, the solid polymer electrolytes comprising the solid ion conducting polymer material of the present invention may be electrochemically stable at low and high potentials. preferable. A common test for electrochemical stability is cyclic voltammetry when the working electrode potential is ramped linearly with time. In this test, a polymer is sandwiched between a lithium metal negative electrode and a blocked stainless steel electrode. Apply a voltage and sweep it positively to a high value (above 4 volts for Li) for stability against oxidation and a low value (0 V for Li for stability against reduction Or lower). The current output is measured to determine if a significant reaction occurs at the electrode interface. High current output at high positive potential indicates that oxidation reactions are taking place, suggesting instability when using positive electrode materials (eg many metal oxides) operating at these or more positive potentials . The high current output at low potential indicates that the reduction reaction occurs, suggesting instability when using negative electrodes (eg, metallic Li or lithiated carbon) operating at these or more negative potentials. FIG. 10 shows a plot of voltage versus current for a solid polymer electrolyte comprising a solid ion conducting polymeric material according to the invention versus lithium metal. Studies show that solid polymer electrolytes are stable up to about 4.4 volts. These results indicate that solid polymer electrolytes may be stable when using low voltage positive electrodes, such as LCO, LMO, NMC and similar positive electrodes with iron phosphate and sulfur positive electrodes as non-limiting examples. Show.

The solid polymer electrolyte comprising the solid ion conducting polymer material of the present invention can achieve the following properties: A) high ionic conductivity ranging from room temperature and wide temperature range (at least -10 ° C to + 60 ° C) B) Flame retardant; C) Reel-reel processing and extrudability to thin films allowing new manufacturing methods; D) Compatibility with lithium metal and other active materials. Thus, the present invention enables the fabrication of true solid state batteries. The present invention enables a new generation of batteries having the following properties:
-No safety issues;
-New form factor;
-Significant improvement in energy density; and-significant improvement in the cost of energy storage.

  Figures 11, 12 and 13 show several elements of a solid state battery comprising the solid ion conducting polymeric material of the present invention, each of them: A) extruded electrolyte; B) extruded negative electrode And C) a final solid state battery that allows for new form factors and flexibility.

  In another aspect, the invention provides a method of making a Li cell comprising the solid ion conducting polymeric material of the invention. FIG. 14 illustrates a method of making a solid state lithium ion battery using the extruded solid ion conducting polymeric material according to the present invention. The materials are compounded into pellets and then extruded through a die to produce films of variable thickness. The electrode can be applied to the film using several methods, such as sputtering or conventional casting in a slurry.

  In yet another aspect, the invention provides a method of making an ionic polymer film comprising the solid ion conducting polymeric material of the invention, which heats the film to a temperature of about 295 ° C. and then solidifies the plastic. Casting the film on a chill roll. This extrusion method is shown in FIG. The resulting film is very thin, and may be in the range of 10 microns thick or thinner. FIG. 16 shows a schematic representation of the structure of an embodiment according to the invention.

II. OH ^- chemical present invention, OH ^- designed to transmit ions, thereby also relates to a solid ion conductive polymer materials in the applicable it for alkaline batteries. For the purposes of the present invention, the term "alkaline battery or alkaline batteries" refers to a battery using an alkaline (OH ^- containing) electrolyte. Such cell chemistries include, but are not limited to: Zn / MnO ₂ , Zn / Ni, Fe / Ni, Zn / air, Al / air, Ni / metal hydrides, silver oxide and others. Zn / Mn
The chemistry of O ₂ is probably the most widely used and is the main choice for household batteries. Although many aspects described herein relate to the chemistry of Zn / MnO ₂ , one skilled in the art will understand that the same principle is broadly applicable to other alkaline systems.

Alkaline batteries rely on OH ^- ion transport for the conduction of electricity. In most cases, OH ^- ions are also participants in the electrochemical process. For example, during discharge of a Zn / MnO ₂ battery, the zinc anode emits two electrons and consumes OH ⁻ ions:
^{(1) Zn + 4OH - →} Zn (OH) 4 2- + 2e -
^{(2) Zn + 2OH - →} Zn (OH) 2 + 2e - → ZnO + H 2 O
(3) Zn (OH) ₂ → ZnO + H ₂ O

During the early stages of battery discharge, reaction (1) produces soluble zincate ions, which may be found in separators and positive electrodes [Linden's Handbook of Batteries, Fourth Edition]. At some point the electrolyte will saturate with zincate ions and the reaction product will turn to insoluble Zn (OH) ₂ (2). Finally, the negative electrode is depleted of water, and zinc hydroxide is dehydrated by the formula (3). In rechargeable batteries, the reaction is reversed during charging of the battery. The formation of soluble zincate ions during the early stages of Zn discharge can prevent recharging.

The positive electrode reaction involves the reduction of Mn ^{4 +} to Mn ^{3 +} by a proton insertion mechanism, resulting in the release of OH ⁻ ions (4). The theoretical ratio MnO ₂ capacity for such one electron reduction is 308 mAh / g. The slow discharge to a lower voltage leads to a further discharge of MnOOH as depicted by equation (5), which yields a total specific capacity (1.33e) of 410 mAh / g. In most prior art applications, the MnO ₂ discharge is limited to one electron process. The utilization of activity is further adversely affected by the formation of soluble low valent Mn species.
(4) MnO ₂ + e ⁻ + H ₂ O → MnOOH + OH ^{−
(5) 3MnOOH + e - →} Mn 3 O 4 + H 2 O + OH -
(6) MnO ₂ + 2e ⁻ + 2H ₂ O → Mn (OH) ₂ + 2OH ⁻

MnO ₂ can theoretically undergo two-electron reduction according to equation (6) and has a theoretical specific capacity of 616 mAh / g, which is not shown in the practice with prior art cells. Crystal structure rearrangement with the formation of an inert phase such as black manganite (Hausmanite) Mn ₃ O _{4 and} outdiffusion of soluble products are among the factors that limit positive electrode capacity.

U.S. Pat. No. 7,972,726 describes the use of pentavalent bismuth metal oxides to enhance the overall discharge performance of alkaline cells. A positive electrode containing 10% AgBiO ₃ and 90% electrolyte MnO ₂ has a discharge rate of 10 mA / g as compared to 287 mAh / g for 100% MnO ₂ and 200 mAh / g for 100% AgBiO ₃ Have been shown to deliver 351 mAh / g to a 0.8 V cut-off. The specific capacity of 351 mAh / g corresponds to the 1.13 electron discharge of MnO ₂ and corresponds to the highest specific capacity delivered in the practically useful discharge rate and voltage range.

In principle, reaction (4) can be reversible, opening the possibility for rechargeable Zn / MnO ₂ cells. In fact, crystal structure collapse and formation of soluble products only allow for a small number of shallow cycling.

The bismuth- or lead-modified MnO ₂ materials disclosed in US Pat. Nos. 5,156,934 and 5,660,953 have theoretical two-electron discharge capacities for many cycles It was claimed that about 80% of the can be delivered. Reference [Y. F. Yao, N. Gupta, H. et al. S. Wroblowa, J. Electroanal. C
hem. , 223, 107, 1987; S. Wroblowa, N .; Gupta, J. Electroanal. Chem. , 238, 93, 1987; Y. Qu, L. et al. Bai, C.I. G. Castledine, B .; E. Conway, J. Electroanal. Chem. , 365, 247, 1994], bismuth or lead cations can stabilize the crystal structure of MnO ₂ during the discharge, and / or through a heterogeneous mechanism involving soluble Mn ²⁺ species It was theorized to allow reaction (6) to proceed. The inclusion of the Mn ²⁺ species appears to be important to obtain high MnO ₂ availability and reversibility. In the high carbon content (30-70%) cathode according to U.S. Pat. Nos. 5,156,934 and 5,660,953 the resulting highly porous structure absorbs soluble species We were able to. However, there is no data to suggest that a complete battery utilizing these positive electrodes was constructed or that it worked with the Zn negative electrode.

Thus, polyelectrolytes that prevent the dissolution and transport of low valent manganese species and zincate ions are very beneficial for improving the MnO ₂ utilization and achieving the rechargeability of Zn / MnO ₂ cells .

MnO ₂ can undergo reduction by Li intercalation in addition to proton insertion. It has been suggested that Li insertion can stabilize the MnO ₂ structure upon reduction, allowing for the possibility of recharge [M. Minakshi, P .; Singh, J. Solid State Elecrochem. 16, 1487, 2012].

The solid ion conducting polymeric materials of the present invention designed to conduct Li ⁺ and OH ^- ions support the proton or lithium insertion, opening the possibility to tune the MnO ₂ discharge mechanism, which has a cycle life of Can act as an additional tool to improve

Accordingly the present invention in one aspect, the base polymer to provide a polymeric material comprising at least one compound containing a dopant and an ion source, wherein the polymeric material is OH ^- solid ion having mobility related ions It is a conductive polymer material. For the purpose of the present application, the term "mobility with respect to OH ^- ions" means a diffusivity greater than 10 ^-11 cm ² / s or a conductivity of 10 ^-4 S / cm at room temperature of 20 ° C. to 26 ° C. Point to. Solid ion conducting polymeric materials are suitable for use in alkaline batteries.

In various aspects, the present invention comprises an electrolyte which is a solid polymer electrolyte for use in alkaline batteries, comprising a solid ion conducting polymer material having mobility with respect to OH ^- ions; one comprising said solid polymer electrolyte One or more cells including the above electrodes; and / or the electrodes are provided.

In another aspect, the present invention provides an electrode comprising a solid polymer electrolyte for use in alkaline batteries, a positive electrode and a negative electrode, wherein the solid polymer electrolyte has high mobility for OH ^- ions and high solid ion conductivity. Contains molecular materials. In yet another aspect, the present invention provides an electrolyte sandwiched between a positive electrode and a negative electrode, wherein the electrolyte, at least one of the positive electrode and the negative electrode has mobility with respect to OH ^- ions, and is a solid ion conducting polymer material including. In another aspect, the invention provides an alkaline battery comprising a positive electrode layer, an electrolyte layer and a negative electrode layer, wherein at least one of the layers comprises a solid ion conducting polymeric material having mobility for OH ^- ions. The latter aspect is exemplarily shown in FIG.

The basic polymer of the solid ion conducting polymer material having mobility with respect to OH ^- ions is a crystalline or semi-crystalline polymer, which is typically 30% to 100%, preferably 50% to 100%. It has a value of crystallinity. 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 base polymer has a melting temperature above 250 ° C., preferably above 280 ° C., more preferably above 280 ° C., most preferably above 300 ° C.

The dopant of the solid ion conducting polymeric material having mobility with respect to the OH ^- ion is an electron acceptor or an oxidant. Typical dopant for use in this aspect of the present invention DDQ, TCNE, SO ₃ and the like.

Compounds containing an ion source of a solid ion conducting polymeric material having mobility with respect to OH ^- ions include salts, hydroxides, oxides or other materials containing hydroxyl ions or convertible to such materials Materials include, but are not limited to, LiOH, NaOH, KOH, Li ₂ O, LiNO _{3, and the} like.

Solid ion conducting materials with mobility for OH ^- ions are characterized by a minimum conductivity of 1 x 10 ^-4 S / cm at room temperature and / or a diffusivity of OH ^- ions greater than 10 ^-11 cm ² / s at room temperature Be

OH ^- MnO _2, the positive electrode of the present invention relating to chemical NiOOH, AgO, include air (O _2), a similar active material. MnO ₂ is a preferred material, and other MnOs including β-MnO ₂ (pyroleite), ramsdellite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ and EMD and CMD. _It may be in the form of _two phases or mixtures thereof.

OH ^- the positive electrode of the present invention relating to chemical, the components of the solid ion-conducting polymer material of the present invention comprising a compound containing a basic polymer, dopant and an ion source, the generation of the solid ion-conducting polymer material The cathode active material is mixed prior to forming a mixture. Alternatively, the positive electrode active material is mixed with the already formed solid ion conductive polymer material.

The mixture is shaped and / or extruded at a temperature of 180 ° C. to 350 ° C., preferably 190 ° C. to 350 ° C., more preferably 280 ° C. to 350 ° C., most preferably 290 ° C. to 325 ° C. The positive electrode active material may include various forms such as powder form, particle form, fiber form and / or sheet form as a non-limiting example. The positive electrode of the present invention is an active material in an amount of 10 wt% to 90 wt%, preferably in an amount of 25 wt% to 90 wt%, more preferably in an amount of 50 wt% to 90 wt% based on the total positive electrode weight. including. The positive electrode may further include an electrically conductive additive, such as a carbon black component, a natural graphite component, a synthetic graphite component, a graphene component, a conductive polymer component, a metal particle component and / or other similar conductive additive. is there. The positive electrode may comprise the electroconductive additive in an amount of 0% to 25% by weight, preferably 10% to 15% by weight, based on the total positive electrode weight. OH ^- the positive electrode of the present invention relating to the chemical, may further comprise one or more functional additives to improve performance. The positive electrode active material may be enclosed by the solid ion conductive polymer material of the present invention.

OH ^- the negative electrode of the present invention relating to the chemical, which may include zinc powder, zinc flakes and other forms, the active material of Zn in the zinc sheet and other forms of embodiment. All such forms of zinc may be alloyed to minimize zinc corrosion.

OH ^- the negative electrode of the present invention relating to chemical, the components of the solid ion-conducting polymer material of the present invention comprising a compound containing a basic polymer, dopant and an ion source, the generation of the solid ion-conducting polymer material The negative active material is mixed to form a mixture. Alternatively, the negative electrode active material is mixed with the already formed solid ion conductive polymer material. The mixture is shaped and / or extruded at a temperature of 180 ° C. to 350 ° C. The negative electrode of the present invention is an active material in an amount of 10 wt% to 90 wt%, preferably in an amount of 25 wt% to 90 wt%, more preferably in an amount of 50 wt% to 90 wt% based on the total negative electrode weight. including. The negative electrode may further include an electrically conductive additive such as a carbon black component, a natural graphite component, a synthetic graphite component, a graphene component, a conductive polymer component, a metal particle component and / or other similar conductive additive. is there. The negative electrode may comprise the electroconductive additive in an amount of 0% to 25% by weight, preferably 10% to 15% by weight, based on the total negative electrode weight. OH ^- the negative electrode of the present invention relating to the chemical, may further comprise one or more functional additives to improve performance. The negative electrode active material may be enclosed by the solid ion conductive polymer material of the present invention.

In another aspect, the present invention provides a Zn / MnO ₂ cell comprising an electrolyte sandwiched between the MnO ₂ positive electrode and Zn negative electrode. The electrolyte in this aspect may include the solid ion conducting material of the present invention having mobility with respect to OH ^- ions or may include a conventional separator filled with a liquid electrolyte. The positive electrode may include the solid ion conductive material having mobility with respect to the OH ^- ion of the present invention, or may include a commercially available MnO ₂ positive electrode. The negative electrode in this aspect may include the solid ion conductive material of the present invention having mobility with respect to OH ^- ions, or may include a Zn negative electrode manufactured by Zn foil, Zn mesh or other method. In the Zn / MnO ₂ battery of the present invention, the solid electron conducting polymer material of the present invention having mobility with respect to OH ⁻ ions is contained in at least one of the positive electrode, the negative electrode and the electrolyte.

III. Polymer-MnO ₂ composite positive electrode The present invention further relates to a primary alkaline battery comprising a polymer-MnO ₂ composite positive electrode having a high specific capacity and a positive electrode. More particularly, the present invention relates to a primary alkaline battery further comprising a polymer-MnO ₂ composite positive electrode and a positive electrode having a specific capacity close to the theoretical two electron discharge. The alkaline cell may be discharged at a current density comparable to the current density of commercial alkaline cells while delivering useful capacity to a typical voltage cut-off of 0.8V.

In various aspects, the invention relates to a positive electrode made of a MnO ₂ active material comprising a large number of active MnO ₂ particles mixed with a solid ion conducting polymeric material comprising a basic polymer, a compound comprising a dopant and an ion source It relates to a method of manufacturing a positive electrode. In another aspect, the present invention relates to an electrochemical cell including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, and a method of manufacturing the positive electrode. The positive electrode is made of a MnO ₂ active material comprising a large number of active MnO ₂ particles mixed with a solid ion conducting polymeric material comprising a basic polymer, a compound comprising a dopant and an ion source. The positive electrode and the electrochemical cell of the present invention are characterized by flat discharge curves.

In aspects of the invention relating to a polymer-MnO ₂ composite cathode, the base polymer may be a semi-crystalline polymer. The base polymer may be selected from the group consisting of conjugated polymers or polymers that may be easily oxidized. Non-limiting examples of base polymers used in this aspect of the invention include PPS, PPO, PEEK, PPA and the like.

In the aspect of the invention relating to a polymer-MnO ₂ composite cathode, the dopant is an electron acceptor or oxidant. Non-limiting examples of dopants are DDQ, tetracyanoethylene also known as TCNE, SO ₃ , ozone, transition metal oxides including MnO ₂ or any suitable electron acceptor.

In the aspect of the invention relating to a polymer-MnO ₂ composite cathode, the compound comprising the ion source is a salt, a hydroxide, an oxide or another material containing hydroxyl ions or a material convertible to such a material And includes, but is not limited to, LiOH, NaOH, KOH, Li ₂ O, LiNO _{3, and the} like.

In the aspect of the present invention relating to a polymer-MnO ₂ composite positive electrode, the MnO ₂ active material is β-MnO ₂ (pyroleite), ramsdellite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ and EMD And other MnO ₂ phases including, but not limited to, CMD, or mixtures thereof.

By mixing a solid ion conducting polymer material containing a large number of active MnO ₂ particles and a compound containing a basic polymer, a dopant and an ion source, and heating the mixture to a predetermined temperature for a predetermined time, polymer-MnO ₂ The positive electrode associated with the composite positive electrode can be manufactured. The heating can optionally be carried out with the application of pressure.

In one embodiment, the polymer-MnO ₂ composite positive electrode of the present invention may be produced by compression molding at temperature. The mixture is shaped and / or extruded at a temperature of 180-350 ° C., preferably 190 ° C.-350 ° C., more preferably 280 ° C.-350 ° C., most preferably 290 ° C.-325 ° C. In another embodiment, the heating is optionally performed at a pressure of 150 to 2000 PSI, preferably 150 to 1000 PSI, more preferably 150 to 500 PSI, most preferably 150 to 250 PSI. The MnO ₂ active material may be present in an amount of 5% to 95% by weight, preferably 50% to 90% by weight, based on the total weight of the composite positive electrode. The composite positive electrode is 5 wt% to 50 wt%, preferably 10 wt% to 50 wt%, more preferably 20 wt% to 40 wt%, most preferably 25 wt% to 35 wt% based on the total weight of the composite positive electrode. It may contain fillers in an amount of%. The dopant may be added in an amount corresponding to a base polymer / dopant molar ratio of 2-10, preferably 2-8, more preferably 2-6, most preferably 3-5. The composite positive electrode may include an electrically conductive additive, such as a carbon black component, a natural and / or synthetic graphite component, a graphene component, an electrically conductive polymer component, a metal particle component and other components, where The components are present in an amount of 5 wt% to 25 wt%, preferably 15 wt% to 25 wt%, more preferably 18 wt% to 22 wt%, based on the total weight of the composite positive electrode. The MnO ₂ active material in the composite positive electrode may be encapsulated by the solid ion conducting polymer material of the present invention.

In a preferred embodiment, the present invention relates to an alkaline battery comprising said polymer-MnO ₂ composite positive electrode and a Zn negative electrode. The Zn anode may be in the form of a slurry comprising Zn or Zn alloy powder, KOH, a gelling agent and optionally other additives. The Zn negative electrode may further contain an electrical conductivity additive similar to the composite positive electrode.

The negative electrode associated with the polymer-MnO ₂ composite of the present invention may comprise Zn, Al, Fe, a metal hydride alloy or similar material. Zn and Al are preferred materials and may be in the form of pure metals or specially designed alloys. The separator may be a conventional non-woven separator used in alkaline batteries. The electrolyte is a solution of KOH, NaOH, LiOH, etc. in water. The alkali concentration may be 4 to 9 M. The electrolyte may further contain an electron conductive additive and / or a functional additive.

IV. Polymer-Sulfur Positive Electrodes The invention further relates to composite polymer-sulfur positive electrodes. The composite polymer-sulfur cathode comprises a solid ion conducting polymeric material comprising a sulfur component and a compound comprising a base polymer, a dopant and an ion source. Composite polymer-sulfur positive electrodes are characterized as having high specific capacity and high capacity retention when used in secondary lithium or Li-ion sulfur batteries. The composite positive electrode is greater than 200 milliamps-hours / gram, preferably 500 milliamps-
It is characterized as having a specific capacity greater than hour / gram, more preferably greater than 750 milliamp-hours / gram, most preferably greater than 1000 milliamp-hours / gram. A composite positive electrode is characterized as having a retention of at least 50%, preferably at least 80%, over more than 500 recharge / discharge cycles. The composite polymer-sulfur cathode of the present invention has direct application to low cost large scale manufacturing enabled by the unique polymer used in this composite electrode. The composite polymer-sulfur positive electrode of the present invention can simultaneously meet the requirements for the production of low cost batteries while providing high performance.

It should be noted that the sulfur positive electrode is reduced during discharge to produce successively lower order polysulfides through the sequence shown in the following formula:
S ₈ → Li ₂ S ₈ → Li ₂ S ₄ → Li ₂ S ₂ → Li ₂ S

The intermediate polysulfides between Li ₂ S ₈ and Li ₂ S ₄ are soluble in the liquid electrolyte. The polysulfide particles thus dissolved can migrate (or "shuttle") across the porous separator and react directly with the negative and positive electrodes during cycling. Polysulfide round trips cause parasitic reactions with the lithium negative electrode and reoxidation at the positive electrode, all causing a loss of capacity. Furthermore, this aspect of the reciprocating reaction is irreversible leading to self-discharge and low cycle life, which has plagued lithium sulfur batteries to date.

  The present invention shows a composite polymer-sulfur positive electrode comprising a sulfur component and a solid ion conducting polymeric material. This positive electrode can be extruded into a flexible thin film via the roll-to-roll method. Such thin films allow for a thin flexible form factor that may be introduced into the design of new flexible batteries. As shown in the examples which follow, this composite polymer-sulfur positive electrode has, for example, an inexpensive carbon black component, for example an electrically conductive additive such as Timcal C45 which has already been used in many commercial battery products. May be included. The composite polymer-sulfur positive electrode comprises, besides typical carbon black components, other electrically conductive additives such as, but not limited to, carbon fibers, graphene components, graphite components, but not limited to these It may include components, metal particles or other metal additives and electrically conductive polymers.

  The engineering properties of the composite polymer-sulfur positive electrode make it possible to extrude the positive electrode to a wide range of possible thicknesses, which in turn offers important advantages in terms of design flexibility in large scale positive electrode production. The composite polymer-sulfur cathode may be extruded as thin as 5 microns, as well as up to several hundred microns thick.

  The comparison of the process steps required to produce a standard lithium ion positive electrode with the process steps required to produce a composite polymer-sulfur positive electrode of the present invention lessons from the inherent lower cost of producing a composite polymer-sulfur positive electrode It is FIG. 18 shows the process steps required to make a standard lithium ion positive electrode, compared to the much simpler preparation of the extruded composite polymer-sulfur positive electrode of the present invention. The extrusion process for the composite polymer-sulfur positive electrode is easily scaled up to mass production, which offers significant advantages over existing lithium ion batteries, as well as much less capital expenditure for factory equipment.

  In addition to extrusion, composite polymer-sulfur positive electrodes may be formed by injection molding, compression molding or other methods involving heat or other methods known to those skilled in the art for engineering plastics.

  As discussed above, the composite polymer-sulfur positive electrode comprises a solid ion conducting polymeric material comprising a sulfur component as well as a compound comprising a base polymer, a dopant, an ion source.

  Basic polymers include liquid crystal polymers and polyphenylene sulfide (PPS) or semi-crystalline polymers having a crystallinity of> 30% or other typical oxygen acceptors.

Dopants include electron acceptors that activate the ion conduction mechanism. These electron acceptors may be premixed together with the other components or may be supplied in the vapor phase as a post doping process. Typical electron acceptor dopants suitable for use include: 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (C ₈ Cl ₂ N ₂ O ₂ ), tetracyanoethylene (TCNE) And (C ₆ N ₄ ) and sulfur trioxide (SO ₃ ), including but not limited to.

Compounds that include an ion source include, but are not limited to, Li ₂ O and LiOH. The use of the composite polymer-sulfur positive electrode in a Li / Sulfur test cell has shown that the composite polymer-sulfur positive electrode is stable to lithium, sulfur and the organic electrolytes typically used in lithium / sulfur batteries.

  The base polymer is a flame retardant polymer that has been shown to self-extinguish and pass the UL-VO burn test. The flame retardancy of the base polymer is a safety benefit for batteries using a composite polymer-sulfur positive electrode. The introduction of a flame retardant composite polymer-sulfur positive electrode into a battery with a flame retardant electrolyte will further improve the safety of the battery, an important attribute for high energy density batteries.

The sulfur component may comprise non-reduced and / or reduced forms of sulfur, including elemental sulfur. In particular, the composite polymer-sulfur positive electrode comprises a sulfur component comprising sulfur in a fully lithiated form (Li ₂ S), wherein Li ₂ S is solid. The composite polymer-sulfur positive electrode may also contain a carbon component. The advantage of using sulfur in the fully lithiated form is that it provides a lithium source for a sulfur battery having a Li ion negative electrode which must be lithiated during initial charge, unlike metallic Li. The combination of a sulfur positive electrode with a Li ion negative electrode benefits in preventing the formation of lithium dendritic that may be formed after cycling of the lithium negative electrode. Dendritic crystals are caused by uneven plating of lithium on the lithium metal negative electrode during charging. These dendrites can grow through the separator material, causing an internal short circuit between the positive and negative electrodes, often leading to high temperatures and dangerous safety of the battery. Materials in which lithium has been reversibly introduced via intercalation or alloying have been proposed for use in high safety lithium / sulfur batteries, reducing the chance of dendritic formation. Composite polymer-sulfur cathodes are for example carbon-based (petroleum coke, amorphous carbon, graphite, carbon nanotubes, graphene etc) materials, such as Sn, SnO, SnO ₂ and Co, Cu, Fe, Mn, Ni etc. Can be used together with negative electrode materials such as Sn-based composite oxides including composite materials with transition metals. Furthermore, silicon has shown promise as a lithium ion negative electrode material in elemental form or as a composite as described for oxides or tin. Other lithium alloying materials (eg, Ge, Pb, B, etc.) could also be used for this purpose. Iron oxides such as Fe ₂ O ₃ or Fe ₃ O ₄ and various vanadium oxide materials have also been shown to reversibly introduce lithium as a Li-ion negative electrode material. Anode materials can be considered in various forms including amorphous and crystalline and nano-sized particles and nanotubes.

The composite polymer-sulfur positive electrode may be combined with an electrolyte comprising a standard liquid electrolyte, a standard non-woven separator and / or a solid ion conducting polymeric material without liquid electrolyte. Examples of standard organic electrolyte solutions include lithium salts dissolved in a mixture of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME), such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) Is included. Additives such as LiNO ₃ can be added to the electrolyte to improve cell performance. In organic liquid electrolytes: Other lithium salts can be used, including LiPF ₆ , LiBF ₄ , LiAsF ₆ , lithium triflate, among others. In addition, other organics such as propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC) as some examples The solvents can be used alone or as a mixture or together with DOL and DME. Examples of standard non-woven separators include polypropylene (PP), polyethylene (PE) and combinations of PP / PE films. Other separator materials include polyimide, PTFE, ceramic coated films and glass mat separators. All of the above materials can be used with the composite polymer-sulfur positive electrode. Furthermore, composite polymer-sulfur positive electrodes can also be used, for example, in gel polymer systems in which a polymer based on PVDF is swollen with an organic electrolyte.

  The ability of the composite polymer-sulfur cathode to provide lithium ion conductivity is believed to simultaneously provide a high voltage to the sulfur cathode while improving the performance of the cell by limiting the polysulfide reciprocation mechanism. In addition, this unique engineering composite polymer-sulfur positive electrode enables the large scale, low cost manufacturing needed for the commercial viability of the positive electrode.

Thus the unique composite polymer-sulfur positive electrode is:
● Improved safety under normal and abuse conditions ● Enabling new battery form factor ● Significant improvement in energy density over existing Li-ion batteries ● Larger charge / discharge by preventing polysulfide reciprocation mechanism Leading to reversibility • Have a number of potential benefits to the battery, including a significant reduction in manufacturing costs (raw materials, processes and capital equipment) leading to an improvement in the cost of energy storage.

V. In one aspect of alkaline batteries, rechargeable Zn / for low rate applications that can match or exceed lithium-ion performance while providing improved stability, robustness and lower cost. The MnO ₂ battery is described.

It has been observed that certain positive electrode formulations comprising solid ion conducting polymeric materials can exhibit much higher active material utilization at low rates, while exhibiting a steeper drop as the discharge rate improves. This is illustrated by FIG. 38, which depicts the rate distribution of a button cell with a positive electrode formulation possibly useful for high energy cells. Most of such formulations show a ratio C / 2 capacity of about 300 mAh / g, which is close to what is theoretically expected for a 1-electron discharge of MnO ₂ (indicated by formulation 1 in FIG. 38) ). In some cases, the cell exhibits a specific capacity that exceeds the theoretical 1-electron discharge. For example, formulation 2 shows almost 400 mAh / g at C / 2 discharge, indicating a deeper discharge of manganese dioxide.

  Optimize zinc and polymer content in the negative electrode, in particular: ZnO type and particle size for desired negative electrode performance, optimization of solid polymer electrolyte composition and preparation method, ZnO to reduce zinc passivation And other functional additives were introduced. The combined effect of greater zinc surface area and improved stability results in improved performance and extended cycle life. Embedding Zn particles in the polymer matrix prevents shape change, aggregation and dendritic growth.

The positive electrode optimized to increase the capacity above 300 mAh / g shows an improvement in the specific MnO ₂ capacity, which has a large influence on the cell energy density of the pouch cell as shown by FIG. 39 .

In one aspect, a rechargeable Zn / MnO ₂ cell incorporating solid ion conducting polymeric materials for high rate and high temperature applications is described.

  Increasing the manganese dioxide content to greater than 80% by weight maintains the excellent active material utilization and high rate performance of the button cell. The significance of this finding is difficult to exaggerate, as high active material loading is essential to achieving high energy density. The improvement in discharge capacity resulting from the optimization of the manganese dioxide content is shown in FIG. As can be seen, the optimized cell worked well even at high currents such as 50 mA (extremely high for button cells) at levels where the limits of the negative and button cell hardware may begin to play a role.

  A positive electrode density of 2.5-3.0 g / cc is sufficient to obtain high energy density. High rate performance under these conditions may be limited by the zinc foil anode rather than the cathode. Zinc anodes with improved surface area to replace zinc foil show improved performance.

  Optimize zinc and anode polymer content, optimize zinc type and particle size, and improve ZnO and other functional additives (like manganese salts) to improve anode rate capacity and extend cycle life Improve the negative electrode by reducing zinc passivation and corrosion. The combined effect of higher zinc surface area and improved stability results in improved performance at high discharge rates and extended cycle life. Furthermore, it has been found that embedding zinc particles in a polymer matrix prevents shape change, aggregation and dendritic growth.

Comparable to or beyond current state-of-the-art Li-ion systems in energy / power density, show> 85% capacity retention in 15C discharge; safe to operate at 80-100 ° C; and A battery with a minimum life of 500 cycles was produced. These Zn / MnO ₂ battery pack (packs) does not require complex battery management and charge control circuit, reduction of profit and cost of additional energy density at the level of the pack is expected.

Example 1
A solid polymer electrolyte was prepared by mixing the PPS base polymer and the ion source compound LiOH monohydrate at a ratio of 67% to 33% (by weight), respectively, and mixing using jet milling. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS. The mixture was heat treated at 325/250 ° C. for 30 minutes under mild pressure (500-1000 PSI). After cooling, the resulting material was pulverized and placed in an NMR fixture.

The self-diffusion coefficient was determined by use of pulsed field gradient solid state NMR technique. The results shown in FIGS. 19 and 20, respectively in the solid polymer electrolyte Li ⁺ and OH ^- is the highest spreading factor among any known solid, Li recently developed in a much more high temperature (140 ° C.) It shows high by more than one digit at room temperature compared to ₁₀ GeP ₂ S ₁₂ ceramic or the best PEO formulation at 90 ° C.

Example 2
The PPS base polymer and the ion source compound LiOH monohydrate were added together at a ratio of 67% by weight to 33% by weight, respectively, and mixed using jet milling. It was prepared positive electrode by further mixing the β-MnO _2, 5% of Bi ₂ O ₃ and 15% of the C45 carbon black from 50% Alfa Aesar. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 PSI), a 1-inch diameter, positive disk about 0.15 mm thick Gave. The resulting disc was punched to a diameter of 19 mm and used as a positive electrode to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn foil negative electrode. 6M LiOH was added as an electrolyte.

The cell was discharged under constant current conditions of 0.5 mA / cm ² using a Biologic VSP test system. The specific capacity of MnO ₂ was 303 mAh / g, or close to the theoretical 1e ⁻ discharge. Figure 21 shows a voltage distribution of the batteries according to Example 2 as a function of the specific capacity of the MnO ₂ in the discharge rate of 0.5 mA / cm ^2.

Example 3
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. It was prepared positive electrode by further mixing the β-MnO _2, 5% of Bi ₂ O ₃ and 15% of the C45 carbon black from 50% Alfa Aesar. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, 1.6-1.8 mm thick A positive disc was provided.

  The resulting positive electrode was used to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn negative electrode slurry extracted from a commercially available alkaline battery. A 6 M KOH solution in water was used as the electrolyte.

The cells were discharged under constant current conditions using a Biologic VSP test system. The specific capacity of MnO ₂ was close to 600 mAh / g at C / 9 discharge rate (35 mA / g) or close to the theoretical 2e ⁻ discharge.

FIG. 22 shows the voltage distribution of the cell according to Example 3 as a function of the specific capacity of MnO ₂ at C / 9 rate (35 mA / g).

Example 4
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. It was prepared positive electrode by further mixing the β-MnO _2, 5% of Bi ₂ O ₃ and 15% of the C45 carbon black from 50% Alfa Aesar. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 PSI), a 1-inch diameter, positive disk about 0.15 mm thick Gave.

  The resulting disc was punched to a diameter of 19 mm and used as a positive electrode to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn foil negative electrode. 6M LiOH was added as an electrolyte.

The cells were discharged and charged using the Biologic VSP test system. Discharge was performed to a cut-off of 0.8 V at a current of 0.5 mA / cm ² . In 0.25 mA / cm ² was charged to 1.65V, then 3 hours 1.65V, or current is held until the decline in 0.02 mA / cm ^2. The passivated Zn anode and separator were replaced with new ones every few cycles. The specific capacity of MnO ₂ as a function of cycle number in the cell according to Example 4 is plotted in FIG. Each column represents a separate battery. Only discharge using a new Zn anode is shown. It is easy to see that the MnO ₂ cathode of the present invention is rechargeable. Only discharge using a new Zn anode is shown.

Example 5
A 2035 button battery was assembled using the solid polymer electrolyte of Example 1 and the Zn foil as the positive electrode and the negative electrode of Example 2. The cells were discharged and charged using the Biologic VSP test system. Discharge was performed to a cut-off of 0.8 V at a current of 0.25 mA / cm ² . In 0.25 mA / cm ² was charged to 1.65V, then 3 hours 1.65V, or current is held until the decline in 0.02 mA / cm ^2. The battery showed reversible behavior during such cycling. FIG. 24 shows the discharge curve of the button cell according to Example 5 as a function of test time.

Example 6
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further provide a positive electrode by mixing C45 carbon black beta-MnO ₂ and 15% from 55% of Alfa Aesar. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, about 0.15 mm thick positive electrode disc Gave.

Using the resulting positive electrode, the electrolyte according to Example 1 and a negative electrode made of Zn powder, a test cell was assembled. The cell was discharged to 0.8 V cut-off at a current density of 0.5 mA / cm ² using a Biologic VSP test system. The specific capacity of MnO ₂ was higher than 401 mAh / g or the theoretical 1-electron discharge. FIG. 25 shows the voltage distribution of the cell according to Example 6 as a function of test time.

Example 7
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further, a negative electrode was manufactured by mixing 60% of Zn powder and 10% of C45 carbon black. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, about 0.15 mm thick positive electrode disc Gave.

  A 2035 button battery was assembled using the resulting negative electrode, a positive electrode according to Example 2, and a commercially available NKK separator containing saturated LiOH as the electrolyte.

  A control button cell was made using a Zn foil as the negative electrode, a positive electrode according to Example 2 and a commercial NKK separator containing saturated LiOH as the electrolyte.

The cell was discharged at a current density of 0.5 mA / cm ² using a Biologic VSP test system. The discharge distribution using the negative electrode of the present invention shows higher capacity at slightly higher voltages, which can be related to the increased surface area of the Zn negative electrode and the retention of soluble zincate within the negative electrode structure. FIG. 26 shows the discharge curve of the button cell according to Example 7 as a function of discharge capacity. Discharge was performed to a 0.7 V cut-off at a current of 0.25 mA / cm ² . Curve A-A battery using the negative electrode of the present invention. A battery using a curved B-Zn foil negative electrode. FIG. 26 shows the discharge curve of the button cell according to Example 7 as a function of discharge capacity. Discharge was performed to a 0.7 V cut-off at a current of 0.25 mA / cm ² . Curve A-A battery using the negative electrode of the present invention. A battery using a curved B-Zn foil negative electrode.

Example 8
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further, a negative electrode was manufactured by mixing 60% Al powder and 10% C45 carbon black. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS. The mixture is compression molded onto stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, about 0.15 mm thick positive electrode disc Gave.

The resulting negative electrode was tested in a test cell containing a commercially available separator containing a Zn counter electrode and a ZnSO ₄ electrolyte. The negative electrode made of Al foil was tested as a control.

The negative electrode was electrokintically polarized at a sweep rate of 1 mV / sec using a Biologic VSP test system. FIG. 27 shows a potentiodynamic scan at 1 mV / sec of the inventive negative electrode (curve A) and a control Al foil (curve B) in ZnSO ₄ electrolyte. The negative electrode of the present invention exhibited a 0.5 V improved corrosion stability as compared to the Al foil.

Comparative Example 9
The discharge distribution at 250 mA discharge of Duracell Coppertop AA cells was obtained from the data sheet. The amount of MnO _{2 in} the cell was calculated by comparison of the published specification and the MSDS to give 8.4 to 9.6 g. A simple conversion yields a current density of 26-30 mA / g. The product of the working time (according to the data sheet) and the discharge current gives the total capacity which can be converted to a specific capacity by dividing it by the weight of MnO ₂ . The voltage distribution of the Coppertop AA cell as a function of the relative MnO ₂ capacity calculated in such a way is shown in FIG. Curve A corresponds to the maximum amount of MnO ₂ (9.6 g), where the specific capacity of the Duracell Coppertop AA cell is under constant current discharge at a 26 mA / g rate. Curve B corresponds to the minimum amount of MnO ₂ (8.4 g), where the specific capacity of the Duracell Coppertop AA cell is under constant current discharge at a rate of 30 mA / g. Curve C shows the specific capacity of a Duracell Coppertop AA cell under a constant current discharge rate of 2.2 mA / g. It is easy to understand that the specific capacity of MnO ₂ calculated to 0.9 V cut-off is 235-270 mAh / g. Extrapolation to a 0.8 V cut-off will yield a slightly higher specific capacity of 245-275 mAh / g. The discharge curve has the typical sloped shape characteristic of Zn / MnO ₂ cells. The difference between the voltage at 5% depth of discharge and the voltage at 95% depth of discharge is 0.5 V or close to 30% of the initial (5% DOD) [2.1-2.4 V / Ah / g]. 2.2 mA / g (MnO in the battery
Coppertop cells discharging at extremely low rates (assuming an average amount of ₂ ) result in the appearance of an additional plateau (curve C). The total specific capacity was 347 mA / g, corresponding to 1.13 electron discharge. Even so, the discharge curve has a typical sloped shape with a voltage difference close to 0.5 V between the 5% depth of discharge and the 95% depth of discharge.

Comparative Example 10
AA batteries were purchased at a retail store and subjected to 250 mA discharge equivalent to mid-rate testing using a Maccor 4300 system. Table 10.1 shows the performance of commercial AA cells under continuous discharge at 250 mA. The total volume delivered by 0.9 V cut-off is shown in Table 10.1. Assuming that the amount of MnO _{2 in} the cell is the same as Comparative Example 9, the total capacity of the cell can be converted to the specific capacity of MnO ₂ . As can be seen, commercial AA batteries deliver 200-280 mAh / g under these discharge conditions. Even taking into account the positive effects of intermittent discharges and the extension of the voltage cut-off to 0.8 V, commercial alkaline batteries are described by the formula (1) and one of MnO ₂ is limited to 308 mAh / g -It is a valid theory to work within electronic reduction.

Comparative Example 11 (according to US Pat. No. 7,972,726)
FIG. 29 shows a 1: 9 AgBiO ₃ : EMD mixture reproduced from AgBiO ₃ cathode (curve (a)), EMD (MnO ₂ ) cathode (curve (b)) and US Pat. No. 7,972,726 Figure 7 shows the discharge curve at a discharge rate of 10 mA / g for an alkaline button cell with a positive electrode based on (curve (c)). Under these conditions, the discharge distribution for EMD (b) was compared to the commercial alkaline cell described in Comparative Example 9 with a 0.5 V difference between the voltage at 5% DOD and the voltage at 95% DOD. It is similar. An MnO ₂ capacity of about 290 mAh / g is consistent with a 1-electron discharge. The positive electrode produced with the AgBiO ₃ : EMD mixture exhibits an additional plateau at about 0.9 V and boosts the MnO ₂ capacity. 1: 9 AgBiO _3: using EMD mixture best performance is reported, it is 0.8V cut - was delivered 351mAh / g up off. This corresponds to the 1.13 electron discharge of MnO ₂ .

Example 12
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. It was prepared positive electrode by further mixing the β-MnO _2, 5% of Bi ₂ O ₃ and 15% of the C45 carbon black from 50% Alfa Aesar. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, 1.6-1.8 mm thick A positive disc was provided.

  The resulting positive electrode was used to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn negative electrode slurry extracted from a commercially available alkaline battery. A 6 M KOH solution in water was used as the electrolyte.

The cells were discharged under constant current conditions using a Biologic VSP test system. FIG. 30 shows the voltage distribution at a constant current discharge of 35 mA / g of the cell according to Example 12 as a function of the specific capacity of MnO ₂ . The discharge distribution shown in FIG. 30 looks significantly flatter as compared to the conventional Zn / MnO ₂ cell. The voltage difference between 5% DOD and 95% DOD is about 0.1 V or less than the initial 10%. The specific capacity of MnO ₂ was close to 600 mAh / g or 97% of the theoretical 2-electron discharge (616 mAh / g).

Example 13
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further, a positive electrode was prepared by mixing 50% of EMD (a mixture of γ- and ε-MnO ₂ ) from Tronox, 5% of Bi ₂ O ₃ and 15% of C 45 carbon black. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), [inclusive] diameter, 1.6 to 1 thick A positive disc of .8 mm was provided.

  The resulting positive electrode was used to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn negative electrode slurry extracted from a commercially available alkaline battery. A 6 M KOH solution in water was used as the electrolyte.

The cells were discharged under constant current conditions using a Biologic VSP test system. FIG. 31 shows the voltage distribution of the cell according to Example 13 as a function of the specific capacity of MnO ₂ at 29 mA / g (curve A) and 59 mA / g (curve B). The specific capacity of MnO ₂ was close to 600 mAh / g at a rate of 29 mA / g and close to 560 mAh / g at a rate of 59 mA / g.

Example 14
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further, a positive electrode was manufactured by mixing 80% of EMD (a mixture of γ- and ε-MnO ₂ ) from Tronox, 5% of C45 carbon black. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, 1.6-1.8 mm thick A positive disc was provided.

  The resulting positive electrode was used to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn negative electrode slurry extracted from a commercially available alkaline battery. A 7 M KOH solution in water was used as the electrolyte.

The cell was discharged under constant current conditions at a rate of 9 mA / g using a Biologic VSP test system. The specific capacity of MnO ₂ was 590 mAh / g. FIG. 32 shows the voltage distribution (curve A) at a discharge rate of 9 mA / g of the battery according to Example 14 as a function of the specific capacity of MnO ₂ and the voltage distribution (curve B) at 2.2 mA / g of a Duracell Coppertop battery. Show. The voltage difference between 5% DOD and 95% DOD was 0.163 V or 13.6% (curve A). The discharge distribution for a Duracell Coppertop cell at 2.2 mA / g is shown for comparison (curve B).

Example 15
PPS base polymer and ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. Further, a positive electrode was manufactured by mixing 80% of EMD (a mixture of γ- and ε-MnO ₂ ) from Erachem, 5% of C45 carbon black. To the resulting mixture was added DDQ dopant in an amount of 1 mole DDQ per 4.2 moles PPS.

  The mixture is compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 325/250 ° C. under mild pressure (500-1000 psi), 1 inch in diameter, 1.6-1.8 mm thick A positive disc was provided.

  The resulting positive electrode was used to assemble a test battery containing a commercially available non-woven separator (NKK) and a Zn negative electrode slurry extracted from a commercially available alkaline battery. A 7 M KOH solution in water was used as the electrolyte.

The cell was discharged under constant current conditions at a rate of 9.5 mA / g using a Biologic VSP test system. The specific capacity of MnO ₂ was 541 mAh / g. FIG. 33 shows that the voltage difference between 5% DOD and 95% DOD was 0.180 V or 14.1% (curve A). The discharge distribution for a Duracell Coppertop cell at 2.2 mA / g is shown for comparison (curve B).

Example 16
The PPS base polymer and the ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (weight / weight), respectively, and mixed using jet milling. The mixture was compression molded at 325 ° C./250° C. for 30 minutes under low pressure. Furthermore, a polymer-sulfur composite positive electrode is obtained by mixing together 25% to 50% sulfur powder, 5% to 15% C45 carbon black and 0% to 10% LiNO ₃ together with a solid ion conductive polymer material Manufactured. The material was compression molded onto a stainless steel mesh (Dexmet) for 30 minutes at 120 ° C. to give a positive electrode disc 15 mm in diameter and 0.3-0.4 mm thick.

The resulting positive electrode was used to assemble a test cell in 2035 button cell hardware. A 25 mm thick, 19 mm diameter polypropylene separator (Celgard) was used with a 15 mm diameter lithium foil negative electrode material. Zero liquid electrolyte of 1 M LiTFSI salt dissolved in a 50/50 (vol / vol) mixture of DOL / DME
. Used together with 5 M LiNO ₃ additive. The cell was assembled in a glove box filled with argon gas with low levels of oxygen and water. The battery was discharged under constant current conditions (1 mA) using a Maccor 4600 battery test system. The discharge was stopped at a voltage of 1.75V.

  FIG. 34 shows a first discharge voltage curve for the Li / composite polymer-sulfur positive electrode in the battery of the present invention. The discharge voltage distribution for the first cycle is shown in FIG. It can be seen that the composite polymer-sulfur positive electrode provides high initial capacities of> 1300 mAh / g based on the amount of sulfur in the positive electrode. The cell in FIG. 34 also shows a discharge voltage curve with two plateaus at -2.3V and -2.1V. This shows that the composite polymer-sulfur system enables high capacity while providing the voltage curve expected for the lithium / sulfur system consistent with the stable electrochemical pair.

Example 17
A composite polymer-sulfur positive electrode was prepared as described in Example 16. These positive electrodes were assembled into button cells using 1 M LiTFSI in DOL / DME electrolyte with lithium metal negative electrode, polypropylene separator and 0.5 M LiNO ₃ additive. The battery was discharged under constant current conditions (1 mA) using a Maccor 4600 battery test system. The discharge was stopped at a voltage of 1.75V. Charge in two stages: first stage at a relatively low charge rate of 0.2 mA current to a maximum voltage of 2.3 V and second charge stage at a relatively high rate of 1 mA current to a maximum voltage of 2.45 V The The overall charge capacity was limited for these test cells. The cells were cycled several times at room temperature.

  FIG. 35 shows discharge capacity curves plotted as a function of cycle number for the Li / composite polymer-sulfur cells of the present invention. This graph shows that the composite polymer-sulfur positive electrode will support reversible charge / discharge with a high reversible capacity of at least 1000 mAh / g based on the amount of sulfur in the positive electrode.

Comparative Example 18
Notable examples of highly ordered organized composite electrodes are given in the literature [Ji, X. et al. Lee, K .; T. Nazar, L .; F. Nature Materials 8, 500-506, 2009]. This composite positive electrode uses CMK-3 mesoporous carbon with sulfur entrenched in the pores via heat treatment at 155 ° C. FIG. 36 compares the first discharge for Li / sulfur-CMK-3 of the literature example with the first discharge for Li / composite polymer-sulfur of the present invention.

The composite positive electrode in this example was slurry cast from cyclopentanone onto a carbon coated aluminum current collector. The positive electrode used 84 wt% of CMK-3 / S composite, 8 wt% of Super-S carbon and 8 wt% of PVDF binder. The electrolyte consists of LiPF ₆ in 1.2M in ethyl methyl sulfone was used metallic Li as an anode. The results for the inventive composite polymer-sulfur cathode described in Example 16 were plotted on the same graph in the comparison. It is apparent that the composite polymer-sulfur cathode of the present invention gives superior results than the examples of the superior or composite sulfur cathode literature.

Comparative Example 19
The use of sulfur-conductive polymer composites as a positive electrode for lithium batteries is shown. In one case, polyacrylonitrile (PAN) is sulfided to form a conductive and chemically active positive electrode material. Polymer sulfurization occurs at relatively high temperatures of -300 ° C. US Patent Application No. 2014/0045059 [He, X., et al. -M. , Et al. An example of the discharge curve for this material as shown in FIG. FIG. 37 shows the signature signatures of typical voltages found for Li / sulfur-polyacrylonitrile (S / PAN) cells. These cells are characterized by one ramped voltage plateau and have an average voltage below 2.0V. In comparison with the voltage curve observed in FIG. 4 for the Li / composite polymer-sulfur cathode in the cell of the invention, it can be seen that the S / PAN cell exhibits significantly lower voltage throughout the discharge, which is wattage Producing lower energy densities on a timely basis. Thus, the voltage behavior exhibited by the composite polymer-sulfur positive electrode of the present invention is superior to that of the positive electrode based on sulfurized PAN.

Example 20
Solid SRT 802 (Liquid Crystal Polymer) polymer is mixed with lithium hydroxide monohydrate as a compound comprising an ion source at a ratio of 2: 1 (by weight), respectively. Molecular electrolyte samples were prepared. DDQ was used as a dopant. The weight ratio of polymer to dopant was 2: 1. The mixture was heat treated at 325/250 ° C. for 30 minutes under mild pressure (500-1000 PSI). The ionic surface conductivity of the sample was measured using a standard AC-EIS. The sample was sandwiched between stainless steel blocking electrodes and placed in the test fixture. AC-impedance was recorded within the range of 800 KHz to 100 Hz using a Bioligic VSP test system to determine electrolyte conductivity. Six samples were prepared and tested. The average conductivity was 3.7 × 10 ⁻⁴ S / cm and the standard deviation was about 19%. The results are shown in Table 20.1 below.

Example 21
Solid high by mixing SRT 900 (Liquid Crystal Polymer) polymer with lithium hydroxide monohydrate as a compound comprising an ion source in a ratio of 2: 1 (by weight) respectively Molecular electrolyte samples were prepared. DDQ was used as a dopant. The weight ratio of polymer to dopant was 2: 1. The mixture was heat treated at 325/250 ° C. for 30 minutes under mild pressure (500-1000 psi). The sample was sandwiched between stainless steel electrodes and placed in the test fixture. AC-impedance was recorded within the range of 800 KHz to 100 Hz using a Bioligic VSP test system to determine electrolyte conductivity. Six samples were prepared and tested. The average conductivity was 1.5 × 10 ⁻³ S / cm, with a standard deviation of about 25%. The results are shown in Table 21.1 below.

Example 22
A polymer electrolyte sample was prepared by mixing the polymer and the compound containing the ion source in various proportions. DDQ was used as a dopant. The molar ratio of polymer to dopant was 4.2. The mixture was heat treated at 325/250 ° C. for 30 minutes under mild pressure (500-1000 psi). The sample was sandwiched between stainless steel electrodes and placed in the test fixture. AC-impedance was recorded within the range of 800 KHz to 100 Hz using a Bioligic VSP test system to determine electrolyte conductivity.

The results are shown in the following table. High conductivity is observed, ⁺ polymer electrolyte ^{Li, K +, Na +,} Ca 2+, Mg 2+, Al 3+, OH - and Cl ^- that can conduct a large number of ions including Suggest.

The ability to conduct ions other than Li ⁺ opens new applications for polyelectrolytes. Energy storage systems based on sodium and potassium are expected as an alternative to Li-ions, driven mainly by the low cost and relative abundance of raw materials.

  Calcium, magnesium and aluminum conductivity are important in the development of multivalent intercalation systems that can improve energy density, perhaps beyond the capacity of Li-ion batteries. There is also the possibility of using such materials to make power sources using metal anodes that are more stable and cheaper than lithium.

Hydroxyl conductivity _is critical Zn / MnO 2, Ni / Zn , Ni-Cd, Ni-MH, Zn- air, for chemical numerous alkali containing Al- air. Polyelectrolytes that conduct hydroxyl ions can also be used in alkaline fuel cells and supercapacitors.

Example 23
Solid ion conductive polymer material:
The polyphenylene sulfide "PPS" (base polymer) and the tetrachloro-1,4-benzoquinone "chloranil" are mixed and heated to form a solid intermediate polymer material, which when mixed with a compound containing an ion source, solid ion conduction Producing a high molecular weight material. The compound contains 10-50% by weight of the base polymer. The heating step raises the temperature of the reaction to 250-350 ° C. and takes about 10 minutes to 8 hours to overnight. In one aspect, a solid ion conducting polymeric material or an intermediate thereof or a reactant thereof is mixed with an additive (e.g., electrically conductive carbon) to be also ion conductive and functional attributes of the additive (e.g., electricity) Composite materials that also provide conductivity) can be formed.

Zn negative electrode:
Solid intermediate polymeric material, lithium hydroxide, conductive carbon, zinc powder (pure powder or zinc powder alloyed with bismuth, indium, calcium, aluminum and other alloying agents known in the art) Additives (e.g. C45 or KS6L graphite by Tincal, EC600 from Akzo Nobel, high surface area carbon etc), additives zinc oxide and / or other corrosion resistant additives. PVDF or Kynar PVDF is used as binder and NMP is used as solvent. A mixer (e.g. Thinky) can be used, and if used for mixing, the mixture is mixed until a uniform slurry is obtained (e.g. 10-30 minutes at 2000 rpm). The slurry is then cast by the doctor blade method onto a current collector (stainless steel, titanium or nickel foil) precoated with a thin layer of graphite primer. The electrodes are then dried at 80-120 ° C. for 2-12 hours, rolled and sliced to the desired dimensions for button cells or pouch cells.

MnO ₂ positive electrode:
EMD MnO ₂ powder is mixed with conductive additives (eg C45, KS6L graphite, EC 600 high surface area carbon etc), solid intermediate polymeric material and ionic compound lithium hydroxide. PVDF (polyvinylidene fluoride) or Kynar PVDF is used as binder and NMP (N-methyl-2-pyrrolidone) is used as solvent. The mixture is mixed using a Thinky brand mixer at 2000 rpm for 10-30 minutes until a uniform slurry is obtained. The slurry is then cast by the doctor blade method onto a current collector (stainless steel, titanium or nickel foil) precoated with a thin layer of graphite primer. The electrodes are then dried at 80-120 ° C. for 2-12 hours, rolled and sliced to the desired dimensions for button cells or pouch cells. Overall the solid ion conducting polymeric material comprises about 2-30% by weight of the total positive electrode weight, the activity (in this case EMD) is 20-80% by weight, and carbon is about 3-30% by weight , And liquid electrolyte

Electrolytes:
Various electrolytes can be used. In one aspect, the electrolyte formulation is an aqueous solution containing 36 wt% potassium hydroxide with zinc oxide as an additive. In one aspect, a 1-3 molar zinc sulfate salt is used in which 0.5-4 wt% of manganese sulfate (or other Mn (ii) salt) is added. These aqueous electrolytes can be added to 0.5-2% by weight of gelling agents such as poly (ethylene glycol) di-acid (or other gelling agents known in the art). In one aspect, a solid ion conducting polymeric material is used as the electrolyte, a separator is not necessary, and a small amount of KOH solution or other liquid electrolyte solution can optionally be added to the negative electrode or positive electrode.

Battery structure:
CR2032 button cells, bobbin type cylindrical cells and single layer and multilayer pouch type cells have all been manufactured using the same combination of positive and negative electrodes. The assembly steps of the battery are the same as those commonly used in the industry, including electrode slurry, closing, crimping. Using a button cell as an example, sandwich the positive and negative electrodes between the layers of the non-woven separator impregnated with the zinc sulfate liquid electrolyte described above. FIG. 41 shows a typical charge-discharge profile of a rechargeable Zn-MnO ₂ cell in the CR2032 button cell type.

  Although this structure is described as a secondary battery, it has also been found to be useful as a primary battery.

  Referring to Table 23.1, a number of structures using solid ion conducting polymeric materials are shown. Primary structures, three (1-3) secondary alkaline structures including solid-state blends and zinc air structures are mentioned.

  Secondary formulation (1) corresponds to FIG. 41 and the related discussion.

  Secondary formulation (2) corresponds to Figures 38-40 and the related discussion. Liquid potassium hydroxide electrolyte was added. The positive and negative electrode fabrication methods do not involve the use of mechanical mixers or slurry casting. The negative and positive electrodes do not contain a binder (no PVDF) and do not require an MNP solvent.

  While the present invention has been described in connection with the preferred embodiments, one of ordinary skill in the art, after reading the foregoing specification, will make various changes, substitutions of equivalents, and other modifications to those shown herein. You will get. Accordingly, the protection conferred by the patent on this specification is intended to be limited only by the definitions contained in the appended claims and their equivalents.

Claims (20)

An electrochemical cell for producing electrical energy via an electrochemical reaction comprising a negative electrode and a positive electrode, comprising:
At least one of the negative electrode and the positive electrode comprises a solid ion conducting polymeric material;
The battery, wherein said solid ion conducting polymeric material is capable of ionically conducting hydroxyl ions, whereby said solid ion conducting polymeric material is capable of conducting hydroxyl ions during said electrochemical reaction.   The battery of claim 1, wherein the positive electrode is capable of providing hydroxyl ions during an electrochemical reaction. The battery of claim 1, wherein the solid ion conducting polymeric material has a crystallinity of at least about 30% or higher. The solid ion conductive polymer material comprises at least one hydroxyl ions, with a 10 ^-11 larger OH- diffusivity at a temperature in the range of 20 ° C. ~ 26 ° C., cell of claim 1.   The battery of claim 1, wherein the positive electrode comprises an active material that produces hydroxyl ions during an electrochemical reaction.   The negative electrode includes a solid ion conductive polymer material, and further includes a negative electrode electrochemical active material, and the solid ion conductive polymer material and the negative electrode electrochemical active material are mixed, whereby the solid ion conductivity is performed. The battery of claim 1, wherein the polymeric material is capable of ionically conducting hydroxyl ions to the negative electrode electrochemically active material.   The positive electrode comprises a solid ion conducting polymeric material and further comprises a positive electrode electrochemical active material, wherein the solid ion conducting polymeric material and the positive electrode electrochemical active material are mixed, whereby the solid ion conducting The battery of claim 1, wherein the polymeric material is capable of ionically conducting hydroxyl ions to the positive electrode electrochemically active material.   7. The battery of claim 6, wherein at least a portion of said solid ion conducting polymeric material is in contact with said negative electrode electrochemically active material.   8. The battery of claim 7, wherein at least a portion of said solid ion conducting polymeric material is in contact with said positive electrode electrochemically active material.   The battery of claim 1, wherein the positive electrode comprises manganese dioxide and the battery has a specific capacity of greater than 308 mAh per gram of manganese dioxide.   The battery of claim 1, wherein said solid ion conducting polymeric material is sandwiched between said negative electrode and positive electrode, whereby the solid ion conducting polymeric material conducts hydroxyl ions between said negative electrode and positive electrode. .   The battery of claim 1, wherein the positive electrode comprises a solid ion conducting polymeric material, and the amount of the solid ion conducting polymeric material is in the range of 1 to 40 weight percent of the positive electrode.   The battery of claim 1, wherein the battery is rechargeable, the positive electrode comprises manganese dioxide, and the amount of manganese dioxide is in the range of 20 to 90 weight percent of the positive electrode.   The battery of claim 1, wherein the battery is a primary battery, the positive electrode comprises manganese dioxide, and the amount of manganese dioxide is in the range of 50 to 95 weight percent of the positive electrode.   The battery of claim 1, wherein the battery further comprises a liquid electrolyte, wherein the liquid electrolyte comprises hydroxyl ions.   Both the negative electrode and the positive electrode contain solid ion conducting polymer material, the battery is in solid state and does not contain any liquid electrolyte, whereby the ion conductivity of the battery is the solid ion conducting polymer The battery of claim 1 enabled through the material.   The battery of claim 1, wherein the negative electrode comprises zinc, the positive electrode comprises manganese dioxide, and the battery is a primary battery.   The battery of claim 1, wherein the negative electrode comprises zinc, the positive electrode comprises manganese dioxide, and the battery is a secondary battery.   The battery of claim 1, wherein the negative electrode comprises aluminum, the positive electrode comprises manganese dioxide, and the battery is a primary battery.   The battery of claim 1, wherein the negative electrode comprises zinc and the positive electrode is fluidly coupled with oxygen such that the oxygen acts as a positive electrode electrochemically active material.

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