JP7071289B2 - Electrochemical battery with solid ion conductive polymer material - Google Patents

Description

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

Federally funded R & D description (not applicable)

Background of the Invention In modern society, batteries are becoming more and more important both in supplying power to a large number of portable electronic devices and as an important component in new environmental protection technologies. These new technologies promise to remove reliance on current energy sources such as coal, petroleum products and natural gas, which contribute to the generation of by-products greenhouse gases. In addition, the capacity of energy storage in both fixed and mobile applications is critical to the success of new energy sources, and the demand for advanced batteries of all dimensions appears to increase rapidly. Especially for batteries for large applications, the low baseline cost of the battery will be important for the introduction and overall success of these applications.

However, ordinary batteries have limitations. For example, lithium ions and other batteries generally use liquid electrolytes, which are dangerous to humans and the environment and can cause fires or explosions. The liquid electrolyte battery is sealed in steel or other strong packaging material, which increases the weight and bulk of the packaged battery. Normal liquid electrolytes suffer from the deposition of solid interface layers at the electrode / electrolyte interface, which results in damage to the battery. Normal lithium-ion batteries also show slow charge times and suffer from a limited number of recharges, which are that the chemical reaction in the battery has reached completion and can be recharged due to corrosion and dendritic formation. This 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 4.8 volts and higher voltages. Normal lithium-ion batteries minimize liquid electrolyte separators that allow ion flow but block electron flow, vents to relieve pressure in the housing, and even more dangerous overcurrents and excess temperatures. Requires safety circuit components to do so.

For alkaline batteries that rely on the transport of OH ^- ions for electrical conduction, at some point the electrolyte is saturated with ions (eg, zincate ions during the discharge of the Zn / MnO ₂ battery), resulting in a negative electrode of water. Is exhausted. In rechargeable alkaline batteries, the reaction reverses during charging. However, the production of the same ions that saturate the electrolyte can interfere with the discharge. The positive electrode reaction results in the release of OH ^- ions. However, the formation of soluble low valence species (eg Mn species during discharge of a Zn / MnO ₂ battery) can adversely affect the utilization of the active material. MnO ₂ theoretically experienced two-electron reduction and could have a theoretical capacity of 616 mAh / g, but in practice did not show a specific capacity close to the theoretical two-electron discharge. Crystal structure rearrangement with the formation of the inert phase and the outward diffusion of soluble products limits the positive electrode capacity.

Patent Document 1 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 compared to 287 mAh / g for 100% MnO ₂ and 200 mAh / g for 100% AgBio ₃ . Was shown to deliver 351 mAh / g up to a cut-off voltage of 0.8 V. The specific volume of 351 mAh / g corresponds to the 1.13 electron discharge of MnO ₂ , which corresponds to the highest specific volume delivered in a practically useful discharge rate and voltage range. It was claimed that the bismuth-or lead-modified MnO ₂ materials disclosed in Patent Documents 2 and 3 can deliver about 80% of the theoretical two-electron discharge capacity for many cycles. In the literature [Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3], bismuth or lead cation can stabilize the crystal structure of MnO ₂ during discharge and / or soluble Mn ²⁺ species. It was theorized to allow two-electron reduction to proceed through a non-uniform mechanism containing. The inclusion of the Mn ²⁺ species appears to be important for obtaining high MnO ₂ utilization and reversibility. In the high carbon content (30-70%) positive electrodes according to Patent Documents 2 and 3, the highly porous structure obtained was able to absorb soluble seeds. However, there is no data to suggest that a complete battery utilizing these positive electrodes was constructed or that it worked with a Zn negative electrode.

Therefore, 1) the dissolution of ions that would saturate the electrolyte if not dissolved and 2) the high molecular weight electrolyte that interferes with the dissolution and transport of low valence species can improve the utilization and rechargeability of alkaline batteries. There will be. Furthermore, it has been suggested that insertion of Li stabilizes the MnO ₂ structure during reduction and enables rechargeability [Non-Patent Document 4]. Polymers designed to conduct Li ⁺ and OH ^- ions open the possibility of adjusting 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, battery technology for many advanced applications is lithium ion (Li ^- ion), but energy density per volume (Wh / L) for portable devices and for electric vehicles and other large applications. The increased demand for higher energy densities, both in terms of energy density per weight (Wh / kg), has indicated the need to approach technologies well beyond the current potential of Li ^- ion batteries. One such promising technique is Li / sulfur batteries. Sulfur-based positive electrodes are attractive due to 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 is attractive because it is very rich, low cost and environmentally friendly, unlike many current Li ^- ion battery materials such as LiCoO ₂ .

In recent years, there has been much activity in Li / Sulfur battery research, with advances in the capacity and cycle life of rechargeable Li / Sulfur batteries. Activities included modifications to the positive, negative, electrolytes and separators, all aimed at reducing polysulfide round trips, thereby improving battery performance. The application of this study to sulfur positives has two main areas: 1) Use of materials designed to enclose and contain sulfur and soluble lithium products, eg: See Patent Document 4, and 2 ) Focused on the use of conductive polymers that react with sulfur to give a "sulfurized" composite positive electrode material. Examples of "polymer sulfides" include reaction products from high temperature exposure to sulfur with polyacrylonitrile (PAN) [see Non-Patent Documents 5 and 6]. Other conductive polymer systems used in sulfur positives include polyvinylpyrrolidone (PVP) [see Non-Patent Document 7] and polypyrrole (PPY) [see Non-Patent Document 8]. These methods have experienced varying degrees of success in limiting the polysulfide shuttle mechanism, but they all rely on the use of expensive materials that are not well suited for large-scale production.

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

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

Provided are solid ion conductive polymer materials having very high ion diffusivity and conductivity at room temperature and over a wide temperature range. The solid ionic polymer material is useful as a solid electrolyte for alkaline batteries and also as a component for manufacturing electrodes for alkaline batteries. The material is not limited to battery applications and is more widely applicable for other purposes such as alkaline fuel cells, electric double layer capacitors, electrochromic devices, sensors and the like. Polymeric materials are flame-retardant and self-extinguishing, which makes them particularly attractive for applications that could otherwise be flammable. In addition, the materials are mechanically strong and may themselves be manufactured using high molecular weight polymer treatment methods and equipment known in the art.

In one aspect of the invention, the solid ion conductive polymer material acts as an electrolyte for transmitting OH ^- ions in alkaline batteries. Alkaline batteries include, but are not limited to, Zn / MnO ₂ , Zn / Ni, FE / NI, Zn / air, Ni / metal hydrides, silver oxide, metals / air and others known in the art. Battery chemistry can be included. Zinc / manganese oxide (Zn / MnNO ₂ ) chemistry is most widely used for household alkaline batteries.

Solid ionic polymer electrolytes for lithium ion batteries containing solid ionic conductive polymeric materials are disclosed in Co-pending US Patent Application No. 13 / 861,170, filed April 11, 2013. , Transferred to the same transferee as the present invention.

In another aspect of the invention, solid ion conductive polymeric materials are used for the formation of positive electrodes, electrolytes and negative electrodes in alkaline batteries. The three layers of the battery are solid and may be extruded simultaneously to effectively form the battery structure. The individual layers can be individually extruded or otherwise formed and layered together to form a battery structure, or can be done instead.

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

Solid ion conductive polymer materials show 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 electron acceptors show chemical shift peaks at about 195 ppm and 107.6 ppm in addition to 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 basic macromolecule and the electron acceptor appears to eliminate the 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 conductive polymer in the transfer from the basic polymer to the solid ion conductive polymer. The chemical shift of the dominant peak in the solid ion conductive polymer is larger than the chemical shift of the dominant peak in the basic polymer.

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

The compound containing an ion source exists 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 1x10 ^-4 S / cm at room temperature of 20 ° C to 26 ° C.

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

The material has an OH ^- diffusion rate greater than ^10-11 cm ² / S at room temperature of 20 ° C to 26 ° C.

Batteries with OH ^- chemistry may or may not be rechargeable.

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

In one embodiment of the battery, the battery comprises a negative electrode; a positive electrode; and where at least one of the negative electrode and the positive electrode comprises a solid ion conductive polymeric material. The battery may be a rechargeable battery or a primary battery. The battery further comprises an electrolyte, which can include a solid ion conductive polymeric material. Batteries may contain additional electrolytes instead or in addition, and the electrolytes may be alkaline. It is an alkaline battery because solid ion conductive polymers can conduct multiple OH ^- ions at temperatures in the range of 20 ° C to 26 ° C and have an OH ^- diffusion rate greater than ^10-11 cm ² / sec. Especially well suited for use on electrodes.

The solid ion conductive polymer material is formed from a reactant product comprising a compound comprising a basic polymer, an electron acceptor and an ion source. A solid ion conductive polymer material may be used as an electrolyte in the negative electrode or the positive electrode. When used in a battery, the positive electrode of the battery is iron salt, iron oxide, cuprous oxide, iodine salt, cupric oxide, mercury (II) oxide, cobalt oxide, manganese oxide, lead dioxide, oxidation. Silver, oxygen, nickel oxyhydroxide, nickel dioxide, silver peroxide, permanganate, bromine salt, silver vanadium oxide, carbon monofluoride, iron disulfide, iodine, vanadium oxide, copper sulfide, sulfur or carbon and It may contain active materials selected from the group comprising combinations thereof. The negative electrode of the battery contains lithium, magnesium, aluminum, zinc, chromium, iron, nickel, tin, lead, hydrogen, copper, silver, palladium, mercury, platinum or gold and combinations thereof and alloying materials thereof. May contain active materials selected from the group.

In alkaline batteries where the positive electrode contains manganese dioxide and the negative electrode contains zinc. Manganese dioxide is β-MnO ₂ (pyrolucite), rams delite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ , electrolytic manganese dioxide (EMD) and chemical manganese dioxide. ) (CMD) and may be a combination of the above forms. Further, at least one of the negative electrode and the positive electrode may contain particles of the active material, and the solid ion conductive polymer material may enclose all of the particles of the at least one active material or the active material. Such positive electrodes showed specific volumes greater than 400 mAh / g, 450 mAh / g and 500 mAh / g.

Alternatively, the battery may contain an electrically conductive additive and / or a functional additive in the negative or 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 at least two combinations of the above 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 or positive) may have a composite structure that may be molded by methods such as injection molding, tube extrusion and compression molding. In one embodiment of the production of a solid ion conductive polymer material, the basic polymer is oxidatively doped in the presence of an ion source. The ion source is a compound that contains at least one hydroxyl group or a compound that can be converted to a compound that contains at least one hydroxyl group, or is also selected from the group consisting of LiOH, Li ₂ O or a mixture of the above two components. It is a compound. The basic polymer is selected from the group comprising liquid crystal polymers, polyetheretherketone (PEEK) and polyphenylene sulfide (PPS) or semi-crystalline polymers with a crystallinity greater than 30% and combinations thereof. Electroreceptors that react with the basic macromolecule in the presence of an ion source consist of 2,3, dichloro-5,6-dicyano-1,4-benzoquinone, TCNE, sulfur trioxide or chloranil and combinations thereof. May be selected from the group. The method may further include a heating step to facilitate the reaction. An electrochemically active material can be added to the mixing step, and if so added, it is encapsulated by the reacted ionic conductive polymer. Such batteries having an MnO ₂ positive electrode, a zinc negative electrode and an alkaline electrolyte, characterized in that the alkaline battery has a flat discharge curve higher than 1 V and a voltage drop of less than 0.3 V at a depth of 5 to 95%.

Since the solid ion conductive polymer material is electrically non-conductive and ionic conductive, it can also be useful as a separator film. Thus, a solid ion conductive polymer material cast or otherwise given as a film may be used as a separator placed between the negative and positive electrodes. In addition, solid ion conductive polymeric materials may be coated on the electrodes to act as separators or to isolate the electrodes or electrode components from other battery components such as aqueous electrolytes. Solid ionic conductive polymer materials allow ionic communication between such isolated components, even though they are physically separated from the remaining battery components and electrically separated. do. The material may also include agglomerated or cast agglomerates of small particles of solid ion conductive polymer material. Such agglomerates can take any form, but may be designed to contain porosity while preserving the designed surface area. Fillers such as hydrophobic materials may be mixed into the material to provide desirable physical properties such as low effective acute porosity. Catalysis may be added to solid ion conductive polymeric materials to allow for a combination of catalysis and ionic conductivity as required in air electrodes for metal / air batteries. Thus, solid ion conductive polymer materials may contain low or very high surface area and low or very high porosity. Shapes such as rings or other castable shapes with desirable physical properties with ionic conductivity of solid ionic conductive polymeric materials can be designed, which is made possible by the present invention.

According to one aspect, the electrochemical cell comprises a solid ion conductive polymer material, which is used in its negative electrode and / or positive electrode.

In one aspect, an electrochemical battery produces electrical energy through an electrochemical reaction involving a negative and a positive; where the solid ion conductive polymer material is capable of ionicly conducting hydroxyl ions, thereby solid. Ion-conducting polymer materials can conduct hydroxyl ions during the electrochemical reaction.

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

Solid ion conductive polymer materials have a crystallinity of at least about 30% or higher.

The solid ion conductive polymer material contains at least one hydroxyl ion and has an OH ^- diffusion rate greater than ^10-11 at temperatures in the range 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 conductive polymer material, further comprising a negative electrode electrochemically active material, wherein the solid ion conductive polymer material and the negative electrode electrochemically active material are mixed, whereby the solid ion conductive polymer material is mixed. The material can ionicly conduct hydroxyl ions to the negative electrochemically active material.

The positive electrode comprises a solid ion conductive polymer material, further comprising a positive electrode electrochemically active material, wherein the solid ion conductive polymer material and the positive electrode electrochemically active material are mixed, whereby the solid ion conductive polymer material is mixed. The material can ionicly conduct hydroxyl ions to the positive electrochemically active material.

Here, at least a part of the solid ion conductive polymer material is in contact with the negative electrode electrochemically active material.

Here, at least a part of the solid ion conductive polymer material is in contact with the positive electrode electrochemically active material.

The positive electrode contains manganese dioxide, where the battery has a specific capacity greater than 308 mAh per gram of manganese dioxide.

The solid ion conductive polymer material is located sandwiched between the negative electrode and the positive electrode, whereby the solid ion conductive polymer material conducts hydroxyl ions between the negative electrode and the positive electrode.

The positive electrode comprises a solid ion conductive polymer material, wherein the amount of the solid ion conductive polymer material is in the range of 1-40 weight percent of the positive electrode.

The battery is rechargeable, where the positive electrode contains manganese dioxide, where the amount of manganese dioxide is in the range of 20-90 weight percent of the positive electrode.

The battery is a primary cell, wherein the positive electrode contains manganese dioxide, wherein the amount of manganese dioxide is in the range of 50-95 weight percent of the positive electrode.

The battery also contains a liquid electrolyte, where the liquid electrolyte contains hydroxyl ions.

Both the negative and positive sides contain a solid ionic conductive polymer material, where the battery is in a solid state and does not contain any liquid electrolyte, whereby the ionic conductivity of the battery is a solid ionic conductive polymer material. It will be possible through.

The negative electrode contains zinc and the positive electrode contains manganese dioxide, where the battery is a primary cell.

The negative electrode contains zinc and the positive electrode contains manganese dioxide, where the battery is a secondary battery.

The negative electrode contains aluminum and the positive electrode contains manganese dioxide, where the battery is a primary cell.

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

The formulas obtained for the crystalline polymer of the present invention are exemplifiedly shown; Illustratively shown is a dynamic scanning colorimeter curve for semi-crystalline polymers; Illustratively the formulations studied for use in the present invention; Schematic representations of amorphous and crystalline polymers; Illustratively showing the structural diagram of 2,3-dicyano-5,6-dichlorodicyanoquinone (DDQ) as a typical electron acceptor dopant for use in the present invention; Illustratively shown plots of conductivity of ionic conductive polymers according to the invention in comparison with liquid electrolytes and polyethylene oxide lithium salt compounds; Illustratively show the mechanical properties of an ion conductive film according to the present invention; Illustratively show the possible mechanism of conduction of solid electrolyte polymers according to the present invention; Illustratively shown is a UL94 combustion test performed on a polymer according to the present invention; Illustratively shown is a plot of the volt vs. current of an ion-conducting polymer according to the present invention for lithium metals; Illustrative illustrations of extruded ionic conductive electrolytes and electrode components according to the present invention; Illustratively shown is a solid state battery according to the invention in which electrodes and electrolytes are bonded together; Illustratively illustrates the final solid-state battery according to the invention with novel and flexible form; Illustratively illustrates the method of the invention comprising the steps for making a solid state battery using extruded polymers; An exemplary extrusion method according to the present invention is shown; Illustrative illustrations of embodiments according to the present invention; Ilkaline batteries with the three layers of the invention are shown schematically; Illustratively shows a comparison of the process steps for the production of a standard Li-ion positive electrode and the process steps for the extrusion of the composite polymer-sulfur positive electrode of the present invention; Illustratively showing the OH-diffusion rate at room temperature in the solid polyelectrolyte of the present invention; Illustratively showing the lithium diffusion rate at room temperature in the solid polyelectrolyte of the present invention; Illustratively show the voltage distribution of the battery of the present invention according to Example 2 as a function of the specific volume of MnO ₂ at a discharge rate of 0.5 mA / cm ² . Illustratively show the voltage distribution of the battery of the invention according to Example 3 as a function of the specific volume of MnO ₂ at C / 9 rate (35 mA / g); The specific capacity of MnO ₂ as a function of the number of cycles in the battery of the present invention according to Example 4 is shown exemplary; The discharge curve of the coin cells of the present invention according to Example 5 as a function of the test time is shown exemplary; Illustratively show the voltage distribution of the battery of the present invention according to Example 6 as a function of test time; The discharge curve of the button cell of the present invention according to Example 7 as a function of the discharge capacity is shown exemplary; An exemplary potentiodynamic scan of the negative electrode (curve A) and control standard Al foil (curve B) of the present invention in a ZnSO ₄ electrolyte at 1 mV / s is shown. Use Zn foil as the counter electrode; Shows the specific capacity of Duracell Coppertop AA batteries under various constant current discharge rates; The discharge curve for alkaline coin cell batteries at a rate of 10 mA / g according to the prior art is shown; The voltage distribution of the battery of the present invention according to Comparative Example 12 in a constant current discharge of 35 mA / g as a function of the specific capacity of MnO ₂ is exemplifiedly shown; Illustratively show the voltage distribution of the battery of the present invention according to Example 13 as a function of the specific capacity of MnO ₂ ; Illustratively show the voltage distribution of the battery of the invention according to Example 14 as a function of the specific capacity of MnO ₂ in comparison with the Duracell Coppertop battery; Illustratively show the voltage distribution of the battery of the invention according to Example 15 as a function of the specific capacity of MnO ₂ in comparison with the Duracell Coppertop battery; Illustratively the first discharge voltage curve for the Li / ionic polymer-sulfur battery of the present invention is shown; Illustratively shown is a discharge capacity curve plotted as a function of the number of cycles for the Li / ionic polymer-sulfur battery of the present invention; An exemplary comparison of the first discharge for Li / sulfur-CMK-3 and the first discharge for Li / ionic polymer-sulfur of the present invention is shown; The charge / discharge voltage curves for Li / sulfur-poly (pyridinopyridine) batteries from the prior art are shown; Shows the rate distribution of button batteries; Shows the positive electrode capacity with respect to battery energy density; The button cell discharge capacity with respect to the discharge current is shown; and A plot of overtime voltage for one battery aspect is shown.

This application is a partial continuation of US Patent Application No. 14 / 559,430, filed December 3, 2014. US Provisional Patent Application No. 62 / 342,432, filed May 27, 2016, is incorporated herein by reference for all purposes.

The present invention includes a solid ion conductive polymer material containing at least one compound including a basic polymer, a dopant and an ion source. Polymeric materials have capacity for ionic conduction over a wide temperature range, including room temperature. Ion "hopping" appears to occur from dense atomic sites. Thus, the polymeric material can function as a means for the supply of ions and has significant material strength.

For the purposes of this application, the term "macromolecule" refers to a polymer having a crystalline or semi-crystalline structure. In some applications, solid ion conductive polymer materials may be molded into a can be folded back shape, allowing for new application-dependent physical forms. do. The basic polymer is selected depending on the desired properties of the composition associated with the desired application.

For the purposes of this application, the term "dopant" refers to an electron acceptor or oxidant or electron donor. Dopants are selected depending on the desired properties of the composition associated with the desired application.

Similarly, compounds containing an ion source are selected depending on the desired properties of the composition associated with the desired application.

I. Li ⁺ chemistry
In one aspect, the invention relates to solid polyelectrolytes, including solid ion conductive polymeric materials in lithium ion batteries.

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

In this aspect, the dopants are 2,3-dicyano-5,6-dichlorodicyanoquinone (C ₈ Cl ₂ N ₂ O ₂ ), also known as DDQ, and tetracyanoethylene (C) known as TCNE, as non-limiting examples. It is an electron acceptor such as ₆ N ₄ ) and 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 in the polymer to allow ionic conductivity. The electron acceptor may be "premixed" with the initial component and extruded without post-treatment, or the electron acceptor may be added to the composition after the material has been made using a doping method such as vapor doping. be.

Typical compounds containing 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 the solid polyelectrolyte film is made.

Other additives, such as carbon particle nanotubes, can be added to solid polymer electrolytes, including solid ion conductive materials, to further enhance electrical conductivity or current density.

The new solid polyelectrolytes allow for lighter weight and much safer construction by eliminating the need for heavy and bulky metal sealed packaging and protective circuit components. New solid polymer batteries containing solid polymer electrolytes may be smaller in size, lighter weight and higher energy density than liquid electrolyte batteries of the same capacity. New polymer electrolyte batteries also benefit from less complex manufacturing methods, lower costs and less safety issues due to the flame retardancy of the electrolyte material. The new polymer electrolyte batteries are capable of battery voltages higher than 4.2 volts and are stable to higher and lower voltages. The novel solid polyelectrolyte may be formed into various shapes by extrusion (and coextrusion), molding and other methods to give the battery various form factorors. It may be shaped specifically to fit within various shaped enclosures in powered equipment or equipment. Moreover, new polymer electrolyte batteries do not require a separator between the electrolyte and the electrodes as in the case of liquid electrolyte batteries. The weight of the new polymer electrolyte battery is substantially lighter than that of a conventional structure battery having a similar capacity. In some embodiments, the weight of the new polymer electrolyte battery may be less than half the weight of a normal battery.

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

In yet another aspect of the invention, the solid polymer electrolyte containing the solid ionic conductive polymer material is in the form of an ionic polymer hollow monofilament. The electrode material and charge collector are applied directly to each surface of the solid ion conductive polymer material (coextrusion), and the terminals are applied to each electrode surface. A light weight protective polymer cover may be applied on the terminals to complete the structure. The structure is thin, flexible, and forms a battery that can be rolled into the intended shape to meet installation requirements, including very small applications.

In yet another aspect of the invention, the solid polyelectrolyte containing the solid ion conductive polymer material has the desired molded shape. Electrode materials for the negative and positive electrodes are placed on the opposite surfaces of the solid polyelectrolyte 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 a multi-cell battery or for connection to a utilization device.

In aspects of the invention related to batteries, electrode materials (positive and negative electrodes) can be combined with a novel solid ion conductive polymer material of some form to further facilitate the movement of ions between the two electrodes. This is similar to a normal liquid electrolyte that penetrates into each electrode material in a normal lithium-ion battery.

A film of the solid ion conductive polymer material of the present invention was extruded to a thickness in the range greater than 0.0003 inches (thickness ranking upward from .0003 inches). The ionic surface conductivity of the film was measured using standard testing of AC-Electrochemical Impedance Spectroscopy (EIS) known to those of skill in the art. A sample of solid ion conductive polymer material film was sandwiched between stainless steel blocking electrodes and placed in a test fixture. AC-impedance was recorded in the range of 800 KHz to 100 KHz using a Biological VSS test system to determine the electrolyte conductivity. The result of the surface conductivity measurement is shown in FIG. The conductivity (Δ) of the solid ion conductive polymer material film according to the present invention is the conductivity of trifluoromethanesulfonate PEO (□) and the liquid electrolyte composed of Li salt solute and EC: PC combination solvent using the Celgard separator. Compare with conductivity (O). The conductivity of solid ion conductive polymer material films according to the present invention tracks the conductivity of liquid electrolytes, far surpassing that of trifluoromethanesulfonated PEO at relatively low temperatures. Further, unlike the PEO electrolyte, the temperature dependence of the conductivity for the polymeric material of the present invention is its glass transition associated with chain mobility described by the temperature-activated Vogel-Tamman-Fulcher behavior. Does not show a sharp improvement at temperatures above temperature. Therefore, it is unlikely that the polymer material of the present invention will have a segmental movement as an ion conduction mechanism. Furthermore, this indicates that the polymer material of the present invention has an ionic conductivity similar to that of a liquid electrolyte.

FIG. 7 shows the mechanical properties of the solid ion conductive polymer material film of the present invention. Mechanical properties were evaluated using the Institute for Interconnecting and Packaging Electrical Circuits IPC-TM-650 Test Methods Manual 2.4.18.3. In the tensile strength vs. elongation curve of FIG. 7, the aspect of "ductile fracture" indicates that the material can be very robust.

The solid ion conductive polymeric materials of the present invention offer three important advantages in their polymeric performance properties: (1) It has a vast temperature range. In laboratory-scale tests, crystalline polymers showed high ionic conductivity both at room temperature and over a wide temperature range. (2
) It is flame retardant. The polymer self-extinguishes and passes the UL-V0 combustion test. The ability to operate at room temperature and flame retardant properties show a transformative safety improvement, which eliminates expensive heat treatment systems. (3) It provides low cost mass production. Rather than spraying the polymer onto the electrodes, the polymer material can be extruded into a thin film via the roll-to-roll method, which is an industrial standard for plastic production. After extruding the film, it is coated with electrodes and charge collector material to build a "from inside out" battery. This allows for a morphological factor of thin flexibility that does not require airtight packaging, leading to easy integration into vehicle and storage applications at low cost.

The solid ion conductive polymer material of the present invention creates a new ion conduction mechanism, which gives a higher density of sites for ion transport, without the risk of thermal runaway or damage to the ion transport sites from, for example, lithium formation. It seems that conductive materials will be able to hold higher voltages. This property allows solid ion conductive polymer materials to be durable for negative electrode materials and thin film applications for higher voltage positive electrodes, resulting in higher energy for batteries that can be used in vehicles and fixed storage applications. Produces density. The ability to hold high voltages in solid ion conductive polymer materials that are mechanically robust, resistant to chemicals and humidity, and flame retardant over a wide range of temperatures, not just room temperature, is today. Allows integration with high performance electrodes without the expensive heat and safety mechanisms used by the industry.

Batteries using solid polymer electrolytes containing the solid ion conductive polymer materials of the present invention have higher energy densities than currently commercially available electrolytes and -40 ° C to 150 ° C with minimal reduced conductivity. It is characterized by the performance range of. A solid polyelectrolyte can be extruded by a method of making a polymer with a thickness of 6 microns, which allows thin film forms under commercial manufacturing conditions on a batch scale. In addition, such extrusion methods enable high throughput, low cost production lines for the production of solid polyelectrolytes, and the methods can be incorporated into a variety of production lines, including lithium and zinc battery production. Battery costs can be reduced by up to 50%.

Furthermore, solid ion conductive polymer materials are not limited to use in batteries and can be used in any device or composition comprising an electrolyte material. For example, novel solid ion conductive polymer 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 a solid ion conductive polymer material on the side of the solid polymer electrolyte of the present invention. A charge carrier complex is formed in the polymer as a result of the doping process (set up).

The combustibility of the solid polyelectrolyte containing the solid ion conductive polymer material of the present invention was tested using the UL94 combustion test. Due to the polymer to be evaluated as UL94-V0, it must be "self-extinguishing" within 10 seconds and "not drip". A solid polyelectrolyte was tested for this property and it was determined that it self-extinguished in 2 seconds and did not drip, thus easily passing the V0 rating. FIG. 9 shows a photograph of the result.

In addition to ionic conductivity, flame resistance, high temperature behavior and excellent mechanical properties, solid polymer electrolytes, including the solid ionic conductive polymer materials of the invention, are electrochemically stable at low and high potentials. preferable. The usual test for electrochemical stability is cyclic voltammetry when the working electrode potential is tilted linearly with time. In this test, a polymer is sandwiched between the lithium metal negative electrode and the blocking stainless steel electrode. Apply a voltage and sweep it positively to a high value (greater than 4 volts for Li) for stability against oxidation and a low value (0V for Li) for stability against reduction. Or lower) to sweep negatively. The current output is measured to determine if a significant reaction occurs at the electrode interface. High current outputs at high positive potentials indicate that an oxidation reaction is taking place, suggesting instability when using positive electrode materials (eg, many metal oxides) that operate at these or more positive potentials. .. High current outputs at low potentials indicate that a reduction reaction occurs, suggesting instability when using negative electrodes operating at these or more negative potentials (eg, metallic Li or carbon lithiumized). FIG. 10 shows a voltage vs. current plot for a solid polyelectrolyte containing a solid ion conductive polymer material according to the present invention for lithium metal. Studies show that solid polyelectrolytes are stable up to about 4.4 volts. These results indicate that the solid polymer electrolyte can be stable when using low voltage positive electrodes, eg, positive electrodes containing LCO, LMO, NMC and similar positives with iron phosphate and sulfur positives as a non-limiting example. show.

The solid polyelectrolyte containing the solid ion conductive polymer material of the present invention can achieve the following properties: A) High ionic conductivity over room temperature and a wide temperature range (at least −10 ° C. to + 60 ° C.). B) Flame retardant; C) Reel-reel processing and extrusion suitability for thin films allowing new manufacturing methods; D) Compatibility with lithium metals and other active materials. Therefore, the present invention enables the fabrication of a true solid state battery. The present invention enables a new generation of batteries with the following properties:
-No safety issues;
-New morphological factor;
-Major improvements in energy density; and-Major improvements in the cost of energy storage.

FIGS. 11, 12 and 13 show some elements of a solid state battery containing the solid ion conductive polymeric material of the invention, which are: A) extruded electrolyte; B) extruded negative electrode, respectively. And positive electrodes; and C) the final solid-state battery that enables new morphological factors and flexibility.

In another aspect, the present invention provides a method for producing a Li battery containing the solid ion conductive polymer material of the present invention. FIG. 14 shows a method for manufacturing a solid state lithium ion battery using an extruded solid ion conductive polymer material according to the present invention. The materials are blended into pellets and then extruded through a die to make a film of variable thickness. Electrodes can be applied to the film using several methods such as sputtering or normal casting in slurry.

In yet another aspect, the invention provides a method of making an ionic polymer film comprising the solid ion conductive polymeric material of the invention, which heats the film to a temperature of about 295 ° C. and then solidifies the plastic. Includes 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 diagram of a structure according to the present invention.

II. Chemistry of OH ^- The invention also relates to solid ion conductive polymeric materials designed to carry OH ^- ions, thereby making them applicable for alkaline batteries. For the purposes of the present invention, the term "alkaline battery or alkaline batteries" refers to a battery that uses an alkaline (OH ^- containing) electrolyte. Chemistries for such batteries 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
O ₂ chemistry is probably the most widely used and is the predominant choice for household batteries. Although many aspects described herein relate to Zn / MnO ₂ chemistry, one of ordinary skill in the art will appreciate that the same principles are widely applicable to other alkaline systems.

Alkaline batteries rely on the transport of OH ^- ions for the conduction of electricity. In most cases, OH ^- ions are also involved in electrochemical processes. For example, during the discharge of a Zn / MnO ₂ battery, the zinc negative electrode emits two electrons and consumes OH ^- ions:
(1) Zn + ^4OH- → Zn (OH) ₄ ^2- + ^2e-
(2) Zn + ^2OH- → Zn (OH) ₂ + ^2e- → ZnO + H _2O
(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 the separator and the positive electrode [Linden's Handbook of Batteries, Fourth Edition]. At some point the electrolyte will saturate with the zincate ion and the reaction product will turn into insoluble Zn (OH) _2. (2). Finally, the negative electrode is depleted of water, and zinc hydroxide is dehydrated by the formula (3). In a rechargeable battery, the reaction reverses during battery charging. The production of soluble zincate ions during the initial 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 volume for such one-electron reduction is 308 mAh / g. A slow discharge to a lower voltage leads to a further discharge of MnOOH as depicted by equation (5), which yields a total specific volume (1.33e) of 410 mAh / g. In most prior art applications, MnO ₂ discharge is limited to a one-electron process. Utilization of activity is further adversely affected by the production of soluble low valence Mn species.
(4) MnO ₂ + e-+ H ₂ O → ^MnOOH + ^OH-
(5) ^3MnOOH + e-→ Mn 3O ₄ + H ₂ O ₊ ^OH-
(6) MnO ₂ + ^2e- + 2H ₂ O → Mn (OH) ₂ + ^2OH-

MnO ₂ can theoretically experience two-electron reduction according to equation (6) and has a theoretical specific volume of 616 mAh / g, which has not been shown in the prior art battery practice. Crystal structure rearrangement with the formation of an inert phase such as Hausmanite Mn ₃ O ₄ and outward diffusion of soluble products are included in the factors limiting the positive cell volume.

US Pat. No. 7,972,726 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 compared to 287 mAh / g for 100% MnO ₂ and 200 mAh / g for 100% AgBio ₃ . Was shown to deliver 351 mAh / g up to 0.8 V cut-off. The specific volume of 351 mAh / g corresponds to the 1.13 electron discharge of MnO ₂ , which corresponds to the highest specific volume delivered in a practically useful discharge rate and voltage range.

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

The bismuth-or lead-modified MnO ₂ material disclosed in US Pat. Nos. 5,156,934 and US Pat. No. 5,660,953 has a theoretical two-electron discharge capacity for many cycles. It was claimed to be able to deliver about 80% of. Reference [Y. F. Yao, N.M. Gupta, H. et al. S. Wróblowa, J. Mol. Electrical. C
hem. , 223, 107, 1987; H. S. Wroblowa, N. et al. By Gupta, J. Mol. Electrical. Chem. , 238, 93, 1987; D. Y. Qu, L. Bai, C.I. G. Castledine, B.I. E. By Conway, J. Mol. Electrical. Chem. , 365, 247, 1994], bismuth or lead cations can stabilize the crystal structure of MnO ₂ during discharge and / or through a non-uniform mechanism containing soluble Mn ²⁺ species. It was theorized to allow reaction (6) to proceed. The inclusion of the Mn ²⁺ species appears to be important for obtaining high MnO ₂ utilization and reversibility. In the high carbon content (30-70%) positive electrode according to US Pat. No. 5,156,934 and US Pat. No. 5,660,953, the highly porous structure obtained 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 a Zn negative electrode.

Thus, polyelectrolytes that interfere with the dissolution and transport of low valence manganese species and zincate ions are very beneficial for improving MnO ₂ utilization and achieving rechargeability of Zn / MnO ₂ batteries. ..

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 during reduction, allowing rechargeability [M. Minakshi, P.M. By Singh, J. Mol. Solid State Elecrochem. 16, 1487, 2012].

The solid ion conductive polymeric materials of the invention designed to conduct Li ⁺ and OH ^- ions open the possibility of adjusting the MnO ₂ discharge mechanism by supporting proton or lithium insertion, which has a cycle lifetime. Can act as an additional tool to improve.

Accordingly, in one aspect, the invention provides a polymeric material comprising at least one compound including a basic polymer, a dopant and an ion source, wherein the polymeric material is a solid ion having mobility with respect to OH ^- ions. It is a conductive polymer material. For the purposes of this application, the term "mobility for OH ^- ions" refers to a diffusion rate greater than 10 ^-11 cm ² / sec or a conductivity of 10 ^-4 S / cm at room temperature between 20 ° C and 26 ° C. Point to. Solid ion conductive polymer materials are suitable for use in alkaline batteries.

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

In another aspect, the invention provides electrodes, positive and negative electrodes containing solid polymer electrolytes for use in alkaline batteries, where the solid polymer electrolytes have high solid ion conductivity with OH ^- ion mobility. Contains molecular materials. In yet another aspect, the invention provides an electrolyte sandwiched between a positive electrode and a negative electrode, where at least one of the electrolyte, the positive electrode and the negative electrode is a solid ion conductive polymeric material having mobility for OH ^- ions. 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 conductive polymeric material having mobility with respect to OH ^- ions. The latter aspect is exemplified in FIG.

The basic polymer of the solid ion conductive polymer material with OH ^- ion mobility is a crystalline or semi-crystalline polymer, which is typically 30% to 100%, preferably 50% to 100%. It has a crystallinity value. The basic polymer of this aspect of the invention has a glass transition temperature higher than 80 ° C, preferably higher than 120 ° C, more preferably higher than 150 ° C, and most preferably higher than 200 ° C. The basic polymer has a melting temperature higher than 250 ° C., preferably higher than 280 ° C., more preferably higher than 280 ° C., and most preferably higher than 300 ° C.

Dopants of solid ion conductive polymeric materials with OH ^- ion mobility are electron acceptors or oxides. Typical dopants for use in this aspect of the invention are DDQ, TCNE, SO ₃ and the like.

Compounds containing the ion source of solid ion conductive polymer materials with OH ^- ion mobility can be converted to salts, hydroxides, oxides or other materials containing hydroxyl ions or such materials. Materials include, but are not limited to, LiOH, NaOH, KOH, Li ₂ O, LiNO ₃ and the like.

Solid ion conductive materials with OH ^- ion mobility are characterized by a minimum conductivity of 1 x 10 ^-4 S / cm at room temperature and / or a diffusion rate of OH ^- ions greater than ^10-11 cm ² / sec at room temperature. Be done.

The positive electrodes of the invention associated with OH ^- chemistry include MnO ₂ , NiOOH, AgO, air (O ₂ ) or similar active materials. MnO ₂ is a preferred material, including but not limited to β-MnO ₂ (pyrolucite), rams delite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ and EMD and CMD. It may be in the form of _two phases or a mixture thereof.

The positive electrode of the present invention related to the chemistry of OH ^- is a component of the solid ion conductive polymer material of the present invention containing a compound containing a basic polymer, a dopant and an ion source, and the solid ion conductive polymer material is produced. It is produced by mixing a positive electrode active material before forming a mixture. Alternatively, the positive electrode active material is mixed with the already formed solid ion conductive polymer material.

The mixture is molded 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 non-limiting examples. The positive electrode of the present invention is an active material in an amount of 10% by weight to 90% by weight, preferably 25% by weight to 90% by weight, more preferably 50% by weight to 90% by weight, based on the total positive electrode weight. including. The positive electrode may further contain 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 electrically conductive additives. be. The positive electrode may contain an electrically conductive additive in an amount of 0% by weight to 25% by weight, preferably 10% by weight to 15% by weight, based on the total weight of the positive electrode. The positive electrodes of the invention associated with OH ^- chemistry may further contain one or more functional additives to improve performance. The positive electrode active material may be encapsulated with the solid ion conductive polymer material of the present invention.

Negative electrodes of the invention related to the chemistry of OH ^- may include zinc powder, zinc flakes and other forms, zinc sheets and Zn active materials in other forms. All such forms of zinc may be alloyed to minimize zinc corrosion.

The negative electrode of the present invention related to the chemistry of OH ^- is a component of the solid ion conductive polymer material of the present invention containing a compound containing a basic polymer, a dopant and an ion source, and the solid ion conductive polymer material is produced. It is produced by mixing a negative polymer with a negative polymer before forming a mixture. Alternatively, the negative electrode active material is mixed with the already formed solid ion conductive polymer material. The mixture is molded 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% by weight to 90% by weight, preferably 25% by weight to 90% by weight, more preferably 50% by weight to 90% by weight, based on the total negative electrode weight. including. The negative electrode may further contain 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 electrically conductive additives. be. The negative electrode may contain an electrically conductive additive in an amount of 0% by weight to 25% by weight, preferably 10% by weight to 15% by weight, based on the total weight of the negative electrode. The negative electrodes of the present invention associated with OH ^- chemistry may further contain one or more functional additives to improve performance. The negative electrode active material may be encapsulated with the solid ion conductive polymer material of the present invention.

In another aspect, the invention provides a Zn / MnO ₂ battery containing an electrolyte sandwiched between a MnO ₂ positive electrode and a Zn negative electrode. The electrolyte in this aspect may include the solid ion conductive material of the present invention having OH ^- ion mobility, or may include a conventional separator filled with a liquid electrolyte. The positive electrode may contain a solid ion conductive material having mobility with respect to the OH ^- ion of the present invention, or may contain a commercially available MnO ₂ positive electrode. Negatives in this aspect may include solid ion conductive materials of the invention that are mobile with respect to OH ^- ions, or may include Zn negatives made by Zn foil, Zn mesh or other methods. In the Zn / MnO ₂ battery of the present invention, the solid electron conductive polymer material of the present invention having mobility with respect to OH ^- ions is contained in at least one of a positive electrode, a negative electrode and an electrolyte.

III. Polymer-MnO ₂ Composite Positive The present invention further relates to a primary alkaline battery including a polymer-MnO ₂ composite positive electrode and a positive electrode having a high specific capacity. More specifically, the present invention relates to a primary alkaline battery comprising a polymer-MnO ₂ composite positive electrode and a positive electrode having a specific capacity close to the theoretical two-electron discharge. Alkaline batteries may be discharged at current densities comparable to those of commercially available alkaline batteries while delivering useful capacity up to a typical 0.8V voltage cutoff.

In various aspects, the invention comprises a positive electrode made of a MnO ₂ active material containing a large number of active MnO ₂ particles mixed with a solid ion conductive polymer material containing a basic polymer, a dopant and a compound containing an ion source, and the like. The present invention relates to a method for producing 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 for manufacturing the positive electrode. The positive electrode is made of a MnO ₂ active material containing a large number of active MnO ₂ particles mixed with a solid ion conductive polymer material containing a basic polymer, a dopant and a compound containing an ion source. The positive electrode and electrochemical cell of the present invention are characterized by a flat discharge curve.

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

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

In aspects of the invention relating to the polymer-MnO ₂ composite positive, the compound containing the ion source is any other material containing salts, hydroxides, oxides or hydroxyl ions or any material convertible to such materials. Yes, including, but not limited to, LiOH, NaOH, KOH, Li ₂ O, Li NO ₃ .

In aspects of the invention relating to the polymer-MnO ₂ composite positive, the MnO ₂ active materials are β-MnO ₂ (pyrolucite), rams delite, 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.

A polymer-MnO ₂ is obtained by mixing a large number of active MnO ₂ particles and a solid ion conductive polymer material containing a compound containing a basic polymer, a dopant and an ion source and heating the mixture to a predetermined temperature for a predetermined time. A positive electrode related to a composite positive electrode can be manufactured. The heating can be carried out while applying pressure as the case may be.

In one embodiment, the polymer-MnO ₂ composite positive electrode of the present invention may be manufactured by compression molding at temperature. The mixture is molded 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, heating is optionally performed at a pressure of 150-2000 PSI, preferably 150-1000 PSI, more preferably 150-500 PSI, most preferably 150-250 PSI. The MnO ₂ active material may be present in an amount of 5% by weight to 95% by weight, preferably 50% by weight to 90% by weight, based on the total weight of the composite positive electrode. The composite positive electrode is 5% by weight to 50% by weight, preferably 10% by weight to 50% by weight, more preferably 20% by weight to 40% by weight, and most preferably 25% by weight to 35% by weight with respect to the total weight of the composite positive electrode. May contain filler in%. The dopant may be added in an amount corresponding to the basic polymer / dopant molar ratio of 2-10, preferably 2-8, more preferably 2-6, most preferably 3-5. The composite positive electrode may contain 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, wherein the composite positive electrode is electrically conductive. The components are present in an amount of 5% by weight to 25% by weight, preferably 15% by weight to 25% by weight, and more preferably 18% by weight to 22% by weight based on the total weight of the composite positive electrode. The MnO ₂ active material in the composite positive electrode may be encapsulated with the solid ion conductive polymer material of the present invention.

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

Negatives associated with the polymer-MnO ₂ composites of the present invention may contain Zn, Al, Fe, metal hydride alloys or similar materials. Zn and Al are preferred materials and may be in the form of pure metals or specially designed alloys. The separator may be a normal non-woven separator used in alkaline batteries. The electrolyte is a solution of KOH, NaOH, LiOH, etc. in water. The alkali concentration may be 4-9M. The electrolyte may further contain electronically conductive and / or functional additives.

IV. Polymer-sulfur positive electrode
Furthermore, the present invention relates to a composite polymer-sulfur positive electrode. The composite polymer-sulfur positive electrode comprises a solid ion conductive polymer material containing a sulfur component as well as a compound containing a basic polymer, a dopant and an ion source. Composite polymer-sulfur positives are characterized as having high specific capacity and high capacity retention when used in secondary lithium or Li ion sulfur batteries. Composite positives are 200mA-greater than hour / gram, preferably 500mA-
It is characterized as having a specific volume greater than hour / gram, more preferably 750 milliamp-hours-greater than hour / gram, most preferably 1000 milliamp-hours / gram. The composite positive electrode is characterized as having a retention of at least 50%, preferably at least 80%, over 500 recharge / discharge cycles. The composite polymer-sulfur positive electrode of the present invention has a 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 provide high performance and at the same time meet the requirements for manufacturing low cost batteries.

It should be noted that the sulfur positive electrode is reduced during the discharge, producing one after another lower order polysulfides in the order represented by the following equation:
S ₈ → Li ₂ S ₈ → Li ₂ S ₄ → Li ₂ S ₂ → Li ₂ S

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

The present invention presents a composite polymer-sulfur positive electrode containing a sulfur component and a solid ion conductive polymer material. This positive electrode can be extruded into a flexible thin film via a roll-to-roll method. Such thin films allow for thin flexibility morphological factors that may be introduced in the design of new flexible batteries. As shown in subsequent examples, this composite polymer-sulfur positive electrode contains, for example, an inexpensive carbon black component, eg, an electrically conductive additive such as Timcal C45, which is already used in many commercially available battery products. May include. In addition to the typical carbon black component, the composite polymer-sulfur positive electrode contains, but is not limited to, other electrically conductive additives such as carbon fiber, graphene component, and graphite component as non-limiting examples. May contain components, metal particles or other metal additives and electrically conductive polymers.

The engineering properties of the composite polymer-sulfur positive electrode allow the positive electrode to be extruded to a wide range of possible thicknesses, which in turn provides an important advantage in terms of design flexibility in large-scale positive electrode production. Composite polymer-sulfur positive electrodes may be extruded as thin as 5 microns, as well as thicker than a few hundred microns.

A comparison of the process steps required to manufacture a standard lithium-ion positive electrode with the process steps required to manufacture a composite polymer-sulfur positive electrode of the present invention is a lesson regarding the inherent lower cost of composite polymer-sulfur positive electrode production. It is a target. FIG. 18 shows the process steps required to produce a standard lithium ion positive electrode compared to the much simpler production of the extruded composite polymer-sulfur positive electrode of the present invention. Extrusion methods for composite polymer-sulfur positives are easily scaled up to mass production, which offers significant advantages over existing lithium-ion batteries as well as much less capital spending on factory equipment.

In addition to extrusion, other methods including injection molding, compression molding or heat or other methods known to those skilled in the art of engineering plastics may form the composite polymer-sulfur positive electrode.

As discussed above, the composite polymer-sulfur positive electrode comprises a solid ion conductive polymer material containing a sulfur component as well as a compound containing a basic polymer, a dopant and an ion source.

Basic polymers include liquid crystal polymers and polyphenylene sulfide (PPS) or semi-crystalline polymers with crystallinity greater than 30% or other typical oxygen receptors.

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

Compounds containing an ion source include, but are not limited to, Li ₂ O and Li OH. The use of the composite polymer-sulfur positive electrode in Li / sulfur test batteries 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 basic polymer is a flame-retardant polymer that is self-extinguishing and has been shown to pass the UL-VO combustion test. The flame retardancy of the basic polymer is a safety benefit to the battery using the 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, which is an important attribute for high energy density batteries.

The sulfur component may include non-reducing and / or reduced forms of sulfur, including elemental sulfur. In particular, the composite polymer-sulfur positive electrode contains a sulfur component containing sulfur (Li ₂ S) in a completely lithium form, where Li ₂ S is a solid. The composite polymer-sulfur positive electrode may also contain a carbon component. The advantage of using a fully lithium-ized form of sulfur is that it provides a lithium source for lithium batteries with a Li-ion negative electrode that must be lithium-ionized during the 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 crystals that may form after cycling the lithium negative electrode. The dendritic crystals are caused by the non-uniform plating of lithium onto the lithium metal negative electrode during charging. These dendritic crystals 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 is reversibly introduced via intercalation or alloying have been proposed for use in highly safe lithium / sulfur batteries, reducing the chances of dendritic crystal formation. Composite polymer-sulfur positives 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 with negative material such as Sn-based composite oxides, including composites with transition metals. Furthermore, silicon has shown promise as a lithium ion negative electrode material in the form of elements or as a composite material as described for oxides or tin. Other lithium alloying materials (eg Ge, Pb, B, etc.) could also be used for this purpose. It has been shown that iron oxides such as Fe ₂ O ₃ or Fe ₃ O ₄ and various vanadium oxide materials are also incorporated reversibly as Li ion negative electrode materials. Negative electrode materials can be considered in various forms including amorphous and crystalline and nano-sized particles as well as nanotubes.

Composite Polymer-Sulfur positives may be combined with electrolytes containing standard liquid electrolytes, standard non-woven separators and / or solid ion conductive polymer materials without liquid electrolytes. An example of a standard organic electrolyte solution is a lithium salt 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 battery performance. In organic liquid electrolytes: Among them, other lithium salts including LiPF ₆ , LiBF ₄ , LiAsF ₆ , and lithium triflate can be used. In addition, other organics such as propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), as some examples. The solvent can be used alone or as a mixture or with DOL and DME. Examples of standard non-woven separators include polypropylene (PP), polyethylene (PE) and PP / PE film combinations. Other separator materials include polyimide, PTFE, ceramic coating films and glass mat separators. All of the above materials can be used with composite polymer-sulfur positive electrodes. Further, the composite polymer-sulfur positive electrode can also be used in, for example, a gel polymer system in which a polymer based on PVDF is swollen with an organic electrolyte.

The ability of the composite polymer-sulfur positive electrode to confer lithium ion conductivity is believed to improve battery performance by limiting the polysulfide reciprocating mechanism while at the same time applying a high voltage to the sulfur positive electrode. In addition, this unique engineering composite polymer-sulfur positive electrode enables the large scale, low cost manufacturing required for the commercial viability of the positive electrode.

Thus, the unique composite polymer-sulfur positive electrode is:
● Improved safety under normal and abuse conditions ● Enable new battery morphology factors ● Significant improvement in energy density over existing Li-ion batteries ● Greater charge / discharge by interfering with polysulfide reciprocating mechanism Leading to reversibility ● Has numerous potential benefits to batteries, including significantly reducing manufacturing costs (raw materials, processes and capital equipment) and leading to improvements in the cost of energy storage.

V. Alkaline battery
In one aspect, rechargeable Zn / MnO ₂ for low-rate applications that can match or exceed lithium-ion performance while offering improved stability, robustness and lower cost. Explain the battery.

It has been observed that certain positive electrode formulations containing solid ion conductive polymeric materials can exhibit much higher active material utilization at lower rates, while exhibiting a steeper decrease as the discharge rate increases. This is shown by FIG. 38, which depicts the rate distribution of button cells with positive electrode formulations that are probably useful for high energy batteries. Most such formulations exhibit a ratio C / 2 volume of about 300 mAh / g, which is close to what is theoretically predicted for the 1-electron discharge of MnO ₂ (indicated by formulation 1 in FIG. 38). ). In some cases, the battery 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.

Optimizing the zinc and polymer content in the negative electrode, especially: ZnO to optimize the zinc type and particle size for the desired negative electrode performance, the composition and fabrication method of the solid polymer electrolyte, and 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 a polymer matrix interferes with shape changes, aggregation and dendritic growth.

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

In one aspect, a rechargeable Zn / MnO ₂ battery introduced with a solid ion conductive polymeric material for high rate and high temperature applications will be described.

When the manganese dioxide content is increased to 80% by weight or more, the excellent active material utilization rate and high rate performance of the button battery are maintained. The significance of this finding cannot be exaggerated, as high active material loads are essential for achieving high energy densities. The improvement in discharge capacity resulting from the optimization of manganese dioxide content is shown in FIG. As you can see, the optimized battery worked well even at high currents such as 50mA (extremely high for coin cell batteries), where the limits of the negative electrode and coin cell hardware may begin to play a role.

A positive electrode density of 2.5-3.0 g / cc is sufficient to obtain a high energy density. High rate performance under these conditions may be limited by the zinc foil negative electrode rather than the positive electrode. A zinc negative electrode with an increased surface area to replace the zinc foil exhibits improved performance.

To improve the negative electrode rate capacity and extend the cycle life, optimize the zinc and negative electrode polymer content, optimize the zinc type and particle size, and ZnO and other functional additives (like manganese salts). ) Is introduced to improve the negative electrode by reducing the passivation and corrosion of zinc. The combined effect of greater zinc surface area and improved stability results in improved performance and extended cycle life at high discharge rates. In addition, embedding zinc particles in the polymer matrix has been found to impede morphological changes, aggregation and dendritic growth.

Comparing or surpassing current state-of-the-art Li-ion systems in energy / power density, showing> 85% capacity retention at 15C discharge; safe to operate at 80-100 ° C; and A battery with a minimum life of 500 cycles was manufactured. These Zn / MnO ₂ battery packs do not require complex battery management and charge control circuits, and additional energy density benefits and cost reductions are expected at the pack level.

Example 1
A solid polyelectrolyte was prepared by mixing the PPS basic polymer and the ion source compound LiOH monohydrate at a ratio of 67% to 33% (by weight), respectively, and mixing them using jet milling. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of 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 finely ground and placed in an NMR fixative.

The self-diffusion coefficient was determined by using a pulsed field gradient solid state NMR technique technique. The results shown in FIGS. 19 and 20 show that the Li ⁺ and OH ^- diffusion rates in the solid polyelectrolyte are the highest of any known solids, respectively, and the recently developed Li at much higher temperatures (140 ° C.). It shows that it is more than an order of magnitude higher at room temperature compared to _{10 GeP} 2S ₁₂ ceramics or the best PEO formulations at 90 ° C.

Example 2
The PPS basic 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. A positive electrode was further prepared by mixing β-MnO ₂ , 5% Bi ₂ O ₃ from 50% Alfa Aesar and 15% C45 carbon black. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of PPS.

The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 PSI) for 30 minutes, a 1 inch diameter positive electrode disc with a thickness of approximately 0.15 mm. Gave. The obtained disk 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.

A Biological VSS test system was used to discharge the batteries under constant current conditions of 0.5 mA / cm ² . The specific volume of MnO ₂ was 303 mAh / g or was close to the theoretical 1e ^- discharge. FIG. 21 shows the voltage distribution of the battery according to Example 2 as a function of the specific volume of MnO ₂ at a discharge rate of 0.5 mA / cm ² .

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

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

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

Batteries were discharged under constant current conditions using a Biological VSS test system. The specific volume of MnO ₂ was close to 600 mAh / g at the C / 9 discharge rate (35 mA / g) or close to the theoretical 2e ^- discharge.

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

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

The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 PSI) for 30 minutes, a 1 inch diameter positive electrode disc with a thickness of approximately 0.15 mm. Gave.

The obtained disk 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.

Batteries were discharged and charged using a Biological VSS test system. Discharging was performed to a cut-off of 0.8 V at a current of 0.5 mA / cm ² . It was charged to 1.65 V at 0.25 mA / cm ² and then held at 1.65 V for 3 hours or until the current diminished to 0.02 mA / cm ² . Passivated Zn negative electrodes and separators were replaced with new ones every few cycles. The specific capacity of MnO ₂ as a function of the number of cycles in the battery according to Example 4 is plotted in FIG. Each pillar shows a separate battery. Only discharges using the new Zn negative electrode are shown. It is easy to see that the MnO ₂ positive electrode of the present invention is rechargeable. Only discharges using the new Zn negative electrode are shown.

Example 5
A 2035 button cell was assembled using the solid polyelectrolyte of Example 1 and the Zn foil as the positive and negative electrodes of Example 2. Batteries were discharged and charged using a Biological VSS test system. Discharging was performed to a cut-off of 0.8 V at a current of 0.25 mA / cm ² . It was charged to 1.65 V at 0.25 mA / cm ² and then held at 1.65 V for 3 hours or until the current diminished to 0.02 mA / cm ² . Batteries showed reversible behavior during such cycling. FIG. 24 shows the discharge curve of the button cell according to Example 5 as a function of the test time.

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

The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 psi) for 30 minutes, a 1 inch diameter positive electrode disc with a thickness of approximately 0.15 mm. Gave.

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

Example 7
The PPS basic polymer and the 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% Zn powder and 10% C45 carbon black. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of PPS.

The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 psi) for 30 minutes, a 1 inch diameter positive electrode disc with a thickness of approximately 0.15 mm. Gave.

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

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

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

Example 8
The PPS basic polymer and the 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. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of PPS. The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 psi) for 30 minutes, a 1 inch diameter positive electrode disc with a thickness of approximately 0.15 mm. Gave.

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

The negative electrode was electropotentially polarized at a sweep rate of 1 mV / sec using a Biological VSP test system. FIG. 27 shows a dynamic potential scan at 1 mV / sec of the negative electrode (curve A) and control standard Al foil (curve B) of the present invention in a ZnSO ₄ electrolyte. The negative electrode of the present invention showed a corrosion stability improved by 0.5 V as compared with the Al foil.

Comparative Example 9
The discharge distribution of the Duracell Coppertop AA battery at 250 mA discharge was obtained from the data sheet. The amount of MnO ₂ in the battery was calculated by comparing the published specification and MSDS, and 8.4 to 9.6 g was given. A simple conversion produces a current density of 26-30 mA / g. The product of working time (according to the data sheet) and discharge current gives the total capacity, which can be converted to specific capacity by dividing by the weight of MnO ₂ . The voltage distribution of the Coppertop AA battery as a function of the ratio MnO ₂ capacitance 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 battery 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 battery is under constant current discharge at a 30 mA / g rate. Curve C shows the specific capacity of the Duracell Coppertop AA battery under a constant current discharge rate of 2.2 mA / g. It is easy to understand that the specific volume of MnO ₂ calculated up to 0.9V cut-off is 235 to 270 mAh / g. Extrapolation to 0.8 V cut-off will result in a slightly higher specific volume of 245-275 mAh / g. The discharge curve has a gradient shape typical of Zn / MnO ₂ batteries. The difference between the voltage at 5% discharge depth and the voltage at 95% discharge depth is 0.5V or close to 30% of the initial (5% DOD) [2.1-2.4V / Ah / g]. 2.2mA / g (MnO in battery)
A Coppertop battery discharging at an extremely low rate (assuming an average amount of ₂ ) results in the appearance of an additional plateau (Curve C). The total specific volume was 347 mA / g, which corresponded to 1.13-electron discharge. Nevertheless, the discharge curve has a typical gradient shape with a voltage difference close to 0.5V between the 5% discharge depth and the 95% discharge depth.

Comparative Example 10
AA batteries were purchased from retail stores and subjected to a 250 mA discharge equivalent to an intermediate-rate test using the Maccor 4300 system. Table 10.1 shows the performance of commercially available AA batteries under continuous discharge of 250 mA. The total volume delivered up to the 0.9V cut-off is shown in Table 10.1. Assuming that the amount of MnO ₂ in the battery is the same as in Comparative Example 9, the total capacity of the battery can be converted to the specific capacity of MnO ₂ . As can be seen, under these discharge conditions, commercially available AA batteries deliver 200-280 mAh / g. A commercially available alkaline battery is described by equation (1), even considering the positive effect of intermittent discharge and the extension of voltage cut-off to 0.8V, 1 of MnO ₂ limited to 308mAh / g. -It is a valid theory that it works within electron reduction.

Comparative Example 11 (according to US Pat. No. 7,972,726)
FIG. 29 shows an AgBio ₃ positive electrode (curve (a)), an EMD (MnO ₂ ) positive electrode (curve (b)) and a 1: 9 AgBio ₃ : EMD mixture reproduced from US Pat. No. 7,972,726. (Curve (c)) shows a discharge curve at a discharge rate of 10 mA / g for an Alikari button battery with a positive electrode. Under these conditions, the discharge distribution (b) for EMD is the commercially available alkaline battery described in Comparative Example 9 having a 0.5 V difference between the voltage at 5% DOD and the voltage at 95% DOD. It is similar. The MnO ₂ capacity of about 290 mAh / g is consistent with 1-electron discharge. Positive electrodes made with the AgBio ₃ : EMD mixture show an additional plateau at about 0.9V, boosting the MnO ₂ capacity. Best performance was reported with a 1: 9 AgBio ₃ : EMD mixture, which delivered 351 mAh / g by 0.8 V cut-off. This corresponds to 1.13-electron discharge of MnO ₂ .

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

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

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

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

Example 13
The PPS basic polymer and the ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. A positive electrode was made by further mixing EMD (a mixture of γ- and ε-MnO ₂ ) from 50% Tronox, 5% Bi ₂ O ₃ and 15% C45 carbon black. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of PPS.

The mixture was compression molded onto a stainless steel mesh (Dexmet) at 325/250 ° C. under mild pressure (500-1000 psi) for 30 minutes, with a diameter of [missing] inches and a thickness of 1.6-1. A 0.8 mm positive electrode disc was given.

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

Batteries were discharged under constant current conditions using a Biological VSS test system. FIG. 31 shows the voltage distribution of the battery according to Example 13 as a function of the specific volume of MnO ₂ at 29 mA / g (curve A) and 59 mA / g (curve B). The specific volume 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
The PPS basic polymer and the ion source compound LiOH monohydrate were added together at a ratio of 67% to 33% (by weight), respectively, and mixed using jet milling. A positive electrode was further prepared by mixing 80% EMD (mixture of γ- and ε-MnO ₂ ) from Tronox and 5% C45 carbon black. DDQ dopant was added to the resulting mixture in an amount of 1 mol DDQ per 4.2 mol of PPS.

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

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

A Biological VSS test system was used to discharge the batteries under constant current conditions at a rate of 9 mA / g. The specific volume of MnO ₂ was 590 mAh / g. FIG. 32 shows the voltage distribution (curve A) at a discharge rate of 9 mA / g for the battery and the voltage distribution (curve B) at 2.2 mA / g for the Duracell Coppertop battery according to Example 14 as a function of the specific capacitance of MnO ₂ . show. The voltage difference between 5% DOD and 95% DOD was 0.163V or 13.6% (Curve A). For comparison, the discharge distribution for the Duracell Coppertop battery at 2.2 mA / g is shown (Curve B).

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

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

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

A Biological VSS test system was used to discharge the batteries under constant current conditions at a rate of 9.5 mA / g. The specific volume of MnO ₂ was 541 mAh / g. FIG. 33 shows that the voltage difference between 5% DOD and 95% DOD was 0.180V or 14.1% (Curve A). For comparison, the discharge distribution for the Duracell Coppertop battery at 2.2 mA / g is shown (Curve B).

Example 16
The PPS basic 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. Further, by mixing 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, a polymer-sulfur composite positive electrode is added. Manufactured. The material was compression molded onto a stainless steel mesh (Dexmet) at 120 ° C. for 30 minutes to give a positive electrode disc with a diameter of 15 mm and a thickness of 0.3-0.4 mm.

The resulting positive electrode was used to assemble a test battery in 2035 button cell hardware. A polypropylene separator (Celgard) with a thickness of 25 microns and a diameter of 19 mm was used with a lithium foil negative electrode material having a diameter of 15 mm. 0 liquid electrolyte of 1M LiTFSI salt dissolved in 50/50 (volume / volume) mixture of DOL / DME
.. Used with 5M LiNO ₃ additive. Batteries were assembled in a glove box filled with argon gas with low oxygen and water levels. A Maccor 4600 battery test system was used to discharge the batteries under constant current conditions (1 mA). The discharge was stopped at a voltage of 1.75V.

FIG. 34 shows the 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. 34. It can be seen that the composite polymer-sulfur positive electrode provides a high initial capacity of> 1300 mAh / g based on the amount of sulfur in the positive electrode. The battery in FIG. 34 also shows a discharge voltage curve with two plateaus at ~ 2.3 V and ~ 2.1 V. This indicates that the composite polymer-sulfur system allows for high capacitance while giving the expected voltage curve for the lithium / sulfur system consistent with the stable electrochemical pair.

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

FIG. 35 shows a discharge capacity curve plotted as a function of the number of cycles for the Li / composite polymer-sulfur battery 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 knitted composite electrodes are presented in the literature [Ji, X. et al. Lee, K. et al. T. Nazar, L. et al. F. Nature Materials 8,500-506, 2009]. This composite positive electrode uses CMK-3 mesoporous carbon having sulfur anchored in the pores through heat treatment at 155 ° C. FIG. 36 compares the first discharge for Li / Sulfur-CMK-3 of Examples in the literature with the first discharge for Li / composite polymer-sulfur of the present invention.

The composite positive electrode in this example was slurry-casted from cyclopentanone onto a carbon-coated aluminum current collector. The positive electrode used was 84% by weight CMK-3 / S composite, 8% by weight Super-S carbon and 8% by weight PVDF binder. The electrolyte consisted of 1.2 M LiPF ₆ in ethylmethyl sulfone and a Li metal was used as the negative electrode. The results for the composite polymer-sulfur positive electrode of the invention described in Example 16 were plotted on the same graph for comparison. It is clear that the composite polymer-sulfur positive electrode of the present invention gives superior or better results than the examples of the composite sulfur positive electrode in the literature.

Comparative Example 19
The use of sulfur-conductive polymer composites as positive electrodes for lithium batteries has been demonstrated. In one case, polyacrylonitrile (PAN) is sulfurized to form a conductive and chemically active positive electrode material. Sulfation of macromolecules occurs at relatively high temperatures of ~ 300 ° C. US Patent Application No. 2014/0045059 [He, X. -M. , Et al. ] Is shown in FIG. 37 as an example of a discharge curve for this material. FIG. 37 shows a characteristic voltage signature found for Li / sulfur-polyacrylonitrile (S / PAN) batteries. These batteries are characterized by a single gradient 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 positive electrode in the battery of the present invention, it was found that the S / PAN battery showed a significantly lower voltage during discharge, which is watts. -Produces lower energy densities based on time. Thus, the voltage behavior exhibited by the composite polymer-sulfur positive electrode of the present invention is superior to that of the sulfurized PAN-based positive electrode.

Example 20
SRT802 (Liquid Crystal Polymer) polymer is mixed with lithium hydroxide monohydrate as a compound containing an ion source at a ratio of 2: 1 (by weight) to a solid height. A molecular electrolyte sample was prepared. DDQ was used as the dopant. The polymer to dopant weight ratio was 2: 1. The mixture was heat treated under mild pressure (500-1000 PSI) at 325/250 ° C. for 30 minutes. The ionic surface conductivity of the sample was measured using standard AC-EIS. The sample was sandwiched between stainless steel blocking electrodes and placed in a test fixture. The AC-impedance was recorded in the range of 800 KHz to 100 Hz using the Biologic VSS test system to determine the electrolyte conductivity. Six samples were prepared and tested. The average conductivity was 3.7 x 10 ^-4 S / cm and the standard deviation was about 19%. The results are shown in Table 20.1.

Example 21
SRT900 (Liquid Crystal Polymer) polymer is mixed with lithium hydroxide monohydrate as a compound containing an ion source at a ratio of 2: 1 (by weight) to a solid height. A molecular electrolyte sample was prepared. DDQ was used as the dopant. The polymer to dopant weight ratio was 2: 1. The mixture was heat treated under mild pressure (500-1000 psi) at 325/250 ° C. for 30 minutes. The sample was sandwiched between stainless steel electrodes and placed in a test fixture. The AC-impedance was recorded in the range of 800 KHz to 100 Hz using the Biologic VSS test system to determine the electrolyte conductivity. Six samples were prepared and tested. The average conductivity was 1.5 x 10 ^-3 S / cm and the standard deviation was about 25%. The results are shown in Table 21.1 below.

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

The results are shown in the table below. The high conductivity observed is that the polyelectrolyte can conduct a large number of ions including Li ⁺ , K ⁺ , Na ⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , OH ^- and ^Cl- . Suggests.

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

Calcium, magnesium and aluminum conductivity are important in the development of multivalent intercalation systems that can increase energy density, perhaps beyond the capabilities of Li-ion batteries. It is also possible to use such materials to create power sources that use metal negatives that are more stable and cheaper than lithium.

The hydroxyl conductivity is decisive for the chemistry of many alkalis including Zn / MnO ₂ , Ni / Zn, Ni-Cd, Ni-MH, Zn-air, Al-air. Polyelectrolytes that conduct hydroxyl ions can also be used in alkaline fuel cells and supercapacitors.

Example 23
Solid Ionic Conductive Polymer Material:
The polyphenylene sulfide "PPS" (basic polymer) and the tetrachloro-1,4-benzoquinone "chloranil" are mixed and heated to form a solid intermediate polymer material, which is solid ion conduction when mixed with a compound containing an ion source. Produces sex polymer materials. The compound contains 10-50% by weight of the basic polymer. The heating step raises the temperature of the reactants to 250-350 ° C. and takes about 10 minutes to 8 hours to overnight. In one aspect, a solid ionic conductive polymer material or an intermediate thereof or a reactant thereof is mixed with an additive (eg, electrically conductive carbon) to be ionic and also functional attributes of the additive (eg, electrical). It is possible to form a composite material that also provides conductivity).

Zn negative electrode:
Zinc powder (pure powder or zinc powder alloyed with bismuth, indium, calcium, aluminum and other alloying agents known in the art) is a solid intermediate polymer material, lithium hydroxide, conductive carbon. Mix with additives (eg C45 or KS6L graphite by Tincal, EC600-high surface carbon from AkzoNobel), additives zinc oxide and / or other corrosion resistant additives. PVDF or Kynar PVDF is used as a binder and NMP is used as a solvent. A mixer (eg, Thinky) can be used and when used for mixing the mixture is mixed until a uniform slurry is obtained (eg at 2000 rpm for 10-30 minutes). The slurry is then cast by the doctor blade method onto a pre-coated current collector (stainless steel, titanium or nickel foil) 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 coin cell or pouch batteries.

MnO ₂ positive electrode:
The EMD MnO ₂ powder is mixed with a conductive additive (eg C45, KS6L graphite, EC600 high surface carbon, etc.), a solid intermediate polymer material and an ionic compound lithium hydroxide. PVDF (polyvinylidene fluoride) or Kynar PVDF is used as a binder, and NMP (N-methyl-2-pyrrolidone) is used as a solvent. Mix the mixture 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 pre-coated current collector (stainless steel, titanium or nickel foil) 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 coin cell or pouch batteries. Overall, the solid ion conductive polymer material constitutes about 2-30% by weight of the total positive electrode weight, the activity (EMD in this case) is 20-80% by weight, and the 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% by weight potassium hydroxide with zinc oxide as an additive. In one aspect, a 1-3 molar concentration zinc sulphate salt with 0.5-4 wt% manganese sulphate (or other Mn (ii) salt) added is used. These aqueous electrolytes can be added to 0.5-2 wt% gelling agents such as poly (ethylene glycol) di-acids (or other gelling agents known in the art). In one aspect, a solid ion conductive polymer material is used as the electrolyte, no separator is required, and a small amount of KOH solution or other liquid electrolyte solution can optionally be added to the negative or positive electrode.

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

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

Reference to Table 23.1 shows a number of structures using solid ion conductive polymeric materials. Three (1-3) secondary alkaline and zinc air structures are mentioned, including the primary structure, solid-state formulation.

The secondary formulation (1) corresponds to FIG. 41 and related discussions.

The secondary formulation (2) corresponds to FIGS. 38-40 and related discussions. Liquid potassium hydroxide electrolyte was added. The positive and negative electrode fabrication methods do not include the use of mechanical mixers or slurry casting. The negative and positive electrodes are binder-free (without PVDF) and do not require an MNP solvent.

Although the present invention has been described in connection with preferred embodiments, those skilled in the art will make various modifications, replacements of equivalents and other modifications to those set forth herein after reading the specification. Will get. Accordingly, the protection provided herein by letter is intended to be limited solely by the appended claims and the definitions contained within their equivalents.

Claims (12)

An electrochemical cell for generating electrical energy through an electrochemical reaction, including a negative electrode and a positive electrode.
At least one of the negative and positive polymers contains a solid ion conductive polymer material formed from a compound containing a basic polymer, an electron acceptor and an ion source, the basic polymer having a glass transition temperature higher than 80 ° C. at room temperature. The electron acceptor contains tetrachloro-1,4-benzoquinone, and the compound contains any of LiOH, NaOH, KOH, Li ₂ O , and LiNO ₃ ;
The polymeric material has an ionic conductivity greater than 1x10 ^-4 S / cm at room temperature;
The solid ion conductive polymer material can conduct hydroxyl ions ionicly, whereby the solid ion conductive polymer material can conduct hydroxyl ions during the electrochemical reaction;
The solid ion conductive polymer material has a crystallinity of at least 30% or higher; and
The negative electrode contains zinc and the positive electrode contains manganese dioxide.
battery. An electrochemical cell for generating electrical energy through an electrochemical reaction, including a negative electrode and a positive electrode.
At least one of the negative and positive polymers contains a solid ion conductive polymer material formed from a compound containing a basic polymer, an electron acceptor and an ion source, the basic polymer having a glass transition temperature higher than 80 ° C. at room temperature. The electron acceptor contains tetrachloro-1,4-benzoquinone, and the compound contains any of LiOH, NaOH, KOH, Li ₂ O , and LiNO ₃ ;
The polymeric material has an ionic conductivity greater than 1x10 ^-4 S / cm at room temperature;
The solid ion conductive polymer material can conduct hydroxyl ions ionicly, whereby the solid ion conductive polymer material can conduct hydroxyl ions during the electrochemical reaction;
The negative electrode contains a solid ion conductive polymer material and further contains a negative electrode electrochemically active material;
The solid ion conductive polymer material and the negative electrode electrochemically active material are mixed so that the solid ion conductive polymer material can ionicly conduct hydroxyl ions to the negative electrode electrochemically active material; and,
The negative electrode contains zinc and the positive electrode contains manganese dioxide.
battery. The battery according to claim 2, wherein at least a part of the solid ion conductive polymer material is in contact with the negative electrode electrochemically active material. An electrochemical cell for generating electrical energy through an electrochemical reaction, including a negative electrode and a positive electrode.
At least one of the negative and positive polymers contains a solid ion conductive polymer material formed from a compound containing a basic polymer, an electron acceptor and an ion source, the basic polymer having a glass transition temperature higher than 80 ° C. at room temperature. The electron acceptor contains tetrachloro-1,4-benzoquinone, and the compound contains any of LiOH, NaOH, KOH, Li ₂ O , and LiNO ₃ ;
The polymeric material has an ionic conductivity greater than 1x10 ^-4 S / cm at room temperature;
The solid ion conductive polymer material can conduct hydroxyl ions ionically, whereby the solid ion conductive polymer material can conduct hydroxyl ions during the electrochemical reaction; the positive electrode. Includes solid ion conductive polymer material and further contains positive electrode electrochemically active material;
Here, the solid ion conductive polymer material and the positive electrode electrochemically active material are mixed, whereby the solid ion conductive polymer material can ionicly conduct hydroxyl ions to the positive electrode electrochemically active material. Yes; and
The negative electrode contains zinc and the positive electrode contains manganese dioxide.
battery. The battery according to claim 4, wherein at least a part of the solid ion conductive polymer material is in contact with the positive electrode electrochemically active material. An electrochemical cell for generating electrical energy through an electrochemical reaction, including a negative electrode and a positive electrode.
At least one of the negative and positive polymers contains a solid ion conductive polymer material formed from a compound containing a basic polymer, an electron acceptor and an ion source, the basic polymer having a glass transition temperature higher than 80 ° C. at room temperature. The electron acceptor contains tetrachloro-1,4-benzoquinone, and the compound contains any of LiOH, NaOH, KOH, Li ₂ O , and LiNO ₃ ;
The polymeric material has an ionic conductivity greater than 1x10 ^-4 S / cm at room temperature;
The solid ion conductive polymer material can conduct hydroxyl ions ionicly, whereby the solid ion conductive polymer material can conduct hydroxyl ions during the electrochemical reaction;
The positive electrode contains a solid ion conductive polymer material;
The amount of the solid ion conductive polymer material ranges from 1 to 40 weight percent of the positive electrode; and
The negative electrode contains zinc and the positive electrode contains manganese dioxide.
battery. The electrochemical battery according to claim 1, 2, 4 or 6, wherein the positive electrode can donate hydroxyl ions during an electrochemical reaction. The electrochemical cell according to claim 2, 4 or 6, wherein the solid ion conductive polymer material has a crystallinity of at least 30% or higher. The solid ion conductive polymer material contains at least one hydroxyl ion and has an OH-diffusion rate determined by the pulsed field gradient solid-state NMR method, which is greater than ^10-11 at temperatures in the range 20 ° C to 26 ° C. , The electrochemical battery according to claim 2, 4 or 6. The electrochemical battery according to claim 1, 2, 4 or 6, wherein the positive electrode contains an active material that produces hydroxyl ions during an electrochemical reaction. The electrochemical battery according to claim 1, 2, 4 or 6, wherein the electrochemical cell has a ratio C / 2 capacity larger than that of 308 mAh / g manganese dioxide. The solid ion conductive polymer material is located sandwiched between the negative electrode and the positive electrode, whereby the solid ion conductive polymer material conducts hydroxyl ions between the negative electrode and the positive electrode during the electrochemical reaction. The battery according to claim 1, 2, 4 or 6, which is conductive.

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