KR102255457B1 - Electrochemical cell with ion conductive solid polymer material - Google Patents

Abstract

The present invention, the anode; And an electrochemical cell having a cathode; At least one of the anode and the cathode relates to an electrochemical cell comprising an ionically conductive solid polymer material capable of ionically conducting hydroxyl ions.

Description

Electrochemical cell with ion conductive solid polymer material

The present invention relates to an electrochemical cell having an ionically conductive solid polymer material.

Statement of investigation or development supported by the federal government

Batteries are becoming increasingly important in the modern world as a key component in new green technologies as well as powering many portable electronic devices. This new technology offers promise to eliminate reliance on current energy sources such as coal, petroleum products, and natural gas that contribute to the production of greenhouse gases as by-products. Furthermore, the ability to store energy in both static and dynamic applications is critical to the success of new energy sources, which is likely to dramatically increase the demand for advanced batteries of all sizes. Especially for batteries for most applications, lowering the base cost of the battery may be the key to introducing these applications and their overall success.

However, conventional batteries have limitations. For example, lithium ion batteries and other batteries are generally dangerous to people and the environment and can ignite or explode using liquid electrolytes. Liquid electrolyte batteries are hermetically sealed in steel or other strong packaging material, which increases the weight and volume of the packaged battery. Conventional liquid electrolytes form a solid interface layer at the electrode/electrolyte interface, which ultimately renders the battery inoperable. Conventional lithium-ion batteries also exhibit slow charging times and a limited number of recharges because rechargeability is limited due to corrosion and the formation of dendrites when chemical reactions in the battery are completed. Also, while new industrial applications often require voltages above 4.8 volts, the liquid electrolyte begins to break down at about 4.2 volts, limiting the maximum energy density. Conventional lithium-ion batteries require liquid electrolyte separators that allow ion flow but block electron flow, vents to relieve pressure in the housing, and, furthermore, safety circuitry that minimizes potentially dangerous overcurrents and overtemperatures.

In alkaline batteries that rely on transporting ^OH- ions to conduct electricity, the electrolyte is saturated with ions (e.g., zincate ions during discharge of _{Zn/MnO 2 batteries) at certain points.} As a result, water is ultimately depleted at the anode. In rechargeable alkaline batteries, this reaction is reversed during charging. However, if the same ions are formed and saturate the electrolyte, it can interfere with discharge. The cathode reaction ^{releases OH-} ions. However, the formation of soluble low valent species (eg, _{Mn species during discharge of a Zn/MnO 2} battery) can adversely affect the use of the active material. Although MnO ₂ can theoretically undergo 2-electron reduction with a theoretical capacity of 616 mAh/g, a specific capacity close to the theoretical 2-electron discharge has not been demonstrated. When an inactive phase is formed and a soluble product diffuses to the outside, the crystalline structure is rearranged, thereby limiting the cathode capacity.

US patent 7,972,726 describes the use of a pentavalent bismuth metal oxide to improve the overall discharge performance of an alkaline cell. A cathode comprising 10% AgBiO ₃ and 90% electrolytic MnO ₂ was 0.8 at 10 mA/g discharge rate compared to 287 mAh/g for _{100% MnO 2 and 200 mAh/g for 100% AgBiO 3} It has been shown to deliver 351 mAh/g until V cut-off. The 351 mAh/g specific capacity _{corresponds to 1.13 electron discharge of MnO 2} and represents the highest specific capacity delivered in the actual usable discharge rate and voltage range. It has been claimed that the bismuth- or lead-modified MnO ₂ material disclosed in US 5,156,934 and US 5,660,953 can deliver about 80% of the theoretical two-electron discharge capacity over many cycles. This is described in YF Yao, N. Gupta, HS Wroblowa, J. Electroanal. Chem., 223 (1987), 107; HS Wroblowa, N. Gupta, J. Electroanal. Chem., 238 (1987) 93; DY Qu, L. Bai, CG Castledine, BE Conway, J. Electroanal. Chem., 365 (1994), 247] in which bismuth or lead cations stabilize the crystalline structure of _{MnO 2} during discharge and/or through a heterogeneous mechanism involving ^{soluble Mn 2 + species.} It was theorized that reduction could proceed. Inclusion of the Mn ^{2 +} species seems to be the key to achieving _{high MnO 2 utilization and reversibility.} In cathodes with high carbon content (30-70%>) according to US 5,156,934 and US 5,660,953, the resulting highly porous structure was able to absorb soluble species. However, there is no data to suggest that an entire cell using this cathode has been formed or that it has operated using a Zn anode.

Thus, a polymer electrolyte that prevents 1) dissolution of ions that may saturate the electrolyte and 2) prevents dissolution and transport of low-valence chemical species can improve the utilization and rechargeability of alkaline batteries. Furthermore, this is [M. Minakshi, P.Singh, J. Solid State Electrochem, 16 (2012), 1487] _{suggested that Li insertion could stabilize the MnO 2} structure upon reduction and enable recharge. Polymers designed to conduct Li ⁺ ions and OH ^- _{ions open up the possibility of tuning the MnO 2} discharge mechanism to insert protons or lithium, which could serve as an additional tool to improve the life cycle.

Furthermore, the battery technology for many advanced applications is lithium-ion (Li-ion), but in terms of volume (Wh/L) for portable devices and weight (Wh/kg) for electric vehicles and other large-scale applications. Increasing demand for higher energy densities in Li-ion cells presented the need to access technologies far beyond the current performance of Li-ion cells. One promising technology for this is the Li/Sulfur battery. Sulfur-based cathodes are attractive due to their high theoretical energy density (1672 mAh/g), which is ~10x better than current Li-ion metal oxide cathode active materials. Also _{, unlike many current Li-ion battery materials such as LiCoO 2} , sulfur is very interesting because it is a very rich, low cost, and environmentally friendly material.

In recent years, there has been a lot of research activity on Li/Sulfur batteries, and the capacity and cycle life of rechargeable Li/Sulfur cells have advanced. All of these activities aimed at improving cell performance by reducing the polysulfide shuttle and included modifying the cathode, anode, electrolyte and separator. The application of this investigation to the sulfur cathode is two main areas: 1) the use of materials designed to surround and contain sulfur and soluble lithium treated products, see for example US patent application 2013/0065128, and 2) The focus has been on using a conductive polymer that reacts with sulfur to produce a "sulfurized" composite cathode material. Examples of "sulfated-polymers" include polyacrylonitrile (PAN) and reaction products resulting from exposure to sulfur at high temperatures [Jeddi, K., et. al. J. Power Sources 2014, 245, 656-662 and Li, L. et. al. J. Power Sources 2014, 252, 107-112]. Another conductive polymer system used for the sulfur cathode is polyvinylpyrrolidone (PVP) [Zheng, G., et. al. Nano Lett . 2013, 13, 1265-1270] and polypyrrole (PPY) [Ma, G., et. al. J. Power Sources 2014, 254, 353-359]. These methods have met several successes by limiting the polysulfide shuttle mechanism, but all of these methods rely on the use of expensive materials and are not well suited for large-scale manufacturing.

Ion conductive solid polymer materials are provided having very high ionic diffusivity and conductivity at room temperature and over a wide temperature range. The ion conductive solid polymer material can be used as a solid electrolyte for an alkaline battery and also as a component for making an electrode for an alkaline battery. The ion conductive solid polymer material is not limited to battery applications, but may be widely applied to various other purposes such as alkaline fuel cells, supercapacitors, electrochromic devices, sensors, and the like. The ionically conductive solid polymeric material is non-flammable and self-extinguishing, making it particularly attractive for applications where it may be flammable. Furthermore, the ionically conductive solid polymer material is mechanically strong and can be manufactured using bulk polymer processing techniques and equipment known in the art.

In one aspect of the present invention, the ion conductive solid polymer material functions as an electrolyte that transfers ^{OH-ions in an alkaline battery.} The alkaline battery includes Zn/MnO ₂ , Zn/Ni, FE/NI, Zn/air, Ni/metal hydride, silver oxide, metal/air, and others known in the art. However, it may contain several battery chemistries, but are not limited to these. The zinc/manganese oxide (Zn/MnNO ₂ ) chemical is most widely used in consumer alkaline batteries.

An ionically conductive solid polymer electrolyte for a lithium ion battery comprising an ionically conductive solid polymer material is disclosed in co-pending US patent application 13/861,170, filed on April 11, 2013 and assigned to the same assignee as the present invention.

In another aspect of the present invention, the ion conductive solid polymer material is used to form the cathode, electrolyte and anode of an alkaline battery. The three layers of the battery are solid and can be coextruded to efficiently form a battery structure. The individual layers may alternatively also or individually extruded or otherwise formed and layered together to form a battery structure.

The ionically conductive solid polymer material includes at least one compound including a base polymer, a dopant, and an ion source. The dopant includes an electron donor, an electron acceptor, or an oxidizing agent. In ^{one embodiment of the battery having OH-} chemical, the base polymer may be polyphenylene sulfide, polyether ether ketone, also known as PEEK, or liquid crystal polymer. In this example, the dopant is, in a non-limiting example, 2,3, dichloro-5,6-dicyano-1,4-benzoquinone, TCNE, sulfur triacid It is an electron acceptor such as sulfur trioxide or chloranil. Other dopants that act as electron acceptors or contain a functional group capable of accepting electrons may be used. The compound containing the ion source includes a compound containing a hydroxyl ion, or a substance chemically convertible to a compound containing the hydroxyl ion, for example, a hydroxide or an oxide thereof. , Salts or mixtures thereof, including, but not limited to, Li ₂ O, Na ₂ O, MgO, CaO, ZnO, LiOH, KOH, NaOH, CaCl ₂ , AlCl ₃ , MgCl ₂ , LiTFSI (lithium Bis-trifluoromethanesulfonimide), LiBOB (lithium bis(oxalate)borate) or a mixture of the two components. .

The ionically conductive solid polymer material exhibits carbon 13 NMR (detected at 500 MHz) chemical shift peaks at about 172.5 ppm, 143.6 ppm, 127.7 ppm, and 115.3 ppm. Scanning the electron acceptor with a similar carbon 13 NMR, we can see chemical shift peaks at about 195 ppm and 107.6 ppm, in addition to the chemical shift peaks at about 172.5 ppm, 143.6 ppm, 127.7 ppm, and 115.3 ppm. In other words, the reaction between the base polymer and the electron acceptor appears to eliminate chemical shift peaks at about 195 ppm and 107.6 ppm. ^{Furthermore, in the 13} C NMR spectrum of the ion conductive solid polymer, the main peak (dominated by aromatic carbon) shifts from the base polymer to the ion conductive solid polymer. The chemical shift of the dominant peak in the ionically conductive solid polymer is greater than the chemical shift of the dominant peak in the base polymer.

The material has a crystallinity index of at least 30% or greater than about 30%.

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

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

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

The material has a tensile strength in the range of 5-100 MPa, a Modulus of Elasticity in the range of 0.5-3.0 GPa, and an Elongation in the range of 0.5-30%.

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

The OH ^- chemical-bearing battery may be rechargeable or non-rechargeable.

In another aspect, the present invention provides an anode; Cathode; And a rechargeable alkaline battery comprising an electrolyte; At least one of the anode, the cathode, and the electrolyte includes an ion conductive solid polymer material.

In one embodiment of the battery, the battery comprises an anode; Including a cathode; At least one of the anode and the cathode comprises an ion conductive solid polymer material. The battery may be a rechargeable battery or a primary battery. The battery may further include an electrolyte, and the electrolyte may include the ion conductive solid polymer material. The battery may alternatively or additionally further include an electrolyte, and the electrolyte may be an alkali. The ion conductive solid polymer ^{can conduct a plurality of OH-} ions, and has an OH ^{- diffusivity exceeding 10 -11} cm ² /sec at a temperature in the range of 20 °C to 26 °C. It is particularly well suited for use.

The ionically conductive solid polymeric material is formed into a reactant product comprising a compound comprising a base polymer, an electron acceptor, and an ion source. The ion conductive solid polymer material may be used as an electrolyte in the anode or cathode. When used in a battery, the cathode of the battery is ferrate, iron oxide, cuprous oxide, iodate, cupric oxide, mercuric oxide, and oxidation. Cobalt oxide, manganese oxide, lead oxide, silver oxide, oxygen, nickel oxyhydroxide, nickel dioxide, silver peroxide, permanganic acid Permanganate, bromate, silver vanadium oxide, carbon monofluoride, iron disulfide, iodine, vanadium oxide, copper sulfide, It may contain an active material selected from the group comprising sulfur or carbon, and combinations thereof. The anode of the battery includes lithium, magnesium, aluminum, zinc, chromium, iron, nickel, tin, lead, hydrogen, copper, silver, palladium, mercury, platinum or gold, and combinations thereof, and alloy materials thereof. It may contain an active substance selected from the group.

In an alkaline battery, the cathode contains manganese dioxide, and the anode contains zinc. The manganese dioxide is β-MnO ₂ (pyrolusite), ramsdellite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ , electrolytic manganese dioxide (EMD), and chemical manganese dioxide (CMD ), and combinations of the above forms. Further, at least one of the anode and the cathode may include particles of an active material, and the ion conductive solid polymer material may encapsulate at least one particle of the active materials or all of the active materials. These cathodes exhibited specific capacities in excess of 400 mAh/g, 450 mAh/g, and 500 mAh/g.

The battery may alternatively further comprise an electrically conductive additive and/or a functional additive at the anode or cathode. The electrically conductive additive may be selected from the group comprising carbon black, natural graphite, synthetic graphite, graphene, conductive polymer, metal particles, and a combination of at least two 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 (anode or cathode) may be a composite structure that can be formed by processes such as injection molding, tube extrusion, and compression molding. In one embodiment of making the ionically conductive solid polymer material, the base polymer is doped by oxidation in the presence of an ion source. The ion source is a compound containing at least one hydroxyl group, or a compound convertible to a compound containing at least one hydroxyl group, or alternatively LiOH, Li ₂ O or 2 It is a compound selected from the group consisting of mixtures of components. The base polymer is selected from the group comprising liquid crystal polymers, polyether ether ketones (PEEK), and polyphenylene sulfides (PPS), or semi-crystalline polymers with a crystallinity index greater than 30%, and combinations thereof. . The electron acceptor reacting with the base polymer in the presence of the ion source comprises 2,3,dichloro-5,6-dicyano-1,4-benzoquinone, TCNE, sulfur trioxide or chloranyl, and combinations thereof. It can be selected from the containing group. The method may further include a heating step for additional reaction. The electrochemically active substance can be added to the mixing step, when so added it is encapsulated by the reacted ionically conductive polymer. In _{a battery having a MnO 2} cathode, a zinc anode, and an alkaline electrolyte, the alkaline battery exhibits a flat discharge curve having a voltage drop of greater than 1 V and less than 0.3 V at a discharge depth of 5 to 95%. It is characterized.

Since the ion conductive solid polymer material is electrically non-conductive and ion conductive, it can also be used as a separator film. The ionically conductive solid polymer material thus cast into a membrane or otherwise formed can be used as a separator positioned between the anode and the cathode. Further, the ion conductive solid polymer material may be coated on the electrode to function as a separator or alternatively to isolate the electrode or electrode component from other battery components such as an aqueous electrolyte. Ion transfer is possible between the separated components regardless of whether they are physically and electrically separated from the remaining battery components by the ion conductive solid polymer material. The material may further include agglomerates in which small particles of the ion conductive solid polymer material are agglomerated or cast. This agglomeration can take any shape but can include engineered porosity while possessing a designed surface area. A filler, such as a hydrophobic material, can be mixed into this material to provide desirable physical properties such as low effective aqueous porosity. By adding a catalyst to the ion conductive solid polymer material, a combination of catalytic reaction and ionic conductivity required for an air electrode of a metal/air battery may be implemented. Thus, the ionically conductive solid polymeric material may comprise a low or very high surface area and/or a low or very high porosity. Shapes such as annular and other moldable shapes can be designed to have desired physical properties with ionic conductivity of the ionically conductive solid polymer material embodied by the present invention.

According to one aspect, an electrochemical cell comprises an ionically conductive solid polymeric material used for its anode or cathode or both.

In one aspect, the electrochemical cell generates electrical energy through an electrochemical reaction; The ionically conductive solid polymer material can ionically conduct hydroxyl ions, whereby the ionically conductive solid polymer material can conduct hydroxyl ions during the electrochemical reaction.

Additional aspects of the electrochemical cell may include one or more of the following individually or in combination:

The cathode can produce hydroxyl ions during the electrochemical reaction.

The ionically conductive solid polymeric material has a crystallinity index of at least about 30% or greater,

The ionically conductive solid polymer material comprises at least one hydroxyl ion and has an OH-diffusion greater than ^{10 -11} at a temperature in the range of 20°C to 26°C,

The cathode contains an active material that generates hydroxyl ions during an electrochemical reaction.

The anode comprises an ion conductive solid polymer material and further comprises an anode electrochemically active material, and the ion conductive solid polymer material and the anode electrochemically active material are mixed, whereby the ion conductive solid polymer material converts hydroxyl ions into the anode electricity. It can conduct ionic conduction with chemically active substances.

The cathode comprises an ion conductive solid polymer material and further comprises a cathode electrochemically active material, and the ion conductive solid polymer material and the cathode electrochemically active material are mixed, whereby the ion conductive solid polymer material converts hydroxyl ions into the cathode. It can conduct ionic conduction with chemically active substances.

At least some of the ionically conductive solid polymeric material contacts the anode electrochemically active material.

At least some of the ionically conductive solid polymer material contacts the cathode electrochemically active material.

The cathode contains manganese dioxide, and the cell has a specific capacity of manganese dioxide greater than 308 mAh/g.

The ionically conductive solid polymeric material is interposed between the anode and the cathode, whereby the ionically conductive solid polymeric material conducts hydroxyl ions between the anode and the cathode.

The cathode comprises an ionically conductive solid polymer material, and the amount of the ionically conductive solid polymer material is in the range of 1 to 40 weight percent of the cathode.

The cell is rechargeable, the cathode contains manganese dioxide, and the amount of manganese dioxide is in the range of 20 to 90 weight percent of the cathode.

The cell is a primary battery, the cathode contains manganese dioxide, and the amount of manganese dioxide is in the range of 50 to 95 weight percent of the cathode.

The cell further contains a liquid electrolyte, and the liquid electrolyte contains hydroxyl ions.

Both the anode and cathode contain an ionically conductive solid polymer material, the cell is in a solid state and does not contain any liquid electrolyte, whereby the ionic conductivity of the cell is made possible through the ionically conductive solid polymer material.

The anode contains zinc, the cathode contains manganese dioxide, and the cell is a primary battery.

The anode contains zinc, the cathode contains manganese dioxide, and the cell is a secondary battery.

The anode contains aluminum, the cathode contains manganese dioxide, and the cell is a primary battery.

The anode contains zinc, and the cathode is simply exposed to oxygen or fluidly connected, whereby the oxygen functions as a cathode electrochemically active material.

1 is a diagram illustrating the final equation for the crystalline polymer of the present invention by way of example;
Fig. 2 is a diagram exemplarily showing a dynamic scan calorimeter curve of a semi-crystalline polymer;
3 is a diagram illustratively showing a formulation irradiated for use in the present invention;
4 is a schematic diagram of an amorphous polymer and a crystalline polymer;
FIG. 5 is a diagram exemplarily showing the chemical formula of 2,3-dicyano-5,6-dichlorodicyanoquinone (DDQ) as a general electron acceptor dopant used in the present invention;
6 is a graph exemplarily showing the conductivity of an ion conductive polymer according to the present invention compared to a liquid electrolyte and a polyethylene oxide lithium salt compound;
Fig. 7 is a diagram exemplarily showing the mechanical properties of the ion conductive film according to the present invention;
8 is a diagram exemplarily showing a possible conduction mechanism of a solid electrolyte polymer according to the present invention;
9 is a diagram illustratively showing a UL94 flammability test performed on a polymer according to the present invention;
10 is a graph exemplarily showing a curve of volts versus current for an ion conductive polymer versus lithium metal according to the present invention;
11 is a schematic diagram exemplarily showing an extruded ion conductive electrolyte and electrode component according to the present invention;
12 is a diagram exemplarily showing a solid state battery according to the present invention in which an electrode and an electrolyte are bonded together;
13 is an exemplary diagram illustrating a final solid state battery according to the present invention with a new flexible form;
14 is a diagram illustratively illustrating a method of the present invention comprising the step of manufacturing a solid state battery using an extruded polymer;
15 is a diagram exemplarily showing an extrusion process according to the present invention;
16 is a diagram schematically illustrating an exemplary embodiment according to the present invention;
17 is a diagram exemplarily showing an alkaline battery having three layers of the present invention;
18 is a diagram showing an exemplary comparison between the process steps of extruding the composite polymer-sulfur cathode of the present invention and the process steps of producing a standard Li-ion cathode;
FIG. 19 is a diagram illustrating an exemplary degree of ^OH- diffusion at room temperature in the solid polymer electrolyte of the present invention;
Fig. 20 is a diagram showing exemplary lithium diffusivity at room temperature in the solid polymer electrolyte of the present invention;
FIG. 21 is a diagram exemplarily showing the voltage profile of a cell of the invention according to Example 2 as a function of the specific capacity of _{MnO 2} at a discharge rate of 0.5 mA/cm ^2;
22 is a diagram exemplarily showing the voltage profile of the inventive cell according to Example 3 as a function of the specific capacity of _{MnO 2} at C/9 discharge rate (35 mA/g);
23 is a diagram exemplarily showing the specific capacity _{of MnO 2} as a function of the number of cycles in the inventive cell according to Example 4;
24 is a diagram exemplarily showing a discharge curve of a coin cell of the present invention according to Example 5 as a function of test time;
25 is a diagram exemplarily showing the voltage profile of a cell of the present invention according to Example 6 as a function of test time;
26 is a diagram exemplarily showing the discharge curve of the coin cell of the present invention according to Example 7 as a function of the discharge capacity;
FIG. 27 is a diagram exemplarily showing a scan of an anode (curve A) and a control Al foil (curve B) of the present invention with a dynamic potential at 1 mV/s in a _{ZnSO 4 electrolyte (wherein the Zn foil is a counter electrode.} Was used);
28 is a diagram showing the specific capacity of a Duracell Coppertop AA cell under several constant current discharge rates;
29 is a diagram showing a discharge curve for an alkaline button cell at 10 mA/g discharge rate according to the prior art;
30 is a diagram exemplarily showing the voltage profile of a cell of the invention according to Example 12 at a constant current discharge of 35 mA/g as a function of the specific capacity of _{MnO 2;}
FIG. 31 is a diagram exemplarily showing the voltage profile of the inventive cell according to Example 13 as a function of the specific capacity of _{MnO 2;}
32 is a diagram exemplarily showing the voltage profile of a cell of the present invention according to Example 14 as a function of the specific capacity of _{MnO 2} compared to a Duracell Coopertop cell;
33 is a diagram exemplarily showing the voltage profile of a cell of the present invention according to Example 15 as a function of the specific capacity of _{MnO 2} compared to a Duracell Coopertop cell;
34 is a diagram exemplarily showing a first discharge voltage curve of a Li/ion conductive polymer-sulfur cell of the present invention;
35 is a graph exemplarily showing a discharge capacity curve as a function of the number of cycles of a Li/ion conductive polymer-sulfur cell of the present invention;
36 is a diagram exemplarily comparing the first discharge for Li/ion conductive polymer-sulfur of the present invention and literature example Li/sulfur-CMK-3;
37 is a diagram showing a charge/discharge voltage curve for a Li/sulfur-poly(pyridinopyridine) cell of the prior art;
38 is a diagram showing the velocity profile of a coin cell;
39 is a diagram showing cathode capacity versus cell energy density;
Fig. 40 is a diagram showing coin cell discharge capacity versus discharge current;
41 is a graph showing voltage over time for one cell embodiment.

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

The present invention includes an ionically conductive solid polymeric material comprising at least one compound comprising a base polymer, a dopant, and an ion source. The polymeric material has ionic conductivity over a wide temperature range including room temperature. It is believed that ion "hopping" occurs from a high density of atomic sites. Thus, the polymeric material can function as a means of supplying ions and has considerable material strength.

In this application, the term "polymer" refers to a polymer having a crystalline or semi-crystalline structure. In some applications, the ionically conductive solid polymer material may be molded into a shape that can be folded over itself, allowing for new physical formats depending on the application. The base polymer is selected according to the desired properties of the composition related to the desired application.

In this application, the term "dopant" refers to an electron acceptor or an oxidizing agent or an electron donor. The dopant is selected according to the desired properties of the composition related to the desired application.

Similarly, the compound comprising the ion source is selected according to the desired properties of the composition related to the desired application.

I. Li ⁺ chemical

In one aspect, the present invention relates to a solid polymer electrolyte comprising an ionically conductive solid polymer material in a lithium ion battery.

In this aspect, the base polymer is characterized as having a crystallinity value of 30% to 100%, preferably greater than 50% to 100%. The base polymer has a glass transition temperature in excess of 80°C, preferably in excess of 120°C, more preferably in excess of 150°C and most preferably in excess of 200°C. The base polymer has a melting temperature in excess of 250°C, preferably in excess of 280°C and more preferably in excess of 320°C. The molecular weight of the monomer units of the base polymer of the present invention is in the range of 100-200 gm/mol and may exceed 200 gm/mol. 1 shows the molecular structure of an exemplary base polymer, wherein the monomer units of the base polymer have a molecular weight of 108.16 g/mol. 2 illustratively shows a dynamic scan calorimeter curve of an exemplary semi-crystalline base polymer. 3 shows an exemplary formulation for an ionically conductive solid polymeric material in which DDQ is a dopant in this aspect of the invention. Typical materials that can be used in the base polymer include liquid crystal polymers, and polyphenylene sulfide, also known as PPS, or any semi-crystalline polymer having a crystallinity index greater than 30%, preferably greater than 50%. In one embodiment, the present invention generally has a crystallization value greater than 30%, a glass transition temperature greater than 200° C., and a melting temperature greater than 250° C. Crystalline or semi-crystalline polymers" are used.

In this aspect, the dopant is, in a non-limiting example, 2,3-dicyano-5,6-dichlorodicyanoquinone (C ₈ Cl ₂ N ₂ O ₂ ), also known as DDQ, tetracyano, also known as TCNE. Electron acceptors such as tetracyanoethylene (C ₆ N ₄ ), and sulfur trioxide (SO _{3 ).} A preferred dopant is DDQ. 5 provides the formula of this preferred dopant. The purpose of the electron acceptor is two-fold, it is considered to release ions for transport and to allow ionic conduction by forming polar sites at a high density in the polymer. The electron acceptor is “pre-mixed” with the initial ingredient and can be extruded without post-treatment, or alternatively, after forming the material, the electron acceptor in the composition using a doping procedure such as vapor doping. Can be added.

Typical compounds comprising an ion source used in this aspect of the invention include, but are not limited to _{, Li 2} O, LiOH, ZnO, TiO ₂ , Al ₃ O _{2, and the like.} Compounds containing suitable ions in a stable form can be denatured after forming a solid polymeric electrolytic film.

Other additives, such as carbon particle nanotubes, may be added to the solid polymer electrolyte containing an ionically conductive solid material to further improve electrical conductivity or current density.

The novel solid polymer electrolyte enables a lighter weight and much more secure architecture by eliminating the need for heavy and bulky metal-tight packaging and protection circuitry. New solid polymer batteries comprising solid polymer electrolytes can have a smaller size, lighter weight, and higher energy density than liquid electrolyte batteries of the same capacity. The novel solid polymer battery has the benefit of a less complex manufacturing process, lower cost, and reduced safety risk because the electrolyte material is non-flammable. The novel solid polymer battery can achieve cell voltages in excess of 4.2 volts and is stable to higher and lower voltages. The novel solid polymer electrolyte can be formed into several shapes by extrusion (and coextrusion), molding, and other techniques to provide different form factors to the battery. Certain shapes can be made to fit into multiple configurations of enclosures in powered devices or equipment. Furthermore, the novel solid polymer battery does not require a separator between the electrolyte and the electrode as in a liquid electrolyte battery. The weight of the novel solid polymer battery is significantly less than that of a conventional structured battery with similar capacity. In some embodiments, the weight of the novel solid polymer battery may be less than half the weight of a conventional battery.

In another aspect of the present invention, the solid polymer electrolyte comprising an ionically conductive solid polymer material is in the form of an ionically conductive polymer membrane. The electrode material is applied directly to each surface of the ion conductive polymer film, and a foil-filled collector or terminal is applied over each electrode surface. A light weight protective polymer sheath can be applied over these terminals to complete the membrane-based structure. The membrane-based structure is flexible to form a thin film battery that can be rolled or folded into an intended shape to suit installation requirements.

In yet another aspect of the invention, the solid polymer electrolyte comprising an ionically conductive solid polymer material is in the form of an ionically conductive polymer hollow monofilament. The electrode material and charge collector are applied directly (co-extrusion) to each surface of the ion conductive solid polymer material, and the terminals are applied to each electrode surface. A light weight protective polymer sheath can be applied over these terminals to complete the structure. The structure is thin and flexible to form a battery that can be wound into an intended shape for installation requirements, including very small applications.

In yet another aspect of the invention, a solid polymer electrolyte comprising an ionically conductive solid polymer material has a desired molding shape. A cell unit may be formed by disposing the anode and cathode electrode materials on each of the opposing surfaces of the solid polymer electrolyte. Electrical terminals may be provided on the anode and cathode electrodes of each cell unit to interconnect with other cell units to provide a multi-cell battery or to connect to a device for use.

In an aspect of the invention with respect to batteries, electrode materials (cathode and anode) can be combined with a novel form of ionically conductive solid polymer material to further improve ion movement between the two electrodes. This is similar to how a conventional liquid electrolyte is impregnated into each electrode material of a conventional lithium-ion battery.

Films of the ionically conductive solid polymer material of the present invention were extruded to thicknesses ranging from 0.0003 inches to more. The surface ionic conductivity of the membrane was measured using a standard test of AC-Electrochemical Impedance spectroscopy (AC-EIS) known to a person skilled in the art. A sample of a membrane of an ionically conductive solid polymer material was sandwiched between stainless steel blocking electrodes and placed on a test rig. The conductivity of the electrolyte was determined by recording the AC-impedance in the range of 800 KHz to 100 Hz using a biological VSP test system. The result of measuring the surface conductivity is shown in FIG. 6. The conductivity (Δ) of the ion conductive solid polymer material membrane according to the present invention is that of trifluoromethane sulfonate PEO (□), and Li salt solute and EC using a Celgard separator. : Compared to that of a liquid electrolyte (O) made from a solvent that combines PC. The conductivity of the membrane of the ionically conductive solid polymer material according to the present invention follows the conductivity of the liquid electrolyte and far exceeds that of the trifluoromethane sulfonate PEO at lower temperatures. Furthermore, unlike PEO electrolytes, the temperature dependence of the conductivity of the polymeric material of the present invention is the glass transition temperature, which is associated with chain mobility, explained by the temperature-activated Vogel-Tamman-Fulcher (VTF) behavior. There is no sharp increase in the above. Thus, it is unlikely that there will be segmental motion in the ion-conducting mechanism in the polymeric material of the present invention. Furthermore, this demonstrates that the polymeric material of the present invention has similar ionic conductivity to a liquid electrolyte.

7 shows the mechanical properties of the film of an ionically conductive solid polymer material of the present invention. This mechanical property was evaluated using the International Institute for Interconnecting and Packaging Electronic Circuits IPC-TM-650 Test Method Manual 2.4.18.3. In the tensile strength versus elongation curve of FIG. 7, the “ductile failure” mode indicates that this material can be very tough.

The ionically conductive solid polymer material of the present invention offers three key advantages in its polymer performance properties, namely: (1) This polymer material has a wide temperature range. In laboratory-scale tests, crystalline polymers showed high ionic conductivity at room temperature and over a wide temperature range. (2) This polymer material is non-flammable. This polymer is self-extinguishing, so it passes the UL-V0 flammability test. The ability to operate at room temperature and its non-flammable properties demonstrate a transitional safety improvement that eliminates costly thermal management systems. (3) This polymeric material provides low-cost, high-volume manufacturing. Instead of spraying this polymer over the electrodes, the polymeric material can be extruded into a thin film through a roll-to-roll process, the industry standard for making plastics. After the film has been extruded, the film can be coated with an electrode and charge collector material to form a battery "from inside to outside". This enables a thin, flexible shape factor, without requiring airtight packaging, so that it can be easily integrated into vehicle and storage applications at low cost.

The ionically conductive solid polymer material of the present invention provides a higher density of sites for ion transport and the conductive material is higher without the risk of thermal runaway or damaging the ion transport site, for example from lithium treatment. It is thought to form a new ion conduction mechanism capable of sustaining voltage. Due to this property, the ionically conductive solid polymer material is durable when applied to anode materials and higher voltage cathode thin films, creating a higher energy density in the battery, allowing it to be used in vehicle and static storage applications. Mechanically robust, chemically resistant and moisture resistant, non-flammable, ionically conductive solid polymer materials not only at room temperature, but also over a wide temperature range, due to their ability to maintain high voltages, the costly heat and energy used industrially today High-performance electrodes can be integrated without a safety mechanism.

Batteries using a solid polymer electrolyte comprising an ionically conductive solid polymer material of the present invention not only improve energy density compared to currently commercially available electrolytes, but also have a performance range of -40°C to 150°C with minimal decrease in conductivity. It is characterized. The solid polymer electrolyte can be extruded by a process of producing a polymer mold having a thickness of 6 microns, and thus can be implemented in a thin film form under commercial manufacturing conditions on a batch scale. Furthermore, this extrusion process can realize a manufacturing line that produces a solid polymer electrolyte at low cost with high throughput, and this process can be integrated into a number of different production lines, including manufacturing lithium and zinc batteries. Battery cost can be reduced by up to 50%.

Furthermore, the ionically conductive solid polymer material is not limited to being used in batteries, but may also be used in any device or composition comprising an electrolyte material. For example, novel ionically conductive solid polymer materials can be used in electrochromic devices, electrochemical sensors, supercapacitors and fuel cells. 8 shows a possible conduction mechanism of an ionically conductive solid polymer material in the solid polymer electrolyte aspect of the present invention. As a result of the doping process, a charge carrier complex is formed in the polymer.

The flammability of the solid polymer electrolyte comprising the ionically conductive solid polymer material of the present invention was tested using the UL94 flame test. In order for a polymer to be UL94-V0 rated, it must be “self-extinguishing” and “not fall apart.” Within 10 seconds, the solid polymer electrolyte was tested for this property and this solid polymer electrolyte was self-extinguishing in 2 seconds , It was determined that it did not fall, and thus easily passed the rating V0. Fig. 9 shows a photograph of the result.

In addition to ionic conductivity, flame resistance, high temperature behavior properties, and excellent mechanical properties, it is desirable that the solid polymer electrolyte comprising the ion conductive solid polymer material of the present invention is electrochemically stable at low and high potentials. A traditional test for electrochemical stability is cyclic voltammetry when the working electrode potential is inclined linearly with time. In this test, the polymer is sandwiched between a lithium metal anode and a block stainless steel electrode. A voltage is applied and this voltage is positively swept with a high value for stability on the oxidation side (value exceeding 4 volts for Li), and a low value for stability on the reducing side (value less than 0 V for Li). It is negatively swept. Measuring the current output can determine whether any significant response has occurred at the electrode interface. If there is a high current output at a positive high potential, this means that an oxidation reaction takes place, and it may imply that the cathode material is unstable to operate at this positive potential (such as many metal oxides) or at a potential above this zero potential. have. If there is a high current output at a low potential, this means that a reduction reaction takes place, suggesting that the operation of the anode at or above this negative potential (such as metal Li or lithium-treated carbon) is unstable. I can. 10 shows a graph of voltage versus current for an ionically conductive solid polymer material versus a solid polymer electrolyte comprising lithium metal in accordance with the present invention. Studies show that solid polymer electrolytes are stable up to about 4.4 volts. These results indicate that solid polymer electrolytes can be stable in cathodes including LCO, LMO, NMC and similar cathodes with low voltage cathodes such as iron phosphate and sulfur cathodes in non-limiting examples.

The solid polymer electrolyte comprising the ionically conductive solid polymer material of the present invention can achieve the following properties, namely: A) high ionic conductivity at room temperature and over a wide temperature range (at least -10°C to +60°C); B) non-flammable; C) the possibility of extruding into thin films, allowing for reel-reel processing and new manufacturing methods; D) Compatibility with lithium metal and other active substances. Thus, the present invention can produce a true solid state battery. The present invention allows a new generation of batteries with the following characteristics:

- No safety issues;

- New shape factor;

- large increase in energy density; And

- Great improvement in energy storage costs.

11, 12 and 13 show several elements of a solid state battery comprising the ionically conductive solid polymer material of the present invention, namely: A) an extruded electrolyte; B) extruded anode and cathode; And C) a final solid state battery that allows for new shape factors and flexibility, respectively.

In another aspect, the present invention provides a method of making a Li battery comprising the ionically conductive solid polymer material of the present invention. 14 shows a method of manufacturing a solid state lithium ion battery using an extruded ion conductive solid polymer material according to the present invention. This material is compounded into pellets and then extruded through a die to produce a film of variable thickness. The electrodes can be applied to the membrane using several techniques including sputtering or conventional slurry casting.

In another aspect, the present invention comprises heating the ionic polymer membrane to a temperature of about 295° C., followed by casting the ionic polymer membrane onto a chill roll that solidifies the plastic. It provides a method of manufacturing an ion conductive polymer membrane comprising a polymer material. This extrusion method is shown in FIG. 15. The resulting film can be very thin in the range of up to 10 microns thick. 16 shows a schematic diagram of the architecture of one embodiment according to the present invention.

II. OH ^- chemical

The present invention also relates to an ion conductive solid polymer material, which is designed to transport ^{OH-ions and can be applied to alkaline batteries.} In the present invention, the term "alkali battery or alkaline batteries" refers to batteries or batteries using an ^{alkaline (including OH −) electrolyte.} Such battery chemicals _{include, but are not limited to, Zn/MnO 2} , Zn/Ni, Fe/Ni, Zn/air, Al/air, Ni/metal hydride, silver oxide, and the like. Zn/MnO ₂ chemicals are probably the most widely used and are the primary option for consumer batteries. Although many of the embodiments described herein _{relate to Zn/MnO 2} chemicals, those skilled in the art will appreciate that the same principles are widely applicable to other alkaline systems.

Alkaline batteries rely on carrying ^OH- ions to conduct electricity. In most cases, OH ^- ions are also participants in the electrochemical process. For example, _{during the discharge of a Zn/MnO 2} battery, the zinc anode releases 2 electrons and consumes ^OH-ions:

^{(1) Zn + 4 OH -} → Zn (OH) 4 2 - + 2e -

^{(2) Zn + 2 OH -} → Zn (OH) 2 + 2e - → ZnO + H 2 O

(3) Zn(OH) ₂ → ZnO + H ₂ O

During the initial phase of battery discharge, reaction (1) produces soluble zincate ions that can be found in the separator and cathode [Linden's Handbook of Batteries, Fourth Edition]. At certain points, the electrolyte is saturated with zincate and the reactant product turns into insoluble Zn(OH) ₂ (2). Eventually, the anode lacks water and the zinc hydroxide is dehydrated by equation (3). In rechargeable batteries, the reaction is reversed during charging of the battery. The formation of soluble zincate ions during the initial stages of Zn discharge can interfere with recharging.

The cathode reaction involves reducing ^{Mn 4 +} to Mn ^{3 +} by a proton insertion mechanism, ^{releasing OH −} ions (4). _{The theoretical specific capacity of MnO 2} for this one-electron reduction is 308 mAh/g. Discharging at a slow rate at a lower voltage further discharges MnOOH as shown by Equation (5), thereby forming a total specific capacity (1.33 e) of 410 mAh/g. In most prior art applications, the MnO ₂ discharge is limited to a one-electron process. The use of activity is exacerbated by the formation of soluble, low-valence Mn species.

^{_{(4) MnO 2 + e -}} + H 2 O → MnOOH + OH -

^{(5) 3 MnOOH + e -} → Mn 3 O 4 + H 2 O + OH -

_{(6) MnO 2 + 2 e} - + 2 H 2 O → Mn (OH) 2 + 2 OH -

MnO ₂ can theoretically represent a 2-electron reduction according to Equation (6) with a theoretical specific capacity of 616 mAh/g in an actual prior art battery, but this has not been proven. One of the factors limiting cathode capacity is that an inactive phase such as Hausmanite Mn ₃ O _{4 is formed and the soluble product diffuses outward to rearrange the crystalline structure.}

US patent 7,972,726 describes the use of a pentavalent bismuth metal oxide to improve the overall discharge performance of an alkaline cell. A cathode comprising 10% AgBiO ₃ and 90% electrolytic MnO ₂ was 287 mAh/g for _{100% MnO 2 and 200 mAh/g for 100% AgBiO 3} compared to 0.8 V cut-off at a discharge rate of 10 mA/g. It has been shown to deliver 351 mAh/g. The specific capacity of 351 mAh/g _{corresponds to 1.13 electron discharge of MnO 2} and represents the highest specific capacity delivered in the actual usable discharge rate and voltage range.

In principle, reaction (4) is reversible, opening up possibilities for _{rechargeable Zn/MnO 2 batteries.} In fact, only shallow cycling is allowed if the crystalline structure collapses and a soluble product is formed.

It has been claimed that the bismuth- or lead-modified MnO ₂ material disclosed in US 5,156,934 and US 5,660,953 can deliver about 80% of the theoretical two-electron discharge capacity over many cycles. This is described in YF Yao, N. Gupta, HS Wroblowa, J. Electroanal. Chem., 223 (1987), 107; HS Wroblowa, N. Gupta, J. Electroanal. Chem., 238 (1987) 93; DY Qu, L. Bai, CG Castledine, BE Conway, J. Electroanal. Chem., 365 (1994), 247] in which bismuth or lead cations _{stabilize the crystalline structure of MnO 2} during discharge and/or reaction (6) can proceed through a heterogeneous mechanism involving ^{soluble Mn 2 + species.} Was theorized to be. Including the Mn ^{2 +} species seems to be the key to achieving high MnO _{2 utilization and reversibility.} At high carbon content (30-70%) cathodes according to US 5,156,934 and US 5,660,953, the resulting highly porous structure was able to absorb soluble species. However, there is no data to suggest that an entire cell using this cathode has been formed or that it has operated using a Zn anode.

Thus, a polymer electrolyte that prevents the dissolution and transport of low valence manganese species and zincate ions can be very advantageous _{in improving MnO 2} utilization and achieving rechargeability of Zn/MnO _{2 cells.}

In addition to proton insertion, MnO ₂ can be reduced by intercalating Li. It has been suggested that Li insertion _{can stabilize the MnO 2} structure upon reduction to realize rechargeability [M. Minakshi, P. Singh, J. Solid State Electrochem, 16 (2012), 1487].

Designed to conduct Li ⁺ ions and OH ^- ions, the ionically conductive solid polymer material of the present invention _{opens up the possibility of tuning the MnO 2} discharge mechanism to insert protons or lithium, which can serve as an additional tool to improve cycle life. have.

Accordingly, in one aspect, the present invention provides a polymeric material comprising at least one compound comprising a base polymer, a dopant, and an ion source, wherein the polymeric material is an ion conductive solid having mobility for ^OH-ions. It is a polymer material. In the present application, ^{the term "mobility for OH-} ions" refers to a diffusivity exceeding ^{10 -11} cm ² /sec or a conductivity of ^{10 -4} S/cm at room temperature of 20°C to 26°C. The ion conductive solid polymer material is suitable for use in alkaline cells.

In various aspects, the present invention provides ^{an electrolyte comprising an ion conductive solid polymer material having mobility for OH-} ions, wherein the electrolyte is a solid polymer electrolyte used in alkaline batteries; An electrode or electrodes including the solid polymer electrolyte; And/or a cell or cells including the electrode or electrodes.

In another aspect, the present invention provides an electrode, a cathode and an anode comprising a solid polymer electrolyte for use in an alkaline cell, the solid polymer electrolyte comprising an ion conductive solid polymer material having mobility for ^OH-ions. In another aspect, the present invention provides an electrolyte interposed between a cathode and an anode, wherein at least one of the electrolyte, the cathode, and the anode comprises an ionically conductive solid polymer material having mobility for ^{OH − ions.} In another aspect, the present invention provides an alkaline battery comprising a cathode layer, an electrolyte layer and an anode layer, wherein at least one of the layers comprises an ionically conductive solid polymer material having mobility for ^OH-ions. The latter aspect is exemplarily shown in FIG. 17.

The base polymer of an ionically conductive solid polymeric material with mobility for OH ^- ions is generally a crystalline or semi-crystalline polymer having a crystallization value of 30% to 100%, preferably greater than 50% to 100%. The base polymer of this aspect of the invention has a glass transition temperature of more than 80°C, preferably more than 120°C, more preferably more than 150°C, most preferably more than 200°C. The base polymer has a melting temperature in excess of 250°C, preferably in excess of 280°C, more preferably in excess of 280°C and most preferably in excess of 300°C.

The dopant of an ionically conductive solid polymeric material with mobility for OH ^{-ions is an electron acceptor or an oxidizing agent.} Typical dopants used in this aspect of the invention are DDQ, TCNE, SO ₃ and the like.

Compounds comprising an ion source of an ionically conductive solid polymeric material having mobility for OH ^- ions include salts, hydroxides, oxides or other substances that contain hydroxyl ions or are convertible to such substances, for example, LiOH, NaOH, KOH, Li ₂ O, LiNO ₃ and the like.

OH ^- ionically conductive solid materials with mobility for ions are characterized by a ^{minimum conductivity of 1 x 10 -4} S/cm at room temperature and/or a diffusivity of ^OH- ions in excess ^{of 10 -11} cm ^{2 /sec at room temperature.} do.

The cathode of the present invention for OH ^- _{chemicals comprises MnO 2} , NiOOH, AgO, air (O ₂ ) or similar active substances. MnO ₂ is a preferred material, β-MnO ₂ (manganese ore), ramsdelite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ and other MnO ₂ phases or mixtures thereof, e.g. EMD and CMD Including, but not limited to, may be in the form of a mixture.

OH ^- The cathode of the present invention for chemicals comprises, prior to forming the ionically conductive solid polymeric material, the components of the ionically conductive solid polymeric material of the invention comprising a compound comprising the base polymer, the dopant, and an ion source. It is prepared by mixing the active material with the cathode to form a mixture. Alternatively, the cathode active material is mixed with an already formed ionically conductive solid 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 cathode active material may, in non-limiting embodiments, comprise several forms such as powder form, particle form, fibrous form, and/or sheet form. The cathode of the present invention is active in an amount of 10% to 90% by weight, preferably 25% to 90% by weight, more preferably 50% to 90% by weight based on the total weight of the cathode. Contains substances. The cathode may further comprise 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. The cathode may contain an electrically conductive additive in an amount of 0% to 25% by weight, preferably 10% to 15% by weight, based on the total weight of the cathode. The cathode of the present invention for OH ^- chemicals may further comprise one or more functional additives to improve performance. The cathode active material may be encapsulated by the ionically conductive solid polymer material of the present invention.

The anode of the present invention for OH ^- chemicals may contain active substances of Zn in the form of zinc powder, zinc flakes and other shapes, zinc sheets, and other shapes. All of these types of zinc can be alloyed to minimize zinc corrosion.

OH ^- The anode of the present invention for chemicals, prior to forming the ionically conductive solid polymeric material, comprises a base polymer, a dopant, and a compound comprising an ion source, and the anode activity. It is prepared by mixing the substances to form a mixture. Alternatively, the anode active material is mixed with an already formed ionically conductive solid polymer material. This mixture is molded and/or extruded at a temperature of 180° C. to 350° C. The anode of the present invention is active in an amount of 10% to 90% by weight, preferably 25% to 90% by weight, more preferably 50% to 90% by weight based on the total weight of the anode. Contains substances. The anode may further comprise 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. The anode may contain an electrically conductive additive in an amount of 0% to 25% by weight, preferably 10% to 15% by weight, based on the total weight of the anode. The anode of the present invention for OH ^- chemicals may further comprise one or more functional additives to improve performance. The anode active material may be encapsulated by the ionically conductive solid polymer material of the present invention.

In another aspect, the present invention provides _{a Zn/MnO 2} battery comprising an electrolyte interposed between a _{MnO 2 cathode and a Zn anode.} The electrolyte in this aspect may comprise ^{an ionically conductive solid material of the present invention having mobility for OH-} ions or may comprise a conventional separator filled with a liquid electrolyte. The cathode may comprise an ionically conductive solid material having mobility for ^OH- ions of the present invention or may comprise a _{commercial MnO 2} cathode. The anode may comprise a Zn foil, a Zn mesh, or a Zn anode comprising the ionically conductive solid material of the present invention having mobility for ^{OH − ions in this aspect, or otherwise prepared.} In the Zn/MnO ₂ battery of the present invention, the electron conductive solid polymer material of the present invention having mobility for ^{OH-ions is included in at least one of a cathode, an anode, and an electrolyte.}

III. Polymer-MnO ₂ composite cathode

The present invention relates to a polymer-MnO ₂ composite cathode having a high specific capacity, and a first alkaline cell comprising the cathode. More specifically, the present invention further relates to a polymer-MnO ₂ composite cathode having a specific capacity close to the theoretical two-electron discharge, and a first alkaline cell comprising the cathode. The alkaline cell can be discharged at a current density comparable to that of a commercial alkaline cell while delivering usable capacity up to a typical 0.8V voltage cutoff.

In a different aspect, the present invention provides a cathode made of a MnO _{2 active material comprising a plurality of active MnO 2} particles intermixed with an ionically conductive solid polymer material comprising a compound comprising a base polymer, a dopant, and an ion source, and the It features a method of making the cathode. In another aspect, the invention features an electrochemical cell comprising a cathode, an anode, and a separator disposed between the cathode and the anode, and a method of making the cathode. The cathode is made of a MnO _{2 active material comprising a plurality of active MnO 2} particles intermixed with an ion conductive solid polymer material comprising a compound comprising a base polymer, a dopant, and an ion source. The cathode and electrochemical cells of the present invention are characterized by a flat discharge curve.

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

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

In the aspect of the invention related to the polymer -MnO ₂ compound cathode, is on the compound including a hydroxyl ion source is contained, or convert the material salts, hydroxides, oxides or other the material, for example, LiOH, NaOH , KOH, Li ₂ O, LiNO ₃ and the like.

In the aspect of the invention regarding the polymer-MnO _{2 composite cathode, the MnO 2} active material is β-MnO ₂ (lead manganese), ramsdelite, γ-MnO ₂ , ε-MnO ₂ , λ-MnO ₂ and other MnO ₂ phases. Or mixtures thereof, such as, but not limited to, EMD and CMD.

The cathode associated with the polymer-MnO ₂ composite cathode comprises the steps of mixing an ionically conductive solid polymer material comprising a compound comprising a base polymer, a dopant, and an ion source with a plurality of active MnO ₂ particles, and mixing the mixture for a specific period of time. It can be prepared by heating to temperature. The heating can optionally be carried out while applying pressure.

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

In a preferred embodiment, the present invention _{features an alkaline battery comprising the polymer-MnO 2} composite cathode and a Zn anode. The Zn anode may be in the form of a slurry containing Zn or Zn alloy powder, KOH, a gelling agent, and optionally other additives. The Zn anode may further include an electrically conductive additive similar to the composite cathode.

_{The anode associated with the polymer-MnO 2} composite of the present invention may include 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 traditional non-woven separator used in alkaline batteries. The electrolyte is a solution in which KOH, NaOH, LiOH, etc. are dissolved in water. The alkali concentration may be 4 to 9 M. The electrolyte may further include an electron conductive additive and/or a functional additive.

IV. Polymer-sulfur cathode

Furthermore, the present invention relates to a composite polymer-sulfur cathode. The composite polymer-sulfur cathode comprises a sulfur component and an ionically conductive solid polymer material comprising a compound comprising a base polymer, a dopant, and an ion source. The composite polymer-sulfur cathode is characterized by having a high specific capacity and high capacity retention when used in a secondary lithium or Li-ion sulfur cell. The composite cathode exceeds 200 milliamp-hr/gm, preferably exceeds 500 milliamp-hr/gm, more preferably exceeds 750 milliamp-hr/gm, most preferably 1000 milliamp-hr/gm It is characterized in that it has a specific capacity exceeding. The composite cathode is characterized by having a retention rate of at least 50%, preferably at least 80% for more than 500 recharge/discharge cycles. The composite polymer-sulfur cathode of the present invention can be directly applied to mass production at low cost made possible by the unique polymer used in this composite electrode. The composite polymer-sulfur cathode of the present invention can meet the requirements of manufacturing a battery at low cost while providing high performance.

In particular, the sulfur cathode is reduced during discharge to sequentially form lower order polysulfides following the sequence shown 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. Thus, the dissolved polysulfide particles can migrate (or “shuttle”) through the porous separator and react directly with the anode and cathode during cycling. The polysulfide shuttle creates a parasitic reaction with the lithium anode and re-oxidizes at the cathode, all of which cause capacity loss. Furthermore, this aspect of the shuttle reaction is irreversible, resulting in self-discharge and low cycle life that have plagued lithium sulfur batteries so far.

The present invention demonstrates a composite polymer-sulfur cathode comprising an ionically conductive solid polymer material and a sulfur component. This cathode can be extruded into a flexible thin film through a roll-to-roll process. These thin films enable thin flexible shape factors that can be incorporated into novel flexible battery designs. As shown in the examples below, this composite polymer-sulfur cathode may contain electrically conductive additives such as inexpensive carbon black components such as Timcal C45, for example, already used in many commercial battery products. In addition to the exemplary carbon black component, the composite polymer-sulfur cathode, for example, in non-limiting examples, includes, but is not limited to, carbon fibers, graphene components, graphite components, carbon components, metal particles or Other metal additives, and other electrically conductive additives such as electrically conductive polymers.

The design properties of the composite polymer-sulfur cathode allow the cathode to be extruded into a wide range of thicknesses as possible, which can provide an important advantage in terms of flexibility in the design of manufacturing large-scale cathodes. Composite polymer-sulfur cathodes can be extruded from thicknesses as thin as 5 microns to thicknesses in excess of a few hundred microns at most.

It is instructive that the cost of manufacturing a composite polymer-sulfur cathode is inherently lower when comparing the process steps required to fabricate a standard lithium ion cathode with the process steps required to fabricate the composite polymer-sulfur cathode of the present invention. 18 shows the process steps required to make a standard lithium ion cathode compared to making the extruded composite polymer-sulfur cathode of the present invention much simpler. The extrusion process of composite polymer-sulfur cathodes can be easily scaled to a scale that can be manufactured in large quantities, which provides significant advantages over conventional lithium-ion batteries as well as much lower capital cost of plant equipment.

In addition to extrusion, the composite polymer-sulfur cathode can be formed by injection molding, compression molding, or any other process involving heat, or other techniques known to those of ordinary skill in the art of designing plastics.

The composite polymer-sulfur cathode comprises a sulfur component and an ionically conductive solid polymer material comprising a compound comprising a base polymer, a dopant, and an ion source as described above.

Base polymers include liquid crystal polymers and polyphenylene sulfide (PPS), or any semi-crystalline polymer with a crystallinity index greater than 30%, or other common oxygen acceptors.

Dopants contain electron acceptors that activate ionic conduction mechanisms. This electron acceptor can be premixed with other constituents, or can be fed into the vapor phase in a post doping process. Common 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 ).

Compounds comprising an ion source include, but are not limited to, _{Li 2 O and LiOH.} The use of a composite polymer-sulfur cathode in a Li/sulfur test cell showed that the composite polymer-stable cathode is stable to lithium, sulfur, and organic electrolytes commonly used in lithium/sulfur batteries.

The base polymer is a non-flammable polymer that is self-extinguishing and has been shown to pass the UL-VO flammability test. The non-flammability of the base polymer is advantageous for the safety of batteries using a composite polymer-sulfur cathode. Inclusion of a non-flammable composite polymer-sulfur cathode in a cell with a non-flammable electrolyte can further improve the safety of the battery, an important attribute for high energy density batteries.

The sulfur component may include a non-reduced and/or reduced form of sulfur including elemental sulfur. In particular, the composite polymer-sulfur cathode contains a sulfur component comprising a form in which the sulfur has been completely treated with lithium (Li _{2 S), where Li 2} S is a solid. The composite polymer-sulfur cathode may further include a carbon component. The advantage of using a form in which sulfur has been completely treated with lithium is that it provides a lithium source for sulfur batteries with Li ion anodes that, unlike metallic Li, must be treated with lithium during initial charging. Combining the sulfur cathode with a Li-ion anode provides the benefit of preventing the formation of lithium dendrites that may form after cycling the lithium anode. Dendrites are caused by the non-uniform plating of lithium on the lithium metal anode during charging. These dendrites grow through the separator material and cause an internal short circuit between the cathode and anode, which can often cause high temperature and safety damage to the battery. A material containing lithium reversibly through intercalation or alloying reduces the likelihood of forming dendrite, and thus it has been proposed to be used in a lithium/sulfur cell with high safety. The composite polymer-sulfur cathode is, for example, a carbon-based (petroleum coke, amorphous carbon, graphite, carbon nanotube, graphene, etc.) material comprising a composite with a transition metal such as Co, Cu, Fe, Mn, Ni, etc. , Sn, SnO, SnO ₂ and Sn-based composite oxides such as anode materials can be used. Furthermore, silicon has shown promise as a lithium ion anode material, in elemental form, or as an oxide or composite material as described for tin. Other lithium alloy materials (eg Ge, Pb, B, etc.) can also be used for this purpose. Iron oxides such as Fe ₂ O ₃ or Fe ₃ O ₄ and several vanadium oxide materials have also been suggested to reversibly contain lithium as a Li-ion anode material. The anode material can be considered in several forms, including amorphous and crystalline, and nano-sized particles as well as nano-tubes.

The composite polymer-sulfur cathode may be combined with an electrolyte comprising a standard liquid electrolyte, a standard nonwoven separator, and/or an ionically conductive solid polymer material without a liquid electrolyte. An example of a standard organic electrolyte solution is lithium bis (trifluoromethane sulfonyl) dissolved in a mixture of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME). Lithium salts such as imide (LiTFSI). Additives such as LiNO ₃ can be added to the electrolyte to improve the cell's performance. In particular _{, other lithium salts including LiPF 6} , LiBF ₄ , LiAsF ₆ , and lithium triflate may be used in the organic liquid electrolyte. Additionally, as some examples, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate : EMC), other organic solvents such as fluoroethylene carbonate (FEC) may be used alone or in combination with DOL and DME, or as a mixture. Examples of standard nonwoven separators include polypropylene (PP), polyethylene (PE), and combinations of PP/PE membranes. Other separator materials include polyimide, PTFE, ceramic coated membranes, and glass-mat separators. All of these materials can be used for composite polymer-sulfur cathodes. Furthermore, composite polymer-sulfur cathodes can also be used in gel-polymer systems, where, for example, PVDF-based polymers are swollen in an organic electrolyte.

The ability of the composite polymer-sulfur cathode to provide lithium ion conductivity is believed to improve the performance of the cell by providing a high voltage to the sulfur cathode while limiting the polysulfide shuttle mechanism. Furthermore, this unique design composite polymer-sulfur cathode enables the large-scale, low-cost production required for commercial implementation of the cathode.

Thus, the unique composite polymer-sulfur cathode offers a number of potential benefits to the battery, including:

정상 조건과 남용 조건 하에서도 개선된 안전

Improved safety even under normal and abuse conditions

새로운 배터리 형상 팩터 구현

Implementing a new battery shape factor

기존의 Li-이온 셀에 비해 에너지 밀도의 큰 증가

Large increase in energy density compared to conventional Li-ion cells

다황화물 셔틀 메커니즘을 방지하여, 충전/방전 가역성 향상

Prevents polysulfide shuttle mechanism, improving reversibility of charging/discharging

제조 비용(원료 물질, 공정 및 자본 장비)을 크게 감소시켜 에너지 저장 비용을 개선

Improve energy storage costs by significantly reducing manufacturing costs (raw materials, processes and capital equipment)

V. Alkaline battery

_{In one aspect, a rechargeable Zn/MnO 2} battery is described for low speed applications that can match or exceed the performance of lithium-ion while providing improved safety, robustness and low cost.

It has been observed that certain cathode formulations comprising an ionically conductive solid polymeric material can exhibit much higher active material utilization at low speeds, while exhibiting a more rapid decline than at increasing release rates. This is shown in FIG. 38 showing the velocity profile of a coin cell with a cathode agent potentially useful for high energy cells. Most of these formulations exhibit a C/2 specific capacity of about 300 mAh/g, which corresponds to the theoretically expected value (shown as formulation 1 in FIG. 38) for a single-electron discharge of _{MnO 2.} close. In some cases, the cell exhibits a specific capacity that exceeds the theoretical single electron emission. For example, Formulation 2 exhibits nearly 400 mAh/g upon C/2 discharge, thus showing a deeper release of manganese dioxide.

The zinc and polymer content of the anode is optimized, in particular the zinc type and particle size, composition and process are optimized for the preparation of a solid polymer electrolyte for the desired anode performance, and zinc passivation by the introduction of ZnO and other functional additives. Decreased. The combined effect of high zinc surface area and improved stability results in improved performance and extended cycle life. Insertion of zinc particles into the polymer matrix prevents shape change, agglomeration and dendritic growth.

_{The cathode optimized to increase the capacity above 300 mAh/g exhibits a MnO 2} specific capacity improvement that significantly affects the cell energy density of the pouch cell, as shown in FIG. 39.

_{In one aspect, a rechargeable Zn/MnO 2} cell comprising an ionically conductive solid polymer material for high speed and high temperature applications is described.

The good active material utilization and high speed performance of the coin cell is preserved when the manganese dioxide content is increased to 80% by weight or more. The importance of this finding is hardly exaggerated as high active material loading is essential to achieving high energy density. The improvement in discharge capacity due to optimization of manganese dioxide content is shown in Figure 40. As can be seen, the optimized cell works well at currents as high as 50 mA (extremely high for coin cells) where level anodes and coin cell hardwere limitations can begin to play a role.

A cathode density of 2.5-3.9 g/cc is sufficient to obtain a high energy density. High speed performance in these conditions may be limited by the zinc foil anode rather than the cathode. Zinc anodes with increased surface area to replace zinc foils exhibit improved performance.

To increase the anode speed performance and improve the cycle life, the anode is improved by introducing ZnO and other functional additives (such as manganese salts) and optimizing the zinc and anode polymer content to reduce zinc passivation and corrosion. The combined effect of high zinc surface area and improved stability results in improved performance and extended cycle life at high discharge rates. It has also been found that inserting zinc particles into the polymer matrix prevents shape change, aggregation and dendritic growth.

It exhibits a capacity retention rate of more than 85% when discharged at 15C; Safe to operate at 80-100°C; With a minimum life of 500 cycles; Cells have been created that match or exceed the current technology's lithium-ion systems in energy/power density. These Zn/MnO ₂ battery packs do not require complex battery management and charge control circuitry, and are expected to benefit from additional energy density and reduce cost at the pack level.

Example 1

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

The self-diffusion coefficient was determined using a pulsed field gradient solid state NMR technique. The results shown in FIGS. 19 and 20 show that Li ⁺ and OH ^- diffusivity in the solid polymer electrolyte is the highest among any known solid, and the recently developed Li ₁₀ GeP ₂ S ₁₂ ceramic at a much higher temperature (140° C.) Or at least one order of magnitude higher at room temperature compared to the best PEO formulation at 90°C, respectively.

Example 2

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

The mixture was extrusion molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 PSI) to produce a 1 inch diameter and about 0.15 mm thick cathode disk. The resulting disk was punched into a diameter of 19 mm and used as a cathode to assemble a test cell including a commercial nonwoven separator (NKK) and a Zn foil anode. 6M LiOH was added as electrolyte.

The cell was discharged under a constant current condition of ^{0.5 mA/cm 2} using a biological VSP test system. The specific capacity of MnO ₂ was 303 mAh/g or was close to the ^{theoretical 1e-discharge.} 21 shows the voltage profile of the cell according to Example 2 as a function of the specific capacity of _{MnO 2} at 0.5 mA/cm ² discharge rate.

Example 3

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

The mixture was extrusion molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and 1.6 to 1.8 mm thick cathode disk.

Using the resulting cathode, a test cell containing a commercial nonwoven separator (NKK) extracted from a commercial alkaline cell and a Zn anode slurry was assembled. A solution in which 6M KOH was dissolved in water was used as an electrolyte.

Cells were discharged under constant current conditions using a biological VSP test system. The specific capacity of MnO ₂ was close to 600 mAh/g at C/9 discharge rate (35 mA/g), or close to the ^{theoretical 2 e-discharge.}

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

Example 4

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 PSI) to produce a 1 inch diameter and about 0.15 mm thick cathode disk.

The resulting disk was punched out to a diameter of 19 mm, and using it as a cathode, a test cell including a commercial nonwoven separator (NKK) and a Zn foil anode was assembled. 6M LiOH was added as electrolyte.

The cell was discharged and charged using a biological VSP test system. Discharge was performed at 0.5 mA/cm ^{2 current until 0.8 V cutoff. Charging was carried out at 0.25 mA/cm 2} to 1.65 V and then held at 1.65 V for 3 hours or until the current decreased to 0.02 mA/cm ^2. Every few cycles, the passivated Zn anode and separator were replaced with new ones. _{The specific capacity of MnO 2} as a function of the number of cycles in the cell according to Example 4 is shown in FIG. 23. Each column represents a separate cell. Only the discharge of the new Zn anode is shown. It can be readily seen that the MnO2 cathode of the present invention is rechargeable. Only the discharge of the new Zn anode is shown.

Example 5

A 2035 coin cell was assembled using the solid polymer electrolyte of Example 1, the cathode of Example 2, and Zn foil as the anode. This cell was discharged and charged using a biological VSP test system. Discharge was carried out at 0.25 mA/cm ^{2 current until 0.8 V cutoff. Charging was carried out at 0.25 mA/cm 2} to 1.65 V and then held at 1.65 V for 3 hours or until the current decreased to 0.02 mA/cm ^2. This cell demonstrated reversible behavior during this cycling. 24 shows the discharge curve of the coin cell according to Example 5 as a function of test time.

Example 6

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1 inch diameter and about 0.15 mm thick cathode disk.

The test cell was assembled using the resulting cathode, the electrolyte according to Example 1, and an anode made of Zn powder. The cells were discharged using a biological VSP test system at a current density of 0.5 mA/cm ^{2 to 0.8 V interruption.} The specific capacity of MnO ₂ was 401 mAh/g or exceeded the theoretical 1-electron discharge. 25 shows the voltage profile of a cell according to Example 6 as a function of test time.

Example 7

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and about 0.15 mm thick cathode disk.

The 2035 coin cell was assembled using the resulting anode, the cathode according to Example 2, and a commercial NKK separator containing saturated LiOH as an electrolyte.

A control coin cell was made using a commercial NKK separator containing Zn foil as an anode, a cathode according to Example 2, and saturated LiOH as an electrolyte.

The cells were discharged using a biological VSP test system at a current density of 0.5 mA/cm ^2. The discharge profile of the anode of the present invention shows a higher capacity at slightly higher voltages, which may be related to the increased surface area of the Zn anode and the maintenance of soluble zincate in the anode structure. 26 shows the discharge curve of the coin cell according to Example 7 as a function of the discharge capacity. Discharge was carried out at 0.25 mA/cm ^{2 current until 0.7 V cutoff.} Curve A-a cell with the anode of the invention. Curve B-Cell with Zn foil anode. 26 shows the discharge curve of the coin cell according to Example 7 as a function of the discharge capacity.

Discharge was carried out at 0.25 mA/cm ^{2 current until 0.7 V cutoff.} Curve A-a cell with the anode of the invention. Curve B-Cell with Zn foil anode.

Example 8

The PPS base polymer and the ion source compound LiOH monohydrate were added together in a ratio of 67% to 33% (weight ratio), respectively, and mixed using jet milling. The anode was prepared by additionally mixing 60% Al powder and 10% C45 carbon black. To the resulting mixture, DDQ dopant was added in an amount of 1 mole of DDQ per 4.2 moles of PPS. The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and about 0.15 mm thick cathode disk.

The resulting anode was tested in a test cell comprising a _{Zn counter electrode and a commercial separator containing a ZnSO 4 electrolyte.} An anode made of Al foil was tested as a control.

The anode was polarized with dynamic potential at a 1 mV/s sweep rate using a biological VSP test system. Figure 27 shows the scanning of the anode of the present invention (curve A) and a control Al foil (curve B) with a dynamic potential of 1 mV/s in a ZnSO4 electrolyte. The anode of the present invention demonstrated corrosion stability improved by 0.5 V compared to Al foil.

Comparative Example 9

The discharge profile of the Duracell Coopertop AA cell at 250 mA discharge was taken from the datasheet. _{The amount of MnO 2} in this cell was calculated by comparing it with published specifications and MSDS, yielding 8.4 to 9.6 g. Current densities of 26 to 30 mA/g were calculated by simple conversion. The total capacity is calculated by multiplying the service time and the discharge current (according to the datasheet), which can be converted to specific capacity by dividing by the weight of _{MnO 2.} The voltage profile of the Coopertop AA cell as a function of _{the MnO 2} specific capacity calculated in this way is shown in FIG. 28. _{Curve A corresponds to the maximum amount MnO 2} (9.6 g) of the Duracell Coopertop AA cell under constant current discharge at a discharge rate of 26 mA/g. Curve B corresponds to the smallest amount of _{MnO 2} (8.4 g) at 30 mA/g discharge rate of the Duracell Coopertop AA cell under constant current discharge. Curve C shows the specific capacity of a Duracell Coopertop AA cell under a constant current discharge rate of 2.2 mA/g. _{It can be easily seen that the calculated MnO 2} specific capacity up to 0.9 V blocking is 235 to 270 mAh/g. Extrapolation to 0.8 V cutoff yields slightly better specific capacity of 245 to 275 mAh/g. The discharge curve has a general slope shape specific to the _{Zn/MnO 2 cell.} At 5% to 95% discharge depth, the voltage difference is close to 0.5 V or close to 30% of the initial (5% DOD) [2.1 to 2.4 V/Ah/g]. At an extremely low discharge rate of 2.2 mA/g (taking the average value of _{MnO 2 in the cell), the discharge Coopertop cell showed an additional plateau (curve C).} The total specific capacity was 347 mA/g, corresponding to 1.13-electron discharge. The discharge curve still has a general slope shape approaching a voltage difference of 0.5 V at 5 to 95% discharge depth.

Comparative Example 10

AA cells were purchased from a retail store and a 250 mA discharge corresponding to a mid-rate test was performed using a Maccor 4300 system. Table 10.1 shows the performance of commercial AA cells under 250 mA continuous discharge. The total dose delivered up to 0.9 V blocking is shown in Table 10.1. Assuming that the amount of the MnO ₂ in the same cell as in Comparative Example 9, the total capacity of the cell can be converted to the specific capacity of the MnO _2. As can be seen, commercial AA cells deliver 200 to 280 mAh/g under these discharge conditions. Even taking into account the positive effects of intermittent discharge and extending the voltage cutoff to 0.8 V, a commercial alkaline cell operates with _{the 1-electron reduction of MnO 2} described in equation (1), and is limited to 308 mAh/g. It is a fair explanation to understand as.

[Table 10.1]

Comparative Example 11 according to US 7,972,726

Figure 29 is for an alkaline button cell having an _{AgBiO 3} cathode (curve (a)), an EMD(MnO ₂ ) cathode (curve (b)) and _{a cathode based on a 1:9 AgBiO 3} :EMD mixture, produced from US 7,972,726. A discharge curve is shown at 10 mA/g discharge rate (curve (c)). Under this condition, the discharge profile for EMD (b) is similar to the commercial alkaline cell described in Comparative Example 9 with a voltage difference of 0.5 V at 5 to 95% DOD. _{The MnO 2} capacity of about 290 mAh/g corresponds to a 1-electron discharge. The _{cathode made of the AgBiO 3} :EMD mixture showed an additional plateau at about 0.9 V, increasing the _{MnO 2 capacity. The best performance was reported with a 1:9 AgBiO 3} :EMD mixture that delivered 351 mAh/g before 0.8 V blocking. This corresponds to the 1.13-electron discharge of _{MnO 2.}

Example 12

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and 1.6-1.8 mm thick cathode disk.

Using the resulting cathode, a test cell containing a commercial nonwoven separator (NKK) extracted from a commercial alkaline cell and a Zn anode slurry was assembled. A solution in which 6M KOH was dissolved in water was used as an electrolyte.

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

Example 13

The PPS base polymer and the ion source compound LiOH monohydrate were added together in a ratio of 67% to 33% (weight ratio), respectively, and mixed using jet milling. The cathode was prepared from Tronox _{by additionally mixing 50% EMD (a mixture of γ- and ε-MnO 2} ), 5% Bi ₂ O ₃ and 15% C45 carbon black. To the resulting mixture, DDQ dopant was added in an amount of 1 mole of DDQ per 4.2 moles of PPS.

The mixture was compression molded on a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1 inch diameter and 1.6-1.8 mm thick cathode disk.

Using the resulting cathode, a test cell containing a commercial nonwoven separator (NKK) extracted from a commercial alkaline cell and a Zn anode slurry was assembled. A solution in which 6M KOH was dissolved in water was used as an electrolyte.

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

Example 14

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and 1.6-1.8 mm thick cathode disk.

Using the resulting cathode, a test cell containing a commercial nonwoven separator (NKK) extracted from a commercial alkaline cell and a Zn anode slurry was assembled. A solution in which 7M KOH was dissolved in water was used as an electrolyte.

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

Example 15

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

The mixture was compression molded over a stainless steel mesh (Dexmet) at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi) to produce a 1" diameter and 1.6-1.8 mm thick cathode disk.

Using the resulting cathode, a test cell containing a commercial nonwoven separator (NKK) extracted from a commercial alkaline cell and a Zn anode slurry was assembled. A solution in which 7M KOH was dissolved in water was used as an electrolyte.

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

Example 16

The PPS base polymer and the ion source compound LiOH monohydrate were added together in 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. A polymer-sulfur composite cathode was prepared by additionally mixing 25% to 50% of sulfur powder, 5% to 15% of C45 carbon black, and 0% to 10% of LiNO _{3 with an ion conductive solid polymer material.} The material was compression molded on a stainless steel mesh (Dexmet) at 120° C. for 30 minutes to produce a 15 mm diameter and 0.3 to 0.4 mm thick cathode disk.

The resulting cathode was used to assemble a test cell in 2035 coin cell hardware. A 25 micron thick and 19 mm diameter polypropylene separator (Celgard) was used with a 15 mm diameter lithium foil anode material. A liquid electrolyte in which 1M LiTFSI salt was dissolved in a 50/50 (volume/volume) mixture of DOL/DME was used together with _{0.5M LiNO 3 additive.} The cell was assembled in a glovebox filled with argon gas at low oxygen and water levels. Cells were discharged under constant current conditions (1 mA) using a Maccor 4600 battery test system. Discharge was terminated at a voltage of 1.75 V.

34 shows a first discharge voltage curve for a Li/composite polymer-sulfur cathode in the cell of the present invention. The discharge voltage profile during the first cycle is shown in FIG. 34. It can be seen that the composite polymer-sulfur cathode provides a high initial capacity of> 1300 mAh/g based on the amount of sulfur in the cathode. In Figure 34 the cell also shows a discharge voltage curve with two plateaus at -2.3V and -2.1V. This shows that the composite polymer-sulfur system enables high capacity while generating the expected voltage curve for a lithium/sulfur system that matches a stable electrochemical couple.

Example 17

A composite polymer-sulfur cathode was prepared as described in Example 16. This cathode was assembled into a coin cell using a lithium metal anode, a polypropylene separator, and a 1M LiTFSI electrolyte dissolved in DOL/DME with _{0.5M LiNO 3 additive.} Cells were discharged under constant current conditions (1 mA) using a Maccor 4600 battery test system. Discharge was terminated at a voltage of 1.75 V. Charging was carried out in two stages, the first stage at a lower charging rate of 0.2 mA current up to a maximum voltage of 2.3 V, and a second charging stage at a higher charging rate of 1 mA current up to a maximum voltage of 2.45 V. The total charge capacity for this test cell was limited. This cell was allowed to cycle several times at room temperature.

35 is a graph showing discharge capacity curves as a function of number of cycles for the Li/composite polymer-sulfur cell of the present invention. This graph shows that the composite polymer-sulfur cathode can support reversible charge/discharge with a high reversible capacity of at least 1000 mAh/g based on the amount of sulfur in the cathode.

Comparative Example 18

Valuable examples of highly ordered interwoven composite electrodes are described in Ji, X.; Lee, K.T.; Nazar, L.F. Nature Materials 2009, 8, 500-506. This composite cathode used CMK-3 mesoporous carbon in which sulfur was formed in the pores through heat treatment at 155°C. Figure 36 compares the first discharge for literature example Li/sulfur-CMK-3 with the inventive Li/composite polymer-sulfur.

In this example the composite cathode was slurry cast from cyclopentanone onto a carbon coated aluminum current collector. The cathode used 84% by weight of CMK-3/S composite, 8% by weight of Super-S carbon, and 8% by weight of PVDF binder. The electrolyte was composed of 1.2 M LiPF ₆ dissolved in ethyl methyl sulphone, and Li metal was used as the anode. In comparison, the results for the inventive composite polymer-sulfur cathode described in Example 16 are plotted on the same graph. It is apparent that the composite polymer-sulfur cathode of the present invention provides better results or is provided superior to the literature examples of composite sulfur cathodes.

Comparative Example 19

It has been demonstrated to use sulfur-conducting polymer composites as cathodes for lithium batteries. In one case, polyacrylonitrile (PAN) is sulfided, forming a conductive and chemically active cathode material. Sulfurization of the polymer takes place at a relatively high temperature of ~300°C. An example of a discharge curve for this material is shown in FIG. 37 presented in US Patent Application 2014/0045059 [He, X.-M., et al.]. 37 shows typical voltage signatures seen for Li/sulfur-polyacrylonitrile (S/PAN) cells. This cell appears as a single ramp voltage plateau with an average voltage of less than 2.0 V. Compared to the voltage curve observed in Figure 4 for the Li/composite polymer-sulfur cathode in the cell of the present invention, the S/PAN cell shows a significantly lower voltage over discharge, based on Watt-hour. It can be seen that it produces a lower energy density. Thus, the voltage behavior presented by the composite polymer polymer-sulfur cathode of the present invention is superior to that of the sulfided PAN-based cathode.

Example 20

A solid polymer electrolyte sample was prepared by mixing SRT802 (liquid crystal polymer) polymer with lithium hydroxide monohydrate as a compound containing an ion source in a ratio of 2:1 (weight ratio), respectively. DDQ was used as a dopant. The weight ratio of polymer to dopant was 2:1. The mixture was heat treated at 325/250° C. for 30 minutes under moderate pressure (500-1000 PSI). The surface ionic conductivity of the sample was measured using standard AC-EIS. The sample was sandwiched between stainless steel block electrodes and placed on the test rig. Electrolyte conductivity was determined by recording AC-impedances in the range of 800 KHz to 100 Hz using a biological VSP test system. Six samples were prepared and tested. The average conductivity was 3.7 x 10 ^-4 S/cm with about 19% standard deviation. The results are presented in Table 20.1 below.

[Table 20.1]

Example 21

A solid polymer electrolyte sample was prepared by mixing the SRT900 (liquid crystal polymer) polymer with lithium hydroxide monohydrate as a compound containing an ion source in a ratio of 2:1 (weight ratio), respectively. DDQ was used as a dopant. The weight ratio of polymer to dopant was 2:1. The mixture was heat treated at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi). The sample was sandwiched between stainless steel electrodes and placed on a test rig. Electrolyte conductivity was determined by recording AC-impedances in the range of 800 KHz to 100 Hz using a biological VSP test system. Six samples were prepared and tested. The average conductivity was 1.5 x 10 ^-3 S/cm with about 25% standard deviation. The results are presented in Table 21.1 below.

[Table 21.1]

Example 22

A polymer electrolyte sample was prepared by mixing a polymer with a compound containing an ion source in various proportions. DDQ was used as a dopant. The polymer to dopant molar ratio was 4.2. The mixture was heat treated at 325/250° C. for 30 minutes under moderate pressure (500-1000 psi). The sample was sandwiched between stainless steel electrodes and placed on a test rig. Electrolyte conductivity was determined by recording AC-impedances in the range of 800 KHz to 100 Hz using a biological VSP test system.

The results are presented in the table below. Higher the observed conductivity of the polymer electrolyte is Li ^+, K ^+, Na ^+, Ca ^{2 +,} Mg ^{2 +,} Al ^{3 +,} OH ^- suggests that it is possible to conduct the multiple ion containing ^-, and Cl.

The ^{ability to conduct ions other than Li +} ions opens up new applications for polymer electrolytes. Sodium- and potassium-based energy storage systems are basically considered as an alternative to Li-ion because their raw materials are low-cost and relatively rich.

Calcium, magnesium and aluminum conductivities are important in developing multivalent intercalation systems that can increase energy density beyond the capabilities of Li-ion batteries. There is also the potential to use these materials to produce power sources with metal anodes that are more stable and at a lower cost than lithium.

Hydroxyl conductivity is _{critical for many alkaline chemicals including Zn/MnO 2} , Ni/Zn, Ni-Cd, Ni-MH, Zn-air and Al-air. Polymer electrolytes that conduct hydroxyl ions can also be used in alkaline fuel cells and supercapacitors.

Example 23

Ion conductive solid polymer material:

Polyphenylene sulfide "PPS" (base polymer) and tetrachloro-1,4-benzoquinone "chloranyl" are mixed and heated to form a solid intermedaite polymer material, comprising an ion source When mixed with, it forms an ionically conductive solid polymer material. The compound contains 10-50% by weight of the base polymer. The heating step raises the temperature of the reactants to 250-350[deg.] C. and takes about 10 minutes to 8 hours overnight. In one aspect, an ionically conductive solid polymeric material or intermediate thereof or a reactant thereof may be mixed with an additive (e.g., electrically conductive carbon) to form a complex that is all ionically conductive and provides the functional properties (electrical conductivity) of the additive. .

Zn anode:

Zinc powder (pure powder or zinc powder alloyed with bismuth, indium, calcium, aluminum and other known alloying agents) is a solid intermediate polymer material, lithium hydroxide, conductive carbon additives (e.g. Timcal's C45 or KS6L graphite, EC600). -Mixed with AkzoNobel's high surface area carbon), additives zinc oxide and/or other corrosion resistant additives. PVDF or Kynar PVDF is used with NMP as a solvent as a binder. A mixer (eg Thinky) can be used and if used to mix the mixture is mixed until a homogeneous slurry is obtained (eg 10-30 minutes at 2000 rpm). The slurry is then cast by doctor blade technology onto a thin layered current collector (stainless steel, titanium or nickel foil) pre-coated with a graphite primer. The electrodes were then dried at 80-120° C. for 2-12 hours, calendared and sliced to the desired dimensions for a coin cell or pouch cell.

MnO ₂ cathode:

EMD MnO ₂ powder is mixed with conductive additives (eg C45, KS6L graphite, EC600 high surface area carbon, etc.), solid intermediate polymer material and ionic compound lithium hydroxide. PVDF (polyvinylidene fluoride) or Kynar PVDF is used as a binder with NMP (N-methyl-2-pyrrolidone) as a solvent. Mix the mixture for 10-30 minutes at 2000 rpm until a homogeneous slurry is obtained using a Thinky brand mixer. The slurry is then cast by doctor blade technology onto a thin layered current collector (stainless steel, titanium or nickel foil) pre-coated with a graphite primer. The electrodes were then dried at 80-120° C. for 2-12 hours, calendered and sliced to the desired dimensions for a coin cell or pouch cell. Overall, the ionically conductive solid polymer material is about 2-30% by weight of the total cathode weight, the activity (in this case EMD) is about 20-80% by weight, the carbon is about 3-30% by weight, and contains a liquid electrolyte. do.

Electrolyte:

A variety of electrolytes can be used. In one aspect, the electrolyte formulation is an aqueous solution containing 36% by weight of potassium hydroxide with zinc oxide as an additive. In one aspect, a 1-3 molar concentration of zinc sulfate salt is used with the addition of 0.5-4% by weight of manganese sulfate (or other Mn(ii) salt) additive. These aqueous electrolytes may be added with 0.5-2% by weight of a gelling agent, for example a poly(ethylene glycol) di-acid (or other known gelling agent). In one aspect, the ionically conductive solid 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 anode or cathode.

Cell configuration:

CR2032 coin cells, bobbin cylindrical cells, single layer and multilayer pouch cells were all fabricated using the same cathode and anode combinations. The cell assembly steps are the same as those commonly used in the industry, including electrode slurry, sealing, and crimping. Taking a coin cell as an example, a cathode and an anode are sandwiched between a non-woven separator layer soaked with the zinc sulfate liquid electrolyte described above as described above. 41 shows a typical charge-discharge profile of a _{rechargeable Zn-MnO 2} battery in CR2032 coin cell format.

This configuration was described as a secondary battery, but it was found to be useful as a primary battery as well.

Referring to Table 23.1, a number of configurations using an ionically conductive solid polymeric material are shown. Zinc air composition, three (1-3) secondary alkali composition is the main composition.

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

Secondary formulation (2) corresponds to Figures 38-40 and related discussion. Liquid potassium hydroxide electrolyte was added. The procedures for cathode and anode manufacturing do not involve the use of mechanical mixers or slurry casting. The anode and cathode did not contain a binder (no PVDF) and did not require an NMP solvent.

The present invention has been described in connection with a preferred embodiment, but those of ordinary skill in the art, after reading the above description, perform various changes, substitutions with equivalents, and other modifications to those presented herein. I will be able to do it. Therefore, the scope to be protected by a patent in this specification is intended to be limited only by the matters defined in the appended claims and their equivalents.

Claims (20)

As an electrochemical cell for producing electrical energy through an electrochemical reaction,
Anode; And
Including; a cathode;
At least one of the anode and the cathode comprises an ion conductive solid polymer material,
The ionically conductive solid polymer material can ionically conduct hydroxyl ions, whereby the ionically conductive solid polymer material can conduct hydroxyl ions during the electrochemical reaction,
The ion conductive solid polymer material has a crystallization index of 30% or more,
The anode comprises aluminum and the cathode comprises manganese dioxide,
Electrochemical cell. As an electrochemical cell for generating electrical energy through an electrochemical reaction,
Anode; And
Including; a cathode;
At least one of the anode and the cathode comprises an ion conductive solid polymer material,
The ionically conductive solid polymer material may ionically conduct hydroxyl ions, whereby the ionically conductive solid polymer material may conduct hydroxyl ions during the electrochemical reaction,
The anode comprises an ion conductive solid polymer material and further comprises an anode electrochemically active material,
The ion conductive solid polymer material and the anode electrochemically active material are mixed, whereby the ion conductive solid polymer material can ionically conduct hydroxyl ions to the anode electrochemically active material, and
The anode comprises aluminum and the cathode comprises manganese dioxide,
Electrochemical cell. As an electrochemical cell for generating electrical energy through an electrochemical reaction,
Anode; And
Including; a cathode;
At least one of the anode and the cathode comprises an ion conductive solid polymer material,
The ionically conductive solid polymer material may ionically conduct hydroxyl ions, whereby the ionically conductive solid polymer material may conduct hydroxyl ions during the electrochemical reaction,
The cathode comprises an ion conductive solid polymer material and further comprises a cathode electrochemically active material,
The ion conductive solid polymer material and the cathode electrochemically active material are mixed, whereby the ion conductive solid polymer material can ionically conduct hydroxyl ions to the cathode electrochemically active material, and
The anode comprises aluminum and the cathode comprises manganese dioxide,
Electrochemical cell. The method of claim 2,
At least a portion of the ionically conductive solid polymer material is in contact with the anode electrochemically active material,
Electrochemical cell. The method of claim 3,
At least a portion of the ionically conductive solid polymer material is in contact with the cathode electrochemically active material,
Electrochemical cell. As an electrochemical cell for generating electrical energy through an electrochemical reaction,
Anode; And
Including; a cathode;
At least one of the anode and the cathode comprises an ion conductive solid polymer material,
The ionically conductive solid polymer material may ionically conduct hydroxyl ions, whereby the ionically conductive solid polymer material may conduct hydroxyl ions during the electrochemical reaction,
The cathode comprises an ion conductive solid polymer material,
The amount of the ionically conductive solid polymer material is in the range of 1 to 40 weight percent of the cathode, and
The anode comprises aluminum and the cathode comprises manganese dioxide,
Electrochemical cell. The method of claim 1, 2, 3 or 6,
The cathode is capable of generating hydroxyl ions during the electrochemical reaction,
Electrochemical cell. The method of claim 2, 3 or 6,
The ionically conductive solid polymer material has a crystallization index of 30% or more,
Electrochemical cell. The method of claim 2, 3 or 6,
The ionically conductive solid polymer material comprises at least one hydroxyl ion and has an OH greater than ^{10 -11} cm ² /sec at a temperature in the range of 20°C to 26°C as determined by pulsed field gradient solid state NMR technology. ^- having diffusivity,
Electrochemical cell. The method of claim 1, 2, 3 or 6,
The cathode comprises an active material that generates hydroxyl ions during the electrochemical reaction,
Electrochemical cell. The method of claim 1, 2, 3 or 6,
The cell has a C/2 specific capacity of manganese dioxide greater than 308mAh/g,
Electrochemical cell. The method of claim 1, 2, 3 or 6,
The ionically conductive solid polymer material is interposed between the anode and the cathode, whereby during the electrochemical reaction, the ionically conductive solid polymer material conducts hydroxyl ions between the anode and the cathode,
Electrochemical cell. delete delete delete delete delete delete delete delete

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