Alkaline electrochemical cell

Abstract

The present invention discloses an alkaline electrochemical battery comprising a cathode, a gel anode, and a separator disposed between the cathode and the anode, wherein the gel anode comprises an anode active material, an alkaline electrolyte, a gelling agent, and about 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant; wherein, relative to the total weight of the anode active material, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Application 62 / 588,550, filed November 20, 2017, the entire contents of which are incorporated herein by reference for any and all purposes. Technical Field

[0002] This application belongs to the field of electrochemical batteries, and more specifically, this application relates to an alkaline battery with improved performance and reliability. Background Technology

[0003] Alkaline electrochemical batteries are used to power a variety of devices used in everyday life. For example, devices such as radios, toys, cameras, flashlights, and hearing aids typically rely on one or more electrochemical batteries to function. Electrochemical batteries generate electrical energy by electrochemically coupling a reactive metal anode to a cathode within the battery via a suitable alkaline electrolyte.

[0004] The reliability and high-rate discharge performance of alkaline batteries depend in part on using the correct anode formulation to minimize zinc anode oxidation when the battery is at rest (especially after partial discharge). This can be achieved by appropriately selecting the anode active material (such as zinc alloy) and through material purification. Metallic impurities present in the zinc alloy can lead to hydrogen gas generation within the battery, causing pressure increases during intermittent use or storage in an undischarged or partially discharged state. Other sources of metallic impurities may originate from other battery components, such as the electrolyte, electrolytic manganese dioxide, graphite, the battery casing, and the anode current collector. Zinc and other impurities can dissolve in the electrolyte, diffuse to the anode via convection, and precipitate on the anode surface during electrochemical corrosion reactions, acting as cathode sites and leading to further gas generation. To mitigate the impact of harmful impurities, electrochemical batteries typically contain corrosion inhibitors or surfactants. The role of anode inhibitors is to form a protective film on the anode surface when the battery is at rest, preventing undesirable reactants from entering the anode surface and effectively reducing the reduction reactions that lead to hydrogen gas formation. In the absence of good inhibitors, the pressure buildup during battery storage can cause the battery to release gas, ultimately leading to battery leakage and malfunction. Therefore, it is desirable to find a means to effectively suppress the generation of gas inside the battery in order to suppress failures caused by leakage, while improving battery storage life and battery performance. Summary of the Invention

[0005] One aspect of the present invention provides an alkaline electrochemical battery comprising a cathode, a gel anode, and a separator disposed between the cathode and the anode. The gel anode comprises an anode active material, an alkaline electrolyte, a gelling agent, and about 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant. The apparent density of the anode active material is about 2.60 g / cc to about 3.35 g / cc. Relative to the total weight of the anode active material, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm, and about 5 wt% to about 25 wt% of the anode active material has a particle size of greater than about 150 μm.

[0006] One aspect of the present invention provides a gel anode comprising an anolyl active material, an alkaline electrolyte, a gelling agent, and about 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant, wherein the apparent density of the anolyl active material is about 2.60 g / cc to about 3.35 g / cc, and relative to the total weight of the anolyl active material, about 15 wt% to about 60 wt% of the anolyl active material has a particle size of less than about 75 μm, and relative to the total weight of the anolyl active material, about 5 wt% to about 25 wt% of the anolyl active material has a particle size of greater than about 150 μm.

[0007] In some embodiments that can be combined with the foregoing aspects and embodiments, the alkoxyalkyl phosphate surfactant comprises polyoxyethylene tridecyl ether phosphate (i.e., tridecyl-6-phosphate). In some embodiments that can be combined with the foregoing aspects and embodiments, the hydroxide concentration of the electrolyte in the gel anode is from about 24 wt% to about 36 wt%. In some embodiments that can be combined with the foregoing aspects and embodiments, the gel anode comprises from about 0.2 wt% to about 1.0 wt% of a gelling agent.

[0008] In some embodiments that can be combined with the foregoing aspects and embodiments, the gelling agent comprises crosslinked polyacrylic acid. In some embodiments, the anode active material comprises a zinc alloy. In some embodiments that can be combined with the foregoing aspects and embodiments, the zinc alloy comprises zinc, indium, and / or bismuth. In other embodiments, the zinc alloy contains about 100 ppm to about 300 ppm of bismuth and about 100 ppm to about 300 ppm of indium. In some embodiments that can be combined with the foregoing aspects and embodiments, the anode comprises about 62 wt% to about 72 wt% of zinc alloy relative to the total weight of the anode. In some embodiments that can be combined with the foregoing aspects and embodiments, the electrochemical cell is an LR14 cell or an LR20 cell.

[0009] In some embodiments that can be combined with the above aspects and implementation methods, about 15 wt% to about 65 wt% of the anolyte active material has a particle size of less than about 75 micrometers relative to the total weight of the anolyte active material, about 5 wt% to about 25 wt% of the anolyte active material has a particle size of greater than about 150 micrometers relative to the total weight of the zinc alloy, and less than about 10 wt% of the anolyte active material has a particle size of less than about 45 micrometers relative to the total weight of the anolyte active material.

[0010] One aspect of the present invention provides a gel anode, wherein the gel comprises an anode active material, an alkaline electrolyte containing about 26 wt% to about 34 wt% potassium hydroxide, about 0.2 wt% to about 1.0 wt% a gelling agent, and about 10 ppm to 250 ppm polyoxyethylene tridecyl ether phosphate, wherein the apparent density of the anode active material is about 2.60 g / cc to about 3.35 g / cc, and relative to the total weight of the anode active material, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm, and relative to the total weight of the anode active material, about 5 wt% to about 25 wt% of the anode active material has a particle size of greater than about 150 μm. Attached Figure Description

[0011] Figure 1 This is a schematic diagram of the outgassing characteristics of an LR20 battery with an undischarged (UD) gel anode, including Example 1.

[0012] Figure 2 This is a schematic diagram of the degassing characteristics of an LR20 battery including the partial discharge (PD) of the gel anode in Example 2.

[0013] Figure 3 This is a schematic diagram of the discharge performance of the LR20 battery according to Example 3, discharged for one hour per day at 2.2Ω.

[0014] Figure 4 This is a schematic diagram of the discharge performance of an LR20 battery, including the gel anode of Example 3, discharged for 2 hours per day at 600mA.

[0015] Figure 5 It is the ampere number after a drop test of the LR20 battery including the gel anode of Example 4.

[0016] Figure 6 This is a schematic diagram of the discharge performance of the LR20 battery in a toy test after being stored at room temperature for three months, according to Example 4.

[0017] Figure 7 This is a schematic diagram of the partial discharge (PD) characteristics of an LR20 battery including the gel anode of Example 4.

[0018] Figure 8This is a schematic diagram of the outgassing characteristics of an LR20 battery, including the gel anode of Example 5, after being stored at approximately 71°C for one week without discharge (UD).

[0019] Figure 9 This is a schematic diagram of the degassing characteristics of an LR20 battery, including the gel anode of Example 5, after being stored at approximately 71°C for one week, showing partial discharge (PD).

[0020] Figure 10 This is a schematic diagram of the gas dissipation characteristics of an LR20 battery, including the gel anode of Example 5, after being stored at 85°C for two days without discharge (UD).

[0021] Figure 11 This is a schematic diagram of the discharge performance of the LR20 battery in heavy industrial flashlight (HIFT) and portable stereo tests after being stored at room temperature for one month.

[0022] Figure 12 This is a schematic diagram of the ANSI discharge performance of an LR20 battery including a gel anode, where the apparent density of zinc powder is 2.77 g / cc and 3.0 g / cc.

[0023] Figure 13 This is a schematic diagram of gas production in an LR20 battery that has been partially discharged after being stored at 160ºC for one week.

[0024] Figure 14 This is a schematic diagram of the ANSI discharge performance of an LR20 battery including a gel anode with HF zinc, where the apparent density of HF zinc at 63% load is 2.77 g / cc.

[0025] Figure 15 This is a schematic diagram of the discharge performance of the LR14 battery in portable stereo, portable lighting, and toy tests after being stored at room temperature for 3 months.

[0026] Figure 16 This is a schematic diagram of the outgassing characteristics of an LR14 battery, including the undischarged (UD) state of the gel anode.

[0027] Figure 17 This is a schematic diagram of the degassing characteristics of an LR14 battery including partial discharge (PD) with a gel anode.

[0028] It should be noted that the designs or configurations of the components shown in the accompanying drawings are not drawn strictly to scale, and / or the drawings are for illustrative purposes only. Therefore, the designs or configurations of the components may differ from those described in this application without departing from the intended scope of the disclosure herein. Consequently, the accompanying drawings should not be considered restrictive. Detailed Implementation

[0029] Various embodiments of this application will be described below. It should be noted that the specific embodiments are not intended to be exhaustive or to limit the broader aspects discussed in this application. An aspect described in connection with a particular embodiment is not necessarily limited to that embodiment and can be implemented in conjunction with any other embodiment.

[0030] As used in this application, "about" will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. Where there is a terminology application that is unclear to those skilled in the art, "about" may mean plus or minus 10% of a particular term in the given context.

[0031] In the context of describing elements (especially in the context of the claims), the terms “a” and “the”, and similar designations, should be interpreted to cover both singular and plural forms, unless otherwise stated or clearly contradicted by the context. Unless otherwise indicated, the enumeration of numerical ranges in this application is intended only as a way of abbreviating each individual value falling within the range, each individual value being incorporated into the specification as if it were described separately in this application. Unless otherwise stated or clearly contradicted by the context, all methods described in this application may be performed in any suitable order. Unless otherwise stated, the use of any and all examples or exemplary language (“e.g.”) provided in this application is intended only to better illustrate the implementation and does not constitute a limitation on the scope of the claims. No language in the specification should be construed as essential to any unclaimed element.

[0032] Ratios, concentrations, quantities, and other numerical data may be presented in range form in this application. It should be understood that the use of range form is merely for convenience and brevity, and should be flexibly interpreted to include not only the values ​​explicitly listed as the limits of the range, but also all individual values ​​or subranges contained within the range, as if each value and subrange were explicitly described. For example, 5 to 40 mol% should be interpreted to include not only the explicitly listed limits of 5% to 40 mol%, but also subranges such as 10 mol% to 30 mol%, 7 mol% to 25 mol%, and individual values ​​within specific ranges such as 15.5 mol%, 29.1 mol%, and 12.9 mol%, etc.

[0033] As used in this application, the term "zinc anode" refers to an anode that includes zinc as the anode active material.

[0034] As used in this application, “fine particles” are particles that pass through a standard 200-mesh sieve during normal sieving operations (e.g., by hand-shaking the sieve). “Dust” consists of particles that pass through a standard 325-mesh sieve during normal sieving operations. “Coarse sieve” consists of particles that do not pass through a standard 100-mesh sieve during normal sieving operations. As described in this application, the sieve aperture size and corresponding particle size are in accordance with the standard test method for sieving analysis of metal powders as described in ASTM B214. Typically, fine particles contain particles with a diameter less than 75 micrometers, coarse particles contain particles with a diameter greater than 150 micrometers, and dust contains particles with a diameter less than 45 micrometers.

[0035] As used in this application, "aspect ratio" refers to a dimension determined by the ratio between the length of the longest dimension of the particle and the relative width of the particle.

[0036] As used in this application, unless otherwise expressly stated, the term "ppm" refers to parts per million by weight.

[0037] This application aims to improve the discharge rate capability of batteries (such as alkaline batteries). This application also aims to improve the anodic discharge efficiency of batteries by appropriately combining the loading of the anodic active material, the type of anodic active material, the type of inhibitor, the inhibitor concentration, the electrolyte concentration, and the particle size distribution of the anodic active material. It has now been surprisingly found that the anodic formulation developed in this application, through the appropriate selection of factors such as zinc particle size distribution, inhibitor, and electrolyte concentration, can significantly improve the performance and reliability of alkaline batteries (such as LR20 and LR14 batteries).

[0038] According to one aspect of the present invention, the present invention relates to an electrochemical battery comprising a cathode, a gel anode, and a separator disposed between the cathode and the anode. Suitable electrochemical battery structures may include alkaline batteries, alkaline cylindrical batteries (such as metal-metal oxide batteries), and galvanic batteries (such as metal-air batteries, zinc-air batteries). In cylindrical metal-metal oxide batteries and metal-air batteries, the anode material is suitable for anode materials used in AA, AAA, AAAA, C, or D batteries, including alkaline batteries LR03, LR06, LR8D425, LR14, and LR20. The electrochemical battery can be applied to non-cylindrical batteries, such as flat batteries (such as prismatic batteries and button batteries) and circular flat batteries (such as those with a cross-sectional shape resembling a racetrack). Metal-air batteries including the anode described in this application can be used to construct button batteries for various applications, such as hearing aid batteries and batteries in watches, clocks, timers, calculators, laser pointers, toys, and other novel items. Suitable electrochemical batteries may also include any metal-air battery using flat, curved, or cylindrical electrodes. Alternatively, the anode could be used as a component in other forms of electrochemical cells.

[0039] The anode of the electrochemical battery is as described above. Therefore, one aspect of the present invention provides an alkaline electrochemical battery comprising a cathode, an anode containing an anode active material, and a separator disposed between the cathode and the anode. In some embodiments of the electrochemical battery, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm relative to the total weight of the anode active material. In various embodiments of the present invention, the anode of the electrochemical battery is a gel anode. In various embodiments of the electrochemical battery, the gel anode comprises an anode active material, wherein about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm relative to the total weight of the anode active material. The gel anode further comprises an alkaline electrolyte comprising a hydroxide material, a gelling agent, and about 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant.

[0040] The cathode of an electrochemical cell may comprise any cathode active material generally recognized in the art for use in alkaline electrochemical cells. The cathode active material may be amorphous or crystalline, or a mixture of amorphous and crystalline. For example, the cathode active material may comprise or be selected from oxides of copper, oxides of manganese of electrolytic, chemical, or natural types (such as EMD, CMD, NMD, or any mixture of two or more), oxides of silver, and / or oxides or hydroxides of nickel, and mixtures of two or more of the aforementioned oxides or hydroxides. Suitable examples of cathode materials include, but are not limited to, MnO2 (EMD, CMD, NMD, and mixtures thereof), NiO, NiOOH, Cu(OH)2, cobalt oxide, PbO2, AgO, Ag2O, Ag2Cu2O3, CuAgO2, CuMnO2, CuMn2O4, Cu2MnO4, Cu 3-x Mn x O3, Cu 1-x Mn x O2, Cu 2-x Mn x O2 (where x < 2), Cu 3-x Mn x O4 (where x < 3), Cu2Ag2O4, or any combination of two or more thereof.

[0041] An electrochemical cell may have a separator between the cathode and the zinc anode, the separator being designed to prevent short circuits between the two electrodes. Generally, any separator material and / or construction suitable for alkaline electrochemical cells, as well as cathode and / or anode materials described above, can be used according to the disclosure of this application. In one embodiment of the invention, the separator is a non-conductive separator. In one embodiment of the invention, the electrochemical cell includes a sealed separator system disposed between the gel anode and cathode described in this application. The separator can be made of any alkali-resistant natural, woven, or nonwoven porous material, including but not limited to polymeric materials, Tencel®, mercerized wood pulp, polypropylene, polyethylene, cellophane, cellulose, methylcellulose, rayon, nylon, and combinations thereof. In some embodiments of the invention, the separator is made of a porous material, including paper formed from one or more polymer fibers. In some embodiments of the invention, the separator porous material includes one or more polymer fibers in which an effective amount of surfactant is embedded. Suitable polymeric materials for polymer fibers include, but are not limited to, polyvinyl alcohol, polyamide, polyethylene terephthalate, propylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride, polyacrylonitrile, polypropylene, polyethylene, polyurethane and their mixtures and copolymers, such as rayon, nylon and combinations thereof.

[0042] Exemplary embodiments of alkaline electrochemical batteries have been described in detail in PCT application with publication number WO 2016 / 183373, the entire disclosure of which is incorporated herein by reference.

[0043] One aspect of the present invention provides a gel anode comprising an anolyte, an electrolyte, a gelling agent, and a surfactant, wherein, relative to the total weight of the anolyte, about 15 wt% to about 60 wt% of the anolyte has a particle size of less than about 75 μm, the electrolyte contains about 24 wt% to about 36 wt% potassium hydroxide, the gelling agent contains about 0.2 wt% to about 1.0 wt%, and the surfactant is about 10 ppm to 250 ppm of alkoxyalkyl phosphate.

[0044] In various embodiments, the anolyte may comprise zinc, which may be used alone or in combination with one or more other metals. The anolyte may be in alloy form. Therefore, in some embodiments, the anolyte may comprise a zinc alloy. In some embodiments, the type of anolyte may be similar to that described in detail in U.S. Patent Publication No. 2015 / 0037627.

[0045] Suitable alloying materials may comprise, alone, an alloying agent in a weight content of about 0.01 wt% to about 0.5 wt%, or in combination with a second alloying agent (such as bismuth, indium, lithium, calcium, aluminum, etc.) in a weight content of about 0.005 wt% to about 0.2 wt%. For example, in one or more embodiments, suitable powders containing zinc may also comprise one or more metals, such as indium, bismuth, calcium, aluminum, lead, etc., or alloyed with them. Therefore, it should be noted that, as used herein, "anodic active material" and / or "zinc" may refer to individual particles or powders, or particles or powders that have optionally been mixed or alloyed with one or more other metals. Anodic active material particles may be present in a variety of forms, such as elongated, round, fibrous, or flake-like particles.

[0046] In some embodiments, the zinc alloy includes indium and bismuth. In some embodiments, the zinc alloy includes zinc, bismuth, and indium. In some embodiments, the zinc alloy includes zinc, bismuth, indium, and aluminum. The concentration of the metal alloyed with zinc can range from about 20 ppm to about 750 ppm. In some embodiments, the alloy metal is present at a concentration of about 50 ppm to 550 ppm. In other embodiments, the alloy metal is present at a concentration of about 130 ppm to 270 ppm. In other embodiments, the alloy metal is present at a concentration of about 150 ppm to 250 ppm. In some embodiments, the zinc alloy includes bismuth and indium as main alloying elements, with concentrations of about 100 ppm to about 300 ppm, respectively. In some embodiments, the zinc alloy includes bismuth and indium as main alloying elements, each with a concentration of about 200 ppm.

[0047] Anode active materials can exist in the anode in the form of coarse, fine, or dust, or any combination thereof. Conventional anode active materials used in electrochemical cells, such as zinc alloy particles (STD), typically have a particle size distribution of about 0.5% to about 2.0% dust, about 5% to about 25% fine powder, and about 25% to about 60% coarse particles. In this application, the anode comprises a high-fineness (HF) anode active material with a higher content of fine forms and a lower content of coarse forms than conventional standard zinc powder. In various embodiments, the anode active material has a particle size distribution of less than about 15 wt% dust, about 10 wt% to about 70 wt% fine powder, and about 5 wt% to about 35 wt% coarse particles. In other embodiments, the anode active material of the present invention has a particle size distribution of less than about 10 wt% dust, about 15 wt% to about 65 wt% fine powder, and about 5 wt% to about 25 wt% coarse particles.

[0048] The anolyte active material has an average particle size of about 70 micrometers to about 175 micrometers, including average particle sizes of about 75 micrometers, about 80 micrometers, about 85 micrometers, about 90 micrometers, about 100 micrometers, about 110 micrometers, about 120 micrometers, about 130 micrometers, about 140 micrometers, or about 150 micrometers. In some embodiments, the anolyte active material has an average particle size of about 100 micrometers to about 170 micrometers. In some embodiments, the anolyte active material comprises zinc alloy particles with an average particle size of about 120 micrometers. The particle size distribution d50 is the particle size of the 50% cumulative distribution. In this application, the anolyte material includes zinc active materials with a d50 of about 60 micrometers to about 120 micrometers, including d50 values ​​of about 80 micrometers, about 85 micrometers, about 90 micrometers, about 95 micrometers, about 100 micrometers, about 105 micrometers, and about 110 micrometers.

[0049] In some embodiments, relative to the total weight of the anolyte material present in the gel anode, greater than about 15 wt% of the anolyte material has a particle size less than about 75 micrometers, including greater than about 20 wt%, greater than about 25 wt%, greater than about 30 wt%, or greater than about 35 wt% of the anolyte material present in the gel anode with a particle size less than about 75 micrometers. In some embodiments, relative to the total weight of the anolyte material present in the gel anode, about 15 wt% to about 60 wt% of the anolyte material has a particle size less than about 75 micrometers, including about 15 wt% to about 60 wt%, about 20 wt% to about 50 wt%, about 25 wt% to about 45 wt%, or about 35 wt% to about 40 wt%, and the range between any two of these values ​​or less than either value. The particle size is less than about 75 micrometers relative to the total weight of the anolyte material present in the gel anode. In some embodiments, relative to the total weight of the anolyte material present in the gel anode, about 30 wt% of the anolyte material has a particle size less than about 75 micrometers. In some embodiments, about 40 wt% of the anolyte active material, relative to the total weight of the anolyte active material present in the gel anode, has a particle size of less than about 75 micrometers. In some embodiments, about 15 wt% to about 60 wt% of the anolyte active material, relative to the total weight of the anolyte active material present in the gel anode, has a particle size of less than about 75 micrometers. In some embodiments, about 20 wt% to about 50 wt% of the anolyte active material, relative to the total weight of the anolyte active material present in the gel anode, has a particle size of less than about 75 micrometers.

[0050] In some embodiments, less than about 35 wt% of the anolyte active material having a particle size greater than about 150 micrometers relative to the total weight of the anolyte active material present in the gel anode. In some embodiments, less than about 30 wt%, less than about 25 wt%, less than about 20 wt%, or less than about 15 wt% of the anolyte active material having a particle size greater than about 150 micrometers relative to the total weight of the anolyte active material present in the gel anode. In some embodiments, less than about 20 wt% of the anolyte active material having a particle size greater than about 150 micrometers relative to the total weight of the anolyte active material present in the gel anode. In some embodiments, relative to the total weight of the anolyte present in the gel anode, about 1 wt% to about 40 wt% of the anolyte has a particle size greater than about 150 micrometers, including embodiments of about 2 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 10 wt% to about 20 wt%, or about 12 wt% to about 18 wt% of the anolyte has a particle size greater than about 150 micrometers, and any two of these values ​​or less than either of these values, relative to the total weight of the anolyte present in the gel anode, as a weight content of the anolyte.

[0051] In some embodiments, less than about 20 wt% of the anolyte active material having a particle size less than about 45 micrometers relative to the total weight of the anolyte active material present in the gel anode includes embodiments where the particle size is less than about 15 wt%, less than about 12 wt%, less than about 10 wt%, or less than about 5 wt% of the anolyte active material having a particle size less than about 45 micrometers relative to the total weight of the anolyte active material present in the gel anode. In some embodiments, about 1 wt% to about 20 wt% of the anolyte active material having a particle size less than about 45 micrometers relative to the total weight of the anolyte active material present in the gel anode includes embodiments where the particle size is about 1 wt% to about 20 wt%, about 2 wt% to about 15 wt%, or about 5 wt% to about 10 wt% of the anolyte active material present in the gel anode, and the range between any two of these values ​​or less than any of these values. The particle size of the active material is less than about 45 micrometers relative to the total weight of the anolyte active material present in the gel anode. In some embodiments, about 2 wt% to about 10 wt% of the anolyte active material has a particle size of less than about 45 micrometers relative to the total weight of the anolyte active material present in the gel anode.

[0052] A suitable zinc particle size distribution may be that, relative to the total weight of the anolyte, about 15 wt% to about 65 wt% of the anolyte has a particle size of less than about 75 micrometers, relative to the total weight of the zinc alloy, about 5 wt% to about 25 wt% of the zinc alloy has a particle size of greater than about 150 micrometers, and relative to the total weight of the anolyte, less than about 10 wt% of the anolyte has a particle size of less than about 45 micrometers.

[0053] The gel anode may include a zinc load lower than that in conventional batteries. For example, the gel anode may have a zinc load of about 75 wt% or less relative to its weight. In some embodiments, the gel anode may have a zinc load of about 72 wt% or less, about 68 wt% or less, about 65 wt% or less, about 64 wt% or less, or about 63 wt% or less relative to its weight. In some embodiments, the gel anode may have a zinc load of about 60 wt% to about 75 wt% relative to its weight, including about 60 wt% to about 75 wt%, about 62 wt% to about 72 wt%, about 65 wt% to about 70 wt%, about 66 wt% to about 69 wt%, or about 67 wt% to about 68 wt%, and relative to the weight of the gel anode, based on the weight of the anode active material, between or less than any of these values. In some embodiments, the gel anode may have a zinc load of about 64 wt% relative to its weight. In other embodiments, the gel anode may have a zinc loading of approximately 63 wt% relative to its weight.

[0054] The surface morphology of zinc alloys affects gas generation, as does their apparent density. It has been found that battery outgassing tends to decrease with increasing apparent density. Apparent density also affects discharge performance. Moderate-flow emissions, such as in the HIFT and toy tests of LR20 batteries, can be enhanced with increasing apparent density. Increasing apparent density results in spherical particles with an aspect ratio greater than 0.6, especially fine particles smaller than approximately 75 micrometers. Spherical particles are expected to have lower surface discontinuities, which are preferred reaction sites for gas generation, thus leading to less hydrogen formation. Furthermore, improved packing density of zinc powder and particle-to-particle contact can result in enhanced discharge performance, particularly at moderate discharge rates in LR14 and LR20 batteries.

[0055] In some embodiments of this application, the anolyte has an apparent density of less than about 5.00 g / cm³ (“cc”). In other embodiments, the apparent density of the anolyte is about 2.00 g / cc to about 4.15 g / cc; in some embodiments, the apparent density of the anolyte is about 2.25 g / cc to about 3.85 g / cc; in some embodiments, the apparent density of the anolyte is about 2.50 g / cc to about 3.50 g / cc; in some embodiments, the apparent density of the anolyte is about 2.60 g / cc to about 3.35 g / cc; in some embodiments, the apparent density of the anolyte is about 2.70 g / cc to about 3.15 g / cc. In other embodiments, the apparent density of the anolyte is about 2.70 g / cc; in some embodiments, the apparent density of the anolyte is about 3.15 g / cc; in some embodiments, the apparent density of the anolyte is about 3.35 g / cc. In other embodiments, the average apparent density of the anolyte is about 2.70 g / cc; in other embodiments, the average apparent density of the anolyte is about 2.95 g / cc; in other embodiments, the average apparent density of the anolyte is about 3.15 g / cc; and in some embodiments, the anolyte has an average apparent density of about 2.80 g / cc to about 3.15 g / cc.

[0056] The gel anode may include an alkaline electrolyte, and in some embodiments, an alkaline electrolyte having a low hydroxide content. Suitable alkaline electrolytes include aqueous solutions of potassium hydroxide, sodium hydroxide, lithium hydroxide, and any combination of two or more thereof. In one particular embodiment, a potassium hydroxide-containing electrolyte is used. In other embodiments, the alkaline electrolyte includes water and potassium hydroxide.

[0057] Advantageously, the electrolyte has a lower hydroxide ion concentration compared to the electrolyte used in conventional batteries. For example, the hydroxide (e.g., potassium hydroxide) content of the electrolyte is less than about 36% based on the total electrolyte weight, including concentrations of hydroxide less than about 35%, less than about 34%, less than about 32%, less than about 30%, less than about 29%, or less than about 28% based on the total electrolyte weight. In various embodiments, the hydroxide concentration of the electrolyte is about 24% to about 36%, about 26% to about 34%, about 27% to about 34%, about 28% to about 34%, or about 28% to about 32%, and values ​​between or less than any of these values. This includes hydroxide concentrations of about 35%, about 34%, about 32%, about 31%, about 30.5%, about 30%, about 29%, or about 28% based on the total electrolyte weight. In one exemplary embodiment, such as a gel anode suitable for use in a battery of size and shape LR14 or LR20 alkaline battery, the hydroxide concentration of the electrolyte is about 30 wt% to about 32 wt% based on the total weight of the electrolyte.

[0058] In some embodiments, the content of hydroxide electrolyte in the gel anode is at least about 24 wt%, at least about 26 wt%, at least about 28 wt%, and less than about 34 wt%, less than about 32 wt%, or less than about 30 wt%, based on the total weight of the gel anode. Therefore, in the gel anode of the present invention, the concentration of electrolyte is typically from about 26 wt% to about 34 wt%, from about 28 wt% to about 32 wt%, or from about 30 wt% to about 32 wt%, based on the total weight of the gel anode.

[0059] The gel anode may further include a gelling agent. The gelling agent is at least partially present in the anode to increase the mechanical structure and / or coat the metal particles, thereby improving the ionic conductivity within the anode during discharge. Suitable gelling agents are those that impart a rigid gel structure, slightly reduce the packing density of the gel anode within the battery, and have a correspondingly larger but more stable anode particle spacing. Therefore, it should be noted that, as used herein, “gel anode” (and variations thereof) generally refers to an anode to which electrolyte (or, in some cases, the remainder of the electrolyte) has been added or introduced. Conversely, “coated metal anode” (and variations thereof) generally refers to an anode to which electrolyte (or all electrolyte) has been added or introduced beforehand.

[0060] The anode can be prepared by: formulating an electrolyte, preparing a coated metal anode including a gelling agent, and combining the electrolyte and the coated metal anode to form a gel anode. The gelling agent disclosed in this application may include highly cross-linked polymer compounds having negatively charged acid groups, such as highly cross-linked polyacrylic acid gelling agents. Highly cross-linked polyacrylic acid gelling agents are available from Lubrizol Corporation (Wycliffe, Ohio) under the trade name Carbopol. ® (Carbopol ® 940, Carbopol ® 934 or Carbopol ® 674) Purchased, or obtained from SNF Holdings (Risboro, Georgia) under the trade name Flogel ® (such as Flogel) ® 700 or Flogel ® Purchased from 3V Sigma Corporation (Georgetown, South Carolina) under the trade name Polygel (800). ® (e.g., Polygel) ® CK or Polygel ® The information is obtained from CA or Polygel CS and is particularly suitable for use in the disclosure of this application.

[0061] A suitable gelling agent can be selected based on various properties, such as degree of crosslinking, viscosity, and / or density. For a given application, the concentration of the gelling agent in the gel anode can be optimized. For example, based on the total weight of the gel anode, the concentration of the gelling agent is at least about 0.20 wt%, including at least about 0.30 wt%, at least about 0.40 wt%, at least about 0.50 wt%, at least about 0.60 wt%, at least about 0.65 wt%, at least about 0.675 wt%, and at least about 0.70 wt%. For example, in various embodiments, the concentration of the gelling agent in the gel anode relative to the total weight of the gel anode can be from about 0.20 wt% to about 1.5 wt%, from about 0.40 wt% to about 1.00 wt%, from about 0.60 wt% to about 0.70 wt%, or from about 0.625 wt% to about 0.675 wt%. In some embodiments, the gel anode may contain about 0.40% to about 1.0% by weight of one or more gelling agents.

[0062] The gel anode material exhibits a suitable viscosity required for good processability and battery discharge performance. For example, the gel anode can exhibit an initial viscosity of about 30,000 centipoise (cps) to about 300,000 cps at about 21°C (i.e., the viscosity measured immediately after preparation, such as the viscosity measured within 60 minutes after preparation). In various embodiments, before and / or after incorporation into an electrochemical cell, the gel anode of the present invention can exhibit a viscosity of at least about 25,000 cps, at least about 40,000 cps, at least about 55,000 cps, at least about 70,000 cps, at least about 85,000 cps, at least about 100,000 cps, at least about 130,000 cps, or higher. In some embodiments, the gel anode disclosed in this application exhibits viscosities of about 25,000 cps to about 250,000 cps, about 40,000 cps to about 180,000 cps, about 60,000 cps to about 150,000 cps, about 80,000 cps to about 130,000 cps, or about 100,000 cps to about 120,000 cps. The viscosity and density of the gel anode disclosed in this application can be determined using conventional methods known in the art. To measure the viscosity of the anode gel and the anode yield stress, a Brookfield DV-E viscometer was used with a switching speed of 0.5 rpm, allowing the anode to stand for two minutes before recording the viscosity reading. To determine the yield stress, a switching speed of 1 rpm was selected to obtain the corresponding viscosity reading after two minutes. The yield strength was calculated by dividing the difference between the readings observed at the 0.5 rpm and 1 rpm switching speeds by 100.

[0063] This application provides gel anodes having a yield stress greater than about 200 cps, including yield stresses of about 200 cps to about 2000 cps, about 400 cps to about 1500 cps, about 600 cps to about 1200 cps, or about 800 cps to about 1000 cps, and any two of these values ​​or less than any one of these values. In some embodiments, the gel anode has a yield stress value of about 800 cps to about 1200 cps.

[0064] Gel anodes may include other components or additives, such as absorbents, organic surfactants, and inorganic corrosion inhibitors. Surfactants are believed to act on the anode-electrolyte interface by forming a hydrophobic film that protects the active anode surface during storage. The inhibitory efficiency of surfactants in increasing the corrosion resistance of the active anode material depends on their chemical structure, concentration, and stability in the electrolyte. Therefore, in some embodiments, surfactants include corrosion or outgassing inhibitors. Exemplary surfactants include organophosphates, such as alkyl and aryl phosphates, with and without ethoxylation. Exemplary organophosphate surfactants include ethylene oxide adducts disclosed by Rösler et al. in U.S. Patent No. 4,195,120, or surfactant-containing anisopolar ethylene oxide additives comprising organophosphates disclosed by Salipli et al. in U.S. Patent No. 4,777,100, as well as commercially available surfactants such as Rhodafac. ® RM-510, Rhodafac ® RS-610, Rhodafac ® RA-600 (all from Solvay); Crodafos ® T6A, Crodafos ® SG-LQ (from Croda); Phospholan ® PS-220, Phospholan ® PS-131, Phospholan ® CS-141 (both from AkzoNobel); Witconate ® 1840X or Mafo ® 13 MOD1 or any combination of two or more thereof. In some embodiments, the organophosphate surfactant includes polyoxyethylene dinonylphenyl ether phosphate (such as Rhodafac, available from Solvay). ® RM-510E). In other embodiments, the surfactant includes polyoxyethylene tridecyl ether phosphate (i.e., tridecyl hexaphosphate, such as Crodafos available from Croda). ® T6A).

[0065] The concentration of the organophosphate surfactant relative to the weight of the anode can be from about 0.0001 wt% to about 10 wt%, including about 0.005 wt% to about 5 wt%, about 0.004 wt% to about 1 wt%, about 0.003 wt% to about 0.01 wt%, about 0.002 wt% to about 0.005 wt%, about 0.001 wt% to about 0.015 wt%, about 0.001 wt% to about 0.008 wt%, or about 0.01 wt% to about 0.1 wt%, and ranges between any two of these values ​​or less than any one of these values. In some embodiments, the concentration of the organophosphate surfactant relative to the total weight of the gel anode mixture is from about 0.001 wt% to about 0.015 wt%.

[0066] Based on the total weight of the electrolyte, the organophosphate surfactant may be present in the electrolyte at a concentration of about 0.1 ppm to about 10,000 ppm. In another embodiment, the organophosphate surfactant is present in the electrolyte at a concentration of about 1 ppm to about 5,000 ppm. In another embodiment, the concentration of the organophosphate surfactant in the electrolyte is about 5 ppm to about 1,000 ppm. In one embodiment, the concentration of the organophosphate surfactant in the electrolyte is about 10 ppm to about 250 ppm. In some embodiments, the concentration of the surfactant in the organophosphate electrolyte is about 20 ppm to about 150 ppm. In some embodiments, the electrolyte contains about 10 ppm to about 250 ppm of polyoxyethylene dinonylphenyl ether phosphate (e.g., Rhodafac). ® RM-510E). In other embodiments, the electrolyte comprises about 10 ppm to about 250 ppm of polyoxyethylene tridecyl ether phosphate or tridecyl phosphate (e.g., Crodafos). ® T6A).

[0067] In addition to the anolyte, gelling agent, and electrolyte, the gel anode may include other components or additives. For example, additives may include absorbents, corrosion inhibitors, or outgassing inhibitors. Suitable absorbent materials may be selected from those commonly known in the art. Exemplary absorbent materials include those sold under the trade names Salsorb™ or Alcasorb™ (e.g., Alcasorb™), which are commercially available from Ciba Specialty (Carroll Strehm, Illinois), or alternatively under the trade name Sunfresh™ (e.g., Sunfresh DK200VB, available from Sanyo Chemical Industries, Ltd., Japan). When present, the concentration of absorbent in the gel anode disclosed in this application is less than about 0.5%, less than about 0.2%, less than about 0.15%, less than about 0.1%, less than about 0.075%, less than about 0.05%, less than about 0.025%, or less than about 0.01% based on the total weight of the anode. In some embodiments, the gel anode does not contain additional additives such as alkali metal hydroxides, metal oxides, or metals. In some embodiments, the gel anode does not contain additives such as lithium hydroxide, cerium oxide, or tin.

[0068] One aspect of the present invention provides a gel anode and / or an electrochemical cell comprising a gel anode, comprising an anode active material wherein, relative to the total weight of the anode active material, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm, an alkaline electrolyte comprising about 24 wt% to about 36 wt% potassium hydroxide, about 0.2 wt% to about 1.0 wt% a gelling agent, and about 10 ppm to 250 ppm an organophosphate surfactant. In some embodiments, the organophosphate surfactant comprises polyoxyethylene tridecyl ether phosphate (i.e., tridecyl hexaphosphate, Crodafos) ® T6A).

[0069] Another aspect of the present invention provides a gel anode, and / or an electrochemical cell including a gel anode, comprising an anode active material, wherein, relative to the total weight of the anode active material, about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm, an alkaline electrolyte comprising about 24 wt% to about 36 wt% potassium hydroxide, about 0.2 wt% to about 1.0 wt% a gelling agent, and about 10 ppm to 250 ppm of polyoxyethylene tridecyl ether phosphate (Crodafos). ®T6A). Another aspect of the invention provides a gel anode, and / or an electrochemical cell comprising a gel anode, comprising an anode active material, wherein, relative to the total weight of the anode active material, about 20 wt% to about 50 wt% of the anode active material has a particle size of less than about 75 μm, an alkaline electrolyte comprising about 26 wt% to about 34 wt% potassium hydroxide, about 0.2 wt% to about 1.0 wt% a gelling agent, and about 10 ppm to 250 ppm of polyoxyethylene tridecyl ether phosphate (Crodafos). ® T6A).

[0070] Compared to conventional batteries, the gel anode and electrochemical battery of this invention offer several advantages: The gel anode of this invention is designed with a high fine powder content and a relatively low zinc loading (e.g., as low as 63 wt%) to improve resistance to drop failure, suppressing further drop and discharge vibration failures in large batteries, and reducing battery outgassing (outgassing after partial battery discharge). The anode material of this invention also allows for greater interparticle contact between zinc particles, thereby improving the reliability of the electrochemical battery.

[0071] Surprisingly, it was found that for electrochemical cells with large-diameter containers (such as the LR14 cell), by utilizing the gel anode of the present invention, undischarged cell leakage can be significantly reduced or even essentially eliminated, resulting in increased reliability—a result contrary to expectations and unexpected. Without being bound by theory, it can be assumed that the reduction in leakage is the result of a combination of factors, including the use of highly fine zinc, optimized KOH concentration, and the type of gelling agent. Furthermore, contrary to expectations, the performance of the electrochemical cell is also improved. Generally, it is known that the use of fine zinc powder inhibits performance. However, in this invention, it was surprisingly observed that the development of a gel anode utilizing highly fine zinc in combination with an electrolyte having a specific hydroxide concentration and a specific gelling agent improves the discharge performance of the electrochemical cell.

[0072] Therefore, one aspect of this application provides a gel anode, and / or an LR20 or LR14 electrochemical cell comprising a gel anode, wherein, relative to the total weight of the anode active material, about 20 wt% to about 55 wt% of the anode active material has a particle size of less than about 75 μm, and about 5 wt% to about 25 wt% of the anode active material has a particle size of greater than about 150 μm; an alkaline electrolyte comprising about 26 wt% to about 34 wt% of potassium hydroxide; about 0.3 wt% to about 0.9 wt% of a gelling agent; and 20 ppm to 150 ppm of an organophosphate surfactant.

[0073] As described in the further detailed description above, the electrochemical cells of the present invention have been observed to exhibit improved performance characteristics, which can be measured or tested according to several methods under the American National Standards Institute (ANSI). The following examples illustrate various test results for the cells of this application.

[0074] One aspect of the present invention provides a method for improving the reliability of an electrochemical cell subjected to outgassing, the method comprising providing a gel anode comprising an anode active material as the active anode of the cell, an alkaline electrolyte, and a gelling agent, wherein about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm relative to the total weight of the anode active material.

[0075] Another aspect of the present invention provides a method for enhancing the discharge performance of an electrochemical battery, the method comprising providing a gel-like anode as the active anode of the battery, the gel-like anode comprising an anode active material, an alkaline electrolyte and a gelling agent, wherein about 15 wt% to about 60 wt% of the anode active material has a particle size of less than about 75 μm relative to the total weight of the anode active material.

[0076] In various embodiments of the method for improving the reliability and / or enhancing the discharge performance of an electrochemical cell, the anode for the electrochemical cell is as described above. Therefore, in various embodiments of the method, the anode of the electrochemical cell is a gel anode. In various embodiments of the method, the gel anode comprises an anode active material, wherein approximately 15 wt% to approximately 60 wt% of the anode active material, relative to the total weight of the anode active material, has a particle size of less than approximately 75 μm. The gel anode further comprises an alkaline electrolyte comprising a hydroxide material, a gelling agent, and approximately 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant.

[0077] The following embodiments describe various implementations of this application. Other implementations within the scope of the appended claims will be apparent to those skilled in the art based on the specification or implementation provided in this application. Therefore, this specification and embodiments are considered exemplary only, and the scope and spirit of this application are as shown in the claims following the embodiments.

[0078] Example In the embodiments given below, the DSC performance of the electrochemical cell of this application, drop test current intensity (before and after drop), partial discharge venting, and storage conditions were tested.

[0079] In the examples given below, a gel anode and an electrochemical cell were prepared according to an improvement of the present invention. The DSC performance of the electrochemical cell, the outgassing of the partially discharged cell, the outgassing of the undischarged cell, and the storage conditions were tested.

[0080] Gel viscosity was measured using a Brookfield digital viscometer and a Teflon-coated spindle #06 at 4 revolutions per minute (rpm). The reading was allowed to stabilize for at least 5 minutes before being recorded.

[0081] As described above, for the measurement of yield stress, the gel viscosity was measured at 1.0 rpm (R1) and 0.5 rpm (R2), and the yield stress was calculated using the following formula: Yield stress = (R2 - R1) / 100.

[0082] Example 1 - Gas release performance of an undischarged battery Gel anodes were prepared using zinc alloy powder, KOH electrolyte, and a zinc loading of 63% relative to the gel weight. The zinc powder contained bismuth and indium as the main alloying elements, at concentrations of approximately 200 ppm and 200 ppm, respectively. The particle size distribution of the zinc anodes comprised highly fine (HF) powder (i.e., less than 75 micrometers or 200 mesh size), with an optimal content greater than 25 wt%. Two inhibitor compositions, including inhibitor A and inhibitor B, were tested in the gel anodes to determine their effects on performance and reliability. Inhibitor A comprised commercially available Crodafos... ® T6A sells phosphate-based anionic surfactants, which are polyethylene glycol ethers of tridecaol. Inhibitor B comprises poly(ethylene oxide dinonylphenyl ether phosphate), commercially marketed as Rhodafac. ® For sale at RM-510 E.

[0083] The undischarged battery characteristics of batteries containing the gel anode prepared as described above were investigated. Figure 1 The undischarge outgassing comparisons of LR20 alkaline batteries prepared with (i) 30.5% KOH and 90 ppm inhibitor A, (ii) 32% KOH and 90 ppm inhibitor A, and (iii) 32% KOH and 90 ppm inhibitor A are shown. For all described batteries, other anode components (such as zinc type, gelling agent, and 63% zinc loading) remained the same. Figure 1 As shown, at 32% KOH, the average outgassing of the undischarged battery with inhibitor A was lower than that of the undischarged battery with inhibitor B. It is generally expected that outgassing increases with decreasing KOH concentration. However, Figure 2 The results show that the outgassing of an undischarged battery using inhibitor A at 30.5% KOH is at least equal to the outgassing of a battery using inhibitor B at 32% KOH.

[0084] Example 2 - Gas release performance of partially discharged batteries The partial discharge outgassing of the battery prepared according to the description in Example 1 was tested. Due to the breakdown of the passivation oxide film on the zinc anode surface caused by the discharge process, the outgassing of the partially discharged battery is expected to increase compared to the undischarged battery. Inhibitors may play a key role in suppressing partial discharge. Figure 2 The outgassing of a partially discharged LR20 battery of Example 1 is shown. It was observed that, at 32% KOH, the outgassing of the partially discharged battery with inhibitor A was reduced compared to that with inhibitor B. Furthermore, even when the KOH concentration was reduced to 30.5%, the outgassing of the partially discharged battery using inhibitor A remained the same as that of the battery using inhibitor B at 32% KOH.

[0085] The difference in outgassing suppression between undischarged and partially discharged batteries is attributed to the unique film properties of inhibitors A and B formed on the zinc anode surface.

[0086] Example 3 - Performance Testing of Toys and Portable Stereo Sounds The LR20 battery discharged in a toy test, characterized by a discharge of 2.2 ohms per day for one hour. Figure 3 The effects of varying KOH concentrations on the performance of LR20 batteries, as well as inhibitors A and B described in Example 1, during toy testing are shown. It was observed that inhibitor A outperformed inhibitor B in the toy test at 32% KOH. Further performance enhancement was observed with inhibitor A at 30.5% KOH. Figure 3 As shown, in toy testing, the average performance enhancement of inhibitor A was approximately 4% at 32% KOH and approximately 5.9% at 30.5% KOH. Similar discharge performance improvements were observed in portable stereo testing, characterized by a 600 mA discharge load for two hours per day (…). Figure 4 ).like Figure 4 As shown, in portable stereo testing, the performance enhancement of inhibitor A was approximately 2.3% at 32% KOH and approximately 3.7% at 30.5% KOH.

[0087] Example 4 - The impact of inhibitors on battery reliability The type of inhibitor can also affect the results of abuse drop tests. For example... Figure 5 As shown, a conventional LR20 battery made with standard zinc (containing 10% fine zinc particles, 32% KOH, and 60 ppm RM510) fails the drop test, requiring a minimum amperage of 4A to pass. In contrast, an LR20 battery made with HF-type zinc in 30.5% KOH and containing 60 ppm inhibitor B passed the test. Further improvement in amperage after drop is observed in LR20 batteries made with finer zinc in 30.5% KOH and containing 60 ppm inhibitor A. Figure 6The corresponding toy's discharge performance can be seen in the image. Figure 7 The corresponding partial discharge battery venting is shown in the figure. At a concentration of 30.5% KOH and 60 ppm inhibitor, the performance and battery venting effect using inhibitors A and B are comparable. Example 5 - The effect of apparent density on battery performance The gel anode was prepared using zinc alloy powder, KOH electrolyte, and a zinc loading of 66% relative to the gel weight. The zinc powder contained bismuth and indium as the main alloying elements, at concentrations of approximately 200 ppm and 200 ppm, respectively. The zinc anode exhibited a particle size distribution comprising highly fine (HF) powder (i.e., less than 75 micrometers or 200 mesh size) at an optimal level above 28% HF. The KOH concentration in the gel was tested at 30.5%. Various inhibitory surfactants, including Novec, were tested. ® 4434、Rhodafac ® RM510 and Crodafos ® The concentrations of T6A were 100 ppm, 6 ppm, and 90 ppm, respectively. Zinc powder with apparent densities ranging from approximately 2.80 g / cc to 3.15 g / cc was tested in gel anodes to determine its effect on outgassing and battery performance.

[0088] Example 6 - LR20 Battery Figure 8 and Figure 9 The images show the gas release of LR20 batteries after one week of storage at 71°C (160°F) with both undischarged and partially discharged batteries, demonstrating the effect of increased apparent zinc density in the batteries. Figure 8 and Figure 9 The data shows that the higher the apparent density, the less battery gas is released, regardless of the type of inhibitory surfactant used to suppress battery gas release. Figure 10 The study showed that after two days of storage at 85°C (185°), the increase in the apparent density of zinc in undischarged LR20 batteries suppressed outgassing.

[0089] Electrochemical batteries can be tested according to American National Standards Institute (ANSI) methods. Testing includes determining battery performance / life under various discharge modes, including pulsed discharge, intermittent discharge, or digital still camera (DSC, i.e., repeatedly applying 1500mW for 2 seconds, 650mW for 28 seconds, for 5 minutes per hour, until the battery voltage reaches a endpoint of 1.05 V). Testing also includes determining battery performance / life by discharging in various devices such as toys, portable stereos, digital audio devices, and heavy industrial flashlights (HIFT). The LR20 battery was discharged in the ASTM Heavy Industrial Flashlight Test (HIFT) at 1.5 ohms for 15 minutes followed by 4 minutes for 8 hours / day; in the portable stereo test, the discharge conditions were 2 hours / day at 600mA. The average discharge performance of the LR20 battery in the HIFT and portable stereo tests is as follows: Figure 11 As shown, the discharge performance improves with increasing apparent density.

[0090] Figure 12 The effects of high-fine zinc on the performance of LR20 batteries, including those with gel anodes, at 63% load, with apparent densities of 2.77 g / cc and 3.00 g / cc, were shown in tests at HIFT (1.5 ohms, 4 minutes out of 15 minutes, 8 hours / day), portable stereo (600 mA, 2 hours / day), toys (2.2 ohms H / D), radios (10 ohms 4 H / D), and light industrial flashlights (LIFT) (2.2 ohms, 4 minutes / hour, 8 hours / day). Figure 13 The diagram shows the corresponding gas release of a partially discharged battery, demonstrating reduced gas release in a battery with an apparent density of approximately 3.0 g / cc. Please refer to... Figure 12 and Figure 13 The LR20 battery's anode gel has a zinc loading of 63% relative to the gel's weight. The zinc powder contains bismuth and indium as the main alloying elements, with concentrations of approximately 200 ppm and 200 ppm, respectively. The gel's KOH concentration was tested at 30.5%. (Rhodafac) ® The concentration of RM-510 was tested at 60 ppm with zinc at an apparent density of 3.0 g / cc, while the reference cell with zinc at an apparent density of 2.77 g / cc was tested at 90 ppm.

[0091] Figure 14 The impact of ANSI performance testing on the LR20 battery is shown. The LR20 battery comprises a gel anode with HF zinc loading of 63% and an apparent density of 2.77 g / cc. The average performance of the above-mentioned HIFT, portable stereo, toy, radio, and LIFT tests is shown. Data shows that... Figure 14The zinc powder in the sample contains bismuth and indium as the main alloying elements, with concentrations of approximately 200 ppm and 200 ppm, respectively. The data in the figure apply to 90 ppm Crodafos T6A and 90 ppm Rhodafac RM510 (containing 30.5% KOH and 32% KOH), as well as 90 ppm Crodafos T6A (32% KOH).

[0092] Example 7 - LR14 Battery The LR14 alkaline battery was prepared according to the procedure described in Example 5, wherein the high-fine zinc had a loading of 63% and an apparent density of 2.77 g / cc. Figure 15 The effect of LR14 battery storage on ANSI performance testing is shown. Figure 15 Average performance is provided for portable stereo (400mA, 2 hours / day to 0.9V), portable lighting (3.9 ohms, 4 minutes / hour, 8 hours / day to 0.9V), and toy testing (3.9, 1 hour / day to 0.8V). Figure 16 and Figure 17 They are shown respectively in Figure 15 The description of the batteries includes the venting of the corresponding undischarged batteries and the venting of the partially discharged batteries. Figure 15 The optimal LR14 battery performance shown is 30.5% KOH, compared to Figure 16 and 17 The reliability data for the venting of the corresponding undischarged and partially discharged batteries shown respectively are consistent.

[0093] Although some embodiments have been shown and described, it should be understood that changes and modifications can be made to the embodiments in accordance with ordinary techniques in the art without departing from the broader scope defined by the appended claims.

[0094] The embodiments exemplarily described in this application may be suitably implemented without the presence of any one or more elements or limitations not specifically disclosed in this application. Therefore, the terms “comprising,” “including,” “containing,” etc., should be read broadly and without limitation. Furthermore, the terms and expressions used in this application have been used as descriptive terms rather than limiting terms, and the use of such terms and expressions does not imply exclusion of any equivalent forms of the features shown and described or portions thereof, and it should be understood that various modifications may be made within the scope of the claims. Additionally, the phrase “consistently composed of…” should be understood to include both the specifically described elements and additional elements that do not materially affect the basic and novel features of the claimed technology, and the phrase “consisting of…” does not include any elements not stated.

[0095] This application is not limited to the specific embodiments described in this specification. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from its spirit and scope. In addition to the functions and methods listed in this specification, functionally equivalent methods and compositions within the scope of this application will be apparent to those skilled in the art based on the foregoing description. Such modifications and variations also fall within the scope of the appended claims. This application is limited only by the terminology of the appended claims and the full scope of their equivalents. It should be understood that the disclosure of this application is not limited to specific methods, reagents, compounds, compositions, or biological systems, which can, of course, be varied. It should also be understood that the terminology used in this application is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0096] Furthermore, when features or aspects of this application are described in accordance with the Markush Group, those skilled in the art will recognize that this application is also described in accordance with any single member or subgroup of the Markush Group.

[0097] As will be understood by those skilled in the art, for any and all purposes, particularly in providing a description, all scopes disclosed in this application also encompass any and all possible subscopes or combinations of subscopes. Any listed scope can be readily identified as sufficiently descriptive, and the same scope can be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed in this application can be readily decomposed into lower thirds, middle thirds, and upper thirds. As will be understood by those skilled in the art, all language, such as “at most,” “at least,” “greater than,” “less than,” etc., includes the listed numbers and refers to a scope that can subsequently be subdivided into subscopes as described above. Finally, as will be understood by those skilled in the art, a scope includes each individual numerical value.

[0098] All publications, patent applications, granted patents, and other documents mentioned in this specification are incorporated herein by reference, as if each individual publication, patent application, granted patent, or other document were expressly and individually indicated to be incorporated herein by reference in its entirety. Where there is any conflict with the definitions in this application, the definitions contained in the text incorporated by reference are excluded.

[0099] This invention may include, but is not limited to, the features and combinations thereof described in the following paragraphs. It should be understood that the following paragraphs should not be construed as limiting the scope of the appended claims or forcing these features to be included in the claims: A. An alkaline electrochemical battery, comprising: cathode; A gel anode comprising an anolyte, an alkaline electrolyte, a gelling agent, and approximately 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant; and A partition is installed between the cathode and the anode; in: The apparent density of the anolyte active material is approximately 2.60 g / cc to approximately 3.35 g / cc; Relative to the total weight of the anolyte active material, approximately 15 wt% to approximately 60 wt% of the anolyte active material has a particle size of less than approximately 75 μm; and Relative to the total weight of the anolyte, approximately 5 wt% to approximately 25 wt% of the anolyte has a particle size greater than approximately 150 μm.

[0100] B. The alkaline electrochemical cell of paragraph A, wherein the alkoxyalkyl phosphate surfactant comprises polyoxyethylene tridecyl ether phosphate.

[0101] C. An alkaline electrochemical cell of paragraph A or paragraph B, wherein the concentration of hydroxide in the electrolyte is from about 24 wt% to about 36 wt%.

[0102] D. Any alkaline electrochemical cell in paragraph AC, wherein the gel anode contains about 0.4 wt% to about 1.0 wt% of a gelling agent.

[0103] E. Any alkaline electrochemical cell in paragraph AD, wherein the gelling agent comprises cross-linked polyacrylic acid.

[0104] F. Any alkaline electrochemical cell in paragraph AE, wherein the anode active material comprises a zinc alloy.

[0105] G. Paragraph F describes an alkaline electrochemical cell in which a zinc alloy contains zinc, indium, and bismuth.

[0106] H. Alkaline electrochemical cells of paragraph F or paragraph G, wherein the zinc alloy contains about 130 ppm to about 270 ppm of bismuth.

[0107] I. Any alkaline electrochemical cell in paragraph FH, wherein the zinc alloy contains about 130 ppm to about 270 ppm of indium.

[0108] J. Paragraph F-1 of any alkaline electrochemical cell, wherein, relative to the total weight of the anode, the zinc alloy is present in the anode at about 62 wt% to about 72 wt%.

[0109] In any alkaline electrochemical cell in paragraph FJ, less than 10 wt% of the anode active material has a particle size of less than about 45 micrometers relative to the total weight of the anode active material.

[0110] In any alkaline electrochemical cell in paragraph FK, approximately 20 wt% to approximately 50 wt% of the anode active material has a particle size of less than approximately 75 μm relative to the total weight of the anode active material.

[0111] M. Paragraph FL: Any alkaline electrochemical cell, wherein the alkaline electrolyte comprises about 26 wt% to about 36 wt% potassium hydroxide.

[0112] N. Any alkaline electrochemical cell in paragraph FM, wherein the alkoxyalkyl phosphate surfactant includes polyoxyethylene tridecyl ether phosphate; and O. Any alkaline electrochemical cell in paragraph FN, wherein the alkaline electrochemical cell is an LR14 cell or an LR20 cell.

[0113] P. A gel anode for use in an alkaline electrochemical cell, the gel anode comprising: The anodic active material has an apparent density of about 2.60 g / cc to about 3.35 g / cc, wherein, relative to the total weight of the anodic active material, about 15 wt% to about 60 wt% of the anodic active material has a particle size of less than about 75 μm, and relative to the total weight of the anodic active material, about 5% to about 25% of the anodic active material has a particle size of more than about 150 μm. Alkaline electrolytes; gelling agents; and Approximately 10 ppm to 250 ppm of alkoxyalkyl phosphate surfactants.

[0114] Q. The gel anode of paragraph P, wherein the alkoxyalkyl phosphate surfactant comprises polyoxyethylene tridecyl ether phosphate.

[0115] R. Gel anode of segment P or segment Q, wherein the alkaline electrolyte contains hydroxide at a concentration of about 24% to about 36%.

[0116] S. Any gel anode in paragraph PR contains about 0.4 wt% to about 1.0 wt% of a gelling agent.

[0117] In paragraph PS, a gelling anode is formed, wherein the gelling agent comprises cross-linked polyacrylic acid.

[0118] In any of the U. segments of PT, the gel anode, wherein the anode active material comprises a zinc alloy.

[0119] V. Gel anode of segment U, wherein the zinc alloy comprises zinc, indium and bismuth.

[0120] W. Gel anode of segment U or segment V, wherein the zinc alloy contains about 130 ppm to about 270 ppm of bismuth.

[0121] X. Any gel anode in paragraph UW, wherein the zinc alloy contains about 130 ppm to about 270 ppm of indium.

[0122] In paragraph Y, UX, any gel anode, wherein the zinc alloy is present in the anode at about 62 wt% to about 72 wt% relative to the total weight of the anode.

[0123] In any gel anode of paragraph Z PY, less than 10 wt% of the anode active material has a particle size of less than about 45 micrometers relative to the total weight of the anode active material.

[0124] AA. Any gel anode in paragraph PZ, wherein, relative to the total weight of the anode active material, about 20 wt% to about 50 wt% of the anode active material has a particle size of less than about 75 μm.

[0125] In paragraphs AB and P-AA, the gel anode contains, by weight, approximately 26% to approximately 36% potassium hydroxide in an alkaline electrolyte; and AC. In any gel anode of paragraphs P-AB, the alkoxyalkyl phosphate surfactant includes polyoxyethylene tridecyl ether phosphate; and Other embodiments are set forth in the appended claims.

Claims

1. An alkaline electrochemical battery, comprising: cathode; A gel anode comprising an anolyte, an alkaline electrolyte, a gelling agent, and approximately 10 ppm to 250 ppm of an alkoxyalkyl phosphate surfactant; and A partition is installed between the cathode and the anode; The apparent density of the anolyte active material is approximately 2.60 g / cc to approximately 3.35 g / cc. Relative to the total weight of the anolyte active material, approximately 15 wt% to approximately 60 wt% of the anolyte active material has a particle size of less than approximately 75 μm; as well as Relative to the total weight of the anolyte, approximately 5 wt% to approximately 25 wt% of the anolyte has a particle size greater than approximately 150 μm.

2. The alkaline electrochemical battery according to claim 1, wherein, The alkoxyalkyl phosphate surfactant comprises polyoxyethylene tridecyl ether phosphate.

3. The alkaline electrochemical battery according to claim 1, wherein, The concentration of the hydroxide in the alkaline electrolyte is from about 24 wt% to about 36 wt%.

4. The alkaline electrochemical battery according to claim 1, wherein, The gel anode contains about 0.4 wt% to about 1.0 wt% of a gelling agent.

5. The alkaline electrochemical battery according to claim 1, wherein, The gelling agent comprises cross-linked polyacrylic acid.

6. The alkaline electrochemical battery according to any one of claims 1-5, wherein, The anodic active material comprises a zinc alloy.

7. The alkaline electrochemical battery according to claim 6, wherein, The zinc alloy contains zinc, indium, and bismuth.

8. The alkaline electrochemical battery according to claim 6, wherein, The zinc alloy contains about 130 ppm to about 270 ppm of bismuth.

9. The alkaline electrochemical battery according to claim 6, wherein, The zinc alloy contains approximately 130 ppm to approximately 270 ppm of indium.

10. The alkaline electrochemical battery according to claim 6, wherein, The zinc alloy content in the anode is approximately 62 wt% to approximately 72 wt% relative to the total weight of the anode.

11. The alkaline electrochemical battery according to claim 1, wherein, The alkaline electrochemical cell is an LR14 cell or an LR20 cell.

12. A gel anode for an alkaline electrochemical cell, the gel anode comprising: The anodic active material has an apparent density of about 2.60 g / cc to about 3.35 g / cc, wherein, relative to the total weight of the anodic active material, about 15 wt% to about 60 wt% of the anodic active material has a particle size of less than about 75 μm, and relative to the total weight of the anodic active material, about 5 wt% to about 25 wt% of the anodic active material has a particle size of greater than about 150 μm. Alkaline electrolytes; gelling agents; and Approximately 10 ppm to 250 ppm of alkoxyalkyl phosphate surfactants.

13. The gel anode according to claim 12, wherein, The alkoxyalkyl phosphate surfactant comprises polyoxyethylene tridecyl ether phosphate.

14. The gel anode according to claim 12, wherein, The concentration of hydroxide in the electrolyte is from about 24% to about 36%.

15. The gel anode of claim 12, comprising about 0.4 wt% to about 1.0 wt% of a gelling agent.

16. The gel anode according to claim 12, wherein, The gelling agent comprises cross-linked polyacrylic acid.

17. The gel anode according to any one of claims 12 to 16, wherein, The anodic active material comprises a zinc alloy.

18. The gel anode according to claim 17, wherein, The zinc alloy contains zinc, indium, and bismuth.

19. The gel anode according to claim 17, wherein, The zinc alloy contains about 130 ppm to about 270 ppm of bismuth.

20. The gel anode according to claim 17, wherein, The zinc alloy contains approximately 130 ppm to approximately 270 ppm of indium.

21. The gel anode according to claim 12, wherein, The anode active material comprises a zinc alloy, and the content of the zinc alloy in the anode is from about 62 wt% to about 72 wt% relative to the total weight of the anode.

22. The gel anode according to claim 12, wherein, Relative to the total weight of the anodic active material, less than 10 wt% of the anodic active material has a particle size of less than about 45 micrometers.

23. The gel anode according to claim 12, wherein, Relative to the total weight of the anode active material, about 20 wt% to about 50 wt% of the anode active material has a particle size of less than about 75 μm; the alkaline electrolyte contains about 26 wt% to about 36 wt% of potassium hydroxide; the alkoxyalkyl phosphate surfactant contains polyoxyethylene tridecyl ether phosphate; and the gel anode contains about 0.4 wt% to about 1.0 wt% of a gelling agent.

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