Electrochemical cells with increased operating time and reduced internal short circuits

Abstract

An alkaline electrochemical cell is provided and a method is provided for reducing or eliminating battery short circuits by preventing zinc oxide reaction precipitates from forming conductive bridges between two electrodes. The alkaline electrochemical cell includes at least dissolved zinc oxide or hydroxide in an electrolyte solution, and / or solid zinc oxide or hydroxide particles in the anode, a silicon donor in the anode, and / or a bilayer separator optimally including a high density layer and a low density layer.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 282,971, filed November 24, 2021, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] Alkaline electrochemical cells are commercially available in cell sizes commonly known as LR6 (AA), LR03 (AAA), LR14 (C), and LR20 (D). These cells have a cylindrical shape that conforms to dimensional standards set by organizations such as the International Electrotechnical Commission. Electrochemical cells are utilized by consumers to power a wide range of electrical devices, such as clocks, radios, toys, electronic games, film cameras that typically include flash bulb units, as well as digital cameras. Such electrical devices produce a wide range of discharge conditions, such as low drain to relatively high drain discharge conditions. Due to the increasing use of high drain devices, such as digital cameras, there is a continuing need for batteries that have desirable high drain discharge characteristics.

[0003] Because batteries are often of a fixed shape and size, battery manufacturers must modify the characteristics of the cells to increase performance. Attempts to address the problem of how to improve battery performance in a particular device, such as a digital camera, typically involve changes to the internal structure and / or chemistry of the cell. For example, cell structure and chemistry have been altered by increasing the amount of active material utilized within the cell.

[0004] Zinc (Zn) is a well-known material commonly used in electrochemical cells as the active anode material. During discharge of an electrochemical cell, zinc is oxidized to form zinc oxide (ZnO). This zinc oxide reaction product forms a passivation layer that can inhibit efficient discharge of the remaining zinc and reduce battery performance. It is believed that cell shorting can also occur due to the formation of crystalline zinc oxide near the separator, forming a bridge through the separator between the cathode and anode.

[0005] The described claims and embodiments are directed to the reduction and elimination of short circuits in alkaline cells containing zinc oxide or zinc hydroxide. Summary of the Invention

[0006] Alkaline electrochemical cells having both solid zinc oxide and dissolved zinc oxide or hydroxide have increased efficiency and increased run times over the prior art due to mechanisms for reducing or eliminating short circuits.

[0007] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; an anode comprising: 1) solid zinc; 2) an anolyte; 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; and 4) a silicon donor; The silicon donor is present in an amount of at least 0.036 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell.

[0008] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; an anode comprising: 1) solid zinc; 2) an anolyte; and 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; the alkaline electrochemical cell comprising at least 3.0 weight percent total zinc oxide; The separator is a dual layer separator, or a low porosity separator, or a laminate separator having a cellophane layer. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional front view of an alkaline electrochemical cell of one embodiment. [Diagram 2] The voltage versus time plot shows the effect of a short circuit on otherwise identical cells. [Figure 3A] 1 shows the effect of total cell electrolyte solution ZnO weight percent on LR6 DSC (ANSI standard digital still camera test) performance in the presence of 2 pulses per minute (ANSI / IEC units). [Figure 3B] 1 shows the effect of total cell electrolyte solution ZnO weight percent on 50 mA run-time performance. [Figure 4A] 1 shows the effect on cell run time of increasing the amount of silicon donor, and therefore the ratio of silicate ions to zinc oxide. [Figure 4B] 1 shows the effect of silica weight percent of the total cell electrolyte solution on 50 mA 5 min / 20 min run times. [Figure 5A] 1 shows the effect of increasing sodium silicate concentration on run time in cells containing different separator types compared to the anode solution and the whole cell electrolyte solution, respectively. [Figure 5B]1 shows the effect of increasing sodium silicate concentration on run time in cells containing different separator types compared to the anode solution and the whole cell electrolyte solution, respectively. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Various embodiments will now be described more fully with reference to the accompanying drawings. Some, but not all, embodiments are illustrated herein. Indeed, various embodiments may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein, but rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numerals refer to like elements throughout. In the following description, various components may be identified as having specific values ​​or parameters, but these items are provided as exemplary embodiments. Indeed, the exemplary embodiments are not intended to limit various aspects and concepts of the embodiments, since many equivalent parameters, sizes, ranges, and / or values ​​may be implemented. Terms such as "first," "second," etc., and "exemplary" do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Furthermore, the terms "a," "an," and "the" do not denote a limitation of quantity, but rather indicate the presence of "at least one" of the referenced item.

[0011] Each embodiment disclosed herein is contemplated to be applicable to each of the other disclosed embodiments. All combinations and subcombinations of the various elements described herein are within the scope of the embodiments.

[0012] Where a parameter range is provided, it is understood that all integers and ranges within that range, as well as tenths and hundredths thereof, are also provided by the embodiment. For example, "5-10%" includes 5%, 6%, 7%, 8%, 9%, and 10%, 5.0%, 5.1%, 5.2%, ....9.8%, 9.9%, and 10.0%, as well as 5.00%, 5.01%, 5.02%, ....9.98%, 9.99%, and 10.00%, as well as, for example, 6-9%, 5.1%-9.9%, and 5.01%-9.99%.

[0013] As used herein, "about" in the context of a numerical value or range means within ±10% of the recited or claimed numerical value or range.

[0014] As used herein, "total cell weight" refers to the weight of the internal elements of the cell, such as the anode (first electrode 18), cathode (second electrode 12), electrolyte shot solution, and any additives. It does not include the container or can 10, closed bottom end 24, top end 22, sidewall 26, terminal cover 20, inner wall 16, bottom end 24, label 28, negative terminal cover 46, closure assembly 40, closure member 42, current collector 44, separator 14, or conductive terminal 46, as shown in FIG. 1 and described in more detail below.

[0015] As used herein, "total cell electrolyte amount" refers to the total mass of alkali metal hydroxide (e.g., KOH) in the cell, and "total cell electrolyte concentration" refers to the total concentration of alkali metal hydroxide in the cell. When reported as a percentage, the total cell electrolyte concentration can be determined by the calculation (total cell electrolyte amount) / (total cell mass of electrolyte solution) multiplied by 100. The total cell mass of the electrolyte solution is calculated as follows: (total cell electrolyte amount)+(total cell mass of aqueous solvent)+(mass of additive in solution). The total additive weight percent in the total cell electrolyte solution can be determined via the calculation (total mass of additive in cell) / (total cell mass of electrolyte solution)×100.

[0016] As used herein, the "total weight percent" of a compound in a cell or portion thereof refers to the total weight of the compound compared to the total mass or weight of other materials in the cell or relevant portion, which may include, but is not limited to, zinc compounds (e.g., zinc oxide or zinc hydroxide), electrolyte, water, separator, active materials, and additives. For example, the "total zinc oxide weight percent of the cell" is calculated as (zinc oxide mass) / (total cell weight)×100%, where "total cell weight" is as described above. The weight percent of a compound for any portion of the cell (e.g., anode) may be calculated similarly by using only the sum of the materials comprising that portion of the cell in the calculation. Water may be from any source in the cell. The concentrations and amounts of all cell components and additives may be determined by any method known in the art. A non-limiting example of such a method is described in U.S. Pat. No. 8,318,350, the contents of which are incorporated herein by reference in their entirety.

[0017] The "weight percent total dissolved zinc oxide" in the entire cell electrolyte is calculated as (mass dissolved zinc oxide in cell) / (mass dissolved zinc oxide in cell + mass electrolyte in cell + mass water in cell) x 100%. This measurement does not take into account the mass of solid (i.e., undissolved) zinc oxide in the anode. The same formula, mutatis mutandis, can be used to calculate the weight percent total dissolved zinc hydroxide.

[0018] As used herein, "percent electrolyte concentration" in an electrode refers to the total weight of the electrolyte in the electrode compared to the total weight of the electrolyte in the electrode and the water in the electrode. For example, the "percent KOH by weight" of an electrode is calculated as (mass of KOH in electrode) / (mass of KOH in electrode+mass of water in electrode)×100%.

[0019] As used herein, "improvement" with respect to a particular capacity means that the particular capacity is increased. In general, an "improvement" of a property or metric of performance of a material or electrochemical cell means that the property or metric of performance is different (compared to the property or metric of a different material or electrochemical cell) in a way that a user or manufacturer of the material or cell considers desirable (i.e., lower cost, lasts longer, provides more power, is more durable, is easier or faster to manufacture, etc.).

[0020] As used herein, "discharge capacity" refers to the total amount of charge from an electrochemical cell when discharged at a particular rate, usually measured in ampere-hours.

[0021] As used herein, "run time" refers to the length of time an electrochemical cell can support a current drain before the closed circuit voltage falls below the functional end point.

[0022] As used herein, describing a solution as being "X% saturated" with a solute means that the solution contains as much as X% of the maximum amount of solute that can be dissolved in the solution at the same temperature, pressure, etc., taking into account all other components of the solution (e.g., dissolved electrolytes, etc.). The saturation values ​​included herein were calculated according to the method of Cheh et al. (J. Electrochem. Soc., Vol. 141, No. 1, Modeling of Cylindrical Alkaline Cells (Jan. 1994)). To facilitate dissolution of zinc oxide or hydroxide, zinc oxide or hydroxide particles can be mixed into a potassium hydroxide solution at 45°C or higher using a stir bar. In certain embodiments, the solution can be more than 100% saturated (i.e., supersaturated).

[0023] As used herein, the term "electrolyte shot" refers to the liquid electrolyte solution that is added to the cell. This electrolyte shot is primarily absorbed by the separator and cathode. Additionally, the term "free electrolyte" refers to the electrolyte solution that is not absorbed by the anode, cathode, separator, or any other part of the battery. Free electrolyte remains in liquid form within the battery during manufacture.

[0024] As used herein, "anolyte" refers to a first aqueous alkaline electrolyte solution that forms part of the anode. In certain embodiments, the anolyte is combined with a gelling agent to form a gel anode. The anolyte includes an alkali metal hydroxide electrolyte and dissolved zinc oxide or zinc hydroxide. The anolyte may additionally include additives such as silicon donors and / or surfactants.

[0025] As used herein, "catholyte" refers to a second aqueous alkaline electrolyte solution that forms part of the cathode. The catholyte comprises an alkali metal hydroxide electrolyte. The catholyte may additionally comprise additives such as silicon donors, dissolved zinc oxide or zinc hydroxide, and / or surfactants.

[0026] Describing an electrochemical cell as having a "total cell saturation of X%" of a compound takes into account both the compound dissolved in the electrolyte shot solution and the compound present in the electrodes. For example, in calculating the total cell saturation of zinc oxide in an electrochemical cell, the amount of zinc oxide dissolved in the electrolyte shot solution must be determined along with the solid zinc oxide and dissolved zinc oxide in the anode. This can result in a total cell saturation percentage of more than 100%.

[0027] As used herein, a "zincate ion source" refers to a zincate ion (Zn(OH)4 2-) Non-limiting examples include zinc oxide (ZnO) and zinc hydroxide (Zn(OH)2). In one embodiment, the term may refer to zinc oxide and zinc hydroxide only. As used herein, "zinc oxide equivalent" refers to the amount of zinc oxide equivalent to the number of ZnO equivalents. 2+ This refers to the amount of zincate ion (such as zinc oxide or zinc hydroxide) source that provides a mole. For example, 0.0994 g (0.001 mole) of Zn(OH)2 is equivalent to 0.0814 g (0.001 mole) of ZnO.

[0028] As used herein, the term "silicon donor" refers not only to elemental silicon, but also to any additive that contains silicon. Examples include, but are not limited to, sodium silicate, silicon dioxide (SiO2, also known as silica), and potassium silicate.

[0029] As used herein, "silicate" refers to any silicate anion, and means any anion composed of silicon and oxygen that can be formed as a result of the addition of a silicon donor to a cell.

[0030] As used herein, "solid zinc oxide" refers to solid zinc oxide particles that are added to a cell and / or the physical characteristics of such particles. "Solid zinc hydroxide" refers to solid zinc hydroxide particles that are added to a cell and / or the physical characteristics of such particles.

[0031] The cell embodiments described herein are directed to the cell as it is constructed. The concentrations of many of the materials within the cell can vary with use, and these changes are often not consistent. Furthermore, even in unused batteries, these concentrations can change slightly due to equilibration over time.

[0032] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte solution; the anode comprises: 1) solid zinc; 2) solid zinc oxide particles or solid zinc hydroxide particles; and 3) a silicon donor; The electrolyte solution contains dissolved zinc oxide or dissolved zinc hydroxide.

[0033] Another embodiment is an alkaline electrochemical cell. The alkaline electrochemical cell comprises: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte solution; the anode comprises: 1) solid zinc; and 2) solid zinc oxide particles or solid zinc hydroxide; the cathode comprises silicon dioxide; The electrolyte solution contains dissolved zinc oxide or dissolved zinc hydroxide.

[0034] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte solution; the anode comprises: 1) solid zinc; and 2) solid zinc oxide particles or solid zinc hydroxide; the electrolyte solution comprises dissolved zinc oxide or dissolved zinc hydroxide; The separator is a dual layer separator.

[0035] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; an anode comprising: 1) solid zinc; 2) an anolyte; 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; and 4) a silicon donor; The silicon donor is present in an amount of at least 0.036 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell.

[0036] One embodiment is an alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; an anode comprising: 1) solid zinc; 2) an anolyte; and 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; the alkaline electrochemical cell comprising at least 3.0 weight percent total zinc oxide; The separator is a dual layer separator, or a low porosity separator, or a laminate separator having a cellophane layer.

[0037] In one embodiment, the separator is a bilayer having a high density layer and a low density layer. In one embodiment, the high density layer has a higher density than the low density layer. In one embodiment, the high density layer has a density of 0.5 to 0.8 grams per cubic centimeter, a thickness of 25 to 50 microns, and an average pore size of less than 1.5 microns, preferably less than 1.0 microns. In one embodiment, the low density layer has a density of 0.2 to 0.5 grams per cubic centimeter, and a thickness of 25 to 75 microns.

[0038] In one embodiment, the anode comprises solid zinc oxide particles and the electrolyte shot solution comprises dissolved zinc oxide.

[0039] In one embodiment, the electrolyte shot solution includes a dissolved zinc oxide equivalent in an amount greater than 0.1 weight percent. In one embodiment, the electrolyte shot solution includes a dissolved zinc oxide equivalent in an amount greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3 , 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent dissolved zinc oxide equivalent.In one embodiment, the electrolyte shot solution is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, .7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7 .7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3 , 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent of dissolved zinc oxide equivalents.In one embodiment, the electrolyte shot solution is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, .6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6 ,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4,8.5,8.6,8.7,8.8,8.9,9.0,9.1,9.2,9.3,9.4,9.5,9.6,9.7,9.8,9.9,10.0,10.1,10.2,10.3,10.4,10.5,10.6,10.7,10.8,10.9,11.0,11.1,11.2,11.3 , 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 percent by weight of dissolved zinc oxide equivalents. In one embodiment, the electrolyte shot solution comprises greater than 2.0 percent by weight of dissolved zinc oxide equivalents. In a further embodiment, the electrolyte shot solution comprises an amount of dissolved zinc oxide equivalents between about 4.0 and 6.5 percent by weight.

[0040] In one embodiment, the anode comprises a gelled electrolyte, the gelled electrolyte being prepared by combining a gelling agent with a first aqueous alkaline electrolyte solution (or "anolyte"), the first aqueous alkaline electrolyte solution comprising an alkali metal hydroxide electrolyte and dissolved zinc oxide or zinc hydroxide. In one embodiment, the first aqueous alkaline electrolyte solution comprises 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7 .6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent dissolved zinc oxide equivalent.In one embodiment, the first aqueous alkaline electrolyte solution is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.1, 10.2, 10.3, 1 .6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6 ,7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent of dissolved zinc oxide equivalents.In one embodiment, the first aqueous alkaline electrolyte solution has a pH of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7 .6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent of the dissolved zinc oxide equivalent. In further embodiments, the first aqueous alkaline electrolyte solution comprises dissolved zinc oxide equivalents in an amount of ≧2.5, ≧2.6, ≧2.7, ≧2.8, ≧2.9, ≧3.0, ≧3.1, ≧3.2, ≧3.3, ≧3.4, ≧3.5, ≧3.6, ≧3.7, ≧3.8, ≧3.9, or ≧4.0 weight percent. In one embodiment, the first aqueous alkaline electrolyte solution comprises dissolved zinc oxide equivalents in an amount of about 2.7 to 3.3 weight percent.

[0041] In one embodiment, the first aqueous alkaline electrolyte solution is at least 5% saturated with zinc oxide or zinc hydroxide. In one embodiment, the anode electrolyte solution is at least 100% saturated with zinc oxide or zinc hydroxide. In one embodiment, the anode electrolyte solution is 5-100% saturated with zinc oxide or zinc hydroxide. In one embodiment, the negative electrolyte solution is saturated with zinc oxide or zinc hydroxide to a value greater than, less than, or equal to about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%, or between any two of these values.

[0042] In one embodiment, the cathode comprises a second aqueous alkaline electrolyte solution (or "catholyte"), the second aqueous alkaline electrolyte solution comprising an alkali metal hydroxide electrolyte and dissolved zinc oxide or zinc hydroxide. In one embodiment, the second aqueous alkaline electrolyte solution is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9. 5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7 .6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent dissolved zinc oxide equivalent.In one embodiment, the second aqueous alkaline electrolyte solution is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.1, 10.2, 10.3, 1 .6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6 ,7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent of dissolved zinc oxide equivalents.In one embodiment, the second aqueous alkaline electrolyte solution has a pH of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7 .6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11. 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent of the dissolved zinc oxide equivalent. In further embodiments, the second aqueous alkaline electrolyte solution comprises dissolved zinc oxide equivalents in an amount of ≧2.5, ≧2.6, ≧2.7, ≧2.8, ≧2.9, ≧3.0, ≧3.1, ≧3.2, ≧3.3, ≧3.4, ≧3.5, ≧3.6, ≧3.7, ≧3.8, ≧3.9, or ≧4.0 weight percent. In further embodiments, the second aqueous alkaline electrolyte solution comprises dissolved zinc oxide equivalents in an amount of about 2.5-4.0 weight percent, or about 2.7-3.3 weight percent.

[0043] In one embodiment, the first aqueous alkaline electrolyte solution and the second aqueous alkaline electrolyte solution are the same.

[0044] In one embodiment, the total dissolved zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.11, 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21, 3.22, 3.23, 3.24, 3.25, 3.26, 3.27, 3.28, 3.29, 3.30, 3.31, 3.32, 3.33, 3.34, 3.35, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41, 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.49, 3.50, 3.51, 3.52, 3.53, 3.54, 3.55, 3.56, 3.57, 3.5 .1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7 .2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11. greater than 0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent.In one embodiment, the total dissolved zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent.In one embodiment, the total dissolved zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7 .2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11. 0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 weight percent. In one embodiment, the total dissolved zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is between about 1.5 and 4.5 weight percent.

[0045] In one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 ,3.8,3.9,4.0,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9,5.0,5.1,5.2,5.3,5.4,5.5,5.6,5.7,5.8,5.9,6.0,6.1,6.2,6.3,6.4,6.5,6.6,6.7,6.8,6.9,7.0,7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5 , 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6, 15.7, 15.8, 15.9, or greater than 16.0 weight percent.In one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 , 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5 ,8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 1 14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6, 15.7, 15.8, 15.9, or 16.0 weight percent.In one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 ,3.8,3.9,4.0,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9,5.0,5.1,5.2,5.3,5.4,5.5,5.6,5.7,5.8,5.9,6.0,6.1,6.2,6.3,6.4,6.5,6.6,6.7,6.8,6.9,7.0,7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.3,8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5 , 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6, 15.7, 15.8, 15.9, or 16.0 weight percent. In one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is between about 2.0 and 4.0 or between about 2.5 and 3.5 weight percent. In one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is greater than about 4.5 weight percent, hi one embodiment, the total zinc oxide equivalent weight percent in the total cell electrolyte solution of the electrochemical cell is between about 0.5 and 4.5 weight percent, or between about 0.5 and 3.0 weight percent, or between about 0.5 and 2.0 weight percent.

[0046] In one embodiment, the total cell electrolyte of the electrochemical cell is saturated at more than 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 55%, 50%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, or 125% in terms of dissolved zinc oxide equivalent. In one embodiment, the total cell electrolyte of the electrochemical cell is saturated at more than 40% in terms of dissolved zinc oxide equivalent.

[0047] In one embodiment, the solid zinc oxide particles or solid zinc hydroxide particles are substituted solid zinc oxide or substituted solid zinc hydroxide, contain a cationic substituent or an anionic substituent, and the substituted solid zinc oxide or substituted solid zinc hydroxide is less soluble than the unsubstituted solid zinc oxide or unsubstituted solid zinc hydroxide.

[0048] In one embodiment, the substituted solid zinc oxide has the formula Zn 1-x Y x O, where Y is at least one cationic substituent and 0 < x ≦ 0.50.

[0049] In one embodiment, the substituted solid zinc hydroxide has the formula Zn 1-x Y x (OH)2, where Y is at least one cationic substituent and 0 < x ≦ 0.50.

[0050] In one embodiment, the substituted solid zinc oxide has the formula ZnO 1-w A (2w / z) where A is at least one anionic substituent, 0 < w ≦ 0.50, and z is the charge of the anionic substituent.

[0051] In one embodiment, the substituted solid zinc hydroxide has the formula Zn(OH) 2-w A (w / z) where A is at least one anionic substituent, 0 < w ≦ 0.50, and z is the charge of the anionic substituent.

[0052] In one embodiment, the substituted solid zinc oxide has the formula Zn1-x Y x O 1-w (OH) 2w having, wherein Y is at least one cationic substituent, 0 < x ≦ 0.50, and 0 < w ≦ 0.50.

[0053] In one embodiment, the substituted solid zinc oxide is a cation-substituted and anion-substituted mixed metal hydroxide. In a further embodiment, the cation-substituted and anion-substituted mixed metal hydroxide has the formula Zn 1-x Y x O 1-w-t (OH) 2w A (2t / z) having, wherein Y is at least one cationic substituent, 0 < x ≦ 0.50, A is at least one anionic substituent, 0 < w ≦ 0.50, 0 < t ≦ 0.50, and z is the charge of the anionic substituent.

[0054] In one embodiment, the cationic substituent is selected from the group consisting of Ca, Bi, Ba, Al, Mg, Si, Be, and Sr, and any combination thereof.

[0055] In one embodiment, the anionic substituent is S 2- , CO3 2- , and PO4 3- , and any combination thereof. In one embodiment, the anionic substituent is S 2- , CO3 2- , and PO4 3- , and a combination thereof.

[0056] In one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount of less than about 5 volume percent, based on the total volume of the anode. In one embodiment, the anode comprises greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 volume percent of solid zinc oxide equivalent particles based on the total volume of the anode. In one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount of less than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 volume percent based on the total volume of the anode. In one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount equal to about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 volume percent based on the total volume of the anode. In one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount of about 0.2 to 5 volume percent based on the total volume of the anode, hi one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount of about 0.1 to 1.5 volume percent based on the total volume of the anode.In one embodiment, the anode comprises solid zinc oxide equivalent particles in an amount of about 0.66 volume percent, based on the total volume of the anode.

[0057] In one embodiment, the anode comprises a silicon donor in an amount of about 0.1, 0.2, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 weight percent based on the total weight of the anode. In one embodiment, the anode comprises a silicon donor in an amount of 0.1 to 4.0, 0.5 to 3.5, 1.0 to 3.0, 1.4 to 2.6, or 1.8 to 2.2 weight percent based on the total weight of the anode. In one embodiment, the anode comprises sodium silicate in an amount of about 0.1 to 4 weight percent based on the total weight of the anode.

[0058] In one embodiment, the anolyte includes a silicon donor in an amount of about 0.1, 0.2, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 weight percent. In one embodiment, the anolyte comprises a silicon donor in an amount of 0.1-4.0, 0.5-3.5, 1.0-3.0, 1.4-2.6, or 1.8-2.2 weight percent based on the total weight of the anolyte, hi one embodiment, the anolyte comprises sodium silicate in an amount of about 0.1-4 weight percent based on the total weight of the anolyte.

[0059] In one embodiment, the alkaline electrochemical cell includes a total zinc oxide equivalent weight percent of about 1.0-12.5%. In one embodiment, the alkaline electrochemical cell includes a total zinc oxide equivalent weight percent of greater than 0.1 weight percent. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 weight percent. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent of less than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 weight percent. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent equal to about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 weight percent. In one embodiment, the alkaline electrochemical cell includes a total zinc oxide equivalent weight percent of about 3.0-8.8%.In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent of about 0.5-3.0%, 1.0-5.0%, about 3.0-4.0%, about 4.0-5.0%, about 5.0-6.0%, about 6.0-7.0%, about 7.0-8.0%, or about 8.0-9.0%. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent of greater than about 3.0%. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent greater than, less than, or equal to about 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 10.5%, 11.0%, 11.5%, or 12.0%. In one embodiment, the alkaline electrochemical cell comprises a total zinc oxide equivalent weight percent of about 4.75%.

[0060] In one embodiment, the anode comprises a percent electrolyte concentration of about 1.0-50.0 wt.%. In one embodiment, the anode comprises a percent electrolyte concentration of about 20.0-36.0 wt.%. In one embodiment, the anode comprises a percent electrolyte concentration of about 14.0-28.0 wt.%. In one embodiment, the anode comprises an electrolyte concentration of less than, greater than, or about 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, or 36 wt.%.

[0061] In one embodiment, the total cell electrolyte concentration is about 1.0-50.0% by weight. In one embodiment, the total cell electrolyte concentration is about 15.0-40.0% by weight. In one embodiment, the total cell electrolyte concentration is 10-32%. In one embodiment, the total cell electrolyte concentration is less than 30.0%. In one embodiment, the total cell electrolyte concentration is less than, greater than, or about 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, or 36% by weight.

[0062] In one embodiment, the total cell saturation of zinc oxide or zinc hydroxide is at least about 5% to at least about 400%. In one embodiment, the total cell saturation of zinc oxide or zinc hydroxide is at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, 210%, 220%, 230%, 240%, 250%, 260%, 270%, 280%, 290%, 300%, 310%, 320%, 330%, 340%, 350%, 360%, 370%, 380%, 390%, 410%, 420%, 430%, 440%, 450%, 460%, 470%, 480%, 490%, 500%, 510%, 520%, 530%, 540%, 550%, 560%, 570%, 580%, 590%, 600%, 600%, 700%, 800%, 900%, 1000%, 1100%, 1200%, 1300%, 1400%, 1500%, 1600%, 1700%, 1800%, 1900%, 2100%, 2200%, 2300%, 2400%, 2500%, 2600%, 2700%, 2800%, 29 %, 150%, 160%, 170%, 180%, 190%, 200%, 210%, 220%, 230%, 240%, 250%, 260%, 270%, 280%, 290%, 300%, 310%, 320%, 330%, 340%, 350%, 360%, 370%, 380%, 390%, or 400%. In one embodiment, the total cell saturation of the zinc oxide or zinc hydroxide is at least about 40%. In one embodiment, the total cell saturation of the zinc oxide or zinc hydroxide is at least about 40-125%. In one embodiment, the total cell saturation of the zinc oxide or zinc hydroxide is about 40-125%. In one embodiment, the total cell saturation of the zinc oxide or zinc hydroxide is at least about 40%, 45%, 50%, 55%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, or 125%.

[0063] In one embodiment, the electrochemical cell is a primary cell. In an alternative embodiment, the electrochemical cell is a secondary cell.

[0064] In one embodiment, the electrolyte solution includes potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), magnesium perchlorate (Mg(ClO4)2), magnesium chloride (MgCl2), or magnesium bromide (MgBr2).

[0065] In one embodiment, an alkaline electrochemical cell has a specific capacity or run-time that exceeds the specific capacity or run-time of a similar alkaline electrochemical cell lacking dissolved zinc oxide or zinc hydroxide in the electrolyte solution or anode. In further embodiments, the specific capacity or run-time is greater than 1% to greater than 200%, or greater than 1% to greater than 150%, or greater than 1% to greater than 100%, or greater than 5% to greater than 90%, or greater than 10% to greater than 80%, or greater than 15% to greater than 70%, or greater than 20% to greater than 60%, or greater than 25% to greater than 50%, or greater than 30% to greater than 40%.

[0066] In one embodiment, the cell has a voltage between 0.1V and 2.0V, 0.2V and 1.9V, 0.3V and 1.8V, 0.4V and 1.7V, 0.5V and 1.6V, 0.6V and 1.5V, 0.7V and 1.4V, 0.8V and 1.3V, 0.9V and 1.2V, 1.0V and 1.1V, or 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V, 1.8V, 1.9V, or 2.0V.

[0067] In one embodiment, the absolute weight of sodium silicate in the anode is 0.005 to 0.03 grams in an LR6 cell.

[0068] In one embodiment, silica is added to the cell to provide a source of silicate anions in solution, which can come from a solution with sodium silicate, potassium silicate, or solid silicon dioxide silica additive.

[0069] In one embodiment, silicon dioxide is added to the cathode.

[0070] In one embodiment, the silicon donor is present in an amount of at least 0.036 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell. In one embodiment, the silicon donor is present in an amount of at least 1.25 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell. In one embodiment, the silicon donor is present in an amount greater than, less than, or equal to 0.036, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, or 1.25 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell, or in a range between any two of these values.

[0071] In one embodiment, the total cell molarity of the dissolved zinc oxide or zinc hydroxide is from about 0.1 to about 1.5. In one embodiment, the total cell molarity of the dissolved zinc oxide or zinc hydroxide is greater than, less than, or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5, or ranges between any two of these values.

[0072] In one embodiment, the total cell zinc oxide equivalent weight is from about 0.05 to about 0.7 g. In one embodiment, the total cell zinc oxide equivalent weight is greater than, less than, or about 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, or 0.7, or a range between any two of these values.

[0073] In one embodiment, the Zn in the cell 2+ The total number of moles is about 0.00061 to about 0.00860. In one embodiment, the Zn 2+ The total number of moles is greater than, less than, or about 0.00061, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, or 0.00860, or a range between any two of these values.

[0074] One way to characterize the charge capacity of a cell is to measure the charge capacity to an inflection point at a given current, as discussed in U.S. Pat. No. 5,780,994, which is incorporated herein by reference in its entirety. Specifically, a voltage vs. time chart can be used to monitor the state of charge of a battery when it is being charged using a constant current. The voltage rises at a constant rate, then rises at a gradually faster rate, but as the battery reaches full charge, the rate slows down and an inflection point (i.e., a peak in the first derivative (dV / dt)) in the voltage vs. time chart is formed. Alternatively, the charge capacity can be measured to a specific voltage cutoff. This charge capacity can be used as an indirect way to determine the amount of ZnO in the cell, where the voltage rises gradually as ZnO is plated to Zn, and then rises sharply as the available ZnO is consumed.

[0075] In one embodiment, the cell has a charge capacity to an inflection of at least 25 mAh when the cell is charged at 0.5 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 0.5 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of 25-500 mAh when the cell is charged at 0.5 mA at 21° C.

[0076] In one embodiment, the cell has a charge capacity to an inflection of at least 22 mAh when the cell is charged at 1 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 1 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of 22-500 mAh when the cell is charged at 1 mA at 21° C.

[0077] In one embodiment, the cell has a charge capacity to an inflection of at least 17 mAh when the cell is charged at 5 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 5 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of between 17 and 500 mAh when the cell is charged at 5 mA at 21° C.

[0078] In one embodiment, the cell has a charge capacity to an inflection of at least 14 mAh when the cell is charged at 10 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 10 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of 14-500 mAh when the cell is charged at 10 mA at 21° C.

[0079] In one embodiment, the cell has a charge capacity to an inflection of at least 13 mAh when the cell is charged at 50 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 50 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of between 13 and 500 mAh when the cell is charged at 50 mA at 21° C.

[0080] In one embodiment, the cell has a charge capacity to an inflection of at least 12 mAh when the cell is charged at 100 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of at least 500 mAh when the cell is charged at 100 mA at 21° C. In one embodiment, the cell has a charge capacity to an inflection of between 12 and 500 mAh when the cell is charged at 100 mA at 21° C.

[0081] In one embodiment, when the cell is charged at 0.5 mA at 21° C., the cell has a charge capacity of at least 25 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 0.5 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 0.5 mA at 21° C., the cell has a charge capacity of 25-500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0082] In one embodiment, when the cell is charged at 1 mA at 21° C., the cell has a charge capacity of at least 22 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 1 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 1 mA at 21° C., the cell has a charge capacity of 22-500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0083] In one embodiment, when the cell is charged at 5 mA at 21° C., the cell has a charge capacity of at least 17 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 5 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 5 mA at 21° C., the cell has a charge capacity of 17-500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0084] In one embodiment, when the cell is charged at 10 mA at 21° C., the cell has a charge capacity of at least 14 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 10 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 10 mA at 21° C., the cell has a charge capacity of 14 to 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0085] In one embodiment, when the cell is charged at 50 mA at 21° C., the cell has a charge capacity of at least 13 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 50 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 50 mA at 21° C., the cell has a charge capacity of 13 to 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0086] In one embodiment, when the cell is charged at 100 mA at 21° C., the cell has a charge capacity of at least 12 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In one embodiment, when the cell is charged at 100 mA at 21° C., the cell has a charge capacity of at least 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V. In an embodiment, when the cell is charged at 100 mA at 21° C., the cell has a charge capacity of 12 to 500 mAh to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V.

[0087] The embodiments may be better understood by reference to FIG. 1. FIG. 1 shows a cylindrical cell 1 with a raised cross section, the cell having a peg- or bobbin-type construction and dimensions comparable to conventional LR6 (AA) size alkaline cells that are particularly suitable for the embodiments. However, it should be understood that cells according to the embodiments may have other sizes and shapes, such as prismatic or button-type shapes, and electrode configurations, as are known in the art. The materials and designs for the components of the electrochemical cell shown in FIG. 1 are for illustrative purposes, and other materials and designs may be substituted. Furthermore, in certain embodiments, the cathode and anode materials may be coated onto the surface of the separator and / or current collector and rolled to form a "jelly roll" configuration.

[0088] In FIG. 1, an electrochemical cell 1 is shown including a container or can 10 having a closed bottom end 24, a top end 22, and a sidewall 26 between the electrochemical cell 1. The closed bottom end 24 includes a terminal cover 20 including a protrusion. The can 10 has an interior wall 16. In an embodiment, the positive terminal cover 20 is welded or otherwise attached to the bottom end 24. In one embodiment, the terminal cover 20 may be formed of plated steel, for example, having a protruding protrusion in its central region. The container 10 may be formed of a metal, such as steel, preferably plated with nickel, cobalt, and / or other metals or alloys, or other materials on its interior, and has sufficient structural properties to be compatible with the various inputs in the electrochemical cell. A label 28 may be formed around the exterior of the container 10 and on the periphery of the positive terminal cover 20 and the negative terminal cover 46, so long as the negative terminal cover 46 is electrically insulated from the container 10 and the positive terminal 20.

[0089] Disposed within the container 10 are a first electrode 18 and a second electrode 12 with a separator 14 disposed therebetween. The first electrode 18 is disposed within a space defined by the separator 14 and a closure assembly 40 secured to an open end 22 of the container 10. The closed end 24, sidewall 26, and closure assembly 40 define a cavity in which the cell's electrodes are housed.

[0090] The closure assembly 40 includes a closure member 42, such as a gasket, a current collector 44, and a conductive terminal 46 in electrical contact with the current collector 44. The closure member 42 preferably includes a pressure relief vent that allows the closure member to burst if the internal pressure of the cell becomes excessive. The closure member 42 can be formed from a polymeric or elastomeric material, for example, an injection moldable polymer blend such as nylon 6,6 or nylon 6,12, a polypropylene matrix combined with poly(phenylene oxide) or polystyrene, or another material such as a metal, provided that the current collector 44 and the conductive terminal 46 are electrically insulated from the container 10, which serves as a current collector for the second electrode 12. In the illustrated embodiment, the current collector 44 is an elongated nail-like or bobbin-shaped component. The current collector 44 is made of a metal or metal alloy such as copper or brass, a conductively plated metal or plastic current collector, or the like. Other suitable materials can be utilized. The current collector 44 is inserted through a hole, preferably centrally located in the closure member 42.

[0091] The first electrode 18 is preferably the negative electrode or anode. The negative electrode includes zinc (as the active material), a conductive material, solid zinc oxide or hydroxide particles, or dissolved zinc oxide or hydroxide, and a mixture of surfactants. The negative electrode may optionally include other additives, such as binders or gelling agents. Preferably, the volume of active material utilized in the negative electrode is sufficient to maintain the desired particle-to-particle contact and the desired anode to cathode (A:C) ratio.

[0092] Interparticle contact should be maintained throughout the life of the battery. If the volume of active material in the negative electrode is too low, the cell voltage may suddenly drop to an unacceptably low value while the cell is powering a device. The voltage drop is believed to be caused by a loss of continuity in the conductive matrix of the negative electrode. The conductive matrix can be formed from undischarged active material particles, conductive electrochemically formed oxides, or a combination thereof. The voltage drop can occur even after oxides begin to form, but before a sufficient network is built to bridge between all the active material particles present.

[0093] Zinc suitable for use in the embodiments may be purchased from several different commercial sources under various designations such as BIA100, BIA115, etc. Umicore SA, Brussels, Belgium, is one example of a zinc supplier. In a preferred embodiment, the zinc powder generally has 25-40 percent fine particles less than 75 microns, preferably 28-38 percent fine particles less than 75 microns. Generally, a low percentage of fine particles will not achieve the desired DSC service, and utilizing a high percentage of fine particles may lead to increased gassing. The correct zinc alloy is necessary to reduce gassing of the negative electrode in the cell and maintain test service results.

[0094] In one embodiment, the solid zinc oxide is a type of zinc oxide material having a Brunauer, Emmett, and Teller (BET) surface area of ​​greater than 4 square meters per gram containing greater than 0.1 weight percent magnesium and / or sodium compounds, such as, but not limited to, magnesium sulfate (MgSO4), magnesium carbonate (MgCO3), magnesium oxide (MgO), sodium sulfate (Na2SO4), and sodium carbonate (Na2CO3). The magnesium and / or sodium compounds in the solid zinc oxide particles allow for uniform discharge across the anode, which helps to mitigate internal cell shorts caused by concentrated ZnO crystals formed at the anode / separator interface. In one embodiment, the BET surface area is greater than 20 square meters per gram. In one embodiment, the BET surface area is greater than 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 meters per gram.

[0095] At the negative electrode, a surfactant is present, which may be either a nonionic surfactant or an anionic surfactant, or a combination thereof. In one embodiment, the surfactant is a phosphate ester surfactant. It has been found that the anode resistance increases during discharge by adding only solid zinc oxide particles, but is mitigated by the addition of a surfactant. The addition of a surfactant increases the surface charge density of the solid zinc oxide particles, as described above, and reduces the anode resistance. It is believed that the use of a surfactant helps to form a more porous discharge product when the surfactant adsorbs onto the solid zinc oxide particles. It is believed that when the surfactant is anionic, it carries a negative charge, and in an alkaline solution, the surfactant adsorbed onto the surface of the solid zinc oxide particles changes the surface charge density of the solid zinc oxide particle surface or the zinc hydroxide particle surface. It is believed that the adsorbed surfactant causes a repulsive electrostatic interaction between the solid zinc oxide particles or the zinc hydroxide particles. It is believed that the surfactant reduces the increase in anode resistance caused by the addition of solid zinc oxide particles or zinc hydroxide particles, because the surfactant adsorbed onto the solid zinc oxide particles results in an enhancement of the surface charge density of the solid zinc oxide particle surface or the zinc hydroxide particle surface. The higher the BET surface area of ​​the solid zinc oxide, the more surfactant can be adsorbed onto the surface of the solid zinc oxide particles. In one embodiment, the surfactant concentration is about 5-50 ppm by weight relative to the electrode active material. In one embodiment, the surfactant concentration is about 10-20 ppm.

[0096] In one embodiment, the negative electrode comprises solid zinc oxide or equivalent particles in an amount of about 0.1 to 12 weight percent, based on the total weight of the negative electrode. In one embodiment, the negative electrode comprises solid zinc oxide or equivalent particles in an amount of about 1 to 7 weight percent. In one embodiment, the negative electrode comprises solid zinc oxide or equivalent particles in an amount of about 0.5 to 1.5 weight percent. In a more preferred embodiment, the negative electrode comprises solid zinc oxide or equivalent particles in an amount of about 1.2 weight percent.

[0097] In one embodiment, the cell comprises solid zinc oxide equivalent particles in an amount of from about 0.05 weight percent to about 5 weight percent of the total cell weight. In one embodiment, the cell comprises solid zinc oxide equivalent particles in an amount of from about 0.1 weight percent to about 5 weight percent of the total cell weight. In one embodiment, the cell comprises solid zinc oxide equivalent particles in an amount of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0 weight percent of the total cell weight.

[0098] In one embodiment, the solid zinc oxide is substituted to reduce its solubility. In one embodiment, a portion of the zinc in the solid zinc oxide is substituted with another cation. In one embodiment, the substituted solid zinc oxide has the formula Zn 1-x Y x O, wherein Y is at least one cationic substituent and 0 < x ≦ 0.50. In one embodiment, the cationic substituent is selected from the group consisting of Ca, Bi, Ba, Al, Mg, Si, Be, and Sr, and any combination thereof. In one embodiment, x is 0.01 to 0.40, or 0.02 to 0.35, or 0.4 to 0.30, or 0.05 to 0.25, or 0.10 to 0.20. In one embodiment, x is ≧ 0.01, ≧ 0.02, ≧ 0.04, ≧ 0.06, ≧ 0.08, ≧ 0.10, ≧ 0.12, ≧ 0.14, ≧ 0.16, ≧ 0.18, ≧ 0.20, ≧ 0.25, ≧ 0.30, ≧ 0.35, or ≧ 0.40.

[0099] In one embodiment, a portion of the oxygen in the solid zinc oxide is substituted with another anion. In one embodiment, the substituted solid zinc oxide has the formula ZnO 1-w A (2w / z)having, wherein A is at least one anionic substituent, 0 < w ≦ 0.50, and z is the charge of the anionic substituent. In one embodiment, the anionic substituent is S 2- , CO3 2- , and PO4 3- , and is selected from the group consisting of any combination thereof. In one embodiment, w is 0.01 to 0.40, or 0.02 to 0.35, or 0.4 to 0.30, or 0.05 to 0.25, or 0.10 to 0.20. In one embodiment, w is ≧ 0.01, ≧ 0.02, ≧ 0.04, ≧ 0.06, ≧ 0.08, ≧ 0.10, ≧ 0.12, ≧ 0.14, ≧ 0.16, ≧ 0.18, ≧ 0.20, ≧ 0.25, ≧ 0.30, ≧ 0.35, or ≧ 0.40. In one embodiment, the solid zinc oxide contains a cationic substituent and an anionic substituent.

[0100] The aqueous alkaline electrolyte solution (or simply "aqueous electrolyte solution") includes an alkali metal hydroxide, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), or a mixture thereof. Potassium hydroxide is preferred. The alkaline electrolyte used to form the gelled electrolyte of the negative electrode contains an alkali metal hydroxide in an amount of about 1 to about 50 weight percent, such as about 16 to about 36 weight percent, or about 16 to about 28 weight percent, specifically about 18 to about 22 weight percent, or about 20 weight percent, based on the total weight of the alkaline electrolyte solution. In one embodiment, the alkali metal hydroxide is present in an amount of 16 to 36 weight percent. In one embodiment, the alkali metal hydroxide is present in an amount of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 weight percent or greater. In one embodiment, the alkali metal hydroxide is present in an amount of less than or equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 weight percent. In one embodiment, the alkali metal hydroxide is present in an amount equal to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 weight percent.

[0101] A gelling agent is preferably utilized in the negative electrode as is well known in the art, such as cross-linked polyacrylic acid, such as Carbopol® 940, available from Noveon, Inc., Cleveland, Ohio, USA. Carboxymethylcellulose, polyacrylamide, and sodium polyacrylate are examples of other gelling agents suitable for use in alkaline electrolyte solutions. A gelling agent is desirable to maintain a substantially uniform dispersion of zinc and solid zinc oxide particles within the negative electrode. The amount of gelling agent present is selected to provide a lower electrolyte separation rate and to avoid too high anode viscosity at yield stress, which can cause problems with anode dispensing.

[0102] Dissolved zinc oxide or zinc hydroxide is present in the anode, preferably via dissolution in the aqueous electrolyte solution, to improve plating on the bobbin or nail current collector and to reduce gassing of the negative electrode shelf. The added dissolved zinc oxide or zinc hydroxide is separate and distinct from the solid zinc oxide or zinc hydroxide particles present in the anode composition. A level of dissolved zinc oxide or equivalent in the amount of 3 to 4 weight percent based on the total weight of the negative electrode electrolyte solution is preferred in one embodiment.

[0103] In one embodiment, the dissolved zinc oxide equivalent is present in the anode electrolyte solution in an amount greater than 0.1 weight percent. In one embodiment, the dissolved zinc oxide equivalent is present in the anode electrolyte solution in an amount greater than 0.1 to greater than 14 weight percent. Soluble zinc oxide or dissolved zinc oxide generally has a specific surface area of ​​about 4 m2 measured using a Micrometrics Tristar 3000 BET specific surface area analyzer with multi-point calibration after the zinc oxide is degassed at 150° C. for 1 hour. 2 / g and a particle size D50 (average diameter) of about 1 micron as measured using a CILAS particle size analyzer as described above.

[0104] The negative electrode can be formed in a number of different ways, as is known in the art, for example, the negative electrode components can be dry blended and added to the cell, the alkaline electrolyte is added separately, or, as in the preferred embodiment, a pre-gelled negative electrode process is utilized.

[0105] In one embodiment, the zinc and solid zinc oxide or hydroxide are powders and other optional powders, except for the gelling agent, are combined and mixed. A surfactant is then introduced into the mixture containing the zinc and solid zinc oxide or hydroxide particles. A pregel containing the alkaline electrolyte solution, soluble zinc oxide or hydroxide, and gelling agent, and optionally other liquid components, is introduced into the surfactant, zinc and solid zinc oxide or hydroxide mixture, which are further mixed to obtain a substantially homogenous mixture before being added to the cell. Alternatively, in a further preferred embodiment, the solid zinc oxide or hydroxide is pre-dispersed in the anode pregel containing the alkaline electrolyte, gelling agent, soluble zinc oxide, and other desired liquids, and blended, such as for about 15 minutes. The solid zinc oxide or hydroxide particles and surfactant are then added, and the anode is blended for an additional period, such as for about 20 minutes. The amount of gelled electrolyte utilized in the negative electrode is generally about 22 to about 47 weight percent, e.g., about 25 to about 35 weight percent, or about 32 weight percent, based on the total weight of the negative electrode. The volume percent of the gelled electrolyte can be about 63 to about 80 percent, e.g., about 70%, based on the total volume of the negative electrode.

[0106] In one embodiment, the weight ratio of the silicon donor to the dissolved zinc oxide or its equivalent is 0.033 to 152.2. In one embodiment, the weight ratio of the silicon donor to the dissolved zinc oxide is 0.05 to 150, or 0.1 to 130, or 0.3 to 110, or 0.5 to 100, or 0.7 to 90, or 1 to 80, or 1.5 to 70, or 2 to 60, or 3 to 50, or 4 to 40, or 5 to 30, or 6 to 20. In one embodiment, the weight ratio of silicon donor to dissolved zinc oxide equivalent is greater than, less than, or equal to about 0.033, 0.05, 0.1, 0.2, 0.5, 1, 1.5, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, or 152.2. In one embodiment, the ratio of silicon donor to dissolved zinc oxide equivalents, by weight percent, is >0.2, >0.3, >0.4, >0.5, >0.6, >0.7, >0.8, >0.9, >1.0, >1.1, >1.2, >1.3, >1.4, >1.5, or >1.6. This ratio may take into account the silicon donor and dissolved zinc oxide equivalents in the anode, electrolyte shot solution, or the entire cell.

[0107] In one embodiment, the weight ratio of the silicon donor to the total zinc oxide equivalent is between 0.012 and 5.7. In one embodiment, the weight ratio of the silicon donor to the total zinc oxide equivalent is between 0.02 and 5.5, or between 0.05 and 5, or between 0.1 and 4.5, or between 0.5 and 4, or between 1.0 and 3.5. In one embodiment, the weight ratio of the silicon donor to the total zinc oxide equivalent is greater than, less than, or equal to about 0.012, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 5.7. In one embodiment, the weight ratio of silicon donor to total zinc oxide equivalents is ≧0.2, ≧0.3, ≧0.4, ≧0.5, ≧0.6, ≧0.7, ≧0.8, ≧0.9, ≧1.0, ≧1.1, ≧1.2, ≧1.3, ≧1.4, ≧1.5, or ≧1.6. This ratio may take into account the silicon donor and dissolved zinc oxide equivalents in the anode, electrolyte shot solution, or the entire cell.

[0108] In one embodiment, the absolute weight of silica (SiO2) in the cell is greater than 0.002 grams in an LR6 battery. In one embodiment, the absolute weight of silicon donor in the cell is greater than 0.002 grams. In one embodiment, the absolute weight of silicon donor in the cell is between 0.002 and 1.0 grams. In one embodiment, the absolute weight of silicon donor in the cell is greater than or less than 0.002, 0.004, 0.006, 0.008, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1.0 grams. , or equal to about 0.002, 0.004, 0.006, 0.008, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1.0 grams, or a range between any two of these values.

[0109] In addition to the aqueous alkaline electrolyte absorbed by the gelling agent during the anode fabrication process, an additional amount of an aqueous solution of an alkali metal hydroxide is added to the cell during the fabrication process. The electrolyte shot may be incorporated into the cell by placing it in the cavity defined by the positive or negative electrode, or a combination thereof. The method used to incorporate the electrolyte shot into the cell is not important, provided the anode, cathode, and separator are accessible. In one embodiment, the electrolyte shot is added both before and after the addition of the anode mix. In one embodiment, about 0.97 grams of 1-50 weight percent potassium hydroxide solution is added as an electrolyte shot to an LR6 type cell. In one embodiment, about 0.97 grams of 34 weight percent potassium hydroxide solution is added as an electrolyte shot to an LR6 type cell, and about 0.87 grams is added to the separator-lined cavity before the anode is inserted. The remaining portion of the 34 weight percent potassium hydroxide solution is injected into the separator-lined cavity after the anode is inserted. In one embodiment, the electrolyte shot solution includes a dissolved zinc oxide equivalent in the range of about 0.01 to 12.0 weight percent. In another embodiment, the electrolyte shot solution includes a dissolved zinc oxide equivalent in the range of at least about 0.1 to at least about 14.0 weight percent. In a preferred embodiment, the electrolyte shot includes a dissolved zinc oxide equivalent amount in the range of about 4.0 to 6.0 weight percent.In an embodiment, the electrolyte shots are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 5.10, 5.11, 5.12, 5.13, 5.14, 5.15, 5.16, 5.17, 5.18, 5.19, 5.20, 5.21, 5.22, 5.23, 5.24, 5.25, 5.26, 5.27, 5.28, 5.29, 5.30, 5.31, 5.32, 5.33, 5.34, 5.35, 5.36, 5.37, 5.38, 5.39, 5.40, 5.41, 5.42, 5.43, 5. 7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, or 14.0 weight percent or less than about 0.1, 0 .2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2 , 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, or 14.0 weight percent dissolved zinc oxide equivalent, or any range between two of these values.

[0110] In an embodiment, the electrolyte shot is dissolved zinc oxide or zinc hydroxide at 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or more than 100%, or about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61% , 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% saturated with dissolved zinc oxide or zinc hydroxide or may be greater than 100% saturated.

[0111] The second electrode 12, also referred to herein as the positive electrode or cathode, comprises an electrochemically active material. Electrolytic manganese dioxide (EMD) is a commonly used electrochemically active material and is generally present in an amount of about 80 to about 92 weight percent, preferably about 86 to 92 weight percent, based on the total weight of the positive electrode, i.e., EMD, conductive material, positive electrode electrolyte, and additives, including organic additives, if present. The positive electrode is formed by combining and mixing the desired components of the electrode, then dispensing a quantity of the mixture into an open end of a container, and then using a ram to form the mixture into a solid tubular configuration that defines a cavity within the container into which the separator 14 and first electrode 18 are later placed. The second electrode 12 has a ledge 30 and an interior surface 32, as shown in FIG. 1. Alternatively, the positive electrode may be formed by preforming a plurality of rings from a mixture including EMD and, optionally, additives, and then inserting the rings into the container to form the tubular second electrode. The cell shown in FIG. 1 typically contains three or four rings.

[0112] The positive electrode may include other components such as a conductive material, e.g., graphite, which when mixed with the EMD provides a substantially conductive matrix throughout the positive electrode. The conductive material may be natural, i.e., mined, or synthetic, i.e., manufactured. In one embodiment, the cell includes a positive electrode having an active material or oxide to carbon ratio (O:C ratio) ranging from about 12 to about 22. If the oxide to carbon ratio is too high, the container and cathode resistance will increase, which may affect the overall cell resistance and potentially affect high rate testing, such as DSC testing, or higher cutoff voltages. Additionally, the graphite may be expanded or unexpanded. Suppliers of graphite for use in alkaline batteries include Timcal America, Inc., Westlake, Ohio, Superior Graphite Company, Chicago, Illinois, and Lonza, Ltd., Basel, Switzerland. The conductive material is generally present in an amount of about 5 to about 10 weight percent based on the total weight of the positive electrode. Too much graphite can reduce EMD input and therefore cell capacity, while too little graphite can increase the container-to-cathode contact resistance and / or bulk cathode resistance. One example of an additional additive is barium sulfate (BaSO4), available from Bario E. Derivati ​​SpA of Massa, Italy. Barium sulfate is generally present in an amount of about 0.5 to about 2 weight percent, based on the total weight of the positive electrode. Other additives can include, for example, barium acetate, titanium dioxide, binders such as coathylene, and calcium stearate.

[0113] In one embodiment, the cathode components (such as EMD), conductive material, and barium sulfate, and optionally additives, are mixed together to form a homogenous mixture. During the mixing process, an alkaline electrolyte solution, including about 1% to about 50% KOH solution, optionally about 37% to about 40% KOH solution, and optionally organic additives, is uniformly dispersed in the mixture, thereby ensuring uniform distribution of the solution throughout the cathode material. In one embodiment, the alkaline electrolyte solution used to form the cathode includes dissolved zinc oxide or zinc hydroxide in any maximum amount, including saturated with dissolved zinc oxide or zinc hydroxide, or supersaturated (>100% saturated) with dissolved zinc oxide or zinc hydroxide. The mixture is then added to a container and molded utilizing a ram. The moisture in the container and the cathode mixture before and after molding, as well as the components of the mixture, are preferably optimized to allow a high quality cathode to be molded. Optimization of the mix moisture allows the cathode to be molded with minimal splash and flash caused by wet mixing, and minimal spalling and excessive tool wear caused by dry mixing, and allows optimization to achieve the desired high cathode weight. The moisture content in the cathode mix can affect the overall cell electrolyte balance, impacting high rate testing.

[0114] One of the parameters utilized by cell designers characterizes the cell design as the ratio of the electrochemical capacity of one electrode to that of the opposing electrode, such as the ratio of anode (A) to cathode (C), i.e., the A:C ratio. For LR6 type alkaline primary cells utilizing zinc for the negative electrode or anode and manganese dioxide (MnO2) for the positive electrode or cathode, the A:C ratio can be greater than 1.32:1, such as greater than 1.34:1, and particularly greater than 1.36:1 for impact molded positive electrodes. The A:C ratio for ring molded positive electrodes can be lower, such as from about 1.3:1 to about 1.1:1.

[0115] The separator 14 is provided to separate the first electrode 18 from the second electrode 12. The separator 14 maintains a physical dielectric separation of the electrochemically active material of the positive electrode from the electrochemically active material of the negative electrode, allowing the transport of ions between the electrode materials. In addition, the separator functions as a wicking medium for the electrolyte and as a collar to prevent fragmented portions of the negative electrode from contacting the top of the positive electrode. The separator 14 may be a layered ion-permeable nonwoven fibrous fabric. The separator may have one layer, or two or more layers. Conventional separators are typically formed by preforming the separator material into a cup-shaped basket and then inserting it under the cavity defined by the second electrode 12 and the closed end 24 and any positive electrode material thereon. Conventional preformed separators are typically constructed of a sheet of nonwoven fabric rolled into a cylindrical shape that conforms to the inner wall of the second electrode and has a closed bottom end. Two or more layers of separators can be formed by inserting two rectangular separator sheets into the cavity to form a basket during cell assembly, with the materials rotated at a 90° angle relative to each other.

[0116] In one embodiment, the separator is a low porosity separator or a laminate separator having a cellophane layer, hi one embodiment, the separator is a low porosity separator having an average pore size of less than 12 microns and a maximum pore size of less than 30 microns.

[0117] In one embodiment, the separator is a bilayer having a high density layer and a low density layer. In some embodiments, the pore size of the high density layer can be 1 micron or less. Without being bound by theory, it is believed that this pore size in the high density layer reduces short circuits in the battery by preventing ZnO reaction product precipitates from forming a conductive network between the electrodes. Additionally, the low density layer improves electrolyte absorption to improve high rate performance, such as that measured by digital still camera (DSC) testing. Additionally, by utilizing a separator with these properties, short circuits are reduced even when a thinner separator thickness is used. This reduction in separator thickness increases the available volume in the cell that can be used for additional active materials and / or more additives (e.g., increasing the amount of silicon donor in the anode without adjusting the amount of other materials in the cell).

[0118] In one embodiment, the bilayer separator comprises at least one layer containing pores having an average diameter of about 0.3 to 20 microns. In one embodiment, the pores have an average diameter of about 1 to 10 microns, or about 2 to 8 microns, or about 3 to 6 microns, or about 4 to 5 microns, or about 4.5 microns. In one embodiment, the pores have an average diameter of greater than, less than, or equal to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 microns, or an average diameter ranging between any two of these values. In one embodiment, the pores have an average diameter of less than or equal to 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 microns.

[0119] All references cited above, and all references cited herein, are incorporated by reference in their entirety.

[0120] Although the embodiments have been illustrated and described in detail above, such illustration and description are to be considered as illustrative or exemplary and not restrictive. It will be understood that changes and modifications may be made by those skilled in the art within the scope and spirit of the following claims. In particular, the embodiments include any combination of features from different embodiments described above and below.

[0121] The embodiments are further described by the following illustrative and non-limiting examples, which provide a better understanding of the embodiments and their many advantages. The following examples are included to demonstrate preferred embodiments. Those skilled in the art will appreciate that the techniques disclosed in the following examples represent techniques used in the embodiments to work well in practicing the embodiments, and therefore can be considered to constitute preferred modes for practicing the same. However, those skilled in the art will appreciate that in light of the present disclosure, many changes can be made to the specific embodiments disclosed and still obtain the same or similar results without departing from the spirit and scope of the embodiments.

[0122] Observations and Examples Discharging a zinc-based battery involves oxidation of the zinc in the anode, as mentioned above, resulting in the formation of zinc oxide. The zinc oxide reaction product forms a passivation layer that inhibits efficient discharge of the remaining zinc. By manufacturing with dissolved zinc oxide or hydroxide (both in the electrolyte shot solution and in the solution contained in the anode) and additional solid zinc oxide or hydroxide particles (in the anode), the solid reaction product is encouraged to form elsewhere. Preventing the passivation layer from coating the anode allows for better utilization of the zinc. This significantly improves run times for high rate testing, specifically digital still camera (DSC) ANSI standard testing.

[0123] Although these show improved performance compared to previous battery models, batteries containing zinc and / or zinc oxide or hydroxide in both the anode and electrolyte shot solution can exhibit internal short circuits during discharge. The short circuit is believed to be related to the crystalline formation of zinc oxide reaction products that cause conductive network bridging between the electrodes. Internal short circuits in such cells occur when there is a conductive path through the separator that contacts the cathode and anode electrodes. The short circuit depletes the battery, thereby reducing the available capacity intended to power the device. The silicates function to change the shape of the crystalline zinc oxide by inhibiting the formation of elongated crystalline chains. Battery run time improves as the amount of silicon donor added increases, and then the concentration of silicates increases because the crystalline chains do not form and bridge the electrodes, thereby reducing short circuits and increasing performance. Many of the embodiments herein refer to sodium silicate and potassium silicate, but other compounds may be used.

[0124] Additionally, the dual layer separator allows electrolyte flow between the anodes while forming a barrier for the zinc oxide crystals. An ideal separator would have a low density layer that is porous enough to facilitate electrolyte absorption and a high density layer with pores small enough to prevent migration of the zinc oxide crystals, which are 1-3 microns in size. While most of the discussion herein refers to zinc oxide being added to the electrodes and electrolyte solution, other compounds that function as a zincate ion source may be used in place of, or in addition to, zinc oxide. For example, the embodiments described herein may contain zinc hydroxide (Zn(OH)2) in the electrodes and / or electrolyte solution in place of, or in addition to, zinc oxide.

[0125] Demonstration of an internal short circuit Figure 2 shows the effect of an internal short circuit on a cell. Specifically, Figure 2 shows a voltage versus time plot comparing two cells of the same construction. Both cells were discharged at 21°C with a current of 50 mA. The discharge was performed for 1 hour every 8 hours (meaning that during the 8 hour period, the current was on for 1 hour and off for 7 hours).

[0126] The voltage of Battery B will drop earlier compared to Battery A due to the internal short circuit. The internal short circuit will degrade the battery performance and make the performance more variable, which is also undesirable.

[0127] Trade-off of DSC run time against low drain run time Figures 3A and 3B show the trade-off of performance improvement with increasing ZnO levels in different types of discharge tests. Specifically, Figure 3A shows a plot of DSC (intermittent, high rate discharge) test performance in run time (measured in minutes) to a cutoff voltage of 1.05 V compared to the total cell electrolyte solution ZnO weight percentage. There is a clear and direct correlation between increasing ZnO weight percentage and increasing DSC performance. On the other hand, FIG. 3B is a plot of constant 50 mA run-time performance (measured in minutes to a 1.0 V voltage cutoff) for cells aged at 45° C. for 3 months versus ZnO saturation in whole cells. Here, for a constant low rate discharge, performance decreases with increasing ZnO saturation. This is due to an increase in internal short circuits at higher ZnO levels. Thus, while increasing ZnO levels can provide improved DSC performance, there is a trade-off with increasing ZnO levels as it also correlates to an increase in internal short circuits.

[0128] Comparison of cell run times for converting silicate to zinc oxide FIG. 4A is a graph showing the change in run time with increasing weight ratio of sodium silicate to dissolved zinc oxide. The test was conducted using two different concentrations of potassium hydroxide (KOH) (30% KOH and 32.2% KOH by weight). An N-grade sodium silicate solution containing 28.7 weight percent silicon dioxide was added to the cell. In a conventional cell, 0.4 weight percent N-grade solution is added. In this test, the weight percent of N-grade solution added to the cell was increased from 0.4 to 1.6.

[0129] The test was performed by discharging each cell at a drain rate of 50 mA for 5 minutes, followed by a 15 minute rest. The discharge cycle continues until the closed circuit voltage (CCV) of the cell reaches a cutoff of 1.0 volts. This test mimics the use of a battery in a device with a low drain rate, such as a remote control or radio. This procedure is effective in determining if the cell has had a short circuit. In the improved cells having a combination of solid zinc and dissolved zinc and / or zinc oxide, short circuits decreased as the amount of sodium silicate in the cell relative to the amount of dissolved zinc oxide in the cell was increased from a weight ratio of 0.04 to a weight ratio of 0.18. These improvements were observed at multiple concentrations of potassium hydroxide. These results confirm that increasing levels of silicate inhibit short circuits in zinc oxide-containing cells.

[0130] The results also show a slight effect of KOH level: specifically, cells with higher KOH levels showed improved run-time.

[0131] FIG. 4B shows a plot of run time (time to 1.0 V) versus the silica weight percent of the total cell electrolyte solution for the cell after aging the cell for 1 month at 60° C. A clear correlation between increased silica weight percent and increased run time is evident.

[0132] Comparison of cell run times for various concentrations of sodium silicate using both a control separator and a dual layer separator. FIG. 5A shows that the amount of increase in cell run time with increasing silicate differs for cells with different separator types. In this test, the cells were stored in an oven having a temperature of 60° C. and a relative humidity of 50% for four weeks and then discharged at a drain rate of 50 mA. As shown in FIG. 5A, in cells utilizing the control separator paper with a larger pore size, increasing the total weight percent of sodium silicate in the anode solution from about 0.4 weight percent to about 1 weight percent improved the average run time by approximately 15 hours, further demonstrating the improvement of the cells when a silicon donor is added.

[0133] Increasing the sodium silicate level in the anode is believed to inhibit the formation of zinc oxide dendrites that provide a short circuit path between the anode and cathode. In contrast, for cells utilizing a bilayer separator with one high density layer and one low density layer, internal cell short circuits were eliminated at both 0.4 and 1.0 weight percent sodium silicate levels. Cell run times were independent of the sodium silicate level in the anode, demonstrating the robustness of the bilayer separator for short circuit protection. Figure 5B shows the same run time data, but the same improvement from the increased silica and bilayer separators is both evident compared to the silica weight percent of the total cell electrolyte solution.

[0134] These results confirm that the dual layer separator is an improvement over previous inventions and works to reduce or eliminate short circuits. This is believed to be because the reduced pore size in the high density layer inhibits the zinc oxide from bridging through the separator, while the low density layer allows for improved electrolyte absorption.

[0135] Numerous modifications and other embodiments will occur to one skilled in the art to which these embodiments pertain having the benefit of the teachings presented in the foregoing description and associated drawings. It is therefore to be understood that these embodiments are not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims and the list of embodiments disclosed herein. Although specific terms are used herein, they are used in a generic and descriptive sense only and not for purposes of limitation. For the embodiments described in this application, it is contemplated that each embodiment disclosed herein is applicable to each of the other disclosed embodiments. For example, although this application describes an embodiment that includes mostly solid zinc oxide and dissolved zinc oxide, similar embodiments in which all or some of the solid zinc oxide and / or dissolved zinc oxide are replaced with zinc hydroxide are also considered to be within the scope of the embodiment. Similarly, for any embodiment that refers to a silicate or SiO2, similar embodiments in which all or some of the silicate or SiO2 are replaced with a different silicon donor are also considered to be within the scope of the embodiment.

Claims

1. 1. An alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; the anode comprising: 1) solid zinc; 2) an anolyte; 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; and 4) a silicon donor; An alkaline electrochemical cell wherein the silicon donor is present in an amount of at least 0.036 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell.

2. 10. The alkaline electrochemical cell of claim 1, wherein the alkaline electrochemical cell comprises about 0.5 to 3.0 weight percent total zinc oxide equivalent weight.

3. 10. The alkaline electrochemical cell of claim 1, wherein the anode comprises a gelled electrolyte, the gelled electrolyte being prepared by combining a gelling agent with a first aqueous alkaline electrolyte solution, the first aqueous alkaline electrolyte solution comprising an alkali metal hydroxide electrolyte and dissolved zinc oxide.

4. 10. The alkaline electrochemical cell of claim 1, wherein the anolyte comprises dissolved zinc oxide equivalents in an amount of 0.1 to 12 weight percent, or the anolyte is at least 5% saturated with zinc oxide or zinc hydroxide.

5. 4. The alkaline electrochemical cell of claim 3, wherein the cathode comprises a catholyte, the catholyte comprising an alkali metal hydroxide electrolyte and dissolved zinc oxide.

6. 10. The alkaline electrochemical cell of claim 1, wherein the electrolyte shot solution comprises dissolved zinc oxide equivalents in an amount greater than 2.0 weight percent.

7. 10. The alkaline electrochemical cell of claim 1, wherein the electrolyte shot solution comprises an alkali metal hydroxide and dissolved zinc oxide.

8. 10. The alkaline electrochemical cell of claim 1, wherein the electrolyte shot solution comprises a silicon donor.

9. 10. The alkaline electrochemical cell of claim 1, wherein the ratio of silicon donor to dissolved zinc oxide equivalent, in weight percent, is ≧0.016, ≧0.020, ≧0.025, ≧0.030, ≧0.035, ≧0.040, ≧0.045, ≧0.050, ≧0.055, ≧0.06, ≧0.065, ≧0.07, or ≧0.075, or the absolute weight of silicon donor ranges from 0.002 to 1 gram in the LR6 cell.

10. The solid zinc oxide particles are 4 m 2 / g, and 10. The alkaline electrochemical cell of claim 1, wherein the zinc oxide contains greater than 0.1 weight percent magnesium and / or sodium compounds.

11. 10. The alkaline electrochemical cell of claim 1, wherein the separator is a dual layer separator including a high density layer and / or a low density layer, and the average pore size of the high density layer may be less than 1 micron.

12. 10. The alkaline electrochemical cell of claim 1, wherein the surfactant concentration is 5 to 50 ppm relative to the anode active material.

13. 10. The alkaline electrochemical cell of claim 1, wherein the silicon donor is potassium silicate or sodium silicate.

14. 10. The alkaline electrochemical cell of claim 1, wherein the cathode comprises a silicon donor or the electrolyte solution further comprises silica.

15. 10. The alkaline electrochemical cell of claim 1, wherein the total cell electrolyte concentration is about 15.0 to 40.0 weight percent.

16. 10. The alkaline electrochemical cell of claim 1, wherein the total dissolved zinc oxide equivalent weight percent in the total cell electrolyte solution of said electrochemical cell is at least about 0.5 weight percent.

17. 10. The alkaline electrochemical cell of claim 1, wherein the entire cell electrolyte of the electrochemical cell is greater than 10% saturated with dissolved zinc oxide or zinc hydroxide.

18. 10. The alkaline electrochemical cell of claim 1, wherein the solid zinc oxide or solid zinc hydroxide is substituted and includes cationic or anionic substituents, and the substituted solid zinc oxide or substituted solid zinc hydroxide is less soluble than the unsubstituted solid zinc oxide or unsubstituted solid zinc hydroxide.

19. 10. The alkaline electrochemical cell of claim 1, wherein the zinc oxide or zinc hydroxide has a total cell saturation of at least about 40%.

20. 1. An alkaline electrochemical cell comprising: a) a container; b) an electrode assembly disposed within the container and including a cathode, an anode, a separator positioned between the cathode and the anode, and an electrolyte shot solution; the anode comprising: 1) solid zinc; 2) an anolyte; and 3) solid zinc oxide particles, solid zinc hydroxide particles, zinc oxide dissolved in the anolyte, or zinc hydroxide dissolved in the anolyte; a total zinc oxide equivalent weight in the total cell electrolyte solution of said alkaline electrochemical cell of at least 3.0 weight percent; An alkaline electrochemical cell, wherein the separator comprises a bilayer separator or a low porosity separator, or a laminate separator having a cellophane layer.

21. 21. The alkaline electrochemical cell of claim 20, wherein the bilayer separator comprises a high density layer and a low density layer.

22. 22. The alkaline electrochemical cell of claim 21, wherein the low density layer is disposed as a first or second paper strip with the high density layer facing the cathode.

23. 21. The alkaline electrochemical cell of claim 20, wherein the bilayer separator has at least one layer containing pores with an average diameter that is less than or equal to 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 microns.

24. 21. The alkaline electrochemical cell of claim 20, wherein the surfactant concentration is 5 to 50 ppm relative to the anode active material.

25. 21. The alkaline electrochemical cell of claim 20, wherein the anode comprises sodium silicate or potassium silicate.

26. 21. The alkaline electrochemical cell of claim 20, wherein the zinc oxide or zinc hydroxide has a total cell saturation of at least about 30% to 400%.

27. 21. The alkaline electrochemical cell of claim 20, wherein the separator is a low porosity separator having an average pore size of less than 12 microns and a maximum pore size of less than 30 microns, or the separator is a laminate separator comprising a nonwoven fabric layer and a cellophane layer.

28. 21. The alkaline electrochemical cell of claim 20, wherein the anode comprises solid zinc oxide particles in an amount of about 0.1 to 12 weight percent, based on the total weight of the negative electrode.

29. 21. The alkaline electrochemical cell of claim 20, wherein the silicon donor is present in an amount of at least 0.036 weight percent of the total cell electrolyte solution of the alkaline electrochemical cell.

30. 30. The alkaline electrochemical cell of any one of claims 1 to 29, wherein the total cell molarity of dissolved zinc oxide or zinc hydroxide is from about 0.1 to about 1.5; the total cell zinc oxide equivalent weight is from about 0.05 to about 0.7 g; or the total number of Zn 2+ moles in the cell is from about 0.00061 to about 0.00860. (i) when the cell is charged at 0.5 mA at 21°C, the cell has a charge-to-inflection capacity of at least 25 mAh. (ii) when the cell is charged at 1 mA at 21°C, the cell has a charge-to-inflection capacity of at least 22 mAh; (iii) when the cell is charged at 5 mA at 21°C, the cell has a charge-to-inflection capacity of at least 17 mAh; (iv) when the cell is charged at 10 mA at 21°C, the cell has a charge capacity to inflection of at least 14 mAh; (v) when the cell is charged at 50 mA at 21°C, the cell has a charge-to-inflection capacity of at least 13 mAh; (vi) when the cell is charged at 100 mA at 21° C., the cell has a charge-to-inflection capacity of at least 12 mAh; (vii) when the cell is charged at 0.5 mA at 21° C., the cell has a charge capacity of at least 25 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V; (viii) when the cell is charged at 1 mA at 21° C., the cell has a charge capacity of at least 22 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V; (ix) when the cell is charged at 5 mA at 21° C., the cell has a charge capacity of at least 17 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V; (x) when the cell is charged at 10 mA at 21° C., the cell has a charge capacity of at least 14 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V; (xi) when the cell is charged at 50 mA at 21° C., the cell has a charge capacity of at least 13 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V; (xii) The alkaline electrochemical cell of any one of claims 1 to 29, wherein the cell has a charge capacity of at least 12 mAh up to a voltage selected from the group consisting of 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2 V when the cell is charged at 100 mA at 21°C.

Images