Pre-aged sodium nickelate cathode materials and their uses - Patents.com

Abstract

Provided herein is a pre-aged desodium-containing sodium nickelate that has been desodium-containing via acid leaching and pre-aged using a hydroxide solution. The pre-aged desodium-containing sodium nickelate exhibits improved stability. Also provided herein are mixtures of such nickelates with EMD, and methods of making such sodium nickelates, as well as alkaline electrochemical cells containing the same.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 363,064, filed April 15, 2022, which is incorporated by reference herein in its entirety for all of its teachings. [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, and digital cameras. Such electrical devices have a wide range of discharge conditions, such as low drain to relatively high drain.

[0003] Since 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 the performance of a battery in a particular device, such as a digital camera, typically involve changes to the internal structure of the cell. For example, the cell structure has been modified by increasing the amount of active material utilized within the cell.

[0004] Nickel oxyhydroxide (NiOOH), nickel dioxide (NiO 2 Higher valent nickel materials, including nickel oxides, nickelates, and nickel oxyhydroxides in various forms, are useful as cathode materials in alkaline systems due to their high capacity and cell voltage. In particular, delithiated LiNiO 2 For example, Li x NiO 2(where x<<1) has an oxidation state higher than 3+, which could potentially lead to the formation of EMD (MnO 2 ) provides a much higher discharge capacity than Li-nickelate. x NiO 2 are not chemically stable and degrade rapidly at high temperatures. Furthermore, these materials are thermodynamically unstable in aqueous electrolytes, which leads to electrochemical reduction of the nickel cathode (loss of electrode capacity). Thus, the shelf life of alkaline cells with high valence nickel cathodes is limited compared to cells containing certain other cathode materials. Summary of the Invention

[0005] One embodiment of the invention is a desodium nickelate material, the cathode material having an X-ray diffraction (XRD) pattern including a first peak between about 11.9° and 14° 2θ, a second set of peaks between about 18° and 22° 2θ, a third peak between about 36.1° and 38.6° 2θ, a fourth peak between about 41° and 44.2° 2θ, a fifth peak between about 55.7° and 58.9° 2θ, a sixth peak between about 65° and 67.3° 2θ, and a seventh peak between about 69.5° and 71.3° 2θ. In alternative embodiments, the desodium nickelate material has an XRD pattern with at least 1, 2, 3, 4, 5, 6, or 7 of these seven peaks or sets of peaks. In one embodiment, the desodium nickelate material has an XRD pattern with peaks between about 69.5° and 71.3° 2θ.

[0006] In one embodiment, the cathode material is a desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.3° and 14.6° 2θ, a second set of peaks between about 17.3° and 22.3° 2θ, a third peak between about 23.8° and 25.9° 2θ, a fourth peak between about 27.2° and 28.2° 2θ, a fifth peak between about 36.2° and 37.7° 2θ, a sixth peak between about 40° and 44° 2θ, a seventh peak between about 55.7° and 58.5° 2θ, an eighth peak between about 65.2° and 67.3° 2θ, and a ninth peak between about 69.5° and 71.1° 2θ. In alternative embodiments, the desodiated nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, or 9 of these nine peaks or sets of peaks.

[0007] One embodiment is a pre-aged desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.9° and 13.8° 2θ, a second peak between about 17° and 19.5° 2θ, a third peak between about 24.7° and 26.5° 2θ, a fourth set of peaks between about 36.3° and 39.2° 2θ, a fifth set of peaks between about 41.9° and 45.7° 2θ, a sixth peak between 47.5° and 49.5° 2θ, a seventh peak between about 50.3° and 52° 2θ, an eighth peak between about 57.4° and 58.7° 2θ, and a ninth set of peaks between about 65° and 68° 2θ. In alternative embodiments, the desodium nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, or 9 of these 9 peaks or sets of peaks. In one embodiment, the desodium nickelate material has an XRD pattern having peaks between about 50.3° and 52° 2θ.

[0008] One embodiment is a pre-aged desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.1° and 14.4° 2θ, a second set of peaks between about 17.2° and 19.9° 2θ, a third peak between about 24.1° and 26.0° 2θ, a fourth set of peaks between about 35.8° and 39.3° 2θ, a fifth set of peaks between about 43.4° and 45.4° 2θ, a sixth peak between 47.7° and 49.4° 2θ, a seventh peak between about 56.8° and 59.6° 2θ, an eighth peak between about 62.8° and 64.5° 2θ, a ninth peak between about 65° and 67.4° 2θ, and a tenth peak between about 68.1° and 69.2° 2θ. In alternative embodiments, the desodiazed nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 of these 10 peaks or sets of peaks.

[0009] One embodiment is a method of producing a pre-aged desodium nickelate material, comprising: i) contacting sodium nickelate with an acid solution to produce an acid leached desodium nickelate; ii) contacting the acid leached desodium nickelate with a pre-aging solution containing hydroxide; and producing a pre-aged desodium nickelate material.

[0010] One embodiment is a pre-aged desodium nickelate material made by any of the methods described herein.

[0011] One embodiment is an alkaline cathode composition comprising any of the pre-aged desodium nickelate materials described herein and electrolytic manganese dioxide (EMD).

[0012] One embodiment is an alkaline cathode composition comprising any of the pre-aged desodium nickelate materials described herein, electrolytic manganese dioxide, graphite, and a binder.

[0013] One embodiment is a method for producing a composition comprising the steps of: i) 15 to 50% by weight of NiO 2 and, ii) 20 to 60 wt. % β-NiOOH; iii) 0 to 25% by weight H 0.61 NiO 2 (H 2 O) 0.91 and, iv) 0 to 25% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and a desodium nickelate material comprising:

[0014] One embodiment is a compound of formula Na x NiO 2 (H 2 O) z where x=0.01-0.05 and z=0.2-1.1. In one embodiment, x is at least, up to, or about 0.01, 0.02, 0.03, 0.04, or 0.05, or within a range defined by any two of these values. In one embodiment, z is at least, up to, or about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1, or within a range defined by any two of these values.

[0015] One embodiment is a method for producing a composition comprising the steps of: i) 4 to 62% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and, ii) 30 to 80 wt. % of (Li 0.39 Ni 0.01 )(NiO 2), and / or (Li 0.49 Ni 0.01 )(NiO 2 ), and / or (Li 0.45 Ni 0.05 )(NiO 2 )and, iii) A nickelate material containing 0 to 50% by weight of β-NiOOH.

[0016] One embodiment is a method for producing a composition comprising the steps of: i) 80 to 85% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and, ii) A nickelate material containing 15 to 20 weight % of β-NiOOH.

[0017] One embodiment is a compound of formula Na x Li y NiO 2 (H 2 O) z wherein x=0.01-0.05, y=0.15-0.45, and z=0.1-0.8. In one embodiment, x is at least, up to, or within a range defined by about 0.01, 0.02, 0.03, 0.04, or 0.05, or any two of these values. In one embodiment, y is at least, up to, or within a range defined by about 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, or 0.45, or any two of these values. In one embodiment, z is at least, up to, or within a range defined by about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8, or any two of these values.

[0018] One embodiment is a nickelate material that exhibits three discharge plateaus versus a Zn / ZnO reference electrode during discharge to a voltage of 1.0 V at a discharge rate of 10 mA / g.

[0019] One embodiment is a composition comprising particles of a nickelate material, the particles comprising: i) an inner core comprising nickelate that has not been pre-aged with hydroxide; and ii) A composition comprising an outer layer comprising a nickelate that has been pre-aged with a hydroxide.

[0020] One embodiment is an alkaline electrochemical cell comprising any of the nickelate materials or compositions described herein. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is a cross-sectional elevation view of an alkaline electrochemical cell of one embodiment. [Diagram 2] 1 shows an X-ray diffraction (XRD) pattern for sodium nickel oxide. [Diagram 3] 1 shows an X-ray diffraction (XRD) pattern for acid treated sodium nickel oxide. [Figure 4] FIG. 1 shows the X-ray diffraction (XRD) pattern for acid-treated NaNiO2 powder aged in 40 wt% KOH / 6 wt% ZnO for 24 hours. [Diagram 5] 1 shows the X-ray diffraction (XRD) patterns for NaxNiO2 pre-aged with LiOH. [Figure 6] 4 shows X-ray diffraction (XRD) patterns for LiOH pre-aged NaxNiO2 after aging in 40 wt% KOH / 6 wt% ZnO for 24 hours. [Figure 7] 1 shows a comparison of the specific capacitance at 1 V of EMD, non-preaged, and LiOH preaged nickelate after half-cell aging at 60° C. for 0, 3, 7, and 14 days. [Figure 8] 1 shows the discharge curves at 10 mA / g of unpreaged and LiOH preaged nickelate before and after aging for 24 hours in 40 wt % KOH / 6 wt % ZnO. [Figure 9]1 shows a comparison of the specific capacitance at 1 V of 0.1 M LiOH / 1 min pre-aged and non-pre-aged nickelate mixed with EMD. [Figure 10] A comparison of the efficiency up to 1 V of nickelate mixed with EMD in 0.1 M LiOH / 1 min pre-aged and non-pre-aged nickelate is shown. [Figure 11] 1 shows the XRD pattern of the synthesized nickelate that was not pre-aged. [Figure 12] 1 shows the XRD patterns of the synthesized nickelates pre-aged with LiOH. [Figure 13] 4 shows the XRD patterns of alpha, beta, and sodium nickelate. [Figure 14] 1 shows a Rietveld analysis of the XRD pattern of non-pre-aged nickelate I (desodium NaNiO2), used for phase quantification. [Figure 15] Figure 1 shows Rietveld analysis of the XRD pattern of non-preaged nickelate II (desodium NaNiO2) for phase quantification. [Figure 16] FIG. 1 shows Rietveld analysis of the XRD patterns of pre-aged nickelate I (0.1 M LiOH, 1 min) derived from non-pre-aged nickelate I for phase quantification. [Figure 17] FIG. 1 shows Rietveld analysis of the XRD patterns of pre-aged nickelate II (0.1 M LiOH, 1 min) derived from non-pre-aged nickelate II for phase quantification. [Figure 18] FIG. 13 shows Rietveld analysis of the XRD pattern of pre-aged nickelate (0.5 M LiOH, 10 min, from Example 4) for phase quantification. [Figure 19] FIG. 1 shows Rietveld analysis of the XRD pattern of pre-aged nickelate (0.1 M LiOH, 10 min, from Example 4) for phase quantification. [Figure 20]A comparison of the discharge characteristics up to 1.5 V of alpha nickelate, beta nickelate, and desodium NaNiO2 before and after 1 min pre-aging in 0.1 M LiOH is shown. [Figure 21] A comparison of the discharge characteristics up to 1.0 V of alpha nickelate, beta nickelate, and desodium NaNiO2 before and after 1 min pre-aging in 0.1 M LiOH is shown, illustrating three discharge regimes that are discussed in more detail below. [Figure 22] FIG. 1 shows a schematic diagram of a representative sodium nickelate particle having a non-preaged inner core and a preaged outer layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] 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 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 "primary," "exemplary," and "secondary," such as "first" and "second," 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.

[0023] This embodiment was designed to overcome the limitations of existing electrochemical cells. Typically, acid leached NaNiO 2 Na brought from xNiO 2 Li is an acid-delithiation x NiO 2 It has a lower capacity than beta-nickelate and has poorer stability than beta-nickelate. A pre-aging process is disclosed that results in a sodium nickelate material with improved chemical stability at high temperatures.

[0024] 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.

[0025] 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%.

[0026] As used herein, "about" in the context of a numerical value or range means within ±10%, ±5%, or ±1% of the recited or claimed numerical value or range.

[0027] As used herein, "nickelate" refers to a salt containing an anion containing nickel or a compound that contains nickel bound to oxygen and at least one other element.

[0028] As used herein, "nickel compound" refers to any compound that contains nickel. "Nickel material" refers to any material that contains nickel.

[0029] As used herein, "sodium nickelate material" or "sodium nickelate compound" refers to any nickelate that contains sodium. Non-limiting examples include Na x NiO 2 wherein: <x≦1である、Na x NiO 2 Examples include:

[0030] As used herein, "desodium nickelate" refers to a nickel compound obtained when some or all of the sodium of a sodium-containing nickel compound is removed.

[0031] As used herein, "oxide" refers to a chemical compound that contains at least one oxygen atom and one other element. As used herein, "nickel oxide" refers to any nickel-containing oxide. Nickel oxide may contain other cations and anions. Non-limiting examples include nickel dioxide (NiO 2 ), Nickel hydroxide (Ni(OH) 2 ), and hydrated alkali nickel oxides, e.g., Na x NiO 2 n(H 2 O) is one example.

[0032] As used herein, "oxyhydroxide" refers to a chemical compound or complex that contains oxide and hydroxide groups. As used herein, "nickel oxyhydroxide" refers to any nickel-containing oxyhydroxide. Nickel oxyhydroxides may contain other cations and anions. A non-limiting example is nickel oxyhydroxide (NiOOH).

[0033] As used herein, "sodium compound" refers to any compound that contains sodium. In one embodiment, the sodium compound contains both sodium and oxygen. Non-limiting examples include NaOH (sodium hydroxide), Na 2 O(Sodium oxide), Na 2 O 2(Sodium peroxide), and Na x NiO 2 (sodium nickel oxide), wherein <x≦1である、Na x NiO 2 Examples include:

[0034] As used herein, "improvement" with respect to storage stability means that the storage stability (i.e., "shelf life") is increased. In general, an "improvement" in 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.).

[0035] As used herein, an "alkali metal" is an element from Group IA of the periodic table. Non-limiting examples include Li, Na, K, Rb, and Cs.

[0036] As used herein, an "alkaline earth metal" is an element from Group IIA of the periodic table. Non-limiting examples include Mg, Ca, and Sr.

[0037] As used herein, a "transition metal" is an element from groups IB-VIIIB of the periodic table. Non-limiting examples include Co, Mn, Zn, Y, Nb, and Ti.

[0038] As used herein, "other metals" or "another metal" includes all metals on the periodic table not included within the groups above, including Al, Ga, In, Sn, Tl, Pb, and Bi.

[0039] As used herein, a "primary" electrochemical cell is a non-rechargeable (i.e., disposable) electrochemical cell. A "secondary" electrochemical cell is a rechargeable electrochemical cell.

[0040] As used herein, "electrical conductivity" refers to the ability of a given material to conduct electric current, typically measured in Siemens per meter (S / m).

[0041] As used herein, the term "pre-aging" or "pre-aged" refers to a controlled process for converting a material such that the resulting phase or mixture of different phases is more stable over time when utilized in an end product. For example, a cathode material may be pre-aged using the processes discussed herein to provide a more storage stable cathode material when included in a battery. In certain embodiments, nickel oxides are pre-aged by exposing the material to specific concentrations of LiOH, NaOH, KOH, and / or other oxides or hydroxides at specific temperatures and for specified periods of time. Another hypothesis is that pre-aging may also form a protective film on the surface of the higher nickel oxidation state of the nickel particles to retard the decomposition reaction from the higher nickel oxidation state to the lower nickel oxidation state.

[0042] In one embodiment, the cathode material has an X-ray diffraction (XRD) pattern including a first peak between about 11.9° and 14° 2θ, a second set of peaks between about 18° and 22° 2θ, a third peak between about 36.1° and 38.6° 2θ, a fourth peak between about 41° and 44.2° 2θ, a fifth peak between about 55.7° and 58.9° 2θ, a sixth peak between about 65° and 67.3° 2θ, and a seventh peak between about 69.5° and 71.3° 2θ. In an alternative embodiment, the desodium nickelate material has an XRD pattern with at least 1, 2, 3, 4, 5, 6, or 7 of these seven peaks or sets of peaks. In one embodiment, the desodium nickelate material has an XRD pattern with peaks between about 69.5° and 71.3° 2θ.

[0043] In one embodiment, the cathode material is a desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.3° and 14.6° 2θ, a second set of peaks between about 17.3° and 22.3° 2θ, a third peak between about 23.8° and 25.9° 2θ, a fourth peak between about 27.2° and 28.2° 2θ, a fifth peak between about 36.2° and 37.7° 2θ, a sixth peak between about 40° and 44° 2θ, a seventh peak between about 55.7° and 58.5° 2θ, an eighth peak between about 65.2° and 67.3° 2θ, and a ninth peak between about 69.5° and 71.1° 2θ. In alternative embodiments, the desodiated nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, or 9 of these nine peaks or sets of peaks.

[0044] In one embodiment, the nickelate material is desodiumed via an acid leaching process.

[0045] One embodiment is a pre-aged desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.9° and 13.8° 2θ, a second peak between about 17° and 19.5° 2θ, a third peak between about 24.7° and 26.5° 2θ, a fourth set of peaks between about 36.3° and 39.2° 2θ, a fifth set of peaks between about 41.9° and 45.7° 2θ, a sixth peak between 47.5° and 49.5° 2θ, a seventh peak between about 50.3° and 52° 2θ, an eighth peak between about 57.4° and 58.7° 2θ, and a ninth set of peaks between about 65° and 68° 2θ. In alternative embodiments, the desodium nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, or 9 of these 9 peaks or sets of peaks. In one embodiment, the desodium nickelate material has an XRD pattern having peaks between about 50.3° and 52° 2θ.

[0046] One embodiment is a pre-aged desodium nickelate material having an X-ray diffraction (XRD) pattern including a first peak between about 11.1° and 14.4° 2θ, a second set of peaks between about 17.2° and 19.9° 2θ, a third peak between about 24.1° and 26.0° 2θ, a fourth set of peaks between about 35.8° and 39.3° 2θ, a fifth set of peaks between about 43.4° and 45.4° 2θ, a sixth peak between 47.7° and 49.4° 2θ, a seventh peak between about 56.8° and 59.6° 2θ, an eighth peak between about 62.8° and 64.5° 2θ, a ninth peak between about 65° and 67.4° 2θ, and a tenth peak between about 68.1° and 69.2° 2θ. In alternative embodiments, the desodiazed nickelate material has an XRD pattern having at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 of these 10 peaks or sets of peaks.

[0047] In one embodiment, the pre-aged desodiated nickelate material is prepared by pre-aging a desodiated nickelate precursor with a pre-aging solution that includes a hydroxide.

[0048] In one embodiment, the hydroxide is selected from the group consisting of alkali and alkaline earth metal hydroxides. In one embodiment, the hydroxide is selected from the group consisting of LiOH, NaOH, KOH, and Ca(OH). 2 In one embodiment, the hydroxide is selected from the group consisting of: In one embodiment, the hydroxide is LiOH or NaOH In one embodiment, the hydroxide is LiOH In one embodiment, the hydroxide is NaOH.

[0049] In one embodiment, the hydroxide concentration of the pre-aging solution is from about 0.005 M to about 1 M. In one embodiment, the hydroxide concentration is at least, up to, or about 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 M, or within a range defined by any two of these values.

[0050] In one embodiment, the ratio of pre-aging solution to desodium nickelate precursor was from about 1 mL / g to about 100 mL / g, hi one embodiment, the ratio was at least, up to, or about 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mL / g, or within a range defined by any two of these values.

[0051] In one embodiment, the desodia nickelate precursor is pre-aged for about 1-60 minutes. In one embodiment, the desodia nickelate precursor is pre-aged for about 1-30 minutes, or for about 1-20 minutes. In one embodiment, the desodia nickelate precursor is pre-aged for at least, up to, or about 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 minutes, or within a range defined by any two of these values.

[0052] In one embodiment, the pre-aged desodiated nickelate material was pre-aged at a temperature of about 0° C. to about 40° C. In one embodiment, the pre-aged desodiated nickelate material was pre-aged at a temperature of at least, up to, or within a range defined by any two of these values.

[0053] One embodiment is a method of producing a pre-aged desodium nickelate material, comprising: i) contacting sodium nickelate with an acid solution to produce an acid leached desodium nickelate; ii) contacting the acid leached desodium nickelate with a pre-aging solution containing hydroxide; and producing a pre-aged desodium nickelate material.

[0054] In one embodiment, the acid leached desodium nickelate has the formula Na x NiO 2 where 0≦x≦0.2. In one embodiment, x is at least, up to, or about 0, 0.025, 0.05, 0.075, 0.1, 0.125, 0.15, 0.175, or 0.2, or within a range defined by any two of these values.

[0055] In one embodiment, the acid solution comprises an acid selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, hydroiodic acid, and perchloric acid, hi one embodiment, the acid is sulfuric acid.

[0056] In one embodiment, the acid is present at a concentration of about 0.01 M to about 10 M. In one embodiment, the acid is present at a concentration of at least, up to, or about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 10 M, or within a range defined by any two of these values.

[0057] In one implementation, step i) is carried out for a period ranging from about 1 minute to about 60 hours, in one embodiment, the period is at least, up to, or about 1, 2, 5, 10, 20, 30, 40, or 50 minutes, or 1, 2, 3, 4, 5, 6, 7, 8, 9, or 60 hours, or within a range defined by any two of these values.

[0058] In one implementation, step i) is carried out at a temperature of about −5 to about 20° C. In one implementation, the temperature is at least, up to, or within a range defined by about −5, 0, 5, 10, 15, or 20° C., or any two of these values.

[0059] In one implementation, step i) is performed using about 10 mL to about 200 mL of acid solution per gram of sodium nickelate. In one implementation, step i) is performed using at least, up to, or about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 mL of acid solution per gram of sodium nickelate, or within a range defined by any two of these values.

[0060] In one embodiment, the hydroxide is selected from the group consisting of alkali and alkaline earth metal hydroxides. In one embodiment, the hydroxide is selected from the group consisting of LiOH, NaOH, KOH, and Ca(OH). 2 In one embodiment, the pre-aging solution is selected from the group consisting of LiOH, NaOH, Ca(OH) 2 The hydroxide is selected from the group consisting of:

[0061] In one embodiment, the hydroxide is present in a concentration of about 0.005 M to about 1 M. In one embodiment, the hydroxide concentration is at least, up to, or about 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 M, or within a range defined by any two of these values.

[0062] In one implementation, step ii) is performed for a period ranging from about 1 to 60 minutes. In one implementation, step ii) is performed for at least, up to, or about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 minutes, or within a range defined by any two of these values.

[0063] In one implementation, step ii) is performed at a temperature of about 0 to about 40° C. In one implementation, step ii) is performed at at least, up to, or about 0, 2, 5, 10, 15, 20, 25, 30, 35, or 40° C., or within a range defined by any two of these values.

[0064] One embodiment is a pre-aged desodium nickelate material made by any of the methods described herein.

[0065] One embodiment is an alkaline cathode composition comprising any of the pre-aged desodium nickelate materials described herein and electrolytic manganese dioxide (EMD).

[0066] In one embodiment, the weight ratio of nickel to manganese is from 99:1 to 1:99. In one embodiment, the ratio of nickel to manganese is at least, up to, or about 99:1, 95:5, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95, or 1:99, or within a range defined by any two of these values.

[0067] One embodiment is an alkaline cathode composition comprising any of the pre-aged desodium nickelate materials described herein, electrolytic manganese dioxide, graphite, and a binder.

[0068] In one embodiment, the pre-aged desodium nickelate material is present in an amount of about 8.8-45.1 wt%, the electrolytic manganese dioxide is present in an amount of about 48-84.3 wt%, the graphite is present in an amount of about 3-8 wt%, and the binder is present in an amount of about 0.1-1.0 wt%, based on the total weight of the nickelate, EMD, graphite, and binder. In one embodiment, the pre-aged desodiated nickelate material is present in an amount of at least, up to, or about 8.8, 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, or 45.1 weight percent, or within a range defined by any two of these values. In one embodiment, the electrolytic manganese dioxide is present in an amount of at least, up to, or about 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, or 84.3% by weight, or within a range defined by any two of these values. In one embodiment, the graphite is present in an amount of at least, up to, or about 3, 4, 5, 6, 7, or 8% by weight, or within a range defined by any two of these values. In one embodiment, the binder is present in an amount of at least, up to, or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 wt. %, or within a range defined by any two of these values.

[0069] In one embodiment, the pre-aged desodium nickelate material and EMD together are present in an amount of about 92-97 wt%, the graphite is present in an amount of about 3-8 wt%, and the binder is present in an amount of about 0.1-1.0 wt%. In one embodiment, the pre-aged desodium nickelate material and EMD together are present in an amount of at least, up to, or about 92, 93, 94, 95, 96, or 97 wt%, or within a range defined by any two of these values. In one embodiment, the graphite is present in an amount of at least, up to, or about 3, 4, 5, 6, 7, or 8 wt%, or within a range defined by any two of these values. In one embodiment, the binder is present in an amount of at least, up to, or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 wt%, or within a range defined by any two of these values.

[0070] One embodiment is a method for producing a composition comprising the steps of: i) 15 to 50% by weight of NiO 2 and, ii) 20 to 60 wt. % β-NiOOH; iii) 0 to 25% by weight H 0.61 NiO 2 (H 2 O) 0.91 and, iv) 0 to 25% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and a desodium nickelate material comprising:

[0071] In one embodiment, NiO 2is present in an amount of at least, up to, or about 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 wt.%, or within a range defined by any two of these values. In one embodiment, β-NiOOH is present in an amount of at least, up to, or about 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, or 60 wt.%, or within a range defined by any two of these values. 0.61 NiO 2 (H 2 O) 0.91 is present in an amount of at least, at most, or 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, or 25% by weight, or within a range defined by any two of these values. 0.61 NiO 2 (H 2 O) 0.91 is absent. In one embodiment, Na 0.33 NiO 2 (H 2 O) 0.54 is present in an amount of at least, up to, or 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, or 25% by weight, or within a range defined by any two of these values. 0.33 NiO 2 (H 2 O) 0.54 does not exist.

[0072] One embodiment is a compound of formula Na x NiO 2 (H 2O) z where x=0.01-0.05 and z=0.2-1.1. In one embodiment, x is at least, up to, or about 0.01, 0.02, 0.03, 0.04, or 0.05, or within a range defined by any two of these values. In one embodiment, z is at least, up to, or about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1, or within a range defined by any two of these values.

[0073] One embodiment is a method for producing a composition comprising the steps of: i) 4 to 62% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and, ii) 30 to 80 wt. % of (Li 0.39 Ni 0.01 )(NiO 2 ), and / or (Li 0.49 Ni 0.01 )(NiO 2 ), and / or (Li 0.45 Ni 0.05 )(NiO 2 )and, iii) A nickelate material containing 0 to 50% by weight of β-NiOOH.

[0074] In one embodiment, Na 0.33 NiO 2 (H 2 O) 0.54is present in an amount of at least, up to, or about 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, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, or 62 weight percent, or within a range defined by any two of these values. 0.39 Ni 0.01 )(NiO 2 ), and / or (Li 0.49 Ni 0.01 )(NiO 2 ), and / or (Li 0.45 Ni 0.05 )(NiO 2 ), is present in an amount of at least, up to, or about 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, or 80 wt.%, or within a range defined by any two of these values. In one embodiment, β-NiOOH is present in an amount of at least, up to, or 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 wt.%, or within a range defined by any two of these values. In one embodiment, β-NiOOH is absent.

[0075] One embodiment is a method for producing a composition comprising the steps of: i) 80 to 85% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and, ii) A nickelate material containing 15 to 20 weight % of β-NiOOH.

[0076] In one embodiment, Na 0.33 NiO 2 (H 2 O) 0.54 is present in an amount of at least, up to, or about 80, 81, 82, 83, 84, or 85 wt.%, or within a range defined by any two of these values. In one embodiment, β-NiOOH is present in an amount of at least, up to, or about 15, 16, 17, 18, 19, or 20 wt.%, or within a range defined by any two of these values.

[0077] One embodiment is a compound of formula Na x Li y NiO 2 (H 2 O) z wherein x=0.01-0.05, y=0.15-0.45, and z=0.1-0.8. In one embodiment, x is at least, up to, or within a range defined by about 0.01, 0.02, 0.03, 0.04, or 0.05, or any two of these values. In one embodiment, y is at least, up to, or within a range defined by about 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, or 0.45, or any two of these values. In one embodiment, z is at least, up to, or within a range defined by about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8, or any two of these values.

[0078] One embodiment is a nickelate material that exhibits three discharge plateaus versus a Zn / ZnO reference electrode during discharge to a voltage of 1.0 V at a discharge rate of 10 mA / g.

[0079] In one embodiment, the nickelate material exhibits a discharge plateau at about 1.85-1.80 V during discharge at a discharge rate of 10 mA / g.

[0080] In one embodiment, the nickelate material exhibits a discharge curve for Zn / ZnO at a discharge rate of 10 mA / g, the discharge curve showing specific capacity versus voltage, the specific capacity being separated into a first region from OCV to 1.63V, a second region from 1.63V to 1.45V, and a third region from 1.45V to 1.00V, the capacity contribution of a given region being the difference between the capacity at the end of the region and the capacity at the beginning of the region; i) the ratio of the volumetric contribution of the second region to the volumetric contribution of the first region is less than 10; or ii) the volumetric contribution of the first region is at least 7.0% to the total volumetric contribution of the first, second, and third regions;

[0081] In one embodiment, the ratio of the volumetric contribution of the second region to the volumetric contribution of the first region is less than 9, 8, 7, 6, 5, 4, 3, 2, or 1. In one embodiment, the volumetric contribution of the first region is at least 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, or 20.0% of the total volumetric contribution of the first, second, and third regions.

[0082] One embodiment is a composition comprising particles of a nickelate material, the particles comprising: i) an inner core comprising nickelate that has not been pre-aged with hydroxide; and ii) A composition comprising an outer layer comprising a nickelate that has been pre-aged with a hydroxide.

[0083] The pre-aged nickelate can be any of the pre-aged desodium nickelates described herein. In one embodiment, the inner core comprises a desodium nickelate described herein.

[0084] In one embodiment, the outer layer has a thickness that constitutes 0.1-99% of the radius of the particle. In one embodiment, the inner core has a radius that constitutes 1%-99.9% of the radius of the particle. This is shown in FIG. 22, where the inner core is shaded, the radius of the particle is labeled as "p", the radius of the inner core is labeled as "i", and the thickness of the outer layer is labeled as "e". The particle radius may be defined as the sum of the radius of the inner core and the thickness of the outer layer (p=i+e).

[0085] One embodiment is an alkaline electrochemical cell comprising any of the nickelate materials or compositions described herein.

[0086] 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, e.g., prismatic or button-shaped shapes, as well as other electrode configurations, as 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.

[0087] 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.

[0088] 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.

[0089] 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 rupture if the internal pressure of the cell becomes excessive. The closure member 42 may be formed from a polymeric or elastomeric material, such as nylon 6,6, an injection moldable polymer blend, such as a combination of a polypropylene matrix 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 may be utilized. The current collector 44 is inserted through a preferably centrally located hole in the closure member 42 .

[0090] The first electrode 18 is preferably the negative electrode or anode. The negative electrode includes a mixture of one or more active materials, a conductive material, solid zinc oxide, and a surfactant. The negative electrode may optionally include other additives, such as a binder or gelling agent.

[0091] Zinc is an exemplary primary active material for the negative electrode of embodiments. Mercury and magnesium may also be used. Preferably, the volume of active material utilized in the negative electrode is sufficient to maintain the desired interparticle 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] The aqueous alkaline electrolyte may include an alkali metal hydroxide, such as potassium hydroxide (KOH) or sodium hydroxide (NaOH), or mixtures thereof. Potassium hydroxide is preferred. The alkaline electrolyte used to form the gel electrolyte of the negative electrode contains an alkali metal hydroxide in an amount of about 26 to about 36 weight percent, such as about 26 to about 32 weight percent, specifically about 26 to about 30 weight percent, based on the total weight of the alkaline electrolyte. It has been found that an interaction occurs between the negative electrode alkali metal hydroxide and the added solid zinc oxide, and lower alkali metal hydroxide improves DSC service. A less alkaline electrolyte is preferred, but may result in rapid electrolyte separation of the anode. An increase in alkali metal hydroxide concentration results in a more stable anode, but may reduce DSC service.

[0094] 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. of 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 may cause problems with anode dispensing.

[0095] Other components that may optionally be present in the anode include, but are not limited to, gassing inhibitors, organic or inorganic corrosion inhibitors, plating agents, binders, or other surfactants. Examples of gassing inhibitors or corrosion inhibitors may include indium salts, such as indium hydroxide, perfluoroalkyl ammonium salts, alkali metal sulfides, and the like. In one embodiment, dissolved zinc oxide is present, preferably via dissolution in the electrolyte, to improve plating on the bobbin or nail current collector and reduce anode storage gassing. The dissolved zinc oxide added is separate and distinct from the solid zinc oxide present in the anode composition. In one embodiment, a level of dissolved zinc oxide in an amount of about 1 weight percent based on the total weight of the anode electrolyte is preferred. Soluble or dissolved zinc oxide generally has a surface area of ​​about 4 m2 as measured utilizing a Tristar 3000 BET specific surface area analyzer with multipoint calibration from Micrometrics after the zinc oxide is degassed at 150° C. for 1 hour. 2 / g or less and has a particle size D50 (median diameter) of about 1 micron as measured using a CILAS particle size analyzer as described above. In a further embodiment, sodium silicate in an amount of about 0.3 weight percent based on the total weight of the negative electrode electrolyte is preferred in the negative electrode to substantially prevent cell shorting through the separator during cell discharge.

[0096] 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.

[0097] The second electrode 12, also referred to herein as the positive electrode or cathode, has a nickelate compound (or "nickelate cathode material") as its electrochemically active material. The active material is generally present in an amount of about 80 to about 98 weight percent, preferably about 81 to 97 weight percent, based on the total weight of the positive electrode, i.e., the nickelate cathode material, binder, conductive material, positive electrolyte, and additives, if present.

[0098] The active cathode material may be a blend of nickelate cathode material with other active materials such as electrolytic manganese dioxide (EMD), chemical manganese dioxide (CMD), and copper oxide. The weight percentage of the nickel-containing compound may range from 5% to 100% of the total active cathode material. The positive electrode is formed by combining and mixing the desired components of the electrode, followed by dispensing a quantity of the mixture into an open end of a container, and then forming the mixture into a solid tubular configuration using a ram, which defines a cavity within the container, and the separator 14 and first electrode 18 are then placed within the cavity (known as impact forming). The second electrode 12 has a ledge 30 and an inner surface 32, as shown in FIG. 1. Alternatively, the positive electrode may be formed by preforming a number of rings from a mixture containing the nickelate cathode material and then inserting the rings into a container to form a tubular shaped second electrode (known as ring molding). The cell shown in Figure 1 typically contains three or four rings.

[0099] The active material can be in the form of particles having any size suitable for use in the electrode mixture. In one embodiment, the active material is in the form of particles having an average size of approximately 1-20 microns, or 1-10 microns, or 1-5 microns, or 7-10 microns. In one embodiment, the active material is in the form of particles having a size in the range of 0.1-40 microns.

[0100] The cathode also includes a binder, which may be any binder known in the art. Non-limiting examples of binders include polyvinylidene fluoride (PVDF), polyethylene, polystyrene, and ethylene / propylene-based copolymers, such as those available under the trade name Kraton® sold by Kraton Corporation (Houston, TX), polytetrafluoroethylene (PTFE), poly(3,4-ethylenedioxythiophene) (PEDOT) copolymers, polystyrene sulfonate (PSS), and PEDOT:PSS polymer mixtures. The binder may be in the form of particles having any size suitable for use in the electrode mixture.

[0101] The cathode also includes a conductive material, which may be conductive carbon. The conductive carbon may be graphite, which may be expanded graphite. The graphite may be in the form of particles having any size suitable for use in the electrode mixture. In one embodiment, the graphite is in the form of particles having an average size ranging from nanoparticle size to 65 microns. In one embodiment, the maximum size of the graphite particles is 110 microns.

[0102] One example of an additional cathode additive is barium sulfate (BaSO), available commercially from Bario E. Derivati ​​SpA of Massa, Italy. 4). The barium sulfate is generally present in an amount of about 1 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® (Axalta Coating Systems, Glen Mills, PA), and calcium stearate.

[0103] 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. Zinc is utilized in the negative electrode or anode, and MnO 2 For alkaline primary cells of the LR6 type utilizing in the cathode or cathode, the A:C ratio can be greater than 1.1:1, such as greater than 1.2:1, specifically 1.3:1, for impact molded cathodes. The A:C ratio for ring molded cathodes can be from about 1.3:1 to about 1.1:1.

[0104] 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. A typical separator usually includes two or more layers of paper. Conventional separators are usually formed either by preforming the separator material into a cup-shaped basket and then inserting the cup-shaped basket under the cavity defined by the second electrode 12 and the closed end 24 and any positive electrode material thereon, or by forming the basket during cell assembly by inserting two rectangular sheets of separator into the cavity and rotating the materials at a 90° angle relative to each other. Conventional preformed separators typically consist 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.

[0105] All references cited above, and all references cited herein, are incorporated by reference in their entirety.

[0106] 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.

[0107] 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.

[0108] Observations and Examples Example 1: NaNiO 2 synthesis Ni(OH) 2 The resulting NiO and Na purchased from Sigma-Aldrich were calcined in air at 650° C. for 6 hours to convert them to NiO. 2 O 2 were added into a ball milling vial to form a mixture with a Na / Ni molar ratio of 1.35. The vial was filled with argon in a glove box, and then the precursors were thoroughly mixed via high energy ball milling for 1 h. The ball milled mixture was then collected and covered in a nickel crucible, and then calcined in a furnace at 680 °C in air for 30 h. The temperature ramp and cooling rates were 5 °C / min and 1 °C / min, respectively. The synthesized material was analyzed for powder XRD patterns with an X-ray diffractometer. The identified phases were NaNiO, NaNiO, and NaNiO, as shown in Figure 2. 2 It is.

[0109] Example 2: Desodium by acid leaching The NaNiO synthesized from Example 1 was subjected to desodiumation by acid leaching. 2 was added into the bottom of a round bottom flask. The flask was immersed in a beaker filled with water from an ice / water mixture. The starting temperature of the water in the beaker was about 2°C. 2 SO 4The solution (10 mL of acid for every 1 gram of powder) was cooled to about -5 to -2 °C in a freezer, then the solution was warmed to a temperature of 0 °C and added to the powder. The first half of the acid was added with a disposable transfer pipette in about 1 to 3 minutes. When half of the acid was added, the remaining acid was poured into the flask. The beaker / flask setup was then transferred into a refrigerator controlled at 2 °C and stirred continuously for 4 hours. The final temperature of the water bath is about 5 °C to 6 °C. Finally, the contents in the round bottom flask were poured into a filtration setup and the powder was filtered and washed until the pH of the filtrate matched that of DI water. The powder was dried under vacuum at 60 °C for 18 hours and then kept in vacuum for another 24 hours after the heat was turned off. The dried powder was found to be mainly nickel oxide (NiO 2 ) by XRD as shown in Figure 3. 2 , PDF 04-010-4751).

[0110] Example 3: Initial powder aged for 24 hours in 40 wt% KOH / 6 wt% ZnO 0.12 g of the initial powder was mixed with 0.6 g of 40 wt % KOH / 6 wt % ZnO in a small beaker and the solution was stirred continuously at room temperature for 24 hours. The contents in the beaker were poured into a filtration set-up and the powder was filtered and washed until the pH of the filtrate matched that of DI water. The powder was dried under vacuum at 60° C. for 18 hours. As shown in FIG. 4, the dried material was mainly composed of Na 0.33 NiO 2 (H 2 O) 0.5 (PDF 04-015-9998).

[0111] Example 4: Pre-aging of nickel oxide from Example 2 with LiOH 0.45 g of powder from Example 2 was placed in a centrifuge tube, and then 30 mL of lithium hydroxide (LiOH) solution was added into the centrifuge tube to pre-age the material. The tube was shaken in a circular motion to disperse the aggregates at the bottom, and then it was allowed to settle and settle for 10 minutes. After pre-aging was completed, the sample was then washed with DI water by vacuum filtration equipment until the pH of the filtrate matched that of the DI water. The powder was then dried under vacuum at 60° C. for 18 hours at −1 bar, and after turning off the heat, the drying was extended for another 24 hours. As shown in FIG. 5, XRD showed that the resulting material contained Na 0.33 NiO(H 2 O) 0.5 (PDF 04-015-9998) and (Li 0.45 Ni 0.05 )(NiO 2 ) (PDF 01-085-1983). Two different concentrations of LiOH (0.1M and 0.5M) were evaluated, and the samples pre-aged in the higher concentration of LiOH (0.5M) showed a stronger (Li 0.45 Ni 0.05 )(NiO 2 ) peak.

[0112] Example 5: Pre-aged powder aged for 24 hours in 40 wt% KOH / 6 wt% ZnO 0.5 g of the pre-aged powder from Example 4 was aged in 40 wt.% KOH / 6 wt.% ZnO according to the same conditions and procedures as in Example 3. The resulting material had the same phase Na as the material in Example 4. 0.33 NiO(H 2 O) 0.5 (PDF 04-015-9998) and (Li 0.45 Ni 0.05 )(NiO 2 ) (PDF 01-085-1983). However, as shown in Figure 6, Na 0.33 NiO(H 2 O) 0.5The intensity of the peak increased significantly after aging in KOH solution.

[0113] Example 6: Pre-aging improves the stability of EMD / nickelate mixtures. Discharge of nickelate / EMD mixtures was performed in a half-cell test fixture to determine electrochemical discharge capacity retention after cell aging at 60° C. for up to 14 days as follows: EMD (50 wt. % Mn based on the total weight of Ni and Mn) was first mixed with 6.4 wt. % SFG 15 graphite and 0.5 wt. % coathylene binder, then non-preaged nickelate or nickelate (50 wt. % Ni based on the total weight of Ni and Mn) preaged with 0.1 M LiOH for 1 minute was added to form the cathode. The total weight percentage of EMD and nickelate relative to the total cathode weight is 93.1 wt. %. Also, as a reference, 93.1 wt% EMD (100 wt% Mn for total Ni and Mn) based on total cathode weight was mixed with 6.4 wt% SFG 15 graphite and 0.5 wt% coathylene binder to form a cathode. 200 mg of the cathode was pressed into a 357 button cell can with a force of 5,000 lbf. The button cell was placed in an acrylic plastic test fixture filled with 40 wt% KOH and 6 wt% ZnO electrolyte. The acrylic plastic test fixtures containing the nickelate / EMD mixture cathodes were aged separately in a 60°C oven for 3, 7, and 14 days. The acrylic plastic test fixtures were then removed from the oven and allowed to cool at room temperature for 1 hour, then the electrolyte was poured off and the acrylic plastic test fixtures were refilled with 15 g of fresh electrolyte. The acrylic plastic test fixtures were discharged at a rate of 10 mA / g with a 1-hour rest after every 5-hour discharge to observe voltage recovery. Figure 7 presents a comparison of the specific capacity at 1 V of EMD, non-preaged and LiOH preaged nickelate after half-cell aging at 60°C for up to 14 days. It can be observed that the nickelate preaged for 1 min in 0.1 M LiOH (LPA-50% Ni) exhibits the highest fresh capacity of 292 mAh / g compared to that of the non-preaged nickelate (NPA-50% Ni, 244 mAh / g) and EMD (268 mAh / g).After 14 days of half-cell aging at 60°C, LPA-50%Ni still maintained a capacity of 268mAh / g, which is higher than that of NPA-50%Ni (214mAh / g) and EMD (257mAh / g), demonstrating the improved stability of the EMD / nickelate mixture due to the pre-aging treatment.

[0114] Example 7: Pre-aging improves the stability of nickelate powders Powder aging tests were performed on both non-preaged and preaged nickelates. The powder aging test procedure is as follows: 0.12 g of initial powder with 0.6 g of 40 wt% KOH / 6 wt% ZnO was first mixed and stirred in a small vial for 24 hours at room temperature. The mixture was then washed with DI water using a filtration device until the pH of the washed product was close to 7. The powder was dried under vacuum at 60° C. for 18 hours and further dried for 24 hours after switching off the heat to obtain the final product. Discharge of the initial powder before and after 24 hours of aging was then performed in a half-cell test apparatus to determine the electrochemical discharge capacity as follows: 49 wt% of the active material was mixed with 49 wt% SFG 15 graphite and 2 wt% coatylene binder to form a cathode mixture. 200 mg of the cathode mixture was pressed into a 357 button cell can with a force of 5,000 lbf. The button cell was placed in an acrylic plastic test fixture filled with 40 wt% KOH and 6 wt% ZnO, and the button cell was discharged at a rate of 10 mA / g with a 1 hour break after every 5 hours of discharge to observe the voltage recovery. Figure 8 shows the discharge curves of the unpreaged and LiOH preaged nickelate before and after 24 hours of aging in 40 wt% KOH / 6 wt% ZnO. The unpreaged nickelate shows the highest initial capacity of 424 mAh / g at 1 V, but only has a capacity of 230 mAh / g after powder aging. In comparison, the nickelates preaged with different concentrated LiOH exhibited much higher capacities of 305-311 mAh / g after powder aging (Table 1), demonstrating the improved stability of the nickelates from the preaging treatment technique. [Table 1]

[0115] Example 8: Optimization of EMD / Pre-Aged Nickelate Mixtures Discharge of 0.1M LiOH pre-aged nickelate / EMD mixtures was performed in a half-cell test fixture to determine electrochemical discharge capacity and efficiency as follows: A specific ratio of 0.1M LiOH pre-aged nickelate and EMD (93.1 wt% total nickelate and EMD based on total cathode weight) was mixed with 6.4 wt% SFG 15 graphite and 0.5 wt% coathylene binder to form a cathode mixture. 200 mg of the cathode mixture was pressed into a 357 button cell can with a force of 5,000 lbf. The button cell was placed in an acrylic plastic test fixture filled with 40 wt% KOH and 6 wt% ZnO, and the button cell was discharged at a rate of 10 mA / g with a 1-hour rest after every 5-hour discharge to observe voltage recovery. 9 and 10 respectively compare the specific capacity and efficiency at 1 V of nickelate / EMD mixtures preaged with 0.1 M LiOH with different relative weight percent Ni. It can be observed that the nickelate / EMD mixture preaged with 0.1 M LiOH with a relative Ni content of 50 wt. % (meaning 50 wt. % Ni with respect to the total amount of nickel and manganese) shows the highest capacity at 1 V compared to the non-preaged nickelate / EMD mixture. In particular, the efficiency of the nickelate / EMD mixture preaged with 0.1 M LiOH is greatly improved compared to the non-preaged nickelate / EMD mixture (FIG. 10). Overall, a relative Ni content of 50 wt. % is the optimal Ni content for the nickelate / EMD mixture preaged with 0.1 M LiOH, which demonstrates good capacity (305 mAh / g) and high efficiency (96%) at 1 V.

[0116] Example 9: XRD Fingerprints before and after pre-aging with LiOH Table 2 below shows the desodium NaNiO 2The XRD peak positions (2θ) of the nickelate pre-aged with LiOH (acid treated and unaged, FIG. 3) and LiOH (acid treated and aged, FIG. 5) are shown along with the XRD peak positions of other nickelate materials described in U.S. Pat. No. 11,560,321 B2. [Table 2]

[0117] Unpreaged desodium NaNiO 2 In FIG. 3, the fifth peak at about 55.7 to 58.9 2θ and the seventh peak at 69.5 to 71.3 2θ are NiO 2 It can be seen that the peaks correspond to the phases and are different from any of those in U.S. Pat. No. 11,560,321 B2. Pre-aged desodium NaNiO 2 In FIG. 5, the seventh peak at about 50.3 to 52 2θ and the eighth peak at about 57.4 to 58.7 2θ are Na 0.33 NiO 2 (H 2 O) 0.54 and (Li 0.45 Ni 0.05 )(NiO 2 ) phase and it can be observed that these are different from the peaks of any of the materials described in US 11,560,321 B2.

[0118] Table 3 below contains the peak positions (2θ) listed in Table 2 along with additional XRD peaks from non-preaged nickelates from additional synthetic routes and nickelates preaged with LiOH. [Table 3]

[0119] Additional synthetic routes of non-preaged nickelates and LiOH preaged nickelates (described in Examples 10-12) were slightly adjusted for scale-up purposes, and the additional synthetic routes exhibited distinct XRD fingerprints, as shown in Figures 11 and 12.

[0120] Peak splitting phenomenon For the non-preaged nickelate, there is a peak split of the main XRD peak at about 17.3-22.3 2θ (FIG. 11), which cannot be observed in the alpha, beta, and sodium nickelates in US 11,560,321B2 (FIG. 13). It can be subdivided into three peaks with different intensity ratios, and the three peaks can be separately 0.61 NiO 2 (H 2 O) 0.91 , β-NiOOH, and NiO 2 Corresponding to the phase.

[0121] For the nickelates preaged with LiOH, there is a peak split at about 17.2-19.9 2θ, a fourth peak at about 36.4-37.8 2θ, and a fifth peak at about 43.4-45.4 2θ (FIG. 12), which cannot be observed in the alpha, beta, and X nickelates (FIG. 13). This suggests that there are multiple phases in the nickelates preaged with LiOH, e.g., β-NiOOH, Na 0.33 NiO 2 (H 2 O) 0.54 , and (Li 0.39 Ni 0.01 )(NiO 2 ) components.

[0122] Unique XRD peaks For the non-preaged nickelate, it can be observed that the fourth peak at about 27.2-28.2 2θ, the seventh peak at 55.7-58.5 2θ, and the ninth peak at 69.5-71.1 2θ (Table 3) are different from any of the peaks in U.S. Pat. No. 11,560,321 B2.

[0123] For the nickelate preaged with LiOH, it can be observed that the fifth peak at about 43.4-45.4 2θ, the seventh peak at 56.8-59.6 2θ, and the tenth peak at 68.1-69.2 2θ (Table 3) are different from any of the peaks in U.S. Pat. No. 11,560,321 B2.

[0124] Example 10: Synthesis of Non-Preaged Nickelate I Ni(OH) 2 The resulting NiO was calcined at 650° C. for 6 hours in air to convert it to NiO. 2 O 2were added into a ball mill vial to form a mixture. The ball mill vial was then purged with argon in a glove box and then mixed via high energy ball milling for 1 hour. The ball milled mixture was then collected on a nickel crucible (55 mL), covered with a lid, and then fired in a furnace at 680° C. in air for 30 hours. The temperature ramp and cooling rates were 5° C. / min and 1° C. / min, respectively. After the powder was removed from the furnace at 120° C., 13 g of powder was added into the bottom of a round bottom flask, which was then immersed in a beaker filled with water from an ice / water mixture. Then, 4 M sulfuric acid (sample mass to volume ratio of 1:10 g / mL) at a temperature of 0° C. was added into the flask and stirred for 4 hours in a refrigerator (2° C.). The sample was then first washed by centrifugation method (1500 / 2000 rpm, 1-2 min, 0-4° C.) to remove the acid. The sample was then washed with DI water through a filtration set-up. The washed sample was dried under vacuum for 10 min, followed by continuous heating at 60° C. for 18 h and cooling for about 22-24 h to obtain the final product, non-preaged nickelate I. FIG. 11 shows the XRD pattern of the synthesized non-preaged nickelate I.

[0125] Example 11: Synthesis of Non-Preaged Nickelate II Ni(OH) 2 The resulting NiO was converted to NiO by calcination at 650 °C in air for 6 h. 11.204 g of NiO and 7.895 g of Na purchased from Sigma-Aldrich were added. 2 O 2were added into two ball mill vials respectively to form a mixture. The ball mill vials were then purged with argon in a glove box and then mixed via high energy ball milling for 1 hour. The ball milled mixture was then collected on a nickel crucible (250 mL), covered with a lid, and then fired in a furnace at 680° C. in air for 30 hours. The temperature ramp and cooling rates were 5° C. / min and 1° C. / min, respectively. After the powder was removed from the furnace at 130° C., 34 g of powder was added into the bottom of two round bottom flasks, which were then immersed separately into beakers filled with water from the ice / water mixture. 4 M sulfuric acid (sample mass to volume ratio of 1:10 g / mL) at a temperature of 0° C. was then added into each flask and stirred in a refrigerator (2° C.) for 4 hours. The samples were then washed using DI water via vacuum filtration using a large ceramic filter cup. The washed sample is dried under vacuum for 10 min, followed by continuous heating at 60 °C for 18 h and cooling for about 22-24 h to obtain the final product, non-preaged nickelate II. Figure 11 shows the XRD pattern of the synthesized non-preaged nickelate II.

[0126] Example 12: Synthesis of nickelate I / II pre-aged with LiOH First, 40 mL of 0.1 M LiOH solution was added to a centrifuge tube containing 0.6 g of non-preaged nickelate I / II powder. After shaking the tube in a circular motion, it was left to stand at room temperature for about 1 minute to pre-age the material. The sample was then washed with DI water using a vacuum filtration setup and dried in a vacuum oven at 60° C. for 18 hours. The final product LiOH pre-aged nickelate I / II was obtained. FIG. 12 represents the XRD pattern of the synthesized LiOH pre-aged nickelate I / II. LiOH pre-aged nickelate was also prepared by a similar process but using 0.5 M LiOH.

[0127] Example 13: Na-nickelate composition before and after pre-aging with LiOH Rietveld refinement of the XRD patterns allows quantification of the weight percentages of the different compounds that make up the unaged and aged nickelates. 2 The alloy consists of two to four phases, i.e., 18 to 50 wt.% NiO 2 (PDF:04-010-4751), 20-60% by weight of β-NiOOH (ICSD:165961), 0-25% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 (ICSD:159386), and 0-22% by weight H 0.61 NiO 2 (H 2 O) 0.91 (ICSD: 159387). After pre-aging in LiOH, the pre-aged nickelates were found to contain two to three phases, namely, 0-50 wt. % β-NiOOH (ICSD 165961), 4-62 wt. % Na 0.33 NiO 2 (H 2 O) 0.54 (ICSD:159386), and 35-80% by weight of (Li 0.39 Ni 0.01 )(NiO 2 )(ICSD:78694), or (Li 0.49 Ni 0.01 )(NiO 2 )(ICSD:78693), or (Li 0.45 Ni 0.05 )(NiO 2 ) (ICSD: 78704). After preaging in NaOH, the preaged nickelate was found to contain 15-20 wt. % β-NiOOH (ICSD 165961) and 80-85 wt. % Na 0.33 NiO 2 (H 2 O) 0.54 (ICSD:159386).

[0128] ICP analysis showed that the formula of the nickelate thus prepared was Na x Li y NiO 2 (H 2 O) z where, before pre-aging, x=0.01-0.05, z=0.2-1.1, and after pre-aging in LiOH, x=0.01-0.05, y=0.15-0.4, z=0.1-0.8.

[0129] A quantified summary of the XRD phase composition and overall chemical composition of the un-preaged and pre-aged nickelates is shown in Table 4 below. [Table 4-1] [Table 4-2]

[0130] Rietveld refinements of the XRD patterns of non-preaged nickelate I and non-preaged nickelate II are found in Figures 14-15, respectively.

[0131] Rietveld refinements of the XRD patterns of pre-aged nickelate I (0.1 M LiOH, 1 min) and pre-aged nickelate II (0.1 M LiOH, 1 min) are found in Figures 16-17, respectively.

[0132] Rietveld refinements of the XRD patterns of pre-aged nickelate (0.5 M LiOH, 10 min) and pre-aged nickelate (0.1 M LiOH, 10 min) prepared according to Example 4 are found in Figures 18-19, respectively.

[0133] Example 14: Based on a discharge rate of 10 mA / g, LiNiO 2 NaNiO compared to nickelates of 2 Characteristics of discharge curves of nickelates derived from LiNiO 2 Unlike the discharge curves of α-nickelate and β-nickelate derived from 2 The discharge curve of contains three distinct discharge plateaus during discharge to a voltage of 1.0 V at a discharge rate of 10 mA / g. Besides the discharge plateaus observed at about 1.60-1.50 V and 1.45-1.35 V, the discharge curve of desodium NaNiO before and after pre-aging with LiOH shows 2 For , there is an additional inherent discharge plateau at about 1.85-1.80 V that cannot be observed in the α and β nickelates. This inherent discharge plateau at the higher voltage of 1.85-1.80 V may be intrinsic to the nickelate resulting from the acid treatment of sodium nickelate instead of lithium nickelate. This is shown in FIG.

[0134] Example 15: Ratio of capacity contributions from different regions of the discharge curve Relatedly, the ratio of capacity contributions from the three regions of the discharge curve shown in Table 5 below shows that the non-pre-aged nickelate (desodium NaNiO 2 The distribution of specific capacity over various voltage regimes for nickelates pre-aged with LiOH and subsequently LiOH differs from that of α- and β-nickelates. To facilitate comparison of the capacity contributions from different voltage regimes, the nickelate discharge curves are divided into three distinct regions 1, 2, and 3, which correspond to OCV ∼ 1.63 V, 1.63-1.45 V, and 1.45-1.00 V, respectively. These regions are shown graphically in FIG. 21. [Table 5]

[0135] Due to the capacity contribution from the intrinsic plateau at 1.85-1.8 V, the ratio of the capacity contribution from region 2 to that of region 1 is in the distinctly lower range of 7.3-9.0 for the unpreaged and LiOH preaged nickelates, and over 10 for the α- and β-nickelates. The percentage of capacity contribution from region 1 among all three regions is in the range of 7.4-10.4% for the unpreaged and LiOH preaged nickelates, and 2.3-6.6% for the α- and β-nickelates.

Claims

1. A desodiumlated nickelate material, wherein the nickelate material is (i) A set of first peaks between approximately 11.9° and 14°²θ, a second peak between approximately 18° and 22°²θ, a third peak between approximately 36.1° and 38.6°²θ, a fourth peak between approximately 41° and 44.2°²θ, a fifth peak between approximately 55.7° and 58.9°²θ, a sixth peak between approximately 65° and 67.3°²θ, and a seventh peak between approximately 69.5° and 71.3°²θ, or (ii) A set of first peaks at approximately 11.3°–14.6°²θ, second peaks at approximately 17.3°–22.3°²θ, third peaks at approximately 23.8°–25.9°²θ, fourth peaks at approximately 27.2°–28.2°²θ, fifth peaks at approximately 36.2°–37.7°²θ, sixth peaks at approximately 40°–44°²θ, seventh peaks at approximately 55.7°–58.5°²θ, eighth peaks at approximately 65.2°–67.3°²θ, and ninth peaks at approximately 69.5°–71.1°²θ. A desodiumated nickelate material having an X-ray diffraction (XRD) pattern including [specific element].

2. A pre-aged desodiumlated nickelate material exposed to an oxide or hydroxide, (i) A set of first peaks at approximately 11.9°–13.8°²θ, second peaks at approximately 17°–19.5°²θ, third peaks at approximately 24.7°–26.5°²θ, fourth peaks at approximately 36.3°–39.2°²θ, fifth peaks at approximately 41.9°–45.7°²θ, sixth peaks at 47.5°–49.5°²θ, seventh peaks at approximately 50.3°–52°²θ, eighth peaks at approximately 57.4°–58.7°²θ, and ninth peaks at approximately 65°–68°²θ, or (ii) A set of first peaks at approximately 11.1°–14.4°²θ, a set of second peaks at approximately 17.2°–19.9°²θ, a set of third peaks at approximately 24.1°–26.0°²θ, a set of fourth peaks at approximately 35.8°–39.3°²θ, a set of fifth peaks at approximately 43.4°–45.4°²θ, a sixth peak at 47.7°–49.4°²θ, a seventh peak at approximately 56.8°–59.6°²θ, an eighth peak at approximately 62.8°–64.5°²θ, a ninth peak at approximately 65°–67.4°²θ, and a tenth peak at approximately 68.1°–69.2°²θ. A pre-aged desodiumlated nickelate material having an X-ray diffraction (XRD) pattern including [specific element].

3. The pre-aged desodium-treated nickelate material according to claim 2, wherein the pre-aged desodium-treated nickelate material is prepared by pre-aging a desodium-treated nickelate precursor using a pre-aging solution containing one or more agents selected from the group consisting of hydroxides.

4. The pre-aged desodium-treated nickelate material according to claim 3, wherein the pre-aging solution comprises a hydroxide selected from the group consisting of LiOH, NaOH, and other alkali and alkaline earth metal hydroxides.

5. A method for producing a pre-aged desodiumlated nickelate material, i) Contacting sodium nickelate with an acid solution to produce acid-leached desodium nickelate, ii) A method comprising contacting the acid-leached desodium-treated nickelate with a pre-aging solution containing hydroxide to produce the pre-aged desodium-treated nickelate material.

6. The acid-leached desodium nickelate is, x NiO 2 The method according to claim 5, wherein the formula has 0 ≤ x ≤ 0.

2.

7. The method according to claim 5, wherein the acid solution comprises an acid selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, hydroiodic acid, and perchloric acid.

8. The aforementioned pre-aging solution contains LiOH, NaOH, and Ca(OH) 2 The method according to claim 5, further comprising a hydroxide selected from the group consisting of other alkalis and alkaline earth metal hydroxides.

9. A pre-aged desodiumlated nickelate material prepared by the method described in claim 5.

10. An alkali cathode composition comprising a pre-aged desodiumlated nickelate material according to any one of claims 2 to 4 and 9, electrolytic manganese dioxide, graphite, and a binder.

11. The following (A), (b), or (C), (A) i) 15-50% by weight of NiO 2 and, ii) 20-60% by weight of β-NiOOH, iii) 0-25% by weight of H 0.61 NiO 2 (H 2 O) 0.91 and, iv) 0 to 25% by weight of Na 0.33 NiO 2 (H 2 O) 0.54 and (B) i) 4-62% by weight of Na 0.33 NiO 2 (H 2 O) 0.54, ii) 30 to 80% by weight of (Li 0.39 Ni 0.01)(NiO2), and / or (Li 0.49 Ni 0.01)(NiO2), and / or (Li 0.45 Ni 0.05)(NiO2), iii) 0-50% by weight of β-NiOOH, (C) i) 80-85% by weight of Na 0.33 NiO 2 (H 2 O) 0.54, ii) 15-20% by weight of β-NiOOH, A desodiumated nickelate material containing this material.

12. Formula (i) Na x NiO 2 (H 2 O) z A desodium-coated nickelate material having the formula, wherein x = 0.01 to 0.05 and z = 0.2 to 1.1, or (ii) A desodiumtrated nickelate material having Na x Li y NiO 2 (H 2 O) z, wherein x = 0.01 to 0.05, y = 0.15 to 0.45, and z = 0.1 to 0.

8.

13. A nickelate material that exhibits three discharge plateaus relative to a Zn / ZnO reference electrode during discharge up to a voltage of 1.0 V at a discharge rate of 10 mA / g.

14. The nickelate material exhibits a discharge curve for Zn / ZnO at a discharge rate of 10 mA / g, the discharge curve shows the voltage-to-specific capacitance, the specific capacitance is separated into a first region from OCV to 1.63 V, a second region from 1.63 V to 1.45 V, and a third region from 1.45 V to 1.00 V, and the capacitance contribution of a given region is the difference between the capacitance at the end of the region and the capacitance at the beginning of the region. i) The ratio of the capacity contribution of the second region to the capacity contribution of the first region is less than 10, or ii) The nickelate material according to claim 13, wherein the capacity contribution of the first region is at least 7.0% of the total capacity contribution of the first, second, and third regions.

15. An alkali electrochemical cell comprising the nickelate material according to any one of claims 1 to 4 and 9.

16. An alkali electrochemical cell comprising the composition described in Claim 10.

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