JP2017191782A - Nickel hydrogen storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nickel hydrogen storage battery arranged to use a rare earth-Ca-Mg-Ni based alloy as an active material of a negative electrode, which causes no remarkable drop in discharge capacity during a time from an initial stage to a time for performing about 10 cycles of charging/discharging cycles.SOLUTION: A battery according to the invention comprises: a negative electrode including a hydrogen-occluding alloy in which rare earth-Ca-Mg-Ni based GdCophases including one or more elements selected from a group consisting of Y, Pr, Nd and Sm, and CeNiphases are layered; and an alkali electrolyte solution containing 2.0 mol/l or more of sodium ions.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a nickel metal hydride storage battery.

  Nickel metal hydride storage batteries are widely used as an alternative to primary batteries, and the demand for such batteries is expanding dramatically.

  As a negative electrode material for such a nickel metal hydride storage battery, a rare earth-Ca- having a crystal structure in which a plurality of crystal phases are laminated in the c-axis direction of the crystal structure with the aim of improving discharge capacity and further improving cycle characteristics. An Mg—Ni alloy (Patent Document 1) has been studied.

International Publication WO2009 / 060666

  However, in the battery using the rare earth-Ca-Mg-Ni alloy as an active material for the negative electrode, there is a problem that the discharge capacity is remarkably lowered during the cycle charge / discharge of about 10 cycles from the initial stage.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, a rare earth-Ca-Mg-Ni alloy containing a specific element is used as a negative electrode, and the sodium ion concentration is adjusted to a predetermined concentration range. It is found that a nickel-metal hydride storage battery can be provided in which no significant decrease in discharge capacity occurs during the cycle charge / discharge of about 10 cycles from the initial stage by configuring the nickel-metal hydride storage battery using the alkaline electrolyte obtained by the present invention. It came to complete.

  That is, the battery according to the first invention of the present application is a rare earth-Ca-Mg-Ni-based hydrogen storage containing one or more elements selected from the group consisting of Y, Pr, Nd and Sm. It comprises a negative electrode containing an alloy and an alkaline electrolyte containing 2.0 mol / l or more of sodium ions.

  The battery according to the second invention of the present application is characterized in that the sodium ion concentration of the alkaline electrolyte of the battery according to the first invention is 5.0 mol / l or more and 7.0 mol / l or less. .

  According to the said structure, since it becomes possible to suppress significantly the fall of the discharge capacity during performing the cycle charging / discharging about 10 cycles from the beginning, it is preferable.

  According to the present invention, in a nickel metal hydride storage battery using a rare earth-Ca-Mg-Ni alloy as a negative electrode, it is possible to suppress a decrease in discharge capacity during a cycle of about 10 cycles from the initial stage.

The schematic diagram which showed one Embodiment of the hydrogen storage alloy.

The hydrogen storage alloy used in the battery of the present invention is a rare earth-Ca-Mg-Ni-based hydrogen storage alloy in which two or more crystal phases having different crystal structures are laminated in the c-axis direction of the crystal structure.
Examples of the crystal phase include a crystal phase composed of a rhombohedral La ₅ MgNi ₂₄ type crystal structure (hereinafter also simply referred to as La ₅ MgNi ₂₄ phase), and a crystal phase composed of a hexagonal Pr ₅ Co ₁₉ type crystal structure (hereinafter simply referred to as simply “La ₅ MgNi ₂₄ phase”). Pr ₅ Co ₁₉ phase), crystal phase composed of rhombohedral Ce ₅ Co ₁₉ type crystal structure (hereinafter also simply referred to as Ce ₅ Co ₁₉ phase), crystal phase composed of hexagonal Ce ₂ Ni ₇ type crystal structure (Hereinafter also simply referred to as Ce ₂ Ni ₇ phase), crystal phase composed of rhombohedral Gd ₂ Co ₇ type crystal structure (hereinafter also simply referred to as Gd ₂ Co ₇ phase), and hexagonal CaCu ₅ type crystal structure crystalline phase (hereinafter, simply referred to as CaCu ₅ phase), crystal phase comprising a cubic AuBe ₅ type crystal structure (hereinafter, simply referred to as AuBe ₅ phase), crystal consisting of rhombohedral PuNi ₃ type crystal structure (Hereinafter, simply referred to as PuNi _3-phase), and the like. Among these, a hydrogen storage alloy containing a Gd ₂ Co ₇ phase and a Ce ₂ Ni ₇ phase in the lamination of the crystal phases is preferably used. The hydrogen storage alloy in which the Gd ₂ Co ₇ phase and the Ce ₂ Ni ₇ phase are laminated has a small difference in expansion / contraction rate between the crystal phases, so that it is difficult to be distorted and deteriorates when the hydrogen storage / release is repeated. It has an excellent property that it does not easily occur.

Here, the Gd ₂ Co ₇ type crystal structure is a crystal structure in which two AB ₅ units are inserted between A ₂ B ₄ units, belongs to a rhombohedral crystal system, and the space group is R-3m. The crystal structure can be assigned to
The La ₅ MgNi ₂₄ type crystal structure is a crystal structure in which ₄ units of AB ₅ units are inserted between A ₂ B ₄ units, and the Pr ₅ Co ₁₉ type crystal structure is A ₂ B ₄ It is a crystal structure in which 3 units of AB ₅ units are inserted between the units, and the Ce ₅ Co ₁₉ type crystal structure is a crystal in which 3 units of AB ₅ units are inserted between the A ₂ B ₄ units. The Ce ₂ Ni ₇ type crystal structure is a crystal structure in which _two AB ₅ units are inserted between A ₂ B ₄ units, and the AuBe ₅ type crystal structure is A ₂ B It is a crystal structure composed of only ₄ units.

The A ₂ B ₄ unit is a structural unit having a hexagonal MgZn ₂ type crystal structure (C14 structure) or a hexagonal MgCu ₂ type crystal structure (C15 structure), and the AB ₅ unit is a hexagonal CaCu ₅ It is a structural unit with a type crystal structure. A represents any element selected from the group consisting of rare earth elements and Mg, and B represents any element selected from the group consisting of transition metal elements and Al.

  The order of lamination of the crystal phases is not particularly limited, and a combination of specific crystal phases may be such that the crystal phases are laminated with periodicity, and each crystal phase is randomly and periodically laminated. It may be.

Further, the content of each of the crystal phases is not particularly limited, but the content of the Gd ₂ Co ₇ phase is preferably 3% by mass or more, and 20% by mass or more in the hydrogen storage alloy. It is more preferable that it is 70 mass% or more. The content of the La ₅ MgNi ₂₄ phase is 50% by mass or less, the content of the Pr ₅ Co ₁₉ phase is 80% by mass or less, and the content of the crystal phase having the Ce ₅ Co ₁₉ type crystal structure is 80% by mass. %, And the Ce ₂ Ni ₇ phase content is preferably 65% by mass or less.

  The crystal structure can be identified by, for example, performing X-ray diffraction measurement on the pulverized alloy powder and analyzing the obtained X-ray diffraction pattern by the Rietveld method.

A schematic diagram of an embodiment of the hydrogen storage alloy is shown in FIG. As shown in FIG. 1, the hydrogen storage alloy as an embodiment includes a PuNi ₃ phase, a Ce ₅ Co ₁₉ phase adjacent to the PuNi ₃ phase, and a Pr ₅ Co ₁₉ adjacent to the Ce ₅ Co ₁₉ phase. A phase and a Ce ₂ Ni ₇ phase adjacent to the Pr ₅ Co ₁₉ phase are laminated in the c-axis direction of the crystal structure.

  It can be confirmed by observing the lattice image of the alloy using TEM that two or more crystal phases having different crystal structures are laminated in the c-axis direction of the crystal structure.

  As described above, the hydrogen storage alloy constituting the negative electrode in the present invention is formed by stacking two or more crystal phases having different crystal structures in the c-axis direction of the crystal structure. The distortion of the crystal phase at the time of occlusion is relaxed by the other adjacent crystal phase. Therefore, the negative electrode comprising the hydrogen storage alloy is less likely to be pulverized and hardly deteriorated even if hydrogen is repeatedly stored and released by charging and discharging. In addition, since the hydrogen storage alloy is a rare earth-Ca-Mg-Ni-based hydrogen storage alloy, the initial discharge capacity is large.

  The hydrogen storage alloy according to the present invention contains one or more elements selected from the group consisting of Y, Pr, Nd and Sm. The content of the element is preferably 2.2 atomic percent or more and 7.7 atomic percent or less. By setting the content of the element in such a range, a battery using the element has a significantly high effect of suppressing a decrease in discharge capacity during the cycle charge / discharge of about 10 cycles from the initial stage.

  Further, the Ca content of the hydrogen storage alloy according to the present invention is preferably 0.7 atomic% or more and 9.5 atomic% or less, and preferably 1.1 atomic% or more and 4.4 atomic% or less. Particularly preferred. A battery using a hydrogen storage alloy having a composition in such a content range achieves a high initial discharge capacity and has significantly improved long-term cycle characteristics.

That is, the composition of the alloy, the following general formula _{R1 u R2 v Ca w Mg x} Ni y R3 z
An alloy represented by
In the general formula, R1 is one or more elements selected from the group consisting of Y and rare earth elements, and preferably one or two elements selected from the group consisting of La and Ce. R2 is one or more elements selected from the group consisting of Y, Pr, Nd and Sm.
R3 is one or more elements selected from the group consisting of Co, Cu, Mn, Al, Cr, Fe, Zn, V, Nb, Ta, Ti, Zr and Hf, preferably , One or more elements selected from the group consisting of Co and Al.
The u, v, w, x, y and z are numbers satisfying u + v + w + x + y + z = 100, and u is preferably 6.7 ≦ u ≦ 17.9, more preferably 11.3 ≦ u ≦ 16.7. preferable. v is preferably 2.2 ≦ u ≦ 9.3, and more preferably 2.2 ≦ u ≦ 7.7. As for w, 0.7 <= w <= 9.5 is preferred and 1.1 <= w <= 4.4 is more preferred. x is preferably 3.3 ≦ x ≦ 5.6. y is preferably 73.3 ≦ y ≦ 78.7, and more preferably 74.4 ≦ y ≦ 78.3. z is preferably 0 ≦ z ≦ 4.4, and more preferably 0 ≦ z ≦ 3.3.
A battery using a hydrogen storage alloy having a composition in the range of the addition amount not only has a remarkable effect that deterioration does not easily progress even after repeated charge and discharge while achieving a high initial discharge capacity. Since the effect which suppresses the fall of the discharge capacity during performing cycle charge / discharge of about a cycle becomes remarkable, it is preferable.

  In particular, in the present invention, an alloy satisfying 3.3 ≦ (y + z) / (u + v + w + x) ≦ 3.7 in the composition can be used more suitably. It is preferable to use an alloy having such a composition because a high hydrogen storage capacity is exhibited.

  The hydrogen storage alloy which comprises a negative electrode can be obtained with the following manufacturing methods. That is, the method for producing a hydrogen storage alloy as one embodiment includes a melting step of melting an alloy raw material blended to have a predetermined composition ratio, and rapid solidification of the molten alloy raw material at a cooling rate of 1000 K / second or more. And an annealing step of annealing the cooled alloy in a pressurized inert gas atmosphere in a temperature range of 860 to 1000 ° C.

  More specifically, first, a predetermined amount of raw material ingot (alloy raw material) is weighed based on the chemical composition of the target hydrogen storage alloy. In the melting step, the alloy raw material is put in a crucible and heated to 1200 to 1600 ° C., for example, in an inert gas atmosphere or in a vacuum to melt the alloy raw material.

In the cooling step, the molten alloy material is cooled and solidified. The cooling rate is preferably 1000 K / second or more (also called rapid cooling). By rapidly cooling at 1000 K / second or more, there is an effect that the alloy composition is refined and homogenized. Moreover, in the said cooling process, the production | generation amount of the CaCu ₅ phase produced | generated in the solidified alloy reduces as a cooling rate becomes high, and when it exceeds a certain speed | rate, the tendency which becomes constant will be shown. Since the discharge capacity is improved by reducing the production amount of the CaCu ₅ phase, the cooling rate is preferably set to a rate at which the production amount of the CaCu ₅ phase can be reduced as described above. It is preferable to set the speed to show a tendency that becomes constant.
From this point of view, as the cooling method, what is called rapid cooling, specifically, a melt spinning method with a cooling rate of 100,000 K / second or more, a gas atomizing method with a cooling rate of about 10,000 K / second, or the like is preferably used. be able to.

In the annealing step, heating is performed at 860 to 1000 ° C. using, for example, an electric furnace in a pressurized state under an inert gas atmosphere. As a pressurizing condition, 0.2 to 1.0 MPa (gauge pressure) is preferable. Moreover, it is preferable that the processing time in this annealing process shall be 3 to 50 hours.
The distortion of the crystal lattice is removed by the annealing process, and the hydrogen storage alloy that has undergone the annealing process finally becomes a hydrogen storage alloy in which two or more crystal phases having different crystal structures are laminated.

  The negative electrode constituting the nickel-metal hydride storage battery of the present invention includes the hydrogen storage alloy obtained as described above as a hydrogen storage medium. When the hydrogen storage alloy is used for an electrode as a hydrogen storage medium, the hydrogen storage alloy is preferably used after being pulverized. The hydrogen storage alloy may be pulverized at the time of electrode fabrication either before or after annealing, but since the surface area is increased by pulverization, it is desirable to pulverize after annealing from the viewpoint of preventing surface oxidation of the alloy. The pulverization is preferably performed in an inert atmosphere to prevent oxidation of the alloy surface. For the pulverization, for example, mechanical pulverization, hydrogenation pulverization, or the like is used.

  Next, an alkaline electrolyte constituting the nickel-metal hydride storage battery according to the present invention will be described. The alkaline electrolyte according to the present invention has a sodium ion concentration of 2.0 mol / liter or more. Moreover, when a sodium ion concentration is 5.0-7.0 mol / liter, the effect which suppresses the fall of the discharge capacity during performing the cycle charge / discharge of about 10 cycles from an initial stage becomes remarkably high, and it is preferable.

  In addition, the alkaline electrolyte includes ionic species other than sodium ions and ion concentration, but generally includes potassium ions and lithium ions. In particular, the sum of the ion concentrations of the sodium ion, the potassium ion, and the lithium ion is preferably 8.0 mol / liter or less, and more preferably 5.0 to 7.0 mol / liter. Furthermore, a sodium ion single system may be used from a viewpoint of suppressing alloy corrosion.

  In addition, various additives can be added to the electrolytic solution in order to improve the corrosion resistance to the alloy, improve the overvoltage at the positive electrode, improve the corrosion resistance of the negative electrode, and improve self-discharge. As this additive, oxides, hydroxides, etc., such as yttrium, ytterbium, erbium, calcium, and zinc, can be used 1 type or in mixture of 2 or more types.

On the other hand, the positive electrode of the nickel metal hydride storage battery is not particularly limited, but generally a nickel hydroxide composite oxide mainly composed of nickel hydroxide and mixed with zinc hydroxide or cobalt hydroxide. A positive electrode including a positive electrode active material can be preferably used, and a positive electrode including the nickel hydroxide composite oxide uniformly dispersed by a coprecipitation method can be more preferably used.
As additives other than the nickel hydroxide composite oxide, cobalt hydroxide, cobalt oxide and the like as a conductive modifier can be used, and the nickel hydroxide composite oxide is coated with cobalt hydroxide. A part of these nickel hydroxide composite oxides oxidized with oxygen or an oxygen-containing gas, or a chemical such as K2S2O8 or hypochlorous acid can be used.
In addition, as the additive, as a substance for improving the oxygen overvoltage, a rare earth element compound such as Y or Yb or a Ca compound can be used. Since some of rare earth elements such as Y and Yb are dissolved and disposed on the negative electrode surface, an effect of suppressing corrosion of the negative electrode active material can be expected.

The positive electrode and the negative electrode may contain a conductive agent, a binder, a thickener, and the like as other components in addition to the main components as described above.
The conductive agent is not limited as long as it is an electron conductive material that does not adversely affect battery performance. Usually, natural graphite (such as scale-like graphite, scale-like graphite, earth-like graphite), artificial graphite, carbon black, acetylene black, A conductive material such as ketjen black, carbon whisker, carbon fiber, vapor-grown carbon, metal (nickel, gold, etc.) powder, metal fiber, or the like can be included as one or a mixture of two or more.
Among these, as the conductive agent, acetylene black is preferable from the viewpoints of electron conductivity and coatability. The addition amount of the conductive agent is preferably 0.1% by mass to 10% by mass with respect to the total weight of the positive electrode or the negative electrode. In particular, it is desirable to use acetylene black after being pulverized into ultrafine particles of 0.1 to 0.5 μm because the necessary carbon amount can be reduced.
As a method of mixing them, a method that can be as uniform as possible is preferable. For example, a powder mixer such as a V-type mixer, an S-type mixer, a grinder, a ball mill, a planetary ball mill, or the like may be dry or wet. The method used in the above can be adopted.
As the binder, usually, thermoplastic resins such as polytetrafluoroethylene (PTFE), polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber A polymer having rubber elasticity such as can be used as one kind or a mixture of two or more kinds. The addition amount of the binder is preferably 0.1 to 3% by mass with respect to the total amount of the positive electrode or the negative electrode.
As said thickener, polysaccharides, such as carboxymethylcellulose, methylcellulose, xanthan gum, etc. can be normally used as 1 type, or 2 or more types of mixtures. The addition amount of the thickener is preferably 0.1 to 0.3% by mass with respect to the total amount of the positive electrode or the negative electrode.

  The positive electrode and the negative electrode are prepared by mixing the active material, the conductive agent, and the binder in an organic solvent such as water, alcohol, and toluene, and then applying the obtained mixed liquid onto a current collector and drying it. Produced suitably. As the application method, for example, a method of applying to any thickness and any shape using means such as roller coating such as applicator roll, screen coating, blade coating, spin coating, and bar coating is suitable. It is not limited to.

As the current collector, an electron conductor that does not adversely affect the exchange of electrons with the active material in the battery that is configured can be used without particular limitation. As the current collector, for example, from the viewpoint of reduction resistance and oxidation resistance, nickel or nickel-plated steel plate can be suitably used as a material, and as a shape, a foam, a molded body of a fiber group, A three-dimensional base material subjected to uneven processing or a two-dimensional base material such as a punching plate can be suitably used. Moreover, there is no limitation in particular also about the thickness of this electrical power collector, The thing of 5-700 micrometers is used suitably.
Among these current collectors, for the positive electrode, it is necessary to use a material having a porous structure, which is made of nickel having excellent corrosion resistance and oxidation resistance to alkali, and having a structure excellent in current collection. preferable. In addition, as a negative electrode, it is preferable to use a punching plate obtained by applying nickel plating for improving reduction resistance to an iron foil which is inexpensive and excellent in conductivity. The punching diameter is preferably 2.0 mm or less, and the opening ratio is preferably 40% or more. This makes it possible to improve the adhesion between the negative electrode active material and the current collector even with a small amount of binder.

As a separator of a nickel metal hydride storage battery, it is preferable that a porous film or a nonwoven fabric exhibiting excellent rate characteristics be used alone or in combination of two or more. Examples of the material constituting the separator include polyolefin resins such as polyethylene and polypropylene.
The basis weight of the separator is preferably 40 g / m 2 to 100 g / m 2. If it is less than 40 g / m 2, the short circuit and the self-discharge performance may be deteriorated, and if it exceeds 100 g / m 2, the ratio of the separator per unit volume increases, so that the battery capacity tends to decrease. The air permeability of the separator is preferably 1 cm / sec to 50 cm / sec. If it is less than 1 cm / sec, the internal pressure of the battery may increase, and if it exceeds 50 cm / sec, the short circuit and the self-discharge performance may be deteriorated. The average fiber diameter of the separator is preferably 1 μm to 20 μm. When the thickness is less than 1 μm, the strength of the separator decreases, and the defect rate in the battery assembly process may increase. When the thickness exceeds 20 μm, the short circuit and the self-discharge performance may decrease. The separator is preferably subjected to a hydrophilic treatment. For example, the surface of polyolefin resin fibers such as polypropylene may be subjected to sulfonation treatment, corona treatment, fluorine gas treatment, plasma treatment, or a mixture of those already subjected to these treatments. In particular, a separator subjected to a sulfonation treatment is preferable because it has a high ability to adsorb impurities such as NO 3−, NO 2−, and NH 3 − that cause a shuttle phenomenon and an eluting element from the negative electrode, and thus has a high self-discharge suppressing effect.

  The sealed nickel-metal hydride storage battery as one embodiment of the present invention is preferably produced by injecting the electrolyte solution before or after laminating the positive electrode, the separator, and the negative electrode, and sealing with an exterior material. Is done. In a sealed nickel-metal hydride storage battery in which a power generation element in which a positive electrode and a negative electrode are stacked via the separator is wound, the electrolyte is injected into the power generation element before or after winding. preferable. As an injection method, it is possible to inject at normal pressure, but a vacuum impregnation method, a pressure impregnation method, and a centrifugal impregnation method can also be used. Examples of the material of the outer package of the sealed nickel-metal hydride storage battery include nickel-plated iron, stainless steel, polyolefin resin, and the like.

  The configuration of the sealed nickel-metal hydride storage battery is not particularly limited, and batteries including a positive electrode, a negative electrode, and a single-layer or multi-layer separator, such as a coin battery, a button battery, a square battery, a flat battery, Alternatively, a cylindrical battery having a roll-shaped positive electrode, a negative electrode, and a separator can be given.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Preparation of negative electrode)
A predetermined amount of a raw material ingot (alloy raw material) shown in Table 1 was weighed and placed in a crucible, and heated to 1200 ° C. to 1600 ° C. using a high-frequency melting furnace in a reduced pressure argon gas atmosphere to melt the material. . After melting, a melt spinning method was applied and quenched at a cooling rate of 1000 K / second or more to solidify the alloy.
Next, the obtained alloy ingot was heated in an electric furnace at 930 ° C. for 5 hours in an argon gas atmosphere pressurized to 0.2 MPa (gauge pressure, the same applies hereinafter).
Furthermore, each hydrogen storage alloy was pulverized to an average particle diameter D50 = 50 μm, and the obtained powder was subjected to conditions of 40 kV, 100 mA (Cu tube) using an X-ray diffractometer (manufactured by BrukerAXS, product number M06XCE). X-ray diffraction measurement was performed. Furthermore, analysis by the Rietveld method (analysis software: Rietan 2000) was performed, and the generation ratio of the crystal phase was calculated. Table 1 shows the generation ratio of the crystal phase.

(Preparation of open nickel metal hydride battery negative electrode)
After adding and mixing 3 parts by mass of nickel powder (INCO # 210) to 100 parts by mass of the hydrogen storage alloy powder obtained as described above, an aqueous solution in which a thickener (methylcellulose) is dissolved is added. A paste made of 1 part by weight of a binder (styrene butadiene rubber) was applied to both sides of a 35μm thick perforated steel sheet (opening ratio 50%), dried, and then pressed to a thickness of 0.33mm. Thus, a negative electrode plate was obtained.
Further, a sinter type nickel hydroxide electrode having a capacity three times as large as the negative electrode capacity was used for the positive electrode plate. The negative electrode is sandwiched between the positive electrode through the separator, these electrodes are fixed so that a pressure of 1 kgf is applied to the electrodes, and an alkaline aqueous solution adjusted to the ion species and concentration shown in Table 2 is injected, and an open cell is assembled. It was.

(Evaluation of open-type nickel metal hydride battery negative electrode)
At 20 ° C, charging for 15 hours at 0.1 ItA (30 mA / g), resting for 1 hour, and charging / discharging cycle at 0.2 ItA to discharge to -0.6 V against the Hg / HgO reference electrode were repeated. Was measured. The value obtained by dividing the maximum discharge capacity in 12 cycles by the mass of the alloy contained in the negative electrode was defined as “maximum discharge capacity (mAh / g)”, and the discharge capacity at the 12th cycle was divided by the mass of the alloy contained in the negative electrode. The value was defined as “12th cycle discharge capacity (mAh / g)”.
And the discharge capacity maintenance factor was computed based on the following formula.
Discharge capacity retention rate (%) = 12th cycle discharge capacity / maximum discharge capacity × 100
The results are shown in Table 2.

  According to the results shown in Table 2, a negative electrode containing a rare earth-Ca-Mg-Ni-based hydrogen storage alloy containing Y, Nd, Pr or Sm, an alkaline electrolyte containing 2.0 mol / l or more of sodium ions, In Examples 1 to 8 having the above, the discharge capacity retention rate was around 99%, and good results were obtained. On the other hand, in Comparative Examples 1 to 4 not containing Y, Nd, Pr or Sm and Comparative Examples 5 to 8 containing sodium ions less than 2.0 mol / l, the discharge capacity retention rate was low. Moreover, when using the hydrogen storage alloy which does not contain Ca (Comparative Examples 9-16), the maximum discharge capacity became 350 mAh / g or less, and it could not be made into a high capacity battery in the first place.

  This result shows that by substituting a part of rare earth elements with Y, Nd, Pr or Sm having a small atomic radius, the hydrogen equilibrium pressure is increased, and an electrolyte containing a predetermined amount or more of Na ions is used. As a result, the difference in charge potential and hydrogen generation potential is reduced by increasing the charge potential, and it is presumed that hydrogen storage is appropriately limited. Thereby, the excessive expansion and contraction of the alloy lattice can be suppressed, and the pulverization of the alloy is suppressed, so that it is considered that the effect of the present invention was achieved.

Claims (2)

Rare earth-Ca-Mg-Ni-based Gd ₂ Co ₇ phase and Ce ₂ Ni ₇ phase containing one or more elements selected from the group consisting of Y, Pr, Nd or Sm are laminated. A nickel-metal hydride storage battery comprising a negative electrode containing a hydrogen storage alloy and an alkaline electrolyte containing 2.0 mol / l or more of sodium ions. The nickel-metal hydride storage battery according to claim 1, wherein the alkaline electrolyte contains 5.0 mol / l or more and 7.0 mol / l or less of sodium ions.

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