Patent Description:
An alkaline storage battery includes an electrode group in which a positive electrode plate, a negative electrode plate, and a separator are laminated. In the electrode group, the separator is arranged between the positive electrode plate and the negative electrode plate. In the alkaline storage battery, for example, the electrode group is wound in a spiral shape, and accommodated together with an alkaline electrolytic solution in a cylindrical outer packaging can having electric conductivity. In the alkaline storage battery, a predetermined electrochemical reaction induced between the positive electrode plate and the negative electrode plate which face each other via the separator, whereby charging and discharging are performed. For example, <CIT> describes a nickel-metal hydride secondary battery as an example of the alkaline storage battery.

Since nickel-metal hydride secondary batteries have a high capacity and are excellent in environmental safety, they have been used in various applications such as compatibility with alkaline batteries, backup power sources, and in-vehicle intended use. As described above, since the applications are expanding, in order to extend the life (improve the cycle life) of the nickel-metal hydride secondary batteries, various methods such as suppression of pulverization by adding Co to hydrogen storage alloy, suppressing of corrosion by subjecting the surface of the alloy to an alkali treatment have been studied.

With respect to conventional nickel-metal hydride secondary batteries, it has been found that the cycle life is improved by adding Co to alloy or subjecting the surface of alloy to an alkali treatment, but in general the reactivity of the alloy is deteriorated, and the discharge characteristic, particularly at low temperature, is deteriorated. As described above, it has been difficult in the nickel-metal hydride secondary batteries to achieve both the improvement of the cycle life and the improvement of the low-temperature discharge characteristic.

The present invention has been made in view of such problems, and has an object to provide a negative electrode for nickel-metal hydride secondary batteriesthat achieve both improvement of cycle life and improvement of low-temperature discharge characteristic, and an nickel-metal hydride secondary battery including the negative electrode. <CIT> discloses a nickel hydrogen secondary battery comprising: an electrode group consisting of a positive electrode and a negative electrode which are superposed on each other through a separator; and an outer package in which the electrode group is housed in a sealed state together with an alkaline electrolyte. The negative electrode contains a hydrogen-storing alloy and fluoride of rare earth elements.

In order to attain the above object, a negative electrode for nickel-metal hydride secondary batteries according to claim <NUM> and a nickel-metal hydride secondary battery according to claim <NUM> are provided. A preferred embodiment is set forth in claim <NUM>.

Hereinafter, an embodiment of a nickel-metal hydride secondary battery <NUM> (hereinafter, also simply referred to as "battery <NUM>") will be described as an example of an alkaline storage battery according to an embodiment. An AA size cylindrical battery <NUM> will be described as an embodiment. However, the battery <NUM> is not limited to this type, and another size such as AAA size may be used, or for example, a square battery may be used.

<FIG> is a perspective view showing a partially broken nickel-metal hydride secondary battery <NUM> (alkaline storage battery) according to the embodiment. <FIG> shows results of a cycle test and a low-temperature discharging test of batteries <NUM> according to examples together with those of comparative examples. For convenience of description, with respect to an axis x of a cylindrical outer packaging can <NUM>, the direction of an arrow a indicates an upper side, and the direction of an arrow b indicates a lower side. Here, the upper side means a side on which a positive electrode terminal <NUM> of the battery <NUM> is provided, and the lower side means a side on which a bottom wall <NUM> of the battery <NUM> is provided and also means the opposite side to the upper side. Further, with respect to a direction perpendicular to the axis x (hereinafter, also referred to as "radial direction"), a direction which is away from the axis x indicates an outer circumferential side (the direction of an arrow c), and a direction which directs to the axis x indicates an inner circumferential side (the direction of an arrow d).

As shown in <FIG>, the battery <NUM> includes an outer packaging can <NUM> having a bottomed cylindrical shape with an upper side thereof (the direction of the arrow a) being opened. The outer packaging can <NUM> has electrical conductivity, and a bottom wall <NUM> provided on the lower side (the direction of the arrow b) functions as a negative electrode terminal. A sealing body <NUM> is fixed to the opening of the outer packaging can <NUM>. The sealing body <NUM> includes a lid plate <NUM> and a positive electrode terminal <NUM>, and seals the outer packaging can <NUM>. The lid plate <NUM> is a disk-shaped member having electrical conductivity. A lid plate <NUM> and a ring-shaped insulating packing <NUM> surrounding the lid plate <NUM> are arranged in the opening of the outer packaging can <NUM>, and the insulating packing <NUM> is fixed to an opening edge <NUM> of the outer packaging can <NUM> by caulking the opening edge <NUM> of the outer packaging can <NUM>. In other words, the lid plate <NUM> and the insulating packing <NUM> cooperate with each other to airtightly close the opening of the outer packaging can <NUM>.

Here, the lid plate <NUM> includes a central through-hole <NUM> in the center thereof, and a rubber valve body <NUM> that blocks the central through-hole <NUM> is arranged on an outer surface which is a surface on the upper side of the lid plate <NUM>. Further, a metal positive electrode terminal <NUM> having a cylindrical shape with a flange is electrically connected onto the outer surface of the lid plate <NUM> so as to cover the valve body <NUM>. The positive electrode terminal <NUM> presses the valve body <NUM> against the lid plate <NUM>. The positive electrode terminal <NUM> is provided with a gas vent hole (not shown).

Normally, the central through-hole <NUM> is airtightly closed by the valve body <NUM>. On the other hand, if gas is generated in the outer packaging can <NUM> and the pressure of the gas increases, the valve body <NUM> is compressed by the pressure of the gas to open the central through-hole <NUM>, so that the gas is discharged from the inside of the outer packaging can <NUM> to the outside thereof through the center through-hole <NUM> and a gas vent hole (not shown) of the positive electrode terminal <NUM>. In other words, the central through-hole <NUM>, the valve body <NUM>, and the positive electrode terminal <NUM> form a safety valve for the battery <NUM>.

As shown in <FIG>, a spiral electrode group <NUM> (electrode group) is accommodated in the outer packaging can <NUM>. This spiral electrode group <NUM> is formed by laminating a belt-shaped positive electrode <NUM>, a belt-shaped negative electrode <NUM>, and a belt-shaped separator <NUM>, respectively. The spiral electrode group <NUM> is formed in a spiral shape with the separator <NUM> being interposed between the positive electrode <NUM> and the negative electrode <NUM>. In other words, the positive electrode <NUM> and the negative electrode <NUM> are laminated on each other in a radial direction via the separator <NUM>. The outermost circumferential side of the spiral electrode group <NUM> is formed by a part of the negative electrode <NUM>, and is in contact with a wall facing the inner circumferential side of the outer packaging can <NUM>. In other words, the negative electrode <NUM> and the outer packaging can <NUM> are electrically connected to each other.

A positive electrode lead <NUM> is arranged between an end portion on the upper side of the spiral electrode group <NUM> and the lid plate <NUM> in the outer packaging can <NUM>. Specifically, one end of the positive electrode lead <NUM> is connected to the positive electrode <NUM>, and the other end thereof is connected to the lid plate <NUM>. Therefore, the positive electrode terminal <NUM> and the positive electrode <NUM> are electrically connected to each other via the positive electrode lead <NUM> and the lid plate <NUM>. A circular upper insulating member <NUM> is arranged between the lid plate <NUM> and the spiral electrode group <NUM>, and the positive electrode lead <NUM> extends through a slit <NUM> provided in the upper insulating member <NUM>. Further, a circular lower insulating member <NUM> is also arranged between the spiral electrode group <NUM> and the bottom wall <NUM> of the outer packaging can <NUM>.

Further, a predetermined amount of alkaline electrolytic solution (not shown) is injected into the outer packaging can <NUM>. This alkaline electrolytic solution is impregnated in the spiral electrode group <NUM>, and induces an electrochemical reaction (charging/discharging reaction) during charging/discharging between the positive electrode <NUM> and the negative electrode <NUM>. It is preferable that an aqueous solution containing at least one kind of KOH, NaOH and LiOH as a solute is used as the alkaline electrolytic solution.

For example, a polyamide fiber nonwoven fabric to which a hydrophilic functional group is imparted, a polyolefin fiber nonwoven fabric of polyethylene, polypropylene or the like to which a hydrophilic functional group is imparted, or the like can be used as the material of the separator <NUM>. Specifically, it is preferable to use a nonwoven fabric made of a polyolefin fiber which has been subjected to a sulfonate treatment to be imparted with a sulfone group. Here, the sulfone group is imparted by treating the nonwoven fabric with an acid containing a sulfuric acid group such as sulfuric acid or fuming sulfuric acid. When the separator is subjected to the sulfonate treatment as described above, it not only imparts hydrophilicity, but also contributes to suppressing self-discharge of the battery.

The positive electrode <NUM> includes an electrically conductive positive electrode base material having a porous structure, and a positive electrode mixture held in pores of the positive electrode base material. For example, nickel-plated net-like, sponge-like or fibrous metal body, or foamed nickel (nickel foam) can be used as the positive electrode base material as described above. The positive electrode mixture includes positive electrode active material particles, an electrically conductive agent, a positive electrode additive and a binder.

The binder of the positive electrode mixture serves to bind the positive electrode active material particles, the electrically conductive agent, and the positive electrode additive, and at the same time, bind the positive electrode mixture to the positive electrode base material. Here, as the binder may be used, for example, carboxymethyl cellulose, methyl cellulose, PTFE (polytetrafluoroethylene) dispersion, HPC (hydroxypropyl cellulose) dispersion or the like. Further, a material which is appropriately selected as necessary in order to improve the characteristics of the positive electrode is added as the positive electrode additive. Main examples of the positive electrode additive include yttrium oxide, zinc oxide, cobalt hydroxide, and the like.

Nickel hydroxide particles which are generally used for nickel hydrogen secondary batteries are used as the positive electrode active material particles. It is preferable that higher-order nickel hydroxide particles are adopted as the nickel hydroxide particles. It is preferable that at least one kind of zinc, magnesium and cobalt is dissolved in these nickel hydroxide particles. The positive electrode active material particles as described above are manufactured by a manufacturing method which is generally used for nickel-metal hydride secondary batteries. Further, for example, one or more kinds selected from cobalt compounds such as cobalt oxide (CoO) and cobalt hydroxide (Co(OH)<NUM>) and cobalt (Co) may be used as the electrically conductive agent. This electrically conductive agent is added to the positive electrode mixture as needed, and it may be added to and contained in the positive electrode mixture in the form of powder or a coating covering the surface of the positive electrode active material.

The positive electrode <NUM> can be manufactured, for example, as follows. First, a positive electrode mixture slurry containing positive electrode active material powder comprising positive electrode active material particles, an electrically conductive agent, a positive electrode additive, water and a binder is prepared. The thus-obtained positive electrode mixture slurry is filled in, for example, a nickel foam, and dried. After drying, the nickel foam filled with nickel hydroxide particles and the like is rolled and then cut into a predetermined shape. As a result, the positive electrode <NUM> holding the positive electrode mixture is manufactured.

Next, the negative electrode <NUM> will be described. The negative electrode <NUM> includes a negative electrode core body formed of metal, and a negative electrode mixture layer carried on the negative electrode core body, and is formed to have a belt-shape as a whole. The negative electrode core body has electrical conductivity. The negative electrode core body is a belt-shaped metal material in which through-holes (not shown) are distributed, and for example, a punching metal sheet can be used. The negative electrode mixture layer is formed of a negative electrode mixture which is coated in the form of a layer on both sides (front surface and back surface) of the negative electrode core body. The negative electrode mixture is not only filled in the through-holes of the negative electrode core body, but also is carried in the form of a layer on the front and back surfaces of the negative electrode core body to form the negative electrode mixture layer. The negative electrode mixture includes particles of hydrogen storage alloy capable of storing and releasing hydrogen as a negative electrode active material, yttrium fluoride (hereinafter, also referred to as YF3), an electrically conductive agent, a binder, and a negative electrode auxiliary agent.

Here, the hydrogen storage alloy is an alloy capable of storing and releasing hydrogen which is a negative electrode active material. The hydrogen storage alloy in the hydrogen storage alloy particles is not particularly limited, and materials which are used for general nickel-metal hydride secondary batteries are preferably used as the hydrogen storage alloy. For example, the hydrogen storage alloy may be a rare earth-Mg-Ni-based hydrogen storage alloy containing a rare earth element, Mg, and Ni. According to the present invention, the particles of the hydrogen storage alloy are formed so that the volume average particle size (MV) thereof is equal to <NUM> or more and <NUM> or less. In the present specification, the volume average particle size (MV) of the particles of the hydrogen storage alloy is defined as follows. A particle size distribution of the particles of the hydrogen storage alloy is measured by a laser diffraction/scattering type particle size distribution measuring apparatus (machine name: SRA-<NUM>, MT-<NUM> manufactured by Microtrac company), and the volume average particle size (MV) means an average particle size which corresponds to <NUM>% in integration based on the volume.

The particles of yttrium fluoride are formed so that the average particle size is equal to <NUM> or more and <NUM> or less, preferably <NUM> or more and <NUM> or less. In the present specification, the average particle size of the particles of yttrium fluoride is defined as follows. A particle size distribution is measured by a laser diffraction/scattering type particle size distribution measuring apparatus (machine name: HRA manufactured by Microtrac company), and the average particle size means a particle size at which the cumulative frequency in all particles is equal to <NUM>% (D50).

The particles of hydrogen storage alloy and the particles of yttrium fluoride are obtained, for example, as follows. First, metal raw materials are measured in weight and mixed so as to have a predetermined composition, and an ingot made from this mixture by a predetermined production method is prepared. The obtained ingot is pulverized and sieved by using a classifier to obtain particles of hydrogen storage alloy and particles of yttrium fluoride having desired particle sizes.

Further, the binder of the negative electrode mixture servers to bind the particles of hydrogen storage alloy, the electrically conductive agent and the like to one another and at the same time bind the particles of hydrogen storage alloy, the electrically conductive agent and the like to the negative electrode core body. Here, the binder is not particularly limited, and for example, a binder which is generally used for nickel-metal hydride secondary batteries such as a hydrophilic or hydrophobic polymer or carboxymethyl cellulose may be used as the binder. Further, styrene-butadiene rubber, sodium polyacrylate, or the like may be used as the negative electrode auxiliary agent. An electrically conductive agent which is generally used for the negative electrodes of nickel-metal hydride secondary batteries is used as the electrically conductive agent. For example, carbon black or the like is used.

The negative electrode <NUM> can be manufactured, for example, as follows. First, hydrogen storage alloy powder which is aggregates of hydrogen storage alloy particles as described above, yttrium fluoride, an electrically conductive agent, a binder, and water are prepared. At this time, with respect to the hydrogen storage alloy powder and yttrium fluoride, metal raw materials are measured in weight and mixed so as to have a predetermined composition, an ingot made from this mixture by a predetermined production method is prepared, and the thus-obtained ingot is pulverized and sieved by using a classifier to obtain particles of hydrogen storage alloy and particles of yttrium fluoride having desired particle sizes. These materials are kneaded to prepare a paste of the negative electrode mixture. The thus-obtained paste is coated on the negative electrode core body, and dried. Thereafter, the resultant is subjected to rolling as a whole to increase the packing density of the hydrogen storage alloy and yttrium fluoride, and then cut into a predetermined shape to manufacture the negative electrode <NUM>.

The positive electrode <NUM> and the negative electrode <NUM> manufactured as described above are spirally wound with the separator <NUM> interposed therebetween to form a spiral electrode group <NUM>. The thus-obtained spiral electrode group <NUM> is accommodated in the outer packaging can <NUM>. Subsequently, a predetermined amount of alkaline electrolytic solution is injected into the outer packaging can <NUM>. Thereafter, the outer packaging can <NUM> in which the spiral electrode group <NUM> and the alkaline electrolytic solution are accommodated is sealed by the sealing body <NUM> having the positive electrode terminal <NUM>, thereby obtaining the battery <NUM> according to the embodiment. The battery <NUM> is subjected to an initial activation treatment to be ready for use.

Next, the actions and effects of the negative electrode <NUM> and the battery <NUM> of the embodiment will be described. As described above, according to the negative electrode <NUM> of the embodiment, the yttrium fluoride particles contained in the negative electrode mixture layer are formed so that the average particle size thereof is equal to <NUM> or more and <NUM> or less, preferably <NUM> or more and <NUM> or less. Therefore, when the negative electrode <NUM> is used for the battery <NUM>, the characteristics of the yttrium fluoride enhances the reactivity of the hydrogen storage alloy during low-temperature discharging, and suppresses corrosion of the hydrogen storage alloy by the alkaline electrolytic solution. Specifically, the characteristics of yttrium enhance the reactivity of the hydrogen storage alloy during low-temperature discharging, and the characteristics of fluorine suppresses the contact between the hydrogen storage alloy and the alkaline electrolytic solution, thereby suppressing the corrosion of the hydrogen storage alloy by the alkaline electrolytic solution. Further, since the average particle size of the yttrium fluoride particles is set to <NUM> or more and <NUM> or less, preferably <NUM> or more and <NUM> or less, the yttrium fluoride particles can be sufficiently dispersed (spotted) in the hydrogen storage alloy. Therefore, the reactivity of the hydrogen storage alloy during low-temperature discharging is further enhanced. Further, the corrosion of the hydrogen storage alloy by the alkaline electrolytic solution is more surely suppressed, and the consumption of the alkaline electrolytic solution caused by the corrosion of the hydrogen storage alloy is reduced, thereby improving the cycle life. In this way, it is possible to provide the negative electrode <NUM> for the nickel-metal hydride secondary battery <NUM> and the battery <NUM> that achieve both the improvement of the cycle life and the improvement of the low-temperature discharge characteristics.

Here, when the yttrium fluoride particles have an average particle size larger than the above-mentioned desired range, yttrium fluoride cannot be sufficiently dispersed into the hydrogen storage alloy. In other words, the distribution of yttrium fluoride is localized. Further, when the yttrium fluoride particles have an average particle size smaller than the above-mentioned desired range, the yttrium fluoride particles aggregate, so that it is impossible to sufficiently disperse yttrium fluoride into the hydrogen storage alloy. As described above, when the average particle size of the yttrium fluoride particles is outside the desired range, the reactivity of the hydrogen storage alloy during low-temperature discharging cannot be sufficiently enhanced, and the corrosion of the hydrogen storage alloy by the alkaline electrolytic solution cannot be sufficiently suppressed.

According to the negative electrode <NUM> of the embodiment, the particles of hydrogen storage alloy are formed so that the average particle size thereof is equal to <NUM> or more and <NUM> or less. Therefore, even when agglomeration of the yttrium fluoride particles occurs, it is considered that the agglomeration of the yttrium fluoride particles can be cracked by the particles of the hydrogen storage alloy. When aggregates of the yttrium fluoride particles can be cracked, the yttrium fluoride can be sufficiently dispersed (spotted) in the hydrogen storage alloy. As a result, the reactivity of the hydrogen storage alloy during low-temperature discharging is enhanced, and the corrosion of the hydrogen storage alloy by the alkaline electrolytic solution is suppressed. In this way, it is possible to provide the negative electrode <NUM> for the nickel-metal hydride secondary battery <NUM> and the battery <NUM> that achieve both the improvement of the cycle life and the improvement of the low-temperature discharge characteristics.

Here, when the particles of hydrogen storage alloy have an average particle size larger than a desired range (<NUM> to <NUM>), it is considered that the distance between the particles of hydrogen storage alloy increases, and thus the aggregates of the particles of yttrium fluoride cannot be cracked. Further, when the particles of hydrogen storage alloy have an average particle size smaller than the desired range (<NUM> to <NUM>), it is considered that the alloy particles aggregate, and thus behave as pseudo large particles due to the aggregation of the alloy particles, so that the aggregates of the yttrium fluoride cannot be cracked.

Aqueous sodium hydroxide solution was gradually added to a mixed aqueous solution of nickel sulfate, zinc sulfate, magnesium sulfate, and cobalt sulfate while stirring the mixed aqueous solution so as to contain <NUM>% by weight of zinc, <NUM>% by weight of magnesium and <NUM>% by weight of cobalt with respect to metallic nickel, thereby stabilizing the pH during the reaction to <NUM> to <NUM> and eluting nickel hydroxide. This eluted substance was washed <NUM> times with pure water whose amount was <NUM> times as large as the eluted substance, and then subjected to dehydration and drying steps to prepare a nickel hydroxide active material. Next, <NUM>% by weight of cobalt hydroxide, <NUM>% by weight of yttrium oxide, <NUM>% by weight of HPC dispersion liquid, and <NUM>% by weight of zinc oxide were mixed with the active material to prepare an active material slurry. This active material slurry was filled in foamed nickel, dried, rolled, and then cut at a predetermined size to prepare a positive electrode.

<NUM> parts by weight of sodium polyacrylate, <NUM> parts by weight of carboxymethyl cellulose (CMC), <NUM> parts by weight of dispersion of <NUM>% of solid content of styrene butadiene rubber (SBR), <NUM> parts by weight of Ketjen Black, <NUM> part by weight of YF3 powder having an average particle size = <NUM>, and <NUM> parts by weight of water were added to <NUM> parts by weight of powder of hydrogen storage alloy having an average particle size MV = <NUM>, and kneaded to prepare a paste of negative electrode mixture. With respect to the hydrogen storage alloy and YF3, an ingot manufactured by a predetermined manufacturing method was crushed and sieved by using a classifier to obtain particles of hydrogen storage alloy having a desired particle size (average particle size MV = <NUM>) and particles of YF3 (average particle size = <NUM>). This paste was uniformly coated on both sides of an iron perforated plate which had a nickel-plated surface and was used as a negative electrode core. After the paste was dried, the perforated plate to which the hydrogen storage alloy powder was attached, that is, the negative electrode core, was further rolled to increase the amount of alloy per volume and cut at a predetermined size to prepare a negative electrode.

The negative electrode and the positive electrode produced in the above steps were combined with each other, and wound together with the separator <NUM>, and a predetermined amount of an electrolytic solution including NaOH, KOH, and LiOH solutions was injected to prepare a nickel-metal hydride secondary battery having a nominal capacity of <NUM> mAh. Thereafter, this battery was charged at <NUM> A for <NUM> hours, and then repeatedly discharged five times at <NUM> A until the battery voltage became <NUM> V, thereby activating the battery.

A nickel-metal hydride secondary battery was manufactured in the same manner as the battery of Example <NUM> except that yttrium fluoride (YF3) having an average particle size of <NUM> was used.

A nickel-metal hydride secondary battery was manufactured in the same manner as the battery of Example <NUM> except that no yttrium fluoride (YF3) was added to the negative electrode mixture.

A cycle life evaluation was conducted on the battery manufactured in the above steps under a condition of "charging: 2A (ΔV = -10mV), pause: <NUM>, discharging: 2A (End V = <NUM>. 0V), pause: <NUM>". Note that ΔV = -<NUM> mV means charging under so-called -ΔV control (hereinafter, simply referred to as -ΔV charging) in which charging is terminated when a battery voltage reaches a maximum value and then drops by <NUM> mV from this maximum value. Charging and discharging under the above-mentioned condition were repeated, and a time point at which discharging was impossible or the discharge capacity decreased to less than <NUM>% of the discharge capacity in the first cycle was defined as the cycle life.

As shown in <FIG>, it is apparent that the cycle life is improved in Comparative Example <NUM> and Examples <NUM> to <NUM> as compared with Comparative Example <NUM>. However, it is also apparent that the cycle lives in Comparative Example <NUM> in which the average particle size of YF3 is equal to <NUM> and Example <NUM> in which the average particle size of YF3 is equal to <NUM> are reduced as compared with Example <NUM> in which the average particle size of YF3 is equal to <NUM> and Example <NUM> in which the average particle size of YF3 is equal to <NUM>. This is conceivably because the distribution of YF3 is localized in the negative electrode and YF3 is not sufficiently dispersed. As described above, in order to improve the cycle life, it can be seen that it is optimal to set the average particle size of YF3 to <NUM> or more and <NUM> or less.

A step of "charging: 2A (-ΔV charge), pause: <NUM> hour, discharging: 2A (End V = <NUM>. 0V), pause: <NUM> hour" was performed at three cycles on the battery manufactured in the above-mentioned steps under an environment of <NUM> to measure an initial capacity of the battery. Thereafter, a step of "charging: 2A (-ΔV charge; <NUM>), pause: <NUM> hours (-<NUM>), discharging: 2A (End V = <NUM>. 0V; -<NUM>), pause: <NUM> hour (<NUM>), discharging: 2A (<NUM>), charging: 2A (-ΔV charging; <NUM>), pause: <NUM> hours (<NUM>), discharging: 2A (End V = <NUM>. 0V; <NUM>)" was performed to measure the discharge capacity, and the ratio between the <NUM> discharge capacity and the -<NUM> discharge capacity was defined as a low-temperature discharge ratio.

Claim 1:
A negative electrode for nickel-metal hydride batteries, the negative electrode comprising:
a negative electrode core body formed of metal; and
a negative electrode mixture layer that contains at least a hydrogen storage alloy and yttrium fluoride and is carried on the negative electrode core body,
wherein particles of the yttrium fluoride are formed so that an average particle size (D50) thereof is equal to <NUM> or more and <NUM> or less, measured by a laser diffraction/scattering type particle size distribution measuring apparatus,
wherein particles of the hydrogen storage alloy are formed so that a volume average particle size (MV) thereof is equal to <NUM> or more and <NUM> or less, measured by a laser diffraction/scattering type particle size distribution measuring apparatus.