Hydrogen storage electrode

Abstract: A C15 type alloy hydrogen storage electrode is described which comprises a body of an alloy of the general formula Zr f V g Ni h M i , wherein f, g, h and i are atomic ratios of Zr, V, Ni and M and M is at least one element selected from Mg, Ca, Y, Hf, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Pd, Cu, Ag, Au, Zn, Cd, Al, Si, In, Sn, Bi, La, Ce, Pr, Nd, Th, Sm and Mm, wherein Mm is a mixture of rare earth elements.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to secondary cells or batteries and more particularly, to hydrogen storage electrodes using hydrogen storage alloys or their hydrides capable of reversibly storing or absorbing and releasing hydrogen. The hydrogen storage electrodes can be utilized in alkaline batteries which are unlikely to produce public nuisance and have high energy densities. Description of the Prior Art Currently, lead acid storage batteries and alkaline storage batteries have been widely used as secondary batteries. Among the alkaline storage batteries, nickel-cadmium batteries are most widely employed. However, the recent development of portable appliances demands a secondary battery or cell of a higher energy density substantially free of any ecological problems. Attempts have been made to use zinc as a negative electrode in place of cadmium. However, the cell using the zinc electrode has not been in wide use because of the problem of life cycle. Now, attention has been drawn to alkaline storage batteries using a hydrogen storage alloy capable of reversibly storing and releasing hydrogen as a negative electrode and a nickel oxide as a positive electrode. This battery may be called a nickel-hydrogen secondary battery. The hydrogen storage battery has a substantially dischargeable energy density higher than existing cadmium batteries and is free of any formation of dendrite as with Zn. In addition, the hydrogen storage battery can be fabricated by known methods. Accordingly, the hydrogen storage battery has been expected as a secondary battery which has a high energy density, long life cycle and low public nuisance. Known hydrogen storage alloys useful as the hydrogen storage electrode include, for example, Ti 2 Ni, TiNi, LaNi 5 , MnNi 5 , and CaNi 5 with or without other additive elements. These alloys are described, for example, in The Journal of Less-Common Metals 129 (1987), pp. 13-30 and 131(1987), pp.311-319. Moreover, United States Patent Nos. 4,551,400 and 4,716,088 describe improved alloys of the formula, Ti 2-x Zr x V 4-y Ni y , in which 0<x≤ 1.5 and 0.6≤ y≤ 3.5. Although Ti 2 Ni, TiNi and substituted alloys thereof have a relatively high dischargeable capacity in electrochemical charge and discharge cycles, a Ti-rich stable phase is formed after repetition of the charge and discharge cycles. This leads to a cycle life problem. On the other hand, LaNi 5 , MnNi 5 and substituted alloys thereof are low in hydrogen storage capacity, so that the discharge capacity is relatively small. Moreover, this type of alloy has further disadvantages in that a variation in performance is great relative to the variation in temperature, the alloy is expensive, and the purities of starting metals are not necessarily satisfactory. Secondary batteries using CaNi 5 and substituted alloys thereof exhibit a high discharge capacity at an initial stage of the charge and discharge cycle, but considerably lower in performance, similar to those using Ti 2 N and TiNi, after repetition of the charge and discharge cycle. The alloys of Ti 2-x Zr x V 4-x Ni y gradually convert into more stable hydrides and, thus, an effective alloy phase reduces in amounts with a problem of the cycle life. SUMMARY OF THE INVENTION It is an object of the present invention to provide a hydrogen storage electrode which is adapted for use in secondary batteries whereby the battery has a high discharge capacity with a long life cycle and involves little ecological problem. It is another object of the invention to provide a hydrogen storage electrode which is made of an alloy or its hydride whose alloy phase is substantially a Laves phase of an intermetallic compound. It is a further object of the invention to provide a hydrogen storage electrode made of an alloy which is capable of storing or releasing a greater amount of hydrogen than known alloys and rarely forms a stable hydride or oxide phase, so that it can maintain a high energy density over a long term when the hydrogen-storing and releasing cycle is repeated. It is a still further object of the invention to provide a method for making a hydrogen storage electrode of the type mentioned above. These objects are solved by a C15 and/or C14 type alloy hydrogen storage electrode as defined in claim 1. With the cubically symmetric MgCu 2 or C15 type structure, the crystal lattice constant, a, should be from 0.692 to 0.77 nm (6.92 to 7.70 angstroms). With the MgZn 2 or C14 type structure, the crystal lattice constants, a and c, should, respectively in the ranges of from 0.48 to 0.52 nm (4.8 to 5.2 angstroms) and from 0.79 to 0.83 nm (7.9 to 8.3 angstroms). With this and these ranges, a high discharge capacity is obtained. The hydrides of the specified alloys are similarly used. The hydrogen storage alloys or hydrides used in the present invention permit theoretically a larger number of hydrogen atoms per unit lattice than known alloys and can thus store or release a larger amount of hydrogen. This is advantageous in that when the storing and releasing cycle of hydrogen is repeated, more stable hydride and oxide phases are unlikely to form. Accordingly, a hydrogen storage electrode using the hydrogen storage alloy maintains a high energy density over a long term. A method of fabricating the hydrogen storage alloy or hydride electrode as described above includes a non-sintering or sintering process. The non-sintering process comprises providing pieces or powder of the alloy or hydride, mixing the powder with a resin binder dissolved in a solvent anda conductive agent to obtain a dispersion or paste, applying the dispersion to a conductive core material, and drying the applied dispersion in a vacuum to obtain an electrode. Preferably, the conductive core material is a porous metal body, such as of Ni, having an average pore size of from 100 to 150 micrometers and a density of from 700 to 800 mg/cm 3 and is applied with the dispersion at a packing rate of 4.5 to 5.0 g/cm 3 in the dry basis. Alternatively, the sintering process may be used in which the powder of the alloy or hydride is mixed with a resin binder dissolved in a solvent and a sintering aid. The dispersion is applied to a conductive core material such a punching metal, dried in vacuum and press molded along with the conductive core material. The resultant molding is sintered in vacuum at a temperature of from 700 to 1200°C, during which the resin binder is thermally decomposed at approximately 400°C. BRIEF DESCRIPTION OF THE DRAWINGS Figs. 1A and 1B are, respectively, X-ray refraction patterns of hydrogen storage alloys of C15-type and C14-type Laves phases, respectively; Fig. 2 is a curve of a relative discharge capacity in relation to the variation in crystal lattice constant; Fig. 3 is a graphical representation of a discharge capacity in relation to the variation in charge and discharge cycle for different hydrogen storage electrodes using alloys according to reference samples ; Fig. 4 is a graphical representation of a discharge capacity in relation to the variation in charge and discharge cycle for different hydrogen storage electrodes obtained according to embodiments of the invention; Fig. 5 is a schematic perspective view, in section, of a sealed cell using hydrogen storage electrodes of the invention. DETAILED DESCRIPTION AND EMBODIMENTS OF THE INVENTION The structures (see the definition of the C14- and C15 structures according to the "Strukturberichte" - classification) are mainly dependent upon the types of constituent elements and also on the manner or conditions of preparation of the alloys. In the practice of the invention, the alloys having structures other than the C14 and/or C15 type structure will not be effective as a hydrogen storage electrode. Moreover, it has been experimentally confirmed that the crystal lattice constants a and b of the C14 type structure should, respectively, values of from 0.48 to 0.52 nm (4.8 to 5.2 angstroms) and from 0.79 to 0.83 nm (7.9 to 8.3 angstroms). With the C15 type structure, the crystal lattice constant, a, should be in the range of from 0.692 to 0.77 nm (6.92 to 7.70 angstroms). Within this or these ranges of the constants, good discharge capacity and charged or discharged ampere-hour characteristics are obtained. The hydrogen storage alloys having the Laves phase having appropriate lattice constant or constants have theoretically greater capability of occupying hydrogen atoms per unit lattice than known alloys. This allows a greater amount of either storing or releasing hydrogen. In addition, the alloys rarely form stable, not reversible, hydride or oxide phases when a storing and releasing cycle of hydrogen is repeated. This is why the electrode using the alloy of the invention can maintain a high energy density over a long term. Through a number of experiments of alloys as defined in the formula indicated above, it has been found that when the alloy has the C14 type Laves phase or the C15 type Laves phase, such an alloy is effective as a hydrogen storage electrode provided that the crystal lattice constant or constants are in the defined range or ranges. The cubically symmetric C15 type Laves phase alloy has a MgCu 2 type crystal structure. The performance of the C15-type alloy as a hydrogen storage material is greatly influenced by the crystal lattice constant as stated above. However, when an alloy having good characteristics in a hydrogen gas phase is used as a hydrogen storage electrode, good results cannot always be obtained. This is because the electrochemical stability of the alloy in an alkaline electrolytic solution is important. It is general that alloys having a satisfactorily high charged and discharged ampere-hour characteristic are small in discharged ampere-hour. We have found that specific alloy compositions of the C14 type structure and the C15 type structure in which the crystal lattice constant or constants are within a certain range or ranges as set forth before are only useful as a hydrogen storage electrode. The crystal structure is dependent greatly on the combination of elements used although the manner and conditions of preparation including a cooling speed, an annealing temperature and the like will, more or less, influence the formation of the structure. Other alloy phases such as of the types C11b, C12, C16 and C 23 are outside the scope of the invention. Typical examples of binary alloys having the C14 type structure are ZrMn 2 , TiMn 2 , ZnCr 2 and the like, and those having the C15 type structure are TiCr 2 , ZrCo 2 , ZrMo 2 and the like. These type structures will develop when an alloy melt is cooled relatively slowly. If the melt is quenched, crystallization may not occur, or other phases may appear predominantly. The crystal structure of the alloys is readily confirmed, for example, through X-ray diffraction analysis. Typical X-ray , diffraction patterns of the C15-type Laves phase, as exemplified by the reference sample ZrMn 0.6 Cr 0.2 Ni 1.2 , and the C14-type Laves phase, as exemplified by the reference sample ZrMn 0.6 Cr 0.2 Al 0.2 Ni 1.0 , are shown in Figs. 1A and 1B, respectively. The numerals in the figures, e.g. (311), indicate Miller Indices. The formation of the C15-type Laves phase will be seen from the existence of peaks corresponding to the Miller indices (222), (311) and (220) in Fig. 1A. Likewise, the peaks corresponding to the Miller indices (004), (201), (112), (103) and (110) ensure the formation of the C14-type Laves phase. In this manner, the crystal structure of prepared alloys can be readily confirmed through the X-ray diffraction analysis. The existence of other peaks will show the development of other phases. As stated above, the formation of the C14 type and/or C15 type Laves phase depends mainly upon the combination of elements, and also upon the manner or conditions of preparation of alloy. In some cases, the C14 and C15 structures appear in one alloy, and such an alloy is usable in the practice of the invention. It is not necessary that alloys of the invention be completely composed of the C14 and/or C15-type phase structure, but other phases may be contained only in small amounts, e.g. up to 10% of the total phases. The claimed, specific Zr alloys have advantages in view of the fact that Zr is likely to form homogeneous alloys which are longer in cycle life and higher in capacity when applied as a negative electrode for hydrogen storage battery. The claimed alloy has the general formula, Zr f V g Ni h M i , in which f, g, h and i are atomic ratios of Zr, V, Ni and M and are f = 0.5 to 1.5, g = 0.01 to 1.2, h = 0.4 to 2.5 and i = 0.01 to 1.8 provided that g + h + i = 1.2 to 3.7 and (g + h + i)/f = 1.0 to 2.5, and M is at least one element selected from Mg, Ca, Y, Hf, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Pd, Cu, Ag, Au, Zn, Cd, Al, Si, In, Sn, Bi, La, Ce, Mm, Pr, Nd, Th and Sm. When the content of V is smaller than 0.01 or larger than 1.2, the discharge capacity becomes small. Similarly, when the content of M is smaller than 0.01 or larger than 1.8, the resultant alloy exhibits a small discharge capacity when applied as a hydrogen storage electrode. Moreover, when the content of Zr is smaller than 0.5, a charge capacity becomes insufficient. Over 1.5, the discharge capacity becomes small. When the nickel content is smaller than 0.4, the cycle life is shortened, whereas over 2.5, the charge capacity becomes small. If the total of (g+h+i) is smaller than 1.2, the resultant alloy is small in discharge capacity. Over 3.7, the charge capacity becomes smaller. When (g+h+i)/f is outside the range of 1.0 to 2.5, the discharge capacity becomes small. Zr and V take part in a charged ampere-hour characteristic. Larger contents of Zr and V lead to a larger charged ampere-hour characteristic but such elements are liable to from a stable hydride, resulting in a smaller discharge rate. The effect of Ni is as discussed in the afore-described classes. The content of M influences a charge and discharge cycle characteristic and a charge potential. A larger content of M can more improve these characteristics, but results in a more reduced charged ampere-hour characteristic. In view of the discharged ampere-hour characteristic, it is preferred that the contents of V and M are, respectively, from 0.2 to 0.7 and 0.2 to 0.8. For the preparation of the hydrogen storage alloys used in accordance with the present invention, commercially available metal pieces of a granular or plate form are provided and weighed in predetermined amounts, and these pieces are melted by argon arc melting or high frequency induction heating in vacuum or an inert gas such as argon. In order to improve the homogeneity and crystallinity of the alloy, once prepared alloys are preferably thermally treated at temperatures lower than a melting point of the alloy in vacuum, an inert gas or air. The treating temperatures below the melting point should preferably be higher than 900°C, although varying depending upon the type of alloy, for ensuring the effect of the thermal treatment. The alloys indicated with reference to Figs. 1A and 1B are thermally treated at 1080°C. The thermal treatment is generally effected for a time of at least one hour. When Fe and V are used in combination to make a hydrogen storage alloy, these elements may be separately added as pieces. It is preferred that ferrovanadium is used as a starting material for Fe and V. This is because when ferrovanadium is used, the resultant alloy has very good homogeneity irrespective of other elements and is better than an alloy using Fe and V as separate pieces with respect to the performance as a negative electrode for alkaline battery. In addition, cost reduction is great. For the fabrication of a hydrogen storage electrode using the hydrogen storage alloys, it is usual to first divide the alloy into pieces having, for example, a size of from 150 to 500 U.S. mesh. The alloy can be divided into pieces by known techniques using the Ellis motor, a jaw crusher, an automatic mortar by a wet process. In general, binary Zr-Ni alloys are relatively difficult to pulverize, but ternary or quaternary alloys are more likely to pulverize. In a sintering process, the pieces are subsequently mixed with from 2 to 10 wt% of a sintering aid based on the weight of the alloy pieces. The sintering aid is a powder of nickel or carbonyl nickel. The mixture is dispersed in a solution of a binder resin to obtain a paste or dispersion. The dispersion is applied to a conductive core material, dried in vacuum and press molded. The press molding is finally sintered in vacuum at a temperature of from 700 to 1200°C for a time sufficient for the sintering, say, 1 hour or over. During the sintering, the resin binder is thermally decomposed at approximately 400°C. The resin binder may be hydrophilic or hydrophobic in nature and is, for example, polyethylene, polyvinyl alcohol, CMC, fluorine resins, synthetic rubbers such as styrene-butadiene rubber, thermoplastic elastomers such as tetrafluoroethylenehexafluoropropylene copolymers, and the like. On the other hand, the electrode may be fabricated by a non-sintering process in which the alloy pieces are mixed with a solution of a resin binder as used in the sintering process along with a conductive agent, to obtain a paste or dispersion. The paste is applied to a conductive core material of a porous structure having a pore size of from 100 to 150 micrometers and a density of from 700 to 800 mg/cm 3 at an appropriate packing rate, e.g. from 4.5 to 5.0 g/cm 3 on the dry basis. The packed paste is dried in vacuum to obtain an electrode. The drying temperature may be not lower than 80°C, preferably about 120°C. The conductive agent used in the non-sintering process may be metal pieces such as Cu, Ni and the like, carbonyl nickel powder, carbon, and the like. The agent is used in an amount of from 0.1 to 60 wt% of the alloy pieces. In both sintering and non-sintering processes, the resin binders are dissolved in suitable solvents including water, alcohols such as ethyl alcohol, glycols such as ethylene glycol, and other organic solvents. Preferably, aqueous solutions of CMC, polyvinyl alcohol and the like having several weight percent are used. The conductive core materials may be a metal mesh, a punching metal sheet, foamed metals, expanded metals, metallic fibers or felts, and the like as is ordinarily used for this purpose. For the sintering process, a punching metal or a metal mesh is preferably used. On the other hand, foamed or expanded metals, and metallic fibers or felts are preferred for the non-sintering process. The fabrication of the electrode from alloy pieces has been described above. The alloy pieces may be absorbed with hydrogen to form an electrochemically reversible hydride. The hydride is advantageous in preventing oxidation of the alloy. The electrochemically stable hydride is different from a non-reversible, stable hydride phase which might be present in the alloys of the invention in small amounts as a kind of solid solution. The use of a hydride as a starting material instead of a hydrogen storage alloy is also within the scope of the invention. It should be noted that when hydrogen storage alloys of the invention are absorbed with hydrogen, a stable hydride phase is invariably formed in the alloy in an amount of about 3 to 7 wt% of the alloy, but the alloys of the invention do not form a higher amount of the stable hydride during the charge-discharge cycle. The electrode may take any form such as a disk, an elongated strip, a sheet, a plate or the like. The present invention is more particularly described by way of examples and reference examples. Reference Example 1 Commercially available metal elements including Zr, Ti, Hf, Ta, Y, Ca, Mg, La, Ce, Mm (Misch metal), Nb, Nd, Sm, Mo, Al, Si, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Si, W and Cd were provided as starting elements and were weighed to give alloy compositions indicated in Table 1. The respective mixtures were molten in an argon arc melting furnace or in a high frequency induction heating furnace in vacuum or in an inert gas such as argon to obtain alloys indicated in Table 1. Part of the respective alloy samples were used for analyses of an alloy composition, crystal structure, crystal lattice constant and homogeneity. The other samples were, respectively, used for the measurement of an amount of stored hydrogen in a hydrogen gas (mainly by a P (pressure)-C (composition)-T (temperature) procedure) and also for evaluation of electrode performance by a single electrode test and a sealed cell test. The P-C-T measurement procedure was effected by placing a sample alloy in a stainless steel reaction container and maintained at a given temperature. The air in the container was evacuated, into which an H 2 gas was introduced to a predetermined level inherent to the sample alloy. The hydrogen gas gradually absorbed as H into the alloy and the absorbing reaction stopped upon arrival at a given equilibrium pressure. The PCT curve at the temperature could be obtained by plotting a logarithm of the variation in pressure as y-axis and the amount of H as x-axis. Part of the tested alloy samples is shown in Table 1 with respect to the alloy composition, crystal lattice constant and discharge capacity. The X-ray diffraction analysis of these alloys reveals that all the alloys indicated in Table 1 have the Laves phase of the C14 or C15 type. More particularly, the alloy Nos. 1 to 4 have the C15 type structure but the crystal lattice constant is smaller than 6.92 angstroms. The alloy Nos. 5 to 7 has a crystal lattice constant larger than 7.70 angstroms. In view of the above results, the crystal lattice constant should be in the range of from 6.92 to 7.70 angstroms. The alloy Nos. 8 to 32 were found to be better with respect to the amount of stored hydrogen when determined by the P-C-T measurement. The alloy Nos. 18 to 20, 25 and 31 are typical alloys containing Ni, and the alloy Nos. 8, 9 and 21 are typical alloys containing Mo. These alloy samples were subjected to a cell test to evaluate the performance as a negative electrode for alkaline storage battery. The test was effected as follows. Each alloy obtained by melting was pulverized to obtain particles having a size of 200 mesh or below (U.S. mesh). About 5 g of the alloy powder was sufficiently mixed with 0.5 g of a polyethylene powder as a binder and 2 g of a carbonyl nickel powder used as a conducting agent. The mixture was applied to a nickel mesh conductive core material having a wire diameter of 0.2 mm and a size of 16 mesh and pressed to obtain a plate. The plate was allowed to stand at 120°C for about 1 hour in vacuum to melt the polyethylene, followed by attachment of lead wires to obtain a hydrogen storage electrode. For evaluation of the electrode as a negative electrode for secondary cell, a sintered nickel electrode or plate which is used in a commercial nickel-cadmium battery was provided as a positive or counter electrode in such a way that the quantity of the positive electrode was in excess in electric capacity over that of the hydrogen storage alloy electrode. A polyamide non-woven fabric was used as a separator and a solution obtained by adding 20 g/liter of lithium hydroxide to a caustic soda aqueous solution having a specific gravity of 1.30 was used as an electrolyte. Subsequently, a charging and discharging cycle at a constant current was repeated at 20°C. The charged ampere-hour was 500 mA x 5 hours and the discharge was effected at 300 mA while cutting 0.8 volts or below. The discharge capacity is shown in Table 1. Fig. 2 shows the relationship between a relative discharge capacity and the crystal lattice constant, in which the relative discharge capacity is a value by percent relative to the maximum discharge capacity. In Fig. 3, there is shown a discharge capacity in relation to the variation in cycle number for the electrodes using the alloy sample Nos. 8,9,19 and 31 and the electrodes for comparison using LaNi 5 and Ti 2 Ni. The alloy sample Nos. 1 to 4 which have the C15 type Laves phase but have a crystal lattice constant not larger than 0.692 nm (6.92 angstroms) are small in discharge capacity. On the other hand, the alloys having a crystal lattice constant larger than 0.77 nm (7.70 angstrom) is also small in discharge capacity. This is because the former alloys have the capability of storing only a small amount of hydrogen during a charging process or cycle. The latter alloys have the capability of storing a large amount of hydrogen, but form a stable hydride during the charge and discharge cycle, so that hydrogen cannot be released readily. Thus, the discharge efficiency is small. From the practical point of view, it may be preferred that the discharge capacity of a cell is not less than approximately 250 mAh/g. This value is 75% or higher of the maximum discharge capacity of the electrodes using the alloys of the invention. As will becomes apparent from the cycle life characteristic of Fig. 3, the known electrodes using Ti 2 Ni and LaNi 5 deteriorate considerably. Example This example illustrates hydrogen storage alloys of the general formula, Zr f V g Ni h M i , in which f = 0.5 to 1.5, g = 0.01 to 1.2, h = 0.4 to 2.5, and i = 0.01 to 1.8 provided that g + h + i = 1.2 to 3.7 and (g + h + i)/f = 1.0 to 2.5, and M is at least one element selected from Mg, Ca, Y, Hf, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Pd, Cu, Ag, Au, Zn, Cd, Al, Si, In, Sn, Bi, La, Ce, Mm, Pr, Nd, Th and Sm. Substantially in the same manner as in the reference example, commercially available Zr, Ni, V, Mg, Ca, Hf, Nb, ta, Cr, Mo, W, Mn, Fe, Co, Pd, Cu, Ag, Au, Zn, Cd, Al, In, Sn, Bi, La, Ce, Mn, Pr, Nd, Th and Sm pieces were used to obtain alloys of the above general formula. The thus obtained alloys are shown in Table 2, in which the alloy Nos. 54 to 104, 109 and 110 are those of the invention and the alloy Nos. 105 to 108 are outside the scope of the invention with respect to the (g+h+i)/f ratio. In addition, the alloy No. 105 has a larger atomic ratio of V than the define value, and the alloy No. 106 is small atomic ratio of Zr. Likewise, the alloy No. 107 had a smaller atomic ratio of Ni and the alloy No. 108 has a larger atomic ratio of M. These alloys were, respectively, subjected to the evaluation test of the performance as a negative electrode of alkaline storage battery. The negative electrode was made by reducing each alloy obtained by an argon arc melting method into pieces having a size of 400 mesh or below, followed by repeating the procedure described in the foregoing examples. The alloys compositions and the discharged ampere-hour of an open system using each electrode at the 10th charge and discharge cycle are shown in Table 2 below. Moreover, the charge and discharge cycle life of several alloy electrodes is shown in Fig. 4. As will be apparent from the results of Table 2 and Fig. 4, the hydrogen storage alloy electrodes of the invention have a large discharge capacity with the good cycle life and initial discharge rise-up characteristic. It was also found that the rapid charge and discharge characteristic was good. Although not particularly shown, when the content of V is smaller than 0.01 or larger than 1.2, the resultant alloys exhibit a small discharge capacity. With the alloys in which the content of an additive element is smaller than 0.01 or larger than 1.8, the discharge capacity is small. Moreover, when the content of Zr is smaller than 0.5, the charge capacity is insufficient. Over 1.5, the discharge capacity is small. When the content of Ni is smaller than 0.4, the cycle life is not satisfactory. Over 2.5, the charge capacity is small. In addition, when the contents of V, Ni and M, i.e. g+h+i, is smaller than 1.2, the resultant alloys has a small discharge capacity. Over 3.7, the charge capacity is small. More particularly, the contents of Zr and V have the relation with the charged ampere-hour, in which larger contents of Zr and V result in a larger charged ampere-hour but lead to a greater tendency toward the formation of a stable hydride, thus leading to a smaller discharge rate. The effect of Ni in this type of alloy is similar to those alloys described in the foregoing examples. The content of the additive element, M, is considered to take part in the charge and discharge cycle characteristic and the discharge potential. A larger content of M results in a more improved charge and discharge cycle characteristic and discharge potential, with a decrease of a charged ampere-hour. Judging the above as a whole, the ratio of the contents of V+Ni+M to the content of Zr should be in the range of from 1.0 to 2.5. The results of the table reveal that preferred ranges of V and an additive element are, respectively, from 0.2 to 0.7 and 0.2 to 0.8. Within these ranges, the discharged ampere-hour is over 280 mAh/g. In addition, a high capacity and a long cycle life are ensured with good economy. For the preparation of the alloy Nos. 60 to 63, and Nos. 99 and 110 of the Table 2, starting materials for the hydrogen storage alloys were ferrovanadium. The use of the ferrovanadium was found to be better with respect to the homogeneity of the resultant alloy than the use of separate Fe and V elements, and contributed to a simpler fabrication process with remarkably reduced production costs. Fig. 11 shows a schematic view of the secondary cell of the cylindrical form which includes a hydrogen storage alloy negative electrode 1, a nickel positive electrode 2 and a separator 3 provided between the electrodes 1 and 2. Indicated by 4 is a case serving also as a terminal for the negative electrode, by 5 and 6 are insulator plates, and by 7 is a safety valve. Indicated by 8 is a terminal for the positive electrode, by 9 is a positive lead, by 10 is a sealing plate, and by 11 is an insulating gasket.

Claims: A C15 and/or C14 type alloy hydrogen storage electrode which comprises a body of an alloy of the general formula, Zr f V g Ni h M i , wherein f, g, h and i are atomic ratios of Zr, V, Ni and M and are f = 0.5 to 1.5, g = 0.01 to 1.2, h = 0.4 to 2.5 and i = 0.01 to 1.8 provided that g + h + i = 1.2 to 3.7 and (g + h + i)/f = 1.0 to 2.5 and M is at least one element selected from Mg, Ca, Y, Hf, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Pd, Cu, Ag, Au, Zn, Cd, Al, Si, In, Sn, Bi, La, Ce, Pr, Nd, Th, Sm and Mm, wherein Mm is a mixture of rare earth elements. The C15 type alloy hydrogen storage electrode according to Claim 1, wherein said alloy contains at least Fe and/or Mn as M and g = 0.2 to 0.7, and i = 0.2 to 0.8.

Inventors: GAMO TAKAHARU, IWAKI TSUTOMU, MORIWAKI YOSHIO, GAMO, TAKAHARU, IWAKI, TSUTOMU, MORIWAKI, YOSHIO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1988
Main classification: H01M4
IPC codes: C01B3, H01M4