CN111471894B - Doped A5B19 type samarium-containing hydrogen storage alloy, battery and preparation method - Google Patents
Doped A5B19 type samarium-containing hydrogen storage alloy, battery and preparation method Download PDFInfo
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Abstract
The invention discloses a doped A5B19A samarium-containing hydrogen storage alloy, a battery and a preparation method thereof. The chemical composition of the hydrogen storage alloy is REaSmbNicMnxAlyMzZruTiv(ii) a a. b, c, x, y, z, u and v represent the atomic ratios of RE, Sm, Ni, Mn, Al, M, Zr and Ti, respectively; RE is one or more of rare earth metal elements, but not Sm; m is selected from one or more of Fe, Sn, Cr, Zn, V, W, Cu, Mo and Si elements; the hydrogen storage alloy does not contain Mg; a is>0，b>0.1，a+b＝3；13>c+x+y+z≥11，4≥x+y>0，3≥z≥0，3≥u+v>0. The hydrogen storage alloy of the present invention has excellent electrochemical activation performance and maximum discharge capacity.
Description
Technical Field
The invention relates to a doped A5B19A samarium-containing hydrogen storage alloy, a battery and a preparation method thereof.
Background
The rare earth hydrogen storage alloy is used as an important energy storage and conversion material, reacts with hydrogen to generate metal hydride, can absorb and discharge a large amount of hydrogen under the conditions of specific temperature and pressure, has quick hydrogen absorption/discharge reaction and excellent reversibility, and can realize large-scale development and utilization of hydrogen energy. The rare earth hydrogen storage alloy has excellent electrochemical performance, and is widely applied to the fields of new energy automobiles, communication base station reserve power supplies, portable electric tools and the like.
AB3-3.8The La-Mg-Ni rare earth hydrogen storage alloy has higher electrochemical capacity (about 380mAh/g), but the melting point of metal Mg in the composition is lower, the saturated vapor pressure is higher, so that the alloy is extremely easy to volatilize and generate dust explosion during metallurgical smelting, great potential safety hazard is brought to the preparation of the alloy, and great difficulty is brought to the control of the content and the phase composition of Mg and the consistency of the performance of an electrode and a battery.
CN101376941A discloses a hydrogen storage alloy with the component formula of LaaM(1-a)NixCuyFezCouMnvAlwThe composition represented by (1), wherein M represents at least two of rare earth metals except lanthanum, and a, x, y, z, u, v and w are the mole fractions of La, Ni, Cu, Fe, Co, Mn and Al, respectively; a is more than or equal to 0.5 and less than or equal to 0.8, x is more than or equal to 2.6 and less than or equal to 3.2, y is more than or equal to 0.5 and less than or equal to 0.9, z is more than or equal to 0.1 and less than or equal to 0.2, u is more than or equal to 0.05 and less than or equal to 0.1, v is more than or equal to 0.4 and less than or equal to 0.6, w is more than or equal to 0.2 and less than or equal to 0.4, and x + y + is more than or equal to 4.8 and less than or equal toz + u + v + w is less than or equal to 5.3. The hydrogen storage alloy has poor maximum discharge capacity and long activation period.
CN108172807A discloses a multi-element single-phase A5B19The chemical composition of the superlattice hydrogen storage alloy electrode material is La1-a-b-c-d-ePraNdbSmcGddMgeNik-x-y-zCoxAlyMnzWherein a, b, c, d, e, k, x, y and z represent molar ratios, and the numerical ranges are: a is more than or equal to 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.15, c is more than or equal to 0 and less than or equal to 0.20, d is more than or equal to 0 and less than or equal to 0.05, e is more than or equal to 0.16 and less than or equal to 0.30, k is more than or equal to 3.65 and less than or equal to 3.80, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0.05 and less than or equal to 0.20, and z is more than or equal to 0 and less than or equal to 0.20. The hydrogen storage alloy electrode material contains metal element Mg, so that the electrochemical performance is improved, but the service life of the hydrogen storage alloy is shorter; and the preparation cost is increased in the metal smelting process, so that the method has great potential safety hazard.
CN108048693A discloses a5B19The hydrogen storage alloy has a chemical composition of La0.6Sm0.2Mg0.2Ni3.6- xCoxAlyWherein x and y represent a molar ratio, x is 0, 0.3, 1 or 1.5; y is 0 or 0.2. The hydrogen storage alloy contains metal element Mg, improves the maximum discharge capacity, but has low capacity of 100 th cycle and electrochemical activation performance. CN104513925B discloses a 2H type A5B19A hydrogen-absorbing alloy electrode material having a chemical composition of LaxMyMgzNirWherein x, y, z and r are each atomic ratio, and x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, z is more than or equal to 0.1 and less than or equal to 0.20, and r is more than or equal to 3.70 and less than or equal to 3.85; and M is one of rare earth elements Pr, Nd, Sm or Gd. The hydrogen storage alloy electrode material contains a metal element Mg.
Disclosure of Invention
The inventors of the present application have conducted intensive studies in order to overcome the drawbacks of the prior art. It is an object of the present invention to provide a doped A5B19Hydrogen storage alloy having excellent electrochemical activation performance and maximum discharge capacity; further, the hydrogen storage alloy has a long service life.Another object of the present invention is to provide a method for producing the above hydrogen occluding alloy. It is a further object of the present invention to provide a battery. The invention adopts the following technical scheme to achieve the purpose.
In one aspect, the invention provides a doped A5B19A samarium-containing hydrogen storage alloy of the type having the following chemical composition:
REaSmbNicMnxAlyMzZruTiv
wherein a, b, c, x, y, z, u and v represent mole fractions of RE, Sm, Ni, Mn, Al, M, Zr and Ti, respectively;
wherein RE is one or more of rare earth metal elements but is not Sm; m is selected from one or more of Fe, Sn, Cr, Zn, V, W, Cu, Mo and Si elements; the hydrogen storage alloy does not contain Mg;
wherein a >0, b >0.1, a + b ═ 3; 13> c + x + y + z is more than or equal to 11, 4 is more than or equal to x + y >0, 3 is more than or equal to z is more than or equal to 0, and 3 is more than or equal to u + v >0.
According to the samarium-containing hydrogen storage alloy of the present invention, preferably, 12.8> c + x + y + z + u + v.gtoreq.11.8.
According to the samarium-containing hydrogen occluding alloy of the present invention, preferably, 11.9> c.gtoreq.10.3.
According to the samarium-containing hydrogen storage alloy of the present invention, preferably, the doped samarium-containing hydrogen storage alloy of the A5B19 type does not contain Co; RE is one or more selected from Y, Gd, Pr, Nd, La, Ce and Sc; m is selected from one or more of Fe, V and Cu elements.
According to the samarium-containing hydrogen storage alloy of the present invention, preferably, 2.5. gtoreq.b/a. gtoreq.1.4; and the RE contains La, wherein La is 50-100 mol% of the total mole number of RE.
According to the samarium-containing hydrogen occluding alloy of the present invention, it is preferable that 12.8> c + x + y + z + u + v.gtoreq.11.8, 1.5. gtoreq.x + y >0.8, 0.5. gtoreq.z.gtoreq.0.
According to the samarium-containing hydrogen occluding alloy of the present invention, preferably, 0.8. gtoreq.u + v > 0.3.
The samarium-containing hydrogen storage alloy according to the present invention preferably has a chemical composition represented by one of the following formulae:
LaSm2Ni10.6Mn0.5Al0.3Zr0.5Ti0.3，
LaSm2Ni11.7Mn0.5Al0.3Zr0.5Ti0.3，
LaSm2Ni10.6Al0.8Zr0.5Ti0.3，
La0.5Ce0.5Sm2Ni10.6Mn0.5Al0.3Zr0.5Ti0.3，
La0.8Ce0.2Sm2Ni10.4Mn0.5Al0.5Zr0.5Ti0.3，
La0.7Ce0.3Sm2Ni10.3Mn0.5Al0.3Fe0.3Ti0.3。
on the other hand, the invention provides a preparation method of the samarium-containing hydrogen storage alloy, which comprises the following steps:
(1) chemical composition such as REaSmbNicMnxAlyMzZruTivPlacing the raw materials in a vacuum smelting furnace, vacuumizing until the vacuum degree is below 20Pa, filling inert gas until the relative vacuum degree is-0.01-0.1 MPa, and smelting at 1300-1500 ℃ to obtain a smelting product;
(2) and forming the smelted product into solid alloy, and carrying out heat treatment for 10-48 h at the relative vacuum degree of-0.1-0.005 MPa and the temperature of 850-1050 ℃ to obtain the samarium-containing hydrogen storage alloy.
In yet another aspect, the invention provides a battery comprising a samarium-containing hydrogen storage alloy as described above.
Doped A of the invention5B19The hydrogen storage alloy contains samarium as a rare earth metal element and at least one other rare earth metal element, and is doped with zirconium and/or titanium, so that the maximum discharge capacity of the hydrogen storage alloy is improved, and the electrochemical activation performance is improved. Furthermore, the service life of the hydrogen storage alloy can be prolonged by selecting the type of the RE element and adjusting the proportion of the elements.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In the present invention, the absolute vacuum degree indicates the actual pressure in the container. The relative vacuum represents the difference between the vessel pressure and 1 standard atmosphere. The inert gas includes nitrogen or argon, etc.
< Hydrogen occluding alloy >
Doped A of the invention5B19The samarium-containing hydrogen storage alloy has the following chemical composition:
REaSmbNicMnxAlyMzZruTiv。
RE in the present invention is selected from one or more of rare earth metal elements, but not Sm. Specifically, RE is selected from one or more of Pm, Eu, Ho, Pr, Nd, Gd, La, Ce, Tb, Dy, Er, Tm, Yb, Y, Lu and Sc elements. Preferably, RE is selected from one or more of Y, Gd, Pr, Nd, La, Ce and Sc elements. More preferably, RE contains La. In some embodiments of the present invention, RE contains La, and La is 50 to 100 mol% of the total moles of RE. In still other embodiments of the present invention, RE is La and Ce; and La accounts for 50-80 mol% of the total mole number of RE. a represents the mole fraction of the rare earth element RE, a > 0; preferably, 1.5> a > 0.5; more preferably, 1.2. gtoreq.a.gtoreq.0.8.
b represents the mole fraction of the rare earth metal element Sm. b > 0.1; preferably, 3> b > 1; more preferably, 2.5. gtoreq.b.gtoreq.1.5. In certain embodiments, 2.5. gtoreq.b/a. gtoreq.1.4. In other embodiments, b/a is 2. The amount of Sm and the ratio of Sm to RE in the hydrogen storage alloy are controlled in a proper range, so that the maximum discharge capacity of the hydrogen storage alloy can be improved, and other electrochemical properties of the hydrogen storage alloy can be improved. The ratio of Sm to RE is controlled in the range of the invention, which can obviously improve the electrochemical activation performance of the hydrogen storage alloy and prolong the service life of the hydrogen storage alloy.
According to one embodiment of the present invention, a + b is 3. According to another embodiment of the present invention, 2.5. gtoreq.b/a. gtoreq.1.4; and the RE contains La, wherein La is 50-100 mol% of the total mole number of RE. According to yet another embodiment of the present invention, a is 1 and b is 2. By controlling RE and Sm within the above range, the maximum discharge capacity and other electrochemical properties of the hydrogen storage alloy cell can be further improved.
c represents the mole fraction of the metal element Ni. In the invention, 12.5> c is more than or equal to 10; preferably, 11.9> c.gtoreq.10.3; more preferably, 11.0> c.gtoreq.10.5. By limiting the amount of Ni to the above range, the electrochemical activation performance of the hydrogen occluding alloy can be improved. When the Ni content is too high or too low, the electrochemical activation performance tends to be lowered.
x represents the mole fraction of the metal element Mn; y represents the mole fraction of the metallic element Al. 4 is more than or equal to x + y and is more than 0; preferably, 2 ≧ x + y ≧ 0.5; more preferably, 1.5. gtoreq.x + y. gtoreq.0.8. The invention controls the Mn and Al dosage in the above range, and can improve the electrochemical activation performance and discharge performance of the hydrogen storage alloy.
z represents a mole fraction of the metal element M. M is selected from one or more of Fe, Sn, Cr, Zn, V, W, Cu, Mo and Si elements; preferably, M is selected from one or more of Fe, V, W, Cu and Si; more preferably, M is selected from one or more of Fe, V and Cu elements. In the invention, z is more than or equal to 3 and more than or equal to 0; preferably, 1 ≧ z ≧ 0; more preferably, 0.5. gtoreq.z.gtoreq.0. According to one embodiment of the invention, 0.5. gtoreq.z.gtoreq.0 and M is selected from one or more of the elements Fe, V and Cu.
In the invention, 13> c + x + y + z is more than or equal to 11; preferably, 13> c + x + y + z ≧ 11.1; more preferably, 11.8> c + x + y + z ≧ 11.1. Controlling the use amounts of Ni, Mn, Al and M within the range can give consideration to the electrochemical activation performance, the maximum discharge capacity and the service life of the hydrogen storage alloy.
In the present invention, u represents the molar fraction of the metal element Zr; v represents the mole fraction of the metallic element Ti. 3 is more than or equal to u + v and is more than 0; preferably, 2. gtoreq.u + v. gtoreq.0.3; more preferably, 0.8. gtoreq.u + v. gtoreq.0.3. The invention controls the Zr and Ti dosage in the above range, which can improve the discharge performance of the hydrogen storage alloy.
According to one embodiment of the invention, 12.8> c + x + y + z + u + v ≧ 11.8; preferably, 1.5 ≧ x + y >0.8, 0.5 ≧ z ≧ 0; more preferably, 0.8 ≧ u + v > 0.3.
The hydrogen storage alloy of the present invention does not contain the metal element Mg. Preferably, the hydrogen storage alloy also does not contain the metallic element Co. More preferably, the hydrogen occluding alloy of the present invention does not contain additional components other than some inevitable impurities.
Specific examples of the hydrogen occluding alloy of the present invention include, but are not limited to, alloys represented by one of the following formulas:
LaSm2Ni10.6Mn0.5Al0.3Zr0.5Ti0.3，
LaSm2Ni11.7Mn0.5Al0.3Zr0.5Ti0.3，
LaSm2Ni10.6Al0.8Zr0.5Ti0.3，
La0.5Ce0.5Sm2Ni10.6Mn0.5Al0.3Zr0.5Ti0.3，
La0.8Ce0.2Sm2Ni10.4Mn0.5Al0.5Zr0.5Ti0.3，
La0.7Ce0.3Sm2Ni10.3Mn0.5Al0.3Fe0.3Ti0.3。
< preparation method >
The hydrogen occluding alloy of the present invention can be produced by various methods such as a mechanical alloying method, a powder sintering method, a high-temperature melting-gas atomization method, a reduction diffusion method, a displacement diffusion method, a combustion synthesis method, a self-propagating high-temperature synthesis method, a high-temperature melting casting method, a high-temperature melting-rapid quenching method, and a chemical method. Specifically, the method for producing a hydrogen occluding alloy of the present invention comprises: (1) smelting; and (2) a heat treatment step. As described in detail below.
In the smelting step, RE is formed according to the chemical compositionaSmbNicMnxAlyMzZruTivPreparing raw materials, then putting the raw materials into a vacuum smelting furnace, and smelting under a vacuum condition to obtain a smelting product. REaSmbNicMnxAlyMzZruTivThe specific components and formulations are as described above and will not be described in detail herein. The rare earth elements RE and Sm may be placed in the upper part of the vacuum melting furnace and the other metals in the bottom of the vacuum melting furnace.
After the raw materials are put in, the vacuum melting furnace may be subjected to a vacuum-pumping operation. Vacuumizing the vacuum melting furnace until the absolute vacuum degree is below 20 Pa; preferably, the vacuum melting furnace is vacuumized until the absolute vacuum degree is below 10 Pa; more preferably, the vacuum melting furnace is evacuated to an absolute vacuum degree of 5Pa or less. Then, filling inert gas into the vacuum smelting furnace until the relative vacuum degree is-0.01 to-0.1 MPa; preferably-0.02 to-0.08 MPa; more preferably-0.03 to-0.06 MPa. Then, a smelting operation is performed. The smelting temperature can be 1300-1500 ℃, preferably 1300-1450 ℃, and more preferably 1350-1450 ℃.
The smelt product is held at a constant temperature for a period of time. The whole smelting process needs about 10-60 min, preferably 15-50 min, and more preferably 15-20 min. Such smelting conditions are favorable for improving the service life of the hydrogen storage alloy and increasing the maximum discharge capacity.
In the heat treatment step, the molten product is formed into a solid alloy (alloy sheet or alloy ingot), and then subjected to heat treatment to obtain the hydrogen storage alloy. The smelted product can be formed into an alloy sheet through a quick quenching melt-spun strip. In certain embodiments, the smelted product is cast to a cooled copper roller and rapidly quenched and spun into an alloy sheet with the thickness of 0.1-0.4 mm. Preferably, the smelting product is cast to a cooling copper roller for quick quenching and casting to form an alloy sheet with the thickness of 0.2-0.4 mm. More preferably, the smelting product is cast to a cooling copper roller for quick quenching and throwing to form an alloy sheet with the thickness of 0.2-0.3 mm.
Further, the molten product may be cast to obtain an alloy ingot. In certain embodiments, the molten product is cast into an alloy ingot having a diameter of 10 to 25 mm. Preferably, the smelting product is cast into an alloy ingot with the diameter of 15-25 mm. More preferably, the smelting product is cast into an alloy ingot with the diameter of 15-20 mm.
According to a specific embodiment of the invention, the vacuum melting furnace is vacuumized until the absolute vacuum degree is less than or equal to 5 Pa; then argon is filled into the vacuum melting furnace until the relative vacuum degree is-0.03 to-0.06 MPa; heating the vacuum smelting furnace to 1350-1450 ℃ for smelting; stopping heating after the raw materials in the vacuum smelting furnace are completely melted, and keeping for a period of time at a constant temperature to obtain a smelting product; and finally, casting the smelting product to a cooling copper roller for quick quenching and casting to obtain an alloy sheet with the thickness of 0.2-0.3 mm.
The heat treatment of the present invention may be carried out at a relative vacuum degree of-0.1 to-0.005 MPa, preferably-0.08 to-0.01 MPa, more preferably-0.05 to-0.025 MPa. The temperature of the heat treatment can be 850-1050 ℃, preferably 850-950 ℃, and more preferably 800-900 ℃. The heat treatment time can be 10-48 h, preferably 12-40 h, and more preferably 24-36 h. In the present invention, the alloy sheet or the alloy ingot may be placed in a heat treatment furnace to be heat-treated.
According to a specific embodiment of the invention, the heat treatment furnace is vacuumized, and then argon is filled into the heat treatment furnace until the relative vacuum degree is-0.05 to-0.025 MPa; then heat treatment is carried out for 24-36 h at 800-900 ℃.
< Battery >
The battery of the present invention includes the above hydrogen storage alloy. The composition of the hydrogen storage alloy is REaSmbNicMnxAlyMzZruTivThe elements and their atoms are as described above and will not be described herein. Specifically, the battery includes a battery case that encloses a battery pack and an alkaline electrolyte. The battery may include a positive electrode, a negative electrode, and a separator. The positive electrode may be nickel hydroxide, preferably sintered Ni (OH) having an excess capacity2A NiOOH electrode; the diaphragm can be porous vinylon non-woven fabric, nylon non-woven fabric or polypropylene fiber membrane. The alkaline electrolyte can be KOH aqueous solution or KOH aqueous solution containing a small amount of LiOH; preferably 6 mol. L–1Aqueous KOH solution.
The negative electrode includes an active material having the above hydrogen storage alloy. The active material and the conductive agent form a negative electrode material, and the negative electrode material is supported on a negative electrode current collector to form a negative electrode. The negative electrode current collector may be metallic copper or nickel foam, preferably nickel foam. The mass ratio of the active substance to the conductive agent is 1: 3-8; preferably 1: 3-6; more preferably 1: 3-5. The hydrogen storage alloy is used in the form of powder, and the particle size of the hydrogen storage alloy can be 200-500 meshes, preferably 200-350 meshes, and more preferably 200-300 meshes. The conductive agent may be nickel carbonyl powder.
Comparative example 1 and examples 1 to 6
A doped samarium-containing hydrogen storage alloy of the A5B19 type was prepared according to the formulation of table 1 by the following steps:
(1) sequentially placing the raw materials into a vacuum smelting furnace from the bottom to the upper part of the vacuum smelting furnace, wherein the rare earth metal raw material is placed on the upper part, and other metal raw materials are placed on the bottom; then the vacuum melting furnace is vacuumized until the absolute vacuum degree is less than or equal to 5Pa, and argon is filled until the relative vacuum degree is-0.055 MPa; heating the vacuum smelting furnace to 1500 ℃, preserving heat for 3min after the raw materials in the vacuum smelting furnace are completely melted, and stopping heating to obtain a smelting product.
(2) Casting the smelted product to a cooling copper roller, and quickly quenching and throwing to obtain an alloy sheet with the thickness of 0.3 mm; and (3) placing the alloy sheet in a heat treatment furnace filled with argon, and carrying out heat treatment for 16h at the relative vacuum degree of-0.025 MPa and the temperature of 875 ℃ to obtain the doped A5B19 type samarium-containing hydrogen storage alloy.
Examples of the experiments
The hydrogen absorbing alloys of comparative example 1 and examples 1 to 6 were mechanically crushed into alloy powders of 200 mesh. Mixing the alloy powder and the conductive agent carbonyl nickel powder in a mass ratio of 1: 4, and preparing the mixture into an electrode slice with the diameter of 15mm under 11 MPa. The electrode plate is placed between two pieces of foamed nickel (negative current collectors), and a nickel strip (tab) is clamped at the same time, so that the hydrogen storage alloy negative electrode is prepared under 11 MPa. And the close contact between the electrode plate and the nickel screen is ensured by spot welding around the electrode plate.
In an open type three-electrode system for testing electrochemical performance, a negative electrode is a hydrogen storage alloy negative electrode, and a positive electrode is sintered Ni (OH) with excessive capacity2The reference electrode is Hg/HgO, electrolyteIs 6 mol. L-1Potassium hydroxide solution. The assembled battery was left to stand for 24h and electrochemical performance was measured by a constant current method using a LAND cell tester.
The test environment temperature was 303K. The charging current density is 60mA g-1The charging time is 7.5 h; discharge current density 60mA g-1The discharge cut-off potential was 0.5V, and the charge/discharge pause time was 15 min. The test results are shown in Table 1.
TABLE 1
As can be seen from the above table, the number of cycles N required for complete activation of the alloy electrodes of examples 1 to 6 is smaller than that of comparative example 1, indicating that the electrochemical activation performance is good. Capacity retention ratio S of alloy electrodes of examples 1 to 6 at 100 th cycle100Larger, indicating a longer cycle life. Maximum discharge capacity C of alloy electrodes of examples 1 to 6maxIs relatively large.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (9)
1. Doped A5B19The samarium-containing hydrogen storage alloy is characterized by comprising the following chemical compositions:
REaSmbNicMnxAlyMzZruTiv
wherein a, b, c, x, y, z, u and v represent mole fractions of RE, Sm, Ni, Mn, Al, M, Zr and Ti, respectively;
wherein RE is selected from one or more of La and Ce; m is selected from one or more of Fe, Sn, Cr, Zn, V, W, Cu, Mo and Si elements; the hydrogen storage alloy does not contain Mg;
wherein, a is more than or equal to 1.2 and more than or equal to 0.8, b is more than or equal to 2.5 and more than or equal to 1.5, and a + b is 3; 13> c + x + y + z is more than or equal to 11, 4 is more than or equal to x + y >0, 3 is more than or equal to z is more than or equal to 0, 3 is more than or equal to u + v >0, 2.5 is more than or equal to b/a is more than or equal to 1.4, and 11.0 is more than or equal to c is more than or equal to 10.5.
2. The samarium-containing hydrogen storage alloy of claim 1, further characterized by 12.8> c + x + y + z + u + v ≥ 11.8.
3. The samarium-containing hydrogen storage alloy of claim 1 wherein the samarium-containing hydrogen storage alloy is free of Co; m is selected from one or more of Fe, V and Cu elements.
4. The samarium-containing hydrogen storage alloy of claim 1, wherein RE comprises La in an amount of 50 to 100 mol% based on the total moles of RE.
5. The samarium-containing hydrogen storage alloy of claim 1, further characterized by 12.8> c + x + y + z + u + v ≥ 11.8, 1.5 ≥ x + y >0.8, 0.5 ≥ z ≥ 0.
6. A samarium-containing hydrogen storage alloy in accordance with claim 5 wherein 0.8. gtoreq.u + v > 0.3.
7. The samarium-containing hydrogen storage alloy of claim 1 having a chemical composition represented by one of the following formulae:
LaSm2Ni10.6Mn0.5Al0.3Zr0.5Ti0.3，
LaSm2Ni11.7Mn0.5Al0.3 Zr0.5Ti0.3，
LaSm2Ni10.6Al0.8 Zr0.5Ti0.3，
La0.5Ce0.5Sm2Ni10.6Mn0.5Al0.3 Zr0.5Ti0.3，
La0.8Ce0.2Sm2Ni10.4Mn0.5Al0.5 Zr0.5Ti0.3，
La0.7Ce0.3Sm2Ni10.3Mn0.5Al0.3Fe0.3Ti0.3。
8. the method of making a samarium-containing hydrogen storage alloy of any of claims 1 to 7 comprising the steps of:
(1) chemical composition such as REaSmbNicMnxAlyMzZruTivPlacing the raw materials in a vacuum smelting furnace, vacuumizing until the vacuum degree is below 20Pa, filling inert gas until the relative vacuum degree is-0.01-0.1 MPa, and smelting at 1300-1500 ℃ to obtain a smelting product;
(2) and forming the smelted product into solid alloy, and carrying out heat treatment for 10-48 h at the relative vacuum degree of-0.1-0.005 MPa and the temperature of 850-1050 ℃ to obtain the samarium-containing hydrogen storage alloy.
9. A battery comprising the samarium-containing hydrogen storage alloy of any of claims 1 to 7.
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