KR970060558A - Hydrogen storage alloy, surface modification method of this alloy, negative electrode and alkaline secondary battery of battery - Google Patents

Abstract

The present invention relates to a hydrogen storage alloy for absorbing and storing hydrogen, in particular, excellent in safety and mechanical grinding characteristics in the hydrogen storage alloy aqueous solution according to the present invention, containing an alloy represented by the following general formula (I) Characterized in that,

Mg ₂ M1 _y (I)

Wherein M1 is at least one element selected from Mg, an element exothermic with hydrogen, and an element not exothermic with hydrogen except Al and B: y is defined as 1y ≦ 1.5.

Description

Hydrogen storage alloy, surface modification method of this alloy, negative electrode and alkaline secondary battery of battery

Since this is an open matter, no full text was included.

6 is a block diagram illustrating an apparatus for evaluating hydrogen absorption and release capability of a temperature-scan method employed in an embodiment of the present invention.

Claims (82)

A hydrogen storage alloy, characterized by containing an alloy represented by the following general formula (I). Mg ₂ M1 _y (I) Wherein M1 is at least one element selected from Mg, an element exothermic to hydrogen, and an element not exothermic to hydrogen except Al and B; y is limited to 1y≤1.5. The hydrogen storage of claim 1, wherein M1 is selected from Mg, an element exothermic to hydrogen, and an element not capable of exothermic to hydrogen except Al and B and has an electronegativity greater than Mg. alloy. The hydrogen storage alloy of claim 2, wherein M 1 is at least one element selected from the group consisting of Ag, Cd, Mn, In, Fe, Ni, and Co. The hydrogen storage alloy according to claim 1, wherein y in the general formula (I) is in a range of 1.01 ≦ y ≦ 1.5. The hydrogen storage alloy according to claim 1, wherein y in the general formula (I) falls within a range of 1.02 ≦ y ≦ 1.5. The hydrogen storage alloy according to claim 1, wherein y in the general formula (I) is in a range of 1.05 ≦ y ≦ 1.5. The hydrogen storage alloy containing the alloy represented by following General formula (II). Mg _2-x M2 _x M1 _y (II) Wherein M2 is at least one element selected from the group consisting of elements, Al and B, which exothermic to hydrogen except Mg; M 1 is at least one element selected from elements that cannot cause exothermic reactions with hydrogen (except Mg and M 2); x is 0 <1,0; y is limited to 1≤y≤2.5. The method according to claim 7, wherein M1 is an element selected from among elements which cannot exothermicly react with hydrogen except for Mg and M2, and has a higher electronegativity than Mg, and 10 at% or less of pure magnesium is used. A hydrogen storage alloy, characterized by providing an alloy having a Mg _1-W M1 _W phase (0 <w ≦ 0.1) crystal lattice when less than the pure magnesium crystal lattice in volume. 8. The hydrogen storage alloy of claim 7, wherein M1 is at least one element selected from the group consisting of Ag, Cd, Mn, In, Fe, Ni and Co. 8. The hydrogen storage alloy according to claim 7, wherein M2 of the general formula (II) is an element exothermic with hydrogen except Mg, an element selected from Al and B and having an electronegativity greater than Mg. . 12. The hydrogen storage alloy of claim 10, wherein M2 is at least one element selected from the group consisting of B, Be, Y, Pd, Ti, Zr, Hf, Th, V, Nb, Ta, Pa, and Al. . 8. The method according to claim 7, wherein the general formula (II) is selected from elements which exothermicly react with Al, B, and hydrogen except for Mg, and when pure magnesium is used at 10at% or less, A hydrogen storage alloy, characterized by providing an alloy having a Mg _1-W M1 _W phase (0 <w ≦ 0.1) crystal lattice less than the crystal lattice of magnesium. 13. The hydrogen storage alloy according to claim 12, wherein M2 is at least one element selected from Li and Al. 8. The method according to claim 7, wherein M2 of the general formula (II) is selected from among elements that exothermicly react with Al, B and hydrogen except Mg, and when pure magnesium is used at 10at% or less, A hydrogen storage alloy, characterized by providing an alloy having a Mg _1-W M1 _W phase (0 <w ≦ 0.1) crystal lattice less than the crystal lattice of magnesium. 8. The hydrogen storage alloy according to claim 7, wherein x in the general formula (II) falls within a range of 0.01 ≦ x ≦ 1.0. 8. The hydrogen storage alloy according to claim 7, wherein y in the general formula (II) falls within a range of 1.01 ≤ y ≤ 2.5. 8. The hydrogen storage alloy according to claim 7, wherein y in the general formula (II) falls within a range of 1.02 ≦ y ≦ 2.5. 8. The hydrogen storage alloy according to claim 7, wherein y in the general formula (II) falls within a range of 1.05 ≦ y ≦ 2.5. A hydrogen storage alloy comprising an alloy represented by the following general formula (III). Mg _2-x M2 _x M1 _y (III) Wherein M is Be, Ca, Sr, Ba, Y, Ra, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ti, Ar, Hf, Pd and At least one element selected from Pt; M2 is at least one element selected from the group consisting of Al and B, an element exothermic with hydrogen (except M); M1 is at least one element selected from elements which are not capable of exothermic reaction with hydrogen (except Mg and M2); x is 0.01 <x≤1.0; y is limited to 0.5 <y≤1.5. 20. The hydrogen storage alloy of claim 19, wherein said M2 is selected from Al, Mn, Cr and V. 20. The hydrogen storage alloy according to claim 19, wherein M is Zr, M1 is Fe and M2 is Cr. 20. The hydrogen storage alloy according to claim 19, wherein M is Zr, M1 is Fe and M2 is V. 20. The hydrogen storage alloy according to claim 19, wherein x in the general formula (III) falls within a range of 0.05 ≦ x ≦ 0.5. 20. The hydrogen storage alloy according to claim 19, wherein y in the general formula (III) is in the range of 1≤y≤1.5. Treating the hydrogen storage alloy with an RX compound, wherein R represents alkyl, alkenyl, alkynyl, aryl or a group substituted therein; x is a halogen atom. Deformation method. The method for modifying the surface of a hydrogen storage alloy according to claim 25, wherein said hydrogen storage alloy contains an alloy represented by the following general formula (IV). Mg _2-x M2 _x M1 _y (Ⅳ) In the formula, M2 is at least one element selected from the group of elements, Al and B exothermic reaction with hydrogen except Mg; M1 is at least one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 0 ≦ x ≦ 1.0; y is limited to 0.5 <y≤2.5. The method for modifying the surface of a hydrogen storage alloy according to claim 25, wherein the alloy is an A ₂ B alloy, A is an element exothermic to hydrogen, and B is an element not exothermic to hydrogen. The method for modifying the surface of a hydrogen storage alloy according to claim 25, wherein the alloy is an AB ₅ alloy, A is an element exothermic to hydrogen, and B is an element not exothermic to hydrogen. 26. The method of claim 25, wherein said R-X compound reacts with said hydrogen storage alloy when there is an organic solvent. 30. The method of modifying a hydrogen storage alloy according to claim 29, wherein said organic solvent is tetrahydroperan. 30. The method of claim 29, wherein said organic solvent is diethyl ether. 30. The method of claim 29, wherein said R-X compound is dissolved in an organic solvent and a catalyst is added thereto. 33. The method of claim 32, wherein said catalyst is a concentrated polycyclic hydrocarbon. Cuk as a reflection source Characterized by the fact that the mid-border Δ (2θ) of at least one peak among the three maximum intensity peaks of the alloy obtained by X-ray diffraction when using a ray falls in the range of 0.2 ° ≤ △ (2θ) ≤50 ° Hydrogen storage alloy. 35. The hydrogen storage alloy according to claim 34, wherein said alloy contains Ni as one of the alloying elements. The hydrogen storage alloy according to claim 34, wherein said hydrogen storage alloy contains an alloy represented by the following general formula (IV). Mg _2-x M2 _x M1 _y (Ⅳ) In the formula, M2 is at least one element selected from the group of elements, Al and B exothermic reaction with hydrogen except Mg; M1 is one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 0 ≦ x ≦ 1.0; y is limited to 0.5 <y≤2.5. 35. The hydrogen storage of claim 34, wherein the mid-butterfly Δ (2θ ₂ ) of at least one peak among the three maximum intensity peak lines falls within a range of 0.3 ° ≤Δ (2θ ₂ ) ≤10 °. alloy. Contains more than 10% magnesium and Cuk as a radiation source When X-ray diffraction, the medium-butterfly Δ (2θ ₁ ) of the alloy in the X-ray diffraction falls within the range of 0.3 ° ≤ △ (2θ ₁ ) ≤10 ° or X-ray diffraction when the ray is used. Δ (2θ ₂ ) is in the range of 0.3 ° ≦ Δ (2θ ₂ ) ≦ 10 °. The hydrogen storage alloy according to claim 38, wherein the alloy is an A ₂ B alloy, A is an element exothermic to hydrogen, and B is an element not exothermic to hydrogen. The hydrogen storage alloy according to claim 38, wherein the hydrogen storage alloy contains an alloy represented by the following general formula (IV). Mg _2-x M2 _x M1 _y (Ⅳ) In the formula, M2 is at least one element selected from the group of elements, Al and B exothermic reaction with hydrogen except Mg; M1 is one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 0 ≦ x ≦ 1.0; y is limited to 0.5 <y≤2.5. A method of surface modification of a hydrogen storage alloy, comprising mechanically treating the hydrogen storage alloy under vacuum or an inert gas or hydrogen gas atmosphere. 42. The method of claim 41, wherein the hydrogen storage alloy comprises nickel as one of the component elements. 42. The surface modification of the hydrogen storage alloy as recited in claim 41, wherein the hydrogen storage alloy is an A ₂ B alloy, A is an element that exothermicly reacts with hydrogen, and B is an element that is not capable of exothermic heating with hydrogen. Way. 42. The method of claim 41, wherein the hydrogen storage alloy contains an alloy represented by the following general formula (IV). Mg _2-x M2 _x M1 _y (Ⅳ) At least one element selected from the group Al, B and an element exothermic to hydrogen except M2 in the formula; M1 is at least one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 0 ≦ x ≦ 1.0; y is limited to 0.5y ≦ 2.5. 42. The method for expressing a hydrogen storage alloy according to claim 41, wherein said hydrogen storage alloy contains an alloy represented by the following general formula (V). Mg _1-X M3 _X ) _20-y M4 (Ⅴ) Wherein M4 is Ni, Fe, Co, Cu, Zn; At least one element selected from Sn and Si; M3 is at least one element selected from the group of elements having a higher electronegativity than Mg except the elements of M4; x is 0 ≦ x ≦ 0.5; y is limited to 0y ≦ 18. 42. The method of claim 41, wherein the hydrogen storage alloy contains an alloy represented by the following general formula (VI). Mg _1-x M5 _x ) _20-y M5 (Ⅵ) Wherein M5 is at least one element having an atomic radius 1 to 1.5 times greater than the atomic radius of Mg (except for elements having a higher electronegativity than Mg); M 6 is Ni, Fe, Co, Cu, Zn; At least one element selected from Sn and Si; x is 0 ≦ x ≦ 0.5 y is limited to 0y ≦ 18. A negative electrode of a battery comprising a hydrogen storage alloy containing an alloy represented by the following general formula (I). Mg ₂ ML _y (Ⅰ) In the above formula, Ml is at least one element selected from Mg, an element exothermic with hydrogen, an element not exothermic with hydrogen except Al and B, and y is limited to 1y ≦ 1.5. 48. The negative electrode of claim 47, wherein Ml is Ni. An alkaline secondary battery comprising a negative electrode containing a minority storage alloy containing an alloy represented by the following general formula (I). Mg ₂ ML _Y (Ⅰ) In the above formula, Ml is at least one element selected from Mg, an element exothermic with hydrogen, an element not exothermic with hydrogen except Al and B, and y is limited to 1y ≦ 1.5. A negative electrode of a battery comprising a hydrogen storage alloy containing an alloy represented by the following general formula (II). Mg _2-x M2 _x M1 _y (II) In the formula, M2 is at least one element selected from the group consisting of Al, B, an element exothermic reaction with hydrogen except Mg; M1 is one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 01.0; y is limited to 1 <y≤2.5. 51. The negative electrode as claimed in claim 50, wherein said Ml or Pt of said Formula (II) or a mixture of Ni and Pt. 51. The negative electrode as claimed in claim 50, wherein M2 in formula (II) is Pd. 51. The negative electrode of claim 50, wherein the negative electrode is in the range of 1.01≤y≤1.5. An alkaline secondary battery having a negative electrode containing a hydrogen storage alloy containing an alloy represented by the following general formula (II). Mg _2-x M2 _x M1 _y (II) Wherein M2 is at least one element selected from the group consisting of Al, B and an element exothermic to hydrogen except Mg; Ml is at least one element selected from the elements which cannot cause exothermic reaction with hydrogen except Mg and M2; x is 01.0; y is limited to 1 <y≤2.5. CuK as radiation source The middle of at least one peak among the three maximum intensity peaks of the alloy obtained by X-ray diffraction when using a ray; hydrogen storage in which the butterfly Δ (2θ) is in the range 0.2 ° ≤ Δ (2θ) ≤50 ° A negative electrode of a battery, characterized by containing an alloy. CuK as radiation source At least one of the three peak intensity peaks of the alloy obtained by X-ray diffraction when using a ray; hydrogen storage alloys in which the butterfly Δ (2θ) is in the range 0.2 ° ≤ Δ (2θ) ≤50 ° An alkaline secondary battery comprising a negative electrode containing a. In the negative electrode of a battery containing a hydrogen storage alloy containing magnesium, when the negative electrode is immersed in an aqueous solution of alkali hydroxide of 6N to 8N, (a) the dissolution rate of magnesium ion in an aqueous alkali oxide solution of normal temperature is 0.5 mg / The dissolution rate of magnesium ions in an alkali hydroxide aqueous solution of kg alloy / hr or less or 60 ° C is 4 mg / kg alloy / hr, and (b) The dissolution rate of alloying element element ions in an alkali oxide aqueous solution having a normal temperature is 1.5. A negative electrode of a battery, wherein the dissolution rate of the alloying elemental ions in an aqueous alkali hydroxide solution at or below mg / kg or 60 ° C. is any one of 20 mg / Kg alloy / hr or less. An alkali secondary containing a hydrogen storage alloy containing magnesium and containing a negative electrode housed in the case, a positive electrode housed in the case so as to face the negative electrode by a separator sandwiched between the negative electrode, and an alkali electrolyte charged therein; An alkaline secondary battery, characterized in that the concentration of magnesium ions in the alkaline electrolyte is less than 2.2 mg / litter after 30 days of charging the alkaline electrolyte in the container. The hydrogen storage alloy, characterized in that it contains an alloy represented by the general formula (V). Mg _1-X M3 _X ) _20-y M4 (Ⅴ) Wherein M4 is Ni, Fe, Co, Cu, Zn; At least one element selected from Sn and Si; M3 is at least one element selected from the group of elements having a higher electronegativity than Mg except the elements of M4; x is 0 ≦ x ≦ 0.5 y is limited to 0y ≦ 18. 60. The hydrogen storage alloy according to claim 59, wherein x in the general formula (V) is in a range of 0.01≤x≤0.4. 60. The hydrogen storage alloy according to claim 59, wherein y in the general formula (V) is in the range of 1 ≦ y ≦ 17.5. A hydrogen storage alloy, characterized by containing an alloy represented by the following general formula (VI). Mg _1-x M5 _x ) _20-y M6 (Ⅵ) Wherein M5 is at least one element having an atomic radius of 1 to 1.5 times larger than the atomic radius of Mg except for elements having a higher electronegativity than Mg; M6 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; x is 0x0.5 y is limited to 0≤y18. 63. The hydrogen storage alloy of claim 62, wherein M5 in formula (VI) is at least one element selected from the group consisting of Ca, Sr, and a combination of Ca and Sr. The hydrogen storage alloy, wherein x in the general formula (VI) is in the range of 0.01 ≦ x ≦ 0.4. The hydrogen storage alloy, wherein y in the general formula (VI) is in the range of 1 ≦ x ≦ 17.5. Alloys having hydrogen absorption storage characteristics; And (a) Group IA element, Group IIA element, Group IIIA element, Group IVA element, Group VA element, Group VIA element, Group A element, Group A element, Group I element, Group IIB element, Group IIIB element, Group IVB element At least one element selected from elements, group VB elements and group VIB elements, (b) an alloy formed by a combination of electrostatic elements in (a), (c) in the group consisting of oxides of the elements defined in (a) above A mixture formed comprising at least one additive selected; The hydrogen storage alloy, characterized in that the mixture is formed by mechanical treatment under vacuum or inert gas or hydrogen atmosphere. 67. The hydrogen storage alloy of claim 66, wherein said mixture comprises from 0.01 to 50% by volume of said additive with respect to the alloy having the same hydrogen absorption storage characteristics. 67. The hydrogen storage alloy of claim 66, wherein the alloy having hydrogen absorption storage characteristics is an A ₂ B alloy, A is an element exothermic to hydrogen, and B is an element not exothermic to hydrogen. . 67. The hydrogen storage alloy according to claim 66, wherein the alloy having hydrogen absorption storage characteristics contains an alloy represented by the following general formula (IV). Mg _2-x M2 _x M1 _y (Ⅳ) In the formula, M2 is at least one element selected from the group of elements, Al and B exothermic reaction with hydrogen except Mg; M1 is one element selected from elements which cannot exothermic to hydrogen except Mg and M2; x is 0 ≦ x ≦ 1.0; y is limited to 0.5 <y≤2.5. 67. The hydrogen storage alloy according to claim 66, wherein the alloy having hydrogen absorption storage characteristics contains an alloy represented by the following general formula (V). Mg _1-X M3 _X ) _20-y M4 (Ⅴ) Wherein M4 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; M3 is at least one element selected from the group of elements having a higher electronegativity than Mg except the elements of M4; x is 0 ≦ x ≦ 0.5 y is limited to 0y ≦ 18. 67. The hydrogen storage alloy according to claim 66, wherein the alloy having hydrogen absorption storage characteristics contains an alloy represented by the following general formula (VI). Mg _1-X M5 _X ) _20-y M6 (Ⅵ) M5 is at least one element having an atomic radius of 1 to 1.5 times larger than the atomic radius of Mg, except for the element having a higher electronegativity than Mg; M6 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; x is 0x0.5 y is limited to 0≤y18. 67. The method of claim 66, wherein at least one element electrostatically charged by (b) is selected from V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ir, Pd, Ni, Pt, Cu. Hydrogen storage alloy, characterized in that selected from the group consisting of, Ag, and Au. 67. The hydrogen storage alloy of claim 66, wherein said alloy defined by (b) is selected from the group consisting of MoCo ₃ , WCo ₃ , MoNi _3, and WNi ₃ . 67. The method of claim 66, wherein the alloy defined by (c) is selected from the group consisting of FeO, RuO ₂ , CoO, Co ₂ O ₃ Co ₃ O ₄ , RhO ₂ IrO ₂ , and NiO. Hydrogen storage alloys. Alloys having hydrogen absorption storage characteristics; And (a) Group IA element, Group IIA element, Group IIIA element, Group IVA element, Group VA element, Group VIA element, Group A element, Group A element, Group IB element, Group IIB element, IIIB At least one element selected from a group element, a group IVB element, a group VB element, and a group VIB element, (b) an alloy formed by a combination of the electrostatic elements in (a), and (c) the element defined in (a) above. A hydrogen storage alloy, selected from the group consisting of oxides, comprising at least one powdered additive in an amount of 0.01 to 50% by volume having an average diameter of 0.01 to 100 μm. 76. The hydrogen storage alloy of claim 75, wherein the alloy having hydrogen absorption storage properties comprises nickel as one component element. 76. The hydrogen storage alloy according to claim 75, wherein the alloy having hydrogen absorption storage characteristics contains an alloy represented by the following general formula (V). Mg _1-X M3 _X ) _20-y M4 (Ⅴ) Wherein M4 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; M3 is at least one element selected from the group of elements having an electronegativity greater than Mg (excluding elements of M4); x is 0x0.5 y is limited to 0≤y18. 76. The hydrogen storage alloy according to claim 75, wherein the alloy having hydrogen absorption storage characteristics contains an alloy represented by the following general formula (VI). Mg _1-X M5 _X ) _20-y M6 (Ⅵ) Wherein M5 is at least one element having an atomic radius of 1 to 1.5 times greater than the atomic radius of Mg (except for elements having a higher electronegativity than Mg); M6 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; x is 0x0.5 y is limited to 0≤y18. An alkali secondary battery comprising a cathode electrode containing a hydrogen storage alloy containing an alloy represented by the following general formula (V). Mg _1-X M3 _X ) _20-y M4 (Ⅴ) Wherein M4 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; M3 is at least one element selected from the group of elements having a higher electronegativity than Mg except the elements of M4; x is 0x0.5; y is limited to 0≤y18. An alkali secondary battery comprising a cathode electrode containing a hydrogen storage alloy containing an alloy represented by the following general formula (VI). Mg _1-X M5 _X ) _20-y M6 (Ⅵ) M5 is at least one element having an atomic radius of 1 to 1.5 times larger than the atomic radius of Mg excluding the element having a higher electronegativity than Mg; M6 is at least one element selected from Ni, Fe, Co, Cu, Zn, Sn and Si; x is 0x0.5; y is limited to 0≤y18. Alloys having hydrogen absorption storage characteristics; And (a) Group IA element, Group IIA element, Group IIIA element, Group IVA element, Group VA element, Group VIA element, Group A element, Group A element, Group I element, Group IIB element, Group IIIB element, Group IVB element At least one element selected from elements, group VB elements and group VIB elements, (b) an alloy formed by a combination of elements defined in (a), and (c) an oxide of an element defined in (a). An alkaline secondary battery comprising a negative electrode containing a hydrogen storage alloy obtained by a mixture comprising at least one additive selected, wherein the mixture is subjected to mechanical treatment under vacuum or an inert gas or hydrogen atmosphere. Alloys having hydrogen absorption storage characteristics; And (a) Group IA element, Group IIA element, Group IIIA element, Group IVA element, Group VA element, Group VIA element, Group A element, Group A element, Group IB element, Group IIB element, IIIB At least one element selected from a group element, a group IVB element, a group VB element and a group VIB element, (b) an alloy formed by a combination of the elements defined in (a), and (c) an element defined in (a). An alkali secondary battery comprising a negative electrode containing a hydrogen storage alloy selected from the group consisting of oxides and containing at least one powdered additive in an amount of 0.01 to 50% by volume having an average diameter of 0.01 to 100 μm. . ※ Note: This is based on the initial application.