WO1996014442A1 - Age-precipitating rare earth metal-nickel alloy, its manufacture, and negative electrode for nickel-hydrogen secondary cell - Google Patents
Age-precipitating rare earth metal-nickel alloy, its manufacture, and negative electrode for nickel-hydrogen secondary cell Download PDFInfo
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- WO1996014442A1 WO1996014442A1 PCT/JP1995/002255 JP9502255W WO9614442A1 WO 1996014442 A1 WO1996014442 A1 WO 1996014442A1 JP 9502255 W JP9502255 W JP 9502255W WO 9614442 A1 WO9614442 A1 WO 9614442A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
- H01M4/385—Hydrogen absorbing alloys of the type LaNi5
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S420/00—Alloys or metallic compositions
- Y10S420/90—Hydrogen storage
Definitions
- the present invention provides an aging-precipitated rare earth metal which has a high capacity and a long life by being used as a negative electrode material of a hydrogen storage container, a heat pump, and a nickel hydrogen secondary battery.
- the present invention relates to a nickel alloy, a method for producing the same, and a negative electrode for a nickel hydrogen secondary battery.
- the M m (mission-shoe main barrel) ⁇ ⁇ i ⁇ C 0 ⁇ ⁇ ⁇ ⁇ A 1 -based AB 5 type alloys of the Mainly used.
- This alloy has a feature that it has a large hydrogen storage capacity as compared with other alloys, and has a hydrogen absorption and desorption pressure at room temperature of 1 to 5 atm and is easy to use.
- this alloy increases the electrical capacity, but at the expense of longer life.
- the rare earth gold alloy is used.
- a segregated portion tends to occur, and cracks and corrosion progress from the segregated portion.
- Japanese Patent Application Laid-Open No. 2-220356 discloses a method in which a molten alloy is ejected onto a high-speed rotating copper roller. A method has been proposed to obtain a homogeneous alloy by rapid solidification.
- Japanese Patent Application Laid-Open No. Hei 6-73346 discloses a method for removing a cooling strain of an alloy produced by the rapid solidification described above in a vacuum or in an inert gas atmosphere. It has been proposed to anneal alloys that have been rapidly solidified at ⁇ 950 ° C for 2-5 hours. With these methods, the homogeneity of the alloy is improved, and the corrosion resistance and electric life are improved.
- the purpose of the present invention is to provide a negative electrode material for a conventional nickel hydrogen secondary battery. Aging-precipitated rare earth metal-nickel alloys that can simultaneously improve both high electric capacity and long life compared to rare earth metal-nickel alloys used for Its purpose is to provide a manufacturing method.
- Another object of the present invention is to provide a negative electrode for a nickel hydrogen secondary battery, which has both high electric capacity and long life.
- R represents a rare earth element containing Y or a mixture thereof
- M represents Co, Al, Mn, Fe, Cu, 1, Ti, Mo, W, B or a mixture thereof.
- the raw material alloy having the composition represented by the formula (1) is added at a temperature of 100 ° C. or more. After solution heat treatment at a temperature, the temperature (TC) is not less than 700 ° C and less than 100 ° C TC).
- a negative electrode for a nickel-hydrogen secondary battery including the age-precipitated rare earth metal-based nickel-based alloy and a conductive agent as negative electrode materials.
- Fig. 1 (a) and (b) are graphs showing the results of experiments performed to determine the conditions for solution treatment of the raw material alloy in producing the alloy of the present invention. is there.
- Fig. 2 (a) and (b) were used to determine the conditions for aging after the solution treatment of the raw material alloy in producing the alloy of the present invention. This is a graph showing the experimental results.
- FIG. 3 is a scanning electron micrograph of the raw material alloy prepared in Example 1 after the die forming.
- FIG. 4 is a scanning electron micrograph of the solution-treated alloy prepared in Example 1.
- FIG. 5 is a scanning electron micrograph of the age-precipitated alloy prepared in Example 1.
- FIG. 6 is a scanning electron micrograph of the raw material alloy prepared in Example 3 after die forming.
- FIG. 7 is a scanning electron micrograph of the solution-treated alloy prepared in Example 3.
- FIG. 8 is a scanning electron micrograph of the age-precipitated alloy prepared in Example 3.
- FIG. 9 shows the rapidity obtained by the simple roll method prepared in Example 12. It is a scanning electron micrograph of the alloy after cold solidification.
- FIG. 10 is a scanning electron micrograph of the age-precipitated alloy prepared in Example 12.
- FIG. 10 is a scanning electron micrograph of the age-precipitated alloy prepared in Example 12.
- the aging precipitation type alloy of the present invention has the following formula (1)
- R represents a rare earth element containing Y or a mixture thereof
- M represents Co, Al, Mn, Fe, Cu, Zr, Ti, Mo, W, B or a mixture thereof.
- X represents 0.5 ⁇ x ⁇ 0.5, preferably 0.1 ⁇ X ⁇ 0.4
- y is 0.45 ⁇ y 0.45, preferably -0.40 ⁇ y ⁇ 0.35.
- AB- 5 type rare-earth metal-nickel alloy having a precipitation length of 0.1 to 20 / zm, preferably 1 to 1 ⁇ . It is. If the average major axis diameter of the precipitated phase is less than 0.1 / m, the life of the alloy used as a negative electrode for a nickel hydrogen secondary battery or the like is not improved. Meanwhile 2 0 mu exceeds ⁇ the alloy of two Tsu c This precipitation phase capacitance in the case of a metal hydride secondary battery negative electrode is lowered, and the this measure Ri by the example scanning electron microscope it can.
- the content ratio of the precipitated phase in the age-precipitable alloy is not particularly limited, but the upper limit is preferably not less than 0.01% by volume, and is not particularly limited as long as the above-mentioned effects are exhibited. However, 30% by volume or less is preferable. More preferably, it is 1 to: 15% by volume.
- the formula (1) representing the composition A if X is less than 0.05, the life of the alloy as a negative electrode for a nickel hydrogen secondary battery or the like is shortened, and if it exceeds 0.5, the surface is excessive. The activity decreases and the hydrogen storage capacity decreases. Further, when y is less than -0.45, the life when the alloy is used as a negative electrode for a nickel hydrogen secondary battery or the like is shortened, and the y is less than 0.4.
- R in the formula can be selected from one or more of rare earth elements including Y.
- the rare earth element is not particularly limited, but for example, La 20 to 100 atomic%, Ce 0 to 60 atomic%, Pr 0 to 15 atomic%, Nd 0 to
- the metal related to M in the formula may be one type or a combination of two or more types. Combinations of two or more metals can be made as appropriate based on the properties of each metal.
- C 0 has a function of expanding the crystal lattice to lower the equilibrium hydrogen pressure and a function of preventing micronization and improving the life.
- the compounding ratio is represented by R as 1 (the compounding ratios of the following metals are also shown on the same basis): 0.1 to 1.5 atomic ratio, particularly 0.3 to 1.0 atomic ratio. Is preferred.
- a 1 has the effect of expanding the crystal lattice to lower the equilibrium hydrogen pressure, and the effect of increasing the hydrogen storage capacity.
- the compounding ratio is preferably from 0.1 to 1.0 atomic ratio, particularly preferably from 0.2 to 0.5 atomic ratio.
- Mn has the effect of expanding the crystal lattice to lower the equilibrium hydrogen pressure and the effect of increasing the hydrogen storage capacity.
- the mixing ratio is preferably from 0.01 to 1.0 atomic ratio, particularly preferably from 0.2 to 0.6 atomic ratio.
- F e has the effect of activating the alloy surface and increasing the rate of hydrogen storage and release.
- the compounding ratio is preferably at most 0.1 atomic ratio, particularly preferably from 0.01 to 0.03 atomic ratio.
- Cu has the effect of expanding the crystal lattice and lowering the equilibrium hydrogen pressure.
- the compounding ratio is preferably from 0.01 to 1,0 atomic ratio, particularly preferably from 0.05 to 0.5 atomic ratio.
- Zr has the effect of improving the hysteresis characteristics of the PCT curve (hydrogen dissociation pressure-composition isotherm) and improving the life of nickel-hydrogen rechargeable batteries by depositing at grain boundaries and preventing cracking. And has the effect of causing
- the mixing ratio is preferably less than 0.1 atomic ratio, particularly preferably from 0.01 to 0.03 atomic ratio.
- T i has the effect of improving the hysteresis characteristics of the PCT curve.
- the mixing ratio is preferably less than 0.1 atomic ratio, particularly preferably from 0.01 to 0.03 atomic ratio.
- Mo, W and B have the effect of increasing the activity and increasing the rate of hydrogen storage and release, respectively.
- the mixing ratio of each is preferably less than 0.1 atomic ratio, particularly preferably from 0.01 to 0.03 atomic ratio.
- composition A As specific examples of the composition A, the following compositions and the like can be preferably mentioned.
- the aging precipitation type alloy of the present invention can be produced, for example, by combining a specific solution treatment and aging.
- a raw material alloy having a composition A represented by the above formula (1) is first subjected to a solution treatment at a temperature of 100 or more.
- the raw material alloy may be any of an alloy lump, an alloy piece, an alloy ribbon, an alloy powder, etc., as long as it shows composition A.
- the method of preparing the raw material alloy is not particularly limited, and may be prepared by a known method, for example, a mold manufacturing method, a molten roll method, a melt centrifugal method, a thermal reduction diffusion method, a gas atomizing method, or the like.
- Preferably above 100 ° C / s, particularly preferably from 500 Raw material alloys obtained by rapid solidification at a cooling rate of 100,000 o ° cz seconds can be used.
- the solution treatment is a process in which an alloy is heated to a temperature equal to or higher than the solubility line of the second phase so that the second phase is dissolved in the first phase and then cooled. Heating under the above-mentioned conditions in an atmosphere of an inert gas such as gon gas, a uniform solid solution (atoms of another element enter into the crystal lattice of a certain metal and still have the same An alloy that retains its crystalline form).
- Solid solution region obtained Ri by the solution treatment of this is described above: Ri far shown in (TBMassals ki et al. Binary Alloy Phase Diagrams, Vol .2.1468 ASM (1 986)), conventional AB 5 type rare earth It was thought to be absent in metal-nickel alloys.
- the solution treatment temperature was determined based on the experimental data of various compositions in the formula (1).
- Fig 1 (a) is an example in which, in equation (1), the Miss metal (M m) is used as the R component, and Al, Co, and M n are used as the M components. is there. That is, the expression
- the proportion of the second phase decreases rapidly above 100 ° C and turns into solution.
- the upper limit is not particularly limited, it is preferably 125 ° C., particularly preferably 1200 ° C.
- the time is preferably 1 to 100 hours, particularly preferably 5 to 50 hours. Cooling in the solution heat treatment is carried out after the solution has been solidified at a temperature of at least 100,000 ⁇ and then quenched by a usual quenching method such as pouring into water or oil, gas cooling, or mist cooling. I can. At this time, the cooling rate can be set at about 100 to 100 ° CZ seconds.
- Aging refers to changing the properties of a metallic material over time and precipitating a fine secondary phase from a non-equilibrium phase, such as a supersaturated solid solution.
- the aging condition was determined based on experimental data of various compositions in equation (1).
- An example is shown in Fig. 2 (a) and (b). 2 (a) and (b) correspond to F ig. 1 Test alloys used in the experiments described in (a) and (b)
- a substantially uniform and fine precipitate phase is not formed, preferably in a temperature range of 800 to 950, by aging for a time that satisfies the above formula (2).
- the aging atmosphere The atmosphere is preferably in an atmosphere of an inert gas such as argon gas.
- the composition and preparation method of the raw material alloy without the solution treatment are carried out, and the aging conditions. Can also be obtained by controlling and.
- the composition of the rapidly solidified solid in the above formula (1) is defined as the y force 0.45 ⁇ y ⁇ 0.3, or 0.2%
- the aging shall be over 1 hour and up to 25 hours, and when y is -0.3 ⁇ y0.2, the aging shall be over 5 hours and up to 50 hours (hereinafter referred to as " ⁇ The other manufacturing method ”) can be obtained.
- a raw material alloy melt can be prepared using a known vacuum melting furnace or the like. Rapid solidification can be performed by a single roll or twin roll quenching process, centrifugal spraying, gas atomization, etc., from the molten metal for more than 100,000 seconds, preferably 500 to 100. Any method that can prepare alloy flakes, alloy thin films, alloy powders, etc. at a cooling rate of 0 000 e CZ seconds is applicable. In the case of (1), the solid solution forcing force of the alloy element is insufficient, and a desired precipitated phase cannot be obtained without performing the solution treatment.
- the obtained rapidly solidified product is aged for a predetermined time at a temperature of at least 700 * C and less than 100 ° C, preferably at 800 to 950 ° C.
- the aging time is controlled in accordance with the above-mentioned composition, the same operation as in the production method of the present invention in which the solution treatment is performed can be performed.
- the negative electrode for a nickel-hydrogen secondary battery of the present invention contains the aging-precipitable alloy and a conductive agent as negative electrode materials.
- the above-mentioned age-precipitable alloy is preferably used as a pulverized material.
- the pulverized particle size is preferably from 20 to: ⁇ ⁇ ⁇ , particularly preferably 40 to 50 / im.
- this pulverization for example, after the age-precipitated alloy obtained with a stamp mill or the like is roughly pulverized, it is mechanically pulverized in a dry or wet method using a ball mill, disc mill, etc. It can be carried out by a method, a hydrogen storage / release pulverization method, or a method combining these methods.
- the content of the aging-precipitable alloy is preferably 70 to 95% by weight, and particularly preferably 80 to 90% by weight, based on the total amount of the negative electrode material. If the amount is less than 70% by weight, the hydrogen storage capacity of the obtained negative electrode decreases, and it is difficult to achieve a high capacity. On the other hand, if the content exceeds 95% by weight, the conductivity is lowered and the durability is deteriorated.
- the conductive agent examples include copper, nickel, cobalt, carbon, and the like.
- the conductive agent in use, although it depends on the preparation method of the negative electrode, it can usually be used as a powder having a particle size of about 1 to 10 ⁇ .
- the metal in the case of a conductive metal such as copper, nickel, and cobalt, the metal can be used in the form of metal plating or the like on the aging-precipitation-type alloy.
- the content of the conductive agent is preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight, based on the total amount of the negative electrode material.
- the negative electrode for a nickel hydrogen secondary battery of the present invention may contain a binder in addition to the essential components.
- the binder include 4 — futsudiraethylene 6 — fluorinated propylene copolymer, polytetrafluoroethylene, carboxymethylcellulose and the like. 14 4
- the content ratio of the binder is less than 10% by weight based on the total amount of the negative electrode material.
- a crushed product of the above-mentioned age-precipitable alloy is prepared by using nickel metal, nickel or copper extruded metal, nickel Alternatively, it can be obtained by binding and forming a conductive agent current collecting base such as copper punching metal, foamed nickel, wool-shaped nickel, or the like.
- the binding molding can be performed by a roll press method, a molding press method, or the like, and the shape is preferably a sheet shape or a pellet shape.
- the obtained negative electrode can be used in the same manner as a normal negative electrode for a nickel hydrogen secondary battery to form a secondary battery.
- the aging precipitation type alloy of the present invention has a precipitation phase having an average major axis of 0.1 to 20 / im, so that when used as a negative electrode material for a nickel hydrogen secondary battery, it has a long life and a high electric capacity. And can be exerted simultaneously.
- the aging precipitation-type alloy can be easily obtained by a simple method of performing a solution treatment and aging on a raw material alloy having a specific composition.
- the negative electrode for a nickel hydrogen secondary battery of the present invention exhibits both long life and high electric capacity at the same time, so that demand for the conventional negative electrode can be expected.
- Mm mismetal
- Santoku Metal Industry Co., Ltd. rare earth composition: La2 5% by weight, Ce 50% by weight, 5% by weight, Nd2 0% by weight
- Table 1 mismetal manufactured by Santoku Metal Industry Co., Ltd.
- the obtained alloy lump was loaded into a heat treatment furnace by electric resistance heating in an argon gas atmosphere, heated at 110 ° C. for 10 hours, and then poured into water to be rapidly cooled.
- the lumps were taken out, dried and then loaded again into a heat treatment furnace in an argon atmosphere, and subjected to aging treatment by heating at 900 ° C for 8 hours.
- FIGS. 3 to 5 show scanning electron micrographs of the alloy after fabrication, solution treatment, and aging in Example 1. These photographs in Example 3 are also shown in FIGS. 3 to 8, it can be seen that the second phase observed in the structure after the preparation is a solid solution after the solution treatment, and that the precipitated phase precipitates after aging.
- the obtained aging-treated alloy is roughly pulverized with a stamp mill, and then in a hexane solvent, having an average particle size of 80 ⁇ m with a planetary ball mill. crushed to m.
- a pellet electrode was fabricated. This electrode was immersed in a 6 N KOH solution, a battery was constructed using a mercury oxide reference electrode, and the electrode characteristics were measured using a potion galvano-stat made by Hokuto Denko. Table 2 shows the results.
- Examples 1 to 7 were prepared using the compositions shown in Table 1 except that La, Ce, Pr, and Nd metals with a purity of 9.9% were used instead of Mm.
- An alloy was prepared in the same manner as described above. The same measurement as in Examples 1 to 7 was performed on the obtained alloy and a battery using the crushed alloy. Table 2 shows the results.
- the molten metal was rapidly solidified by a single roll method to obtain an alloy ribbon having a thickness of 0.3 to 0.4 mm. At this time, the cooling rate was about 100,000 / sec. Subsequently, the obtained alloy ribbon was loaded into a heat treatment furnace by electric resistance heating in an argon atmosphere, heated at 110 ° C. for 5 hours, and then poured into water to be rapidly cooled. Next, after the quenched product was dried, it was again charged into a heat treatment furnace in an argon atmosphere and subjected to a heat aging treatment at 85 Ot for 10 hours. The same measurement as in Examples 1 to 7 was performed on the obtained alloy and a battery using the alloy pulverized product. Table 2 shows the results.
- the melt was quenched and solidified by a gas atomization method using argon gas to obtain alloy particles having an average particle size of about 90 ⁇ .
- the cooling rate was about 500,000 seconds, and as a result of microscopic observation, no precipitation of coarse second phase was observed in any case, indicating the state of the non-equilibrium phase forcibly dissolved.
- Each alloy particle was aged under the conditions shown in Table 2, and the same measurement as in Examples 1 to 7 was performed for the obtained alloy and batteries using the pulverized alloy. Table 2 shows the results.
- Example 2 Each measurement was performed on the battery using the high frequency melted lump prepared in Example 1 and the lump and lump pulverized material obtained in the same manner as in Examples 1 to 7 without performing solution treatment and aging. Performed similarly to ⁇ 7. Table 2 shows the results.
- Example 2 The high-frequency melted ingot prepared in Example 1 was subjected to only solution treatment to obtain an alloy in the same manner as in Examples 1 to 7 without aging. Each measurement of the obtained alloy and a pond using the pulverized alloy was performed in the same manner as in Examples 1 to 7. Table 2 shows the results.
- Example 1 An alloy was obtained in the same manner as in Examples 1 to 7, except that the high-frequency molten mass produced in Example 1 was not subjected to solution treatment but was only subjected to aging. Each measurement of the obtained alloy and the battery using the pulverized alloy was performed in the same manner as in Examples 1 to 7. Table 2 shows the results.
- Example 12 After the raw material having the same composition as in Example 12 was subjected to high frequency melting, when the molten metal was solidified by a single roll method, the cooling water of the roll was destroyed and dissolved. An alloy was obtained in the same manner as in Example 12 except that the cooling rate was about 500 ° C.sec under the condition that the amount of hot water was added. The same measurement as in Examples 1 to 7 was performed on the obtained alloy and the battery using the crushed alloy. Table 2 shows the results.
- Example 12 The alloy strip made of the single-roll method produced in Example 12 was heat-treated at 850 ° C. for 3 hours in an argon atmosphere to obtain an alloy. The same measurement as in Examples 1 to 7 was performed on the obtained alloy and the battery using the crushed alloy. Table 2 shows the results.
- Example 17 After the raw material having the same composition as in Example 17 was subjected to high frequency melting, the molten metal was rapidly solidified by a single roll method in the same manner as in Example 11 to obtain an alloy ribbon.
- the ribbon was heat-treated at 800 ° C for 5 hours in an argon atmosphere to obtain an alloy.
- the same measurement as in Examples 1 to 7 was performed on the obtained alloy and the battery using the pulverized alloy. Table 2 shows the results.
- Example 11 An alloy was obtained in the same manner as in Example 11 except that the solution treatment was performed under the conditions shown in Table 2 and the aging was not performed. The same measurement as in Examples 1 to 7 was performed on the obtained alloy and the battery using the alloy pulverized product. Table 2 shows the results.
- a raw material melt having the same composition as in Example 11 was rapidly solidified by a single roll method in the same manner as in Example 11 to obtain an alloy ribbon. Then the solution 96/14442
- Example 1 Comparative example 1 to 3 0.25 0.50 0.05 0.20 3.30 0.30 0.70 0.40 0.02 ⁇ One ⁇ 0.30 One 0.28
- Example 2 0.25 0.50 0.05 0.20 3.40 0.30 0.75 0.40-0.02-One 0.30 one 0.13
- Example 3 0.25 0.50 0.05 0.20 3.90 0.30 0.70 0.40 One-0.02-0.27 + 0.32
- Example 4 0.25 0.50 0.05 0.20 3.65 0.20 0.85 0.50---0.02 0.30 + 0.22
- Example 5 0.25 0.50 0.05 0.20 3.20 0.20 0.80 0.50 0.02---0.32 -0.28
- Example 6 0.25 0.50 0.05 0.20 3.90 0.30 0.60 0.40 0.02---0.34 + 0.22
- Example 7 0.25 0.50 0.05 0.20 2.80 0.30 1.10 0.60 0.02 ⁇ ⁇ ⁇ 0.42 one 0.18
- Example 8 1 .00 3.20 0.30 0.80 0.40
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95936098A EP0751229B1 (en) | 1994-11-07 | 1995-11-06 | Age precipitation-containing rare earth metal-nickel alloy, method of producing the alloy, and anode for nickel-hydrogen rechargeable battery |
JP51519596A JP3924319B2 (ja) | 1995-11-06 | 1995-11-06 | 時効析出型希土類金属−ニッケル系合金、その製造法及びニッケル水素2次電池用負極 |
US08/669,447 US6053995A (en) | 1994-11-07 | 1995-11-06 | Method of producing an age precipitation-containing rare earth metal-nickel alloy |
DE69523148T DE69523148T2 (de) | 1994-11-07 | 1995-11-06 | Ausscheidungsgehärtete seltene erden-nickellegierung, ihre herstellung und negative elektrode für nickel-wasserstoff-sekundärzelle |
KR1019960703652A KR100207906B1 (ko) | 1994-11-07 | 1995-11-06 | 시효석출형 희토류 금속-니켈계 합금, 그 제조법 및 니켈수소 2차전지용 음극 |
AT95936098T ATE206771T1 (de) | 1994-11-07 | 1995-11-06 | Ausscheidungsgehärtete seltene erden- nickellegierung, ihre herstellung und negative elektrode für nickel-wasserstoff-sekundärzelle |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6296018A JPH09209065A (ja) | 1994-11-07 | 1994-11-07 | 時効析出型希土類金属−ニッケル系合金、その製造法及びニッケル水素2次電池用負極 |
JP6/296018 | 1994-11-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996014442A1 true WO1996014442A1 (en) | 1996-05-17 |
Family
ID=17828058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1995/002255 WO1996014442A1 (en) | 1994-11-07 | 1995-11-06 | Age-precipitating rare earth metal-nickel alloy, its manufacture, and negative electrode for nickel-hydrogen secondary cell |
Country Status (8)
Country | Link |
---|---|
US (2) | US6053995A (ja) |
EP (1) | EP0751229B1 (ja) |
JP (1) | JPH09209065A (ja) |
KR (1) | KR100207906B1 (ja) |
CN (1) | CN1071798C (ja) |
AT (1) | ATE206771T1 (ja) |
DE (1) | DE69523148T2 (ja) |
WO (1) | WO1996014442A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0817290A1 (en) * | 1996-06-28 | 1998-01-07 | Furukawa Denchi Kabushiki Kaisha | Hydrogen occlusion alloys for electrical cells |
US9490477B2 (en) | 2012-09-27 | 2016-11-08 | Gs Yuasa International Ltd. | Nickel-metal hydride storage battery including negative electrode containing yttrium substituted hydrogen storage alloy and electrolyte solution containing sodium hydroxide |
Families Citing this family (17)
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JP3027532B2 (ja) * | 1995-12-26 | 2000-04-04 | 昭和電工株式会社 | 水素吸蔵合金の製造方法 |
JP4087454B2 (ja) * | 1996-09-06 | 2008-05-21 | 株式会社三徳 | 希土類金属―ニッケル系水素吸蔵合金及びその製造法、並びにニッケル水素2次電池用負極 |
EP0867957B1 (en) * | 1997-03-28 | 2008-05-14 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for alkaline storage batteries |
US6197448B1 (en) * | 1997-05-30 | 2001-03-06 | Duracell Inc. | Hydrogen storage alloy |
EP0965652B1 (en) * | 1997-12-26 | 2003-02-26 | Toyota Jidosha Kabushiki Kaisha | Hydrogen absorbing alloys, processes for producing hydrogen absorbing alloys, hydrogen absorbing alloy electrode, process for producing hydrogen absorbing alloy electrode, and battery |
EP0969110A3 (en) * | 1998-06-16 | 2000-01-19 | Mitsubishi Materials Corporation | Hydrogen occluding alloy |
US6013387A (en) * | 1998-06-22 | 2000-01-11 | Li-Ho Yao | Hydrogen absorbing alloy for battery application |
JP2000038606A (ja) * | 1998-07-22 | 2000-02-08 | Shin Etsu Chem Co Ltd | 水素吸蔵合金粉末、該製造方法及びアルカリ二次電池 |
JP3697996B2 (ja) * | 1999-12-24 | 2005-09-21 | 三菱マテリアル株式会社 | 高率初期活性化処理で少ない充放電回数での高放電容量化並びに低温高率放電容量の向上を可能とする電池負極用水素吸蔵合金 |
TWI315344B (en) * | 2005-03-23 | 2009-10-01 | Chih Kang Shih | Hydrogen storage alloy |
CN100443610C (zh) * | 2005-04-04 | 2008-12-17 | 施志刚 | 储氢合金 |
US7854809B2 (en) * | 2007-04-10 | 2010-12-21 | Siemens Energy, Inc. | Heat treatment system for a composite turbine engine component |
EP2576657B1 (en) | 2010-05-27 | 2017-01-18 | Dow Global Technologies LLC | Methods for producing crosslinkable silyl group-containing polyoxyalkylene polymers |
JP2015203119A (ja) * | 2014-04-11 | 2015-11-16 | プライムアースEvエナジー株式会社 | 水素吸蔵合金、ニッケル水素蓄電池、及び水素吸蔵合金の製造方法 |
CN105140574B (zh) * | 2015-07-22 | 2017-03-08 | 深圳市朗泰通电子有限公司 | 一种镍氢动力电池及其制备方法 |
JP6818202B2 (ja) * | 2017-05-08 | 2021-01-20 | 日本重化学工業株式会社 | リチウムイオン電池の処理方法 |
CN114941058B (zh) * | 2022-07-07 | 2023-05-23 | 上海大学 | 一种高纯度Pr5Co19型La-Y-Ni超点阵合金及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0466636A (ja) * | 1990-07-06 | 1992-03-03 | Matsushita Electric Ind Co Ltd | 水素吸蔵合金電極およびその製造法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2399484A1 (fr) * | 1977-08-02 | 1979-03-02 | Anvar | Nouveaux alliages a base de lanthane et de nickel, leur fabrication et leurs applications electrochimiques |
JPS60131958A (ja) * | 1983-12-20 | 1985-07-13 | Sumitomo Metal Ind Ltd | 析出強化型Νi基合金の製造法 |
NL9001677A (nl) * | 1990-07-24 | 1992-02-17 | Koninkl Philips Electronics Nv | Elektrochemische cel met hydride vormende intermetallische verbinding. |
EP0557522B1 (en) * | 1990-10-29 | 1996-02-07 | Yuasa Corporation | Hydrogen-storing electrode, nickel electrode, and nickel-hydrogen battery |
EP0789409B1 (en) * | 1992-09-14 | 2003-07-09 | Kabushiki Kaisha Toshiba | Hydrogen-absorbing alloy for battery, method of manufacturing the same, and secondary nickel-metal hydride battery |
US5496424A (en) * | 1992-10-07 | 1996-03-05 | Sanyo Electric Co., Ltd. | Hydrogen absorbing alloy and process for preparing same |
US5441826A (en) * | 1993-04-28 | 1995-08-15 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy electrode |
US5512385A (en) * | 1994-02-28 | 1996-04-30 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy and nickel-metal hydride storage battery using the same |
-
1994
- 1994-11-07 JP JP6296018A patent/JPH09209065A/ja active Pending
-
1995
- 1995-11-06 EP EP95936098A patent/EP0751229B1/en not_active Expired - Lifetime
- 1995-11-06 CN CN95191812A patent/CN1071798C/zh not_active Expired - Fee Related
- 1995-11-06 KR KR1019960703652A patent/KR100207906B1/ko not_active IP Right Cessation
- 1995-11-06 US US08/669,447 patent/US6053995A/en not_active Expired - Lifetime
- 1995-11-06 WO PCT/JP1995/002255 patent/WO1996014442A1/ja active IP Right Grant
- 1995-11-06 AT AT95936098T patent/ATE206771T1/de not_active IP Right Cessation
- 1995-11-06 DE DE69523148T patent/DE69523148T2/de not_active Expired - Lifetime
-
1998
- 1998-12-03 US US09/204,317 patent/US5985054A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0466636A (ja) * | 1990-07-06 | 1992-03-03 | Matsushita Electric Ind Co Ltd | 水素吸蔵合金電極およびその製造法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0817290A1 (en) * | 1996-06-28 | 1998-01-07 | Furukawa Denchi Kabushiki Kaisha | Hydrogen occlusion alloys for electrical cells |
US9490477B2 (en) | 2012-09-27 | 2016-11-08 | Gs Yuasa International Ltd. | Nickel-metal hydride storage battery including negative electrode containing yttrium substituted hydrogen storage alloy and electrolyte solution containing sodium hydroxide |
Also Published As
Publication number | Publication date |
---|---|
US5985054A (en) | 1999-11-16 |
KR100207906B1 (ko) | 1999-07-15 |
CN1142251A (zh) | 1997-02-05 |
EP0751229A1 (en) | 1997-01-02 |
CN1071798C (zh) | 2001-09-26 |
ATE206771T1 (de) | 2001-10-15 |
DE69523148T2 (de) | 2002-02-07 |
JPH09209065A (ja) | 1997-08-12 |
DE69523148D1 (de) | 2001-11-15 |
US6053995A (en) | 2000-04-25 |
EP0751229A4 (en) | 1998-02-25 |
EP0751229B1 (en) | 2001-10-10 |
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