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AB5-base hydrogen storage alloy, electrode for Ni-MH battery, secondary battery and method for preparing hydrogen storage alloy

A hydrogen storage alloy and nickel-metal hydride battery technology, which is applied in the direction of secondary batteries, battery electrodes, alkaline storage battery electrodes, etc., can solve the problems of affecting cycle life, difficulty in adjusting the balance voltage of element ratio, and reduced life of nickel-hydrogen batteries, etc., to achieve Effect of improving corrosion resistance and cycle life, improving corrosion resistance and economy, and improving high-rate discharge performance

Active Publication Date: 2019-04-05
SOUTH CHINA UNIV OF TECH +2
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  • Application Information

AI Technical Summary

Problems solved by technology

AB in the past 3 Type and A 2 B 7 There are many studies on the substitution of Sm on the A side in the research of A-type alloys, but from the reviewed literature, only Pan Hongge has tried 5 A very small amount of Sm is added to the alloy, that is, only 0.1at%, but no effect on AB 5 Any special properties of the alloy, that is to say, a small amount of addition to AB 5 Alloys do not improve
[0005] In the process of realizing the present invention, the inventor finds that there are at least the following problems in the prior art: AB 5 In the alloy, the addition of low-Co elements will lead to a decrease in the life of the Ni-MH battery, and the control of the element ratio is difficult to adjust the equilibrium pressure, which makes it difficult to meet the charge-discharge kinetic performance of the electrode material.
In addition, the role of Sm in the previous literature is unknown, and it has not been reported by fixing the metal La:Ce ratio; the previous AB 5 In type alloys, since there is no large amount of Sm added, the heat treatment temperature is lower than 1000 °C, it is difficult to achieve AB 5 The composition of the type alloy is evenly distributed, and even affects its cycle life

Method used

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  • AB5-base hydrogen storage alloy, electrode for Ni-MH battery, secondary battery and method for preparing hydrogen storage alloy
  • AB5-base hydrogen storage alloy, electrode for Ni-MH battery, secondary battery and method for preparing hydrogen storage alloy
  • AB5-base hydrogen storage alloy, electrode for Ni-MH battery, secondary battery and method for preparing hydrogen storage alloy

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Set La(3.0～3.2)x Ce x Zr y SM (1-(4.0～4.2)x-y) Ni z co u mn v Al w The hydrogen storage alloy contains La 7.79at%, Ce 2.49at%, Zr 0.46at%, Sm 5.39at%, Ni 71.60at%, Co 2.63at%, Mn 4.08at% and Al 5.64at%, among which the elements La, Ce , Zr, and Sm are A-side elements, and elements Ni, Co, Mn, and Al are B-side elements, thus forming AB 5 Type hydrogen storage alloy La 0.50 Ce 0.16 SM 0.34 Zr 0.03 Ni 4.57 co 0.17 mn 0.26 Al 0.36 . Among them, by fixing the atomic number ratio of La and Ce to about 3.1 to meet the overcharge performance of the electrode material, a large number of Sm elements are replaced on the A side, that is, the Sm atomic ratio accounts for about 33% of the A side, thereby overcoming the low The problem of reduced lifespan caused by Co; use the ratio of Sm to La and Ce to adjust the equilibrium voltage to meet the charge-discharge kinetics of the electrode material; the A-side element is added with an atomic ratio of about 2.9% relative...

Embodiment 2-18

[0037] The hydrogen storage alloy is obtained by low vacuum induction melting method, cooling method and annealing treatment.

[0038] Weigh each element according to the composition of following Table 1, carry out heat treatment to its alloy ingot with ZG type vacuum induction melting electric furnace in argon atmosphere, then cool, the specific steps of this heat treatment and the step of cooling are the same as the steps of embodiment 1 ( 1), then carry out annealing treatment, in the specific process of annealing treatment, except heat treatment temperature, other process conditions are identical with the step (2) of embodiment, its heat treatment temperature, time, 120mA / g discharge capacity and 5C discharge capacity The percentages are shown in Table 1 below:

[0039]

[0040]

[0041] To the nickel-hydrogen battery negative electrode material La prepared in embodiment 1 0.50 Ce 0.16 SM 0.34 Zr 0.03 Ni 4.57 co 0.17 mn 0.26 Al 0.36 The charge and discharge t...

Embodiment 19

[0045] Step (1) Place pure metals 362.0g La, 120.0g Ce, 395.0g Sm, 11.4g Zr, 1429.0g Ni, 50.0g Co, 82.8g Mn and 50.0g Al in an induction melting furnace (ZG type vacuum induction furnace, The same below.) In the crucible, cover the furnace cover and evacuate until the vacuum degree is 10 -1 Pa, filled with argon to a pressure of 0.07MPa, smelted at 1550°C for 2 hours to obtain a metal smelting solution; pour the metal smelting solution into a water-cooled ingot mold, cool it out of the furnace, and obtain an alloy ingot;

[0046] Step (2) Place the alloy ingot of step (1) in a protective atmosphere furnace, and vacuumize to a vacuum degree of 10 -1 Pa, filled with argon to a pressure of 0.08MPa, and annealed at 1020°C for 10h to obtain a magnesium-free A 2 B 7 Type Catalyzed AB 5 Ni-MH battery anode material La 0.42 Ce 0.14 SM 0.42 Zr 0.02 Ni 3.92 co 0.14 mn 0.24 Al 0.30 ;

[0047] the above La 0.42 Ce 0.14 SM 0.42 Zr 0.02 Ni 3.92 co 0.14 mn 0.24 Al 0.30 Th...

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Abstract

The invention relates to a hydrogen storage alloy, an electrode for a Ni-MH battery, a secondary battery and a method for preparing the hydrogen storage alloy. The chemical composition of the hydrogenstorage alloy is represented by the general formula La(3.0-3.2)x CexZrySm (1- (4.0~4.2)x-y)NizCouMnvAlw, wherein x, y, z, u, v, w are molar ratios; 0.14 <= x <= 0.17; 0.02 <= y <= 0 .03; 4.60 <= z +u + v + w <= 5.33; 0.10 <= u <= 0.20; 0.25 <= v <= 0.30; and 0.30 <= w <= 0.40. The overcharge performance of the electrode material is satisfied by fixing a ratio of lanthanum (La) to cerium (Ce) to3.0 - 3.2. A large number of samarium (Sm) elements on a side A are replaced, namely, the ratio of Sm atoms accounts for 25.6 to 42% of the side A to overcome a decrease in service life caused by lowcobalt (Co). The equilibrium pressure is adjusted by changing the ratios of Sm and La to Ce in order to satisfy the charge and discharge dynamics performance of the electrode material. The nucleationrate of a solidification process is increased by adding zirconium (Zr) having an atomic ratio of 2 to 3% relative to the elements at the side A to the elements at the side A. The Ni-MH battery anode material obtained by using the hydrogen storage alloy has high overcharge resistance, high rate discharge performance and good cycle stability.

Description

technical field [0001] The invention relates to the technical field of batteries and battery hydrogen storage materials, in particular to a preparation method of an AB5-based hydrogen storage alloy, an electrode for a nickel-hydrogen battery, a secondary battery and the hydrogen storage alloy. Background technique [0002] Nickel-hydrogen batteries have the advantages of good safety, no pollution, high energy density, no memory effect, and affordable prices. They have become one of the most promising "green energy" batteries and are widely used in portable vehicles such as hybrid vehicles and mobile power supplies. High-power equipment such as electric tools, electronic products, and electric and hybrid vehicles are of great significance for mobile power, resource conservation, energy peak shaving, and environmental protection. [0003] The currently researched hydrogen storage alloy anode materials mainly include AB 5 Type rare earth nickel hydrogen storage alloy, AB 2 Se...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/24H01M4/26H01M4/38H01M10/30
CPCH01M4/242H01M4/26H01M4/385H01M10/30Y02E60/10C22C1/023C22C19/03H01M10/345H01M2004/027H01M4/134C22C2202/04
Inventor 欧阳柳章谈诚朱敏闵德王辉罗统钊肖方明唐仁衡
Owner SOUTH CHINA UNIV OF TECH
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