CN1175120C - New-type hydrogen-storing RE electrode alloy and its heat treatment process - Google Patents
New-type hydrogen-storing RE electrode alloy and its heat treatment process Download PDFInfo
- Publication number
- CN1175120C CN1175120C CNB011452501A CN01145250A CN1175120C CN 1175120 C CN1175120 C CN 1175120C CN B011452501 A CNB011452501 A CN B011452501A CN 01145250 A CN01145250 A CN 01145250A CN 1175120 C CN1175120 C CN 1175120C
- Authority
- CN
- China
- Prior art keywords
- alloy
- electrode
- storing
- hydrogen
- new
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses novel hydrogen-storing RE electrode alloy and a heat treatment method thereof. A molecular formula of the novel hydrogen-storing RE electrode alloy is A<1-y>B<y>C<x>, wherein A is composed of one or two or more than two kinds of components of La, mixed rare earth Ml rich in the La, Ce, mixed rare earth Mm rich in the Ce, Pr and Nd, B is composed of one or two or more than two kinds of components of Mg, Ca, Be, Sr and Ba C is composed of one or two or more than two kinds of components of Mn, Fe, Mo, Co, Al, Si, Ga, S, Pt, Sc, Ti, V, Cr, Cu, Zn, Zr, Nb, Ru, Pd, Cd, W, Hf, Ta, B and P and y and x meet the following requirements of 0.01 <=y<=0.8 and 2.0<=x<=4.0. The heat treatment method of the present invention comprises the steps that firstly, the hydrogen-storing electrode alloy is heated up to certain temperature under high vacuum environment; then, heat is preserved for numbers of hours for annealing treatment. Because an internal structure of the electrode alloy which is treated by using the heat method is more uniform, and some segregation phases are eliminated simultaneously, the electrochemical performance of discharge capacity, cycle life, etc. of an alloy electrode is obviously improved.
Description
Technical field
The present invention relates to secondary cell, especially relate to a kind of nickel-metal hydrides (Ni-MH) secondary battery cathode material New-type hydrogen-storing RE electrode alloy and preparation method thereof.
Background technology
In recent years; along with popularizing of household electrical appliance such as mobile telephone, portable computer and pick up camera; demand to chargeable battery increases day by day, and simultaneously because requirement on environmental protection, countries in the world all have high-energy-density, long lifetime and pollution-free green battery being devoted to research.Because nickel-metal hydrides (Ni-MH) secondary cell, with respect to the Ni-Cd secondary cell, advantages such as having the capacity height, have extended cycle life, memory-less effect, anti-over-charging are crossed the strong and non-environmental-pollution of exoergic power and become the focus of lot of domestic and foreign scholar's research.
The anodal general nickel electrode that adopts of nickle-metal hydride secondary battery, negative material then is selected from hydrogen-storage alloy.Theoretically, the hydrogen-storage alloy that can be used as the Ni-MH secondary battery cathode material comprises rare earth based AB
5Type alloy, AB
2Type Laves phase alloy, Magnuminium and vanadium radical sosoloid alloy.Wherein, people are to rare earth based AB
5The research of type alloy is the most ripe, and it has high-energy-density density, high charge-discharge speed, and overcharging resisting, cross and put, memory-less effect, good comprehensive performances such as low pollution have now realized industrialization production.But, rare earth based AB
5Type hydrogen-occlussion alloy electrode finite capacity is about about 280～320mAh/g, and the shortcoming of their ubiquity battery lack of homogeneitys.Here except that cell integrated design, negative pole technology and the influence of other associated materials, unstable properties also was one of reason during storage alloy material for hydrogen was produced in enormous quantities.In addition, from the requirement in Ni/MH battery practical application market, battery need reach 1C, 100%DOD, and cycle life improves the erosion resistance of alloy material in alkaline electrolyte and is still an important topic more than 500 time.Moreover, battery in the 1C charging later stage, press too high and when 1C discharges average voltage on the low side, this also is a big problem.
At present in the world the research of high-performance hydrogen-storage electrode metal is mainly concentrated on AB
2Type Laves hydrogen storage alloy phase, magnesium base hydrogen-storing alloy and vanadium radical sosoloid alloy.AB
2Type Laves hydrogen storage alloy phase exists alloy P-C-T curve platform gradient bigger, and the electrode surface reaction resistance is higher, causes the high-rate discharge ability of electrode relatively poor relatively bigger with the inclination of battery discharge voltage platform.In addition, AB
2Also there are problems such as the initial stage activation is difficult, the prices of raw and semifnished materials are higher relatively in type Laves hydrogen storage alloy phase.
The V radical sosoloid alloy is not owing to itself possess electrode activity, thereby its electrochemical applications seldom studied, though studies show that recently by after separating out the good TiNi grade in an imperial examination two-phase of electro catalytic activity on the crystal boundary of V based solid solution, can obtain high electrochemistry capacitance, but its cyclical stability is very poor, remain further to be studied to improve, and the price of V is higher.
Magnesium base hydrogen-storing alloy is a much-talked-about topic in the research of Ni/MH battery, but the chemical impellent of Mg-H reaction is very low, and the hydride of formation is too stable, is difficult to carry out more much practical applications.Alloy loading capacity decline simultaneously is very fast, and the corrosion in alkaline electrolyte is still a great problem, and also need effort for a long time make a breakthrough.
New-type hydrogen-storing RE electrode alloy has higher electrochemical discharge capacity.Kohno has studied La
5Mg
2Ni
23The electrochemical discharge capacity of type hydrogen-occlussion alloy electrode can reach 400mAh/g, has surmounted rare earth based AB greatly
5The loading capacity of type hydrogen-occlussion alloy electrode.And its alloy electrode has good cyclical stability, good high magnification characteristic and advantage such as activation capacity and low price and has demonstrated powerful application prospect in electrolytic solution.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of New-type hydrogen-storing RE electrode alloy.
1) New-type hydrogen-storing RE electrode alloy places vacuum magnetic suspension smelting furnace or arc melting, and the molecular formula of said alloy is A
1-yB
yC
xWherein A is one or both or the two or more composition among La, Ce, Pr, the Nd, B is one or both compositions among Mg, the Ca, C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ga, S, Ti, V, Cr, Cu, Zn, Zr, B, the Sn, 0.01≤y≤0.8,2.0≤x≤4.0.
2) melted as cast condition hydrogen-storing alloy as electrode is placed on is evacuated to 10 in the vacuum annealing furnace
-2-10
-5Pascal;
3) hydrogen-storing alloy as electrode is heated to 650-1300 ℃ and be incubated 1-48 hour;
4) the hydrogen-storing alloy as electrode furnace cooling after the insulation is handled.
The A that adopts preparation method of the present invention to handle
1-yB
yC
xAfter hydrogen-storing alloy as electrode, the especially 850-950 ℃ * 8h thermal treatment, the loading capacity of alloy electrode is greatly improved, and simultaneously, the cyclical stability of alloy electrode also is improved, thereby has improved A
1-yB
yC
xThe comprehensive electrochemical of hydrogen-storing alloy as electrode.A of the present invention
1-yB
yC
xThe heat treating method of hydrogen-storing alloy as electrode will (comprise rare earth based AB for improving other hydrogen-storing alloy as electrode
5Type alloy, AB
2Type alloy, Magnuminium and vanadium radical sosoloid alloy) comprehensive electrochemical provide the reference frame of usefulness.
Description of drawings
Accompanying drawing is the loading capacity of cast alloy electrode of the alloy electrode handled according to embodiment and unprocessed mistake and the relation curve between the cycle index.
Embodiment
Novel rare-earth is A
1-yB
yC
xThe Heating temperature of the annealing furnace among the preparation method of hydrogen-storing alloy as electrode is 950 ℃, and soaking time is 8h.
Embodiment
According to novel rare-earth is A
1-yB
yC
xThe design mix of hydrogen-storing alloy as electrode adopts vacuum magnetic suspension stove or arc melting alloy, is designated as alloy X.Wherein, the purity of alloy constituent element is all more than 90%.Get alloy part X and enclose respectively in the vitreosil Glass tubing, the vacuum tightness in the quartz glass tube is 10
-5Pascal.Respectively pipe is put into annealing furnace then and carry out heat tracing.Heating condition is 950 ℃ * 8h, treat that soaking time arrives after, turn off annealing furnace, the alloy furnace cooling.The test of chemical property is to carry out in an open type three-electrode system, and it comprises a working electrode (being hydrogen-occlussion alloy electrode), a sintering Ni (OH)
2/ NiOOH supporting electrode and a Hg/HgO reference electrode.Electrolytic solution adopts the 6N KOH aqueous solution, and probe temperature remains on 303K.All test electrodes all are to form by uniform mixing 100mg hydrogen-storage alloy powder (300 order) and 300mg carbonyl nickel powder and the electrode slice that is pressed into diameter 10mm, thickness 1mm under the pressure of 20Mpa.Electrode adopts the electric current of 400mA/g to charge and discharge, and wherein the duration of charging is 5 hours, and the discharge stopping potential is-0.5V (with respect to the Hg/HgO reference electrode).
Comparing embodiment
The alloy X of melting does not do any processing among the selected part embodiment, makes electrode and carries out the test of electrochemistry cycle life according to the described method of embodiment.
From figure as can be seen, the high electrochemistry capacitance of alloy X under as-cast condition only has 357mAh/g, and after carrying out 950 ℃ * 8h thermal treatment, its high electrochemistry capacitance becomes 396mAh/g, improved 39mAh/g, and after 250 circulations, its capacity still is higher than the loading capacity of cast alloy.
Claims (2)
1. the preparation method of a New-type hydrogen-storing RE electrode alloy is characterized in that, it comprises the following steps:
1) New-type hydrogen-storing RE electrode alloy places vacuum magnetic suspension smelting furnace or arc melting, and the molecular formula of said alloy is A
1-yB
yC
xWherein A is one or both or the two or more composition among La, Ce, Pr, the Nd, B is one or both compositions among Mg, the Ca, C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ga, S, Ti, V, Cr, Cu, Zn, Zr, B, the Sn, 0.01≤y≤0.8,2.0≤x≤4.0.
2) melted as cast condition hydrogen-storing alloy as electrode is placed on is evacuated to 10 in the vacuum annealing furnace
-2-10
-5Pascal;
3) hydrogen-storing alloy as electrode is heated to 650-1300 ℃ and be incubated 1-48 hour;
4) the hydrogen-storing alloy as electrode furnace cooling after the insulation is handled.
2. the preparation method of a kind of New-type hydrogen-storing RE electrode alloy according to claim 2 is characterized in that, the Heating temperature of said annealing furnace is 850-950 ℃, and soaking time is 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011452501A CN1175120C (en) | 2001-12-26 | 2001-12-26 | New-type hydrogen-storing RE electrode alloy and its heat treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011452501A CN1175120C (en) | 2001-12-26 | 2001-12-26 | New-type hydrogen-storing RE electrode alloy and its heat treatment process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1375571A CN1375571A (en) | 2002-10-23 |
| CN1175120C true CN1175120C (en) | 2004-11-10 |
Family
ID=4678093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011452501A Expired - Fee Related CN1175120C (en) | 2001-12-26 | 2001-12-26 | New-type hydrogen-storing RE electrode alloy and its heat treatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1175120C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100399607C (en) * | 2004-03-23 | 2008-07-02 | 株式会社东芝 | Nonaqueous electrolyte secondary battery |
| CN102517487B (en) * | 2011-12-13 | 2013-11-06 | 浙江大学 | Hydrogen-storage alloy producing high-pressure hydrogen |
| CN105970069B (en) * | 2016-05-16 | 2018-10-02 | 昆明贵金属研究所 | More pivot equimolars are than noble metal high-entropy alloy |
| CN114107739B (en) * | 2021-11-10 | 2022-05-10 | 浙江大学 | Solid rare earth hydrogen storage alloy with low hysteresis and high pulverization resistance and preparation and application thereof |
-
2001
- 2001-12-26 CN CNB011452501A patent/CN1175120C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1375571A (en) | 2002-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Effects of size of nickel powder additive on the low-temperature electrochemical performances and kinetics parameters of AB5-type hydrogen storage alloy for negative electrode in Ni/MH battery | |
| CN102104146B (en) | Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof | |
| CN101552337A (en) | Superlattice hydrogen storage alloy and preparation method thereof | |
| CN1235302C (en) | New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment | |
| CN1235301C (en) | New type hydrogen storage alloy as well as method of its preparation and quench treatment method | |
| CN1175120C (en) | New-type hydrogen-storing RE electrode alloy and its heat treatment process | |
| CN1173055C (en) | New-type hydrogen-storing RE electrode alloy for secondary Ni-metal oxide battery | |
| Zhang et al. | Structure and electrochemical hydrogen storage characteristics of La0. 8− x Pr x Mg0. 2Ni3. 15Co0. 2Al0. 1Si0. 05 (x= 0–0.4) electrode alloys | |
| CN1175121C (en) | Hydrogen-bearing rare-earth alloy as electrode and its quenching process | |
| CN1129196C (en) | Rare-earth alloys for hydrogen-bearing electrode and its preparing process | |
| CN1162924C (en) | Nickel-metal hydride (Ni-MH) secondary cell | |
| CN1205680C (en) | Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy | |
| CN1234891C (en) | New-type of hydrogen-storing alloy and its fast solidifying prepn process | |
| CN1173057C (en) | Hydrogen-bearing mixed rare-earth alloy as electrodes of secondary nickel-metal oxide battery | |
| CN1173056C (en) | High-capacity long-service-life hydrogen-bearing rare-earth alloy as electrodes of secondary nickel-metal oxide battery | |
| Zhang et al. | Structures and electrochemical hydrogen storage performance of Si added A2B7-type alloy electrodes | |
| CN101383413B (en) | AB5 type negative pole hydrogen storing material | |
| Zhong et al. | Electrochemical kinetic performance of V–Ti-based hydrogen storage alloy electrode with different particle sizes | |
| CN1141745C (en) | Non-stoichiometric low-co hydrogen-bearing electrode material | |
| CN115261675B (en) | Single-phase or multi-phase AB 4 La-Y-Ni based superlattice hydrogen storage alloy and preparation method thereof | |
| CN1102014A (en) | Magnesium base hydrogen-storing alloy electrode | |
| Cao et al. | Effects of Mo0. 46Fe0. 54 Alloy on Microstructure and Electrochemical Hydrogen Storage Performances of La0. 75Ce0. 25Ni4. 2Mn0. 9-xCu0. 3 (Mo0. 46Fe0. 54) x (x= 0-0.20) Alloys | |
| CN1297021C (en) | Cathode material in use for nickel-hydrogen battery in high capacity | |
| CN1111917C (en) | Process for preparing alloy material as negative electrode of Ni-H battery | |
| CN1129195C (en) | Mixed RE-Ni-Hz electrode alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |