CN1187696A - Hydrogen-occluding alloy pretreatment method, and its use - Google Patents
Hydrogen-occluding alloy pretreatment method, and its use Download PDFInfo
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- CN1187696A CN1187696A CN97118613A CN97118613A CN1187696A CN 1187696 A CN1187696 A CN 1187696A CN 97118613 A CN97118613 A CN 97118613A CN 97118613 A CN97118613 A CN 97118613A CN 1187696 A CN1187696 A CN 1187696A
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
A method of pretreating a hydrogen-occluding alloy, by electrically plating the hydrogen-occluding alloy with a Co-V alloy or a Co-Mo alloy. A nickel-hydrogen secondary battery manufactured using the pretreated hydrogen-occluding alloy has an increased initial activation rate and an increased high rate discharge characteristic.
Description
The present invention relates to a secondary battery, and more particularly, to a method for pretreating a hydrogen-absorbing alloy (hydrogen-absorbing alloy), a hydrogen-absorbing alloy pretreated by the method, and a nickel-hydrogen secondary battery using the pretreated hydrogen-absorbing alloy as an anode.
Since hydrogen is burned into water, unlike fossil fuels, carbon dioxide gas is not generated, and thus hydrogen can be used as a clean energy source. If this property is applied electrochemically, hydrogen is oxidized to water when it generates electrical energy, i.e., is discharged. If the water is re-supplied with electrical energy, i.e. charged, the hydrogen is restored. In this case, if oxygen is used for the cathode, the hydrogen and oxygen are mixed in the container unless a special cell structure is used. In order to prevent this phenomenon, nickel is used for the cathode of the nickel-hydrogen battery that has been used, and a hydrogen-occluding alloy is used for the anode.
In particular, a nickel-hydrogen secondary battery using a hydrogen-occluding alloy as an anode active material is more widely used than a nickel-zinc battery or a nickel-cadmium battery. This is because the hydrogen-occluding alloy itself exhibits little charge and high efficiency of active material utilization, and its specific gravity is larger than cadmium (Cd) or zinc (Zn), so that the volumetric energy density of the battery can be increased.
A nickel-hydrogen storage battery comprises a nickel cathode, an anode made of a hydrogen-occluding alloy, an electrolytic solution made of an aqueous alkali solution, and a separator which is highly hydrophilic and stable in the aqueous alkali solution.
During charging, the reaction of the cathode and anode of a nickel-hydrogen battery can be represented by the following formula:
cathode:
anode:
total cell reaction: where M denotes a hydrogen occluding alloy.
The hydrogen occluding alloy capable of reversibly occluding and releasing hydrogen occludes hydrogen generated from the anode during charging and releases hydrogen during discharging, so that electrochemical consumption of hydrogen occurs on the surface thereof.
General hydrogen occluding alloys are mainly classified into AB series alloys such as TiFe; AB2Alloys of the series, e.g. ZrMn2、ZrV2And ZrNi2And the like; AB5Alloys of the series, e.g. CaNi5、LaNi5And MmNi5(Mm: a mixture of rare earth metals; a group of rare earth metals, e.g. La or Ce) and A2Alloys of the B series, e.g. Mg2Ni and Mg2Cu or the like, where A represents an exothermic metal and B represents an endothermic metal. If the battery is to use a hydrogen-occluding alloy, its capacity for occluding hydrogen must be excellent, the equilibrium pressure for occluding and releasing hydrogen must be about 0.1 to 5MPa, and it must have strong corrosion resistance.
However, in the active material in the form of an hydrogen-occluding alloy forming the anode of a nickel-hydrogen battery, a metal component such as Co, Mn, or Vd is easily dissolved in an alkaline solution and exists as an impurity. Therefore, if the hydrogen occluding alloy forming the anode is used with a strongly alkaline electrolytic solution for a long period of time, the anode composition is changed to shorten the battery life, which impairs the battery performance.
Therefore, if the hydrogen occluding alloy is to be used as an anode material, the alloy surface needs to be pretreated.
The hydrogen-occluding alloy is generally pretreated in an aqueous alkali solution at 80 ℃ for several hours, and stirred with a glass rod or mechanically stirred with a glass rod with a propeller. By this pretreatment, the oxide film on the surface of the hydrogen-occluding alloy is removed, and a specific metal component is stripped from the surface of the alloy to change the composition of the surface of the alloy. An anode for a nickel-hydrogen battery is produced by pretreating an occluding hydrogen alloy, thereby improving the performance of the battery.
AB pretreated by etching in alkaline solution5When the series occludes the hydrogen alloy, the electrode produced by this is sufficiently activated after 2 to 3 cycles, and exhibits a high capacitanceat a high discharge current of about 1C. That is, the high-rate discharge characteristic is excellent. However, the problems arising from the severity of the alkaline etching process itself cannot be avoided. When AB is based on Zr or Ti2When the series of hydrogen occluding alloys is not sufficiently activated by such alkali treatment, then the electrode produced with the material requires cycles of charge and discharge of about 10 to 20 for activation. In addition, if the discharge current increases, the capacitance sharply decreases. AB based on Zr or Ti2The drastic reduction in the capacitance of the series alloy is due to its poor electrochemical catalytic properties. Therefore, in order to solve this problem,separate processing must be performed.
In order to solve the above problems, it is an object of the present invention to provide a pretreatment method of a hydrogen-occluding alloy to increase the initial activation rate of a nickel-hydrogen battery and improve high-rate discharge characteristics.
It is another object of the present invention to provide a hydrogen occluding alloy which has excellent high-rate discharge characteristics after being pretreated by the above pretreatment method.
It is another object of the present invention to provide a nickel-hydrogen storage battery using an anode pretreated with a hydrogen-occluding alloy as an active material.
Therefore, in order to attain the first object, there is provided a pretreatment method of a hydrogen-occluding alloy, comprising electroplating a Co-V alloy or a Co-Mo alloy onto a surface of the hydrogen-occluding alloy.
The pretreated hydrogen occluding alloy is provided with an electroplated layer made of Co-V alloy or Co-Mo alloy, thereby achieving the second object.
The nickel-hydrogen storage battery uses the hydrogen-absorbing alloy plated with Co-V alloy or Co-Mo alloy as the anode to achieve the third purpose.
The hydrogen occluding alloy is preferably AB based on Zr or Ti2A series of alloys.
In the present invention, a nickel-hydrogen storage battery is provided, in which the initial activation rate of the battery is increased by pretreating a hydrogen-occluding alloy with a Co-V alloy or a Co-Mo alloy.
The content of the plating layer is preferably 1 to 20% by weight based on the hydrogen occluding alloy of the present invention. If the content of the plating layer is less than 1% by weight, the plating pretreatment is not so effective. On the contrary, if the plating layer content is more than 20% by weight, the absolute amount of the hydrogen-occluding alloy is decreased, and the hydrogen gas storage amount is decreased, which is not desirable.
Further, the plating composition for plating the hydrogen occluding alloy contains cobalt sulfate (CoSO)4) Sodium citrate and urea, preferably in concentrations of 0.1-2mol/l, 0.1-1mol/l and 1-5mol/l, respectively. In addition, the Co-V electroplated plating composition also contains vanadium oxide (V)2O5) The electroplating composition for Co-Mo electroplating also includes ammonium molybdate. In this case, the contents of vanadium oxide and ammonium molybdate are preferably 10 respectively-5-10-1mol/l. Within this range, the plating process proceeds smoothly. During the electroplating process, the electroplating current is preferably 100-700mA/cm2。
The present invention will be described in detail below by way of examples. However, the present invention is not limited to the following examples.
Example 1
Hydrogen occluding alloy (ZrNi) produced by high frequency induction furnace1.1V0.3Mn0.4Cr0.1Co0.1) And then crushed. From crushed alloysA powder with a particle diameter of about 75 μm was selected. 500g of the selected powder was put into an electrode composed of a nickel mesh, and then placed in an electroplating apparatus.
Using a catalyst consisting of 0.5mol/l CoSO40.5mol/l sodium citrate, 0.0004mol/l V2O5And 3mol/l urea to form a Co-V plating layer on the surface of the hydrogen-occluding alloy. In addition, pure cobalt was used as the electrode. While the solution was slowly stirred with argon, the plating was carried out at room temperature for 10 minutes to form a Co-V plating layer on the surface of the hydrogen occluding alloy at a current of 300mA/cm2。
The paste was produced by a conventional electrode forming method using a pretreated hydrogen occluding alloy, polyvinyl alcohol (PVA) and water. The nickel foam having a porosity of not less than 95% was filled with a paste, dried, and then extruded to produce a hydrogen-occluding alloy anode. A nickel hydroxide anode having a capacity twice that of the anode was used as a counter electrode of the anode, and a 31 wt% aqueous solution of potassium hydroxide was used as an electrolytic solution, thereby forming a half cell. The charge and discharge cycles of the half cell were repeated to determine the activation rate, here charging for 15 hours to 150% with 0.1C, and then discharging at 0.1C until the cell voltage reached 0.9V. After the battery was completely activated, it was charged with 0.1C under the same conditions until the battery voltage reached 0.9V to evaluate its high-rate discharge characteristics. The results are shown in Table 1.
Example2
A plating layer formed of a Co-Mo alloy was formed on the surface of the hydrogen occluding alloy in the same manner as described in example 1 except that ammonium molybdate was used in place of V2O5Producing the electroplating solution. Subsequently, charge and discharge tests were performed in the manner described in example 1, and the results thereof are also shown in table 1.
Comparative example
For comparison, a nickel-hydrogen storage battery was produced using the hydrogen occluding alloy without an electroplated layer in the same manner as described in example 1, and then subjected to a test. The results are shown in Table 1.
TABLE 1
| Number of cycles | 1 | 3 | 10 | 20 | High speed (1C) Discharge capacity |
| Example 1 | 270mAh/g | 322mAh/g | 327mAh/g | 330mAh/g | 290mAh/g |
| Example 2 | 275mAh/g | 325mAh/g | 330mAh/g | 330mAh/g | 300mAh/g |
| Comparative example | 50mAh/g | 100mAh/g | 250mAh/g | 320mAh/g | 200mAh/g |
As is clear from the results of the examples and comparative examples, the activation rate of a nickel-hydrogen storage battery is greatly improved and the high-rate discharge characteristic thereof is also greatly enhanced by using as the anode the hydrogen-occluding alloy having a plated layer of Co-Mo alloy or Co-V alloy pretreated in accordance with the present invention.
As described above, according to the present invention, the hydrogen-occluding alloy having a plating layer formed of a Co-Mo alloy or a Co-V alloy is used as an anode active material of a nickel-hydrogen storage battery, so that the initial activation rate can be greatly increased and the high-rate discharge characteristics can be greatly improved, thereby expanding the range of applications of the battery.
Claims (9)
1. A method of pretreatment comprising the steps of:
a Co-V alloy or a Co-Mo alloy is plated on the surface of the hydrogen occluding alloy.
2. The pretreatment method according to claim 1, wherein the hydrogen occluding alloy is AB based on Zr or Ti2A series of alloys.
3. The pretreatment method according to claim 1, wherein a plating current during plating is 100mA/cm2。
4. The pretreatment method of claim 1, wherein the Co-V electroplating solution comprises cobalt sulfate (CoSO)4) Sodium citrate, urea and vanadium oxide (V)2O5)。
5. The pretreatment method of claim 1, wherein the Co-Mo electroplating solution comprises cobalt sulfate (CoSO)4) Sodium citrate, urea and ammonium molybdate.
6. A hydrogen occluding alloy pretreated by the method of claim 1, which has a plating layer made of a Co-V alloy or a Co-Mo alloy.
7. The hydrogen occluding alloy according to claim 6, wherein the hydrogen occluding alloy is AB based on Zr or Ti2A series of alloys.
8. A nickel-hydrogen storage battery using an anode having a hydrogen occluding alloy plated with a Co-V alloy or a Co-Mo alloy as an active material.
9. The nickel-hydrogen storage battery according to claim 8, wherein the hydrogen occluding alloy is AB based on Zr or Ti2A series of alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118613A CN1187696A (en) | 1996-12-31 | 1997-09-15 | Hydrogen-occluding alloy pretreatment method, and its use |
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| Application Number | Priority Date | Filing Date | Title |
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| KR80194/96 | 1996-12-31 | ||
| CN97118613A CN1187696A (en) | 1996-12-31 | 1997-09-15 | Hydrogen-occluding alloy pretreatment method, and its use |
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| CN1187696A true CN1187696A (en) | 1998-07-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465313A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Method for pretreating lead base inert anode for electro-deposit copper |
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1997
- 1997-09-15 CN CN97118613A patent/CN1187696A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465313A (en) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | Method for pretreating lead base inert anode for electro-deposit copper |
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