CN1270396C - Alkaline secondary cell - Google Patents
Alkaline secondary cell Download PDFInfo
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- CN1270396C CN1270396C CNB031400450A CN03140045A CN1270396C CN 1270396 C CN1270396 C CN 1270396C CN B031400450 A CNB031400450 A CN B031400450A CN 03140045 A CN03140045 A CN 03140045A CN 1270396 C CN1270396 C CN 1270396C
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- Prior art keywords
- nickel
- electrode
- alkaline secondary
- secondary cell
- nickel hydroxide
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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
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Abstract
The present invention relates to an alkaline secondary cell which comprises a positive pole, a diaphragm, a negative pole and an electrolytic solution which are arranged in a metallic shell, wherein the positive pole forms a nickel hydroxide electrode in a mode that a nickel hydroxide active substance is coated on an electrode basal body; at least one of alanate, aluminum hydroxide and aluminate in the nickel hydroxide electrode is used as an additive; a weight ratio of aluminum to nickel hydroxide is 0.1 to 5:100. The additive is used, which can enhance the charging efficiency of the alkaline secondary cell at high temperature, enhance the high-temperature discharge capacity and decelerate the circulation volume attenuation at high temperature.
Description
[technical field]
The present invention relates to a kind of alkaline secondary cell, relate to a kind of alkaline secondary cell or rather with nickel hydroxide electrode.
[background technology]
Alkaline secondary cell such as nickel-cadmium cell, Ni-MH battery since its stable performance, cheap price and can adapt to multiple condition of work be subjected to using widely always.With the nickel-cadmium cell is example, and its positive and negative electrode reaction is as follows respectively:
Anodal
Negative pole
Cell reaction:
Nickel-cadmium cell generally is designed to positive limited, and promptly capacity of negative plates is excessive.After positive pole was full of electricity, anodal current potential raise like this, the anodal oxygen evolution reaction that takes place.
And at negative pole, because negative pole is excessive, at this moment the reaction that is taken place is still the charging reaction of active material, if the anodal oxygen that produces can arrive negative pole by barrier film, and negative pole has strong absorbability to oxygen, then at this moment also the oxygen recombination reaction will take place at negative pole, can eliminate the anodal oxygen that produces so effectively, reduce cell internal pressure, negative pole is in the underfill electricity condition always simultaneously.
Above-mentioned is at normal temperatures ideal situation.But under higher ambient temperature, perhaps make at quickly charging battery under the situation of battery temperature rising, have a comparatively serious problem, promptly this moment, the nickel hydroxide electrode charge efficiency was not high.At this moment, because battery temperature is higher, the overpotential of separating out of oxygen reduces on nickel electrode, approach the charging potential of nickel hydroxide electrode, the evolution reaction (formula 4) of oxygen becomes a pair of competitive reaction on the charging reaction (formula 1) of nickel hydroxide electrode and the nickel electrode, thereby make the nickel electrode charging not exclusively, reduce charge efficiency, and then influence discharge capacity of the cell.Simultaneously, because battery is in the state of poor efficiency for a long time, it is more that positive pole is analysed oxygen, will make battery circulation time capacity attenuation very fast.
Be to improve nickel electrode charge efficiency at high temperature, it is poor normally to increase on nickel hydroxide charging reaction (formula 1) and the nickel electrode oxygen evolution reaction (formula 4) equilibrium potential between the two.Can adopt two kinds of methods: (1) reduces the current potential of nickel hydroxide charging reaction; (2) improve oxygen deposition potential on the nickel electrode.
In nickel hydroxide electrode, add the material that contains cobalt, perhaps coat cobalt compound, can make to form the favorable conductive network in the nickel hydroxide electrode, reduce the charging potential of nickel hydroxide electrode at the nickel hydroxide particle surface.But the discharge voltage plateau of battery will be reduced, and this is that we are undesirable.
Therefore, the deposition potential of oxygen is more feasible method on the raising nickel electrode.Generally be in nickel electrode, to add additive, or directly coat crystal layer, change the interfacial property between nickel hydroxide particle and the electrolyte, separate out the purpose of overpotential thereby reach raising oxygen at the nickel hydroxide particle surface.
Application number is in 98123290.6 the Chinese patent, adopt mechanical mode of averaging or reaction crystallization, coat by cobalt compound and be selected from the metal of at least a element in calcium, titanium, niobium, chromium, yttrium, the ytterbium or the crystal layer that oxide is formed at the nickel hydroxide particle surface.Make nickel hydroxide electrode form the conductive network of good homogeneous, improved nickel electrode surface oxygen and separated out overpotential, both improved the charge efficiency under the battery high-temperature, also guaranteed battery discharge capacity at normal temperatures.In addition, propose among the Japanese patent laid-open 6-103973, in nickel electrode, add the oxide or the hydroxide of elements such as a small amount of yttrium, indium, antimony, barium, beryllium, not only can improve nickel electrode charge efficiency at high temperature, can also keep nickel electrode utilance at normal temperatures.
Japanese patent laid-open 9-147908 report: coat by Co (OH) at the nickel hydroxide particle surface
2And Zn (OH)
2, Mg (OH)
2Any solid solution layer of forming among both.Zn (OH)
2, Mg (OH)
2Can improve O
2Separate out overpotential, thereby improve nickel electrode charge efficiency at high temperature.
Japanese patent laid-open 10-79248 proposes, and adds cobalt compound and dysprosium or holmia in nickel electrode, and during primary charging, additive is dissolved into complex ion in electrolyte, and diffusion covers the nickel hydroxide particle surface, thereby improves the O on nickel electrode surface
2Separate out overpotential.
Japanese patent laid-open 5-290879 proposes to add Sr (OH) in nickel electrode
2, can effectively improve O
2Separate out overpotential.
In addition, add cadmium oxide or cadmium hydroxide powder in nickel electrode, the relative scale etc. that improves NaOH in the electrolyte also is a method comparatively commonly used.
Said method can improve nickel electrode charge efficiency at high temperature to a certain extent, but its deficiency is all arranged.As in nickel electrode, adding cadmium oxide or cadmium hydroxide, need more addition just can obtain positive effect, and this will influence the capacity of nickel electrode; For another example, coat crystal layer, the nickel hydroxide manufacturing cost will be increased at the nickel hydroxide particle surface; And for example, in nickel electrode, add some oxides or hydroxide,, make its additive effect not obvious because its solubility in alkali lye is limited; And the relative scale of NaOH will make battery discharge performance at normal temperatures reduce in the raising electrolyte.
[summary of the invention]
The objective of the invention is, provide a kind of employing to have the alkaline secondary cell of higher high-temperature charging efficient.
The objective of the invention is to be achieved through the following technical solutions:
A kind of alkaline secondary cell, comprise positive pole, barrier film, negative pole and electrolyte, be accommodated in the metal shell, wherein, the anodal mode that adopts the nickel hydroxide active material to be coated on the electrode matrix forms nickel hydroxide electrode, also contain at least a as additive in aluminum oxide, aluminium hydroxide, the aluminate in the described nickel hydroxide electrode, wherein the weight ratio of aluminium and nickel hydroxide is 0.1-5: 100.
Technique scheme of the present invention further is improved to:
Described additive is to add in the mode with the blend of nickel hydroxide active material.
Described additive is to inject metal shell by the form that is dissolved in the electrolyte, and deposition covers the nickel hydroxide particle surface.
Described additive also comprises cobalt/cobalt oxide or cobalt hydroxide.
Also comprise at least a in nickel powder, cadmium powder, carbon black, the graphite in the described additive as conductive agent.
Described nickel hydroxide electrode, its matrix are any in nickel foam, nickel fibre felt, the nickel plating perforated steel ribbon.
Described negative pole is any in cadmium oxide electrode, the hydrogen-occlussion alloy electrode.
Described negative pole is to be matrix with in nickel foam, nickel fibre felt, the nickel plating perforated steel ribbon any, coating negative electrode active material mode and the bonded electrode that forms.
The advantage of alkaline secondary cell of the present invention is: battery at high temperature has higher charge efficiency and discharge capacity, and the circulation volume decay under the high temperature is slower.
[description of drawings]
Fig. 1 is embodiment two, three and comparative example cycle performance comparison diagram under 50 ℃ of environment.
[embodiment]
The mode that the positive pole of alkaline secondary cell of the present invention adopts the nickel hydroxide active material to be coated on the electrode matrix forms nickel hydroxide electrode, also contain at least a in aluminum oxide, aluminium hydroxide, the aluminate in the described nickel hydroxide electrode as additive, because above-mentioned additive is easy to dissolving in alkaline electrolyte, the diffusion of dissolving back covers the nickel hydroxide particle surface, can effectively improve nickel electrode surface O
2Separate out overpotential, improve battery charge efficiency at high temperature, thereby at high temperature had alkaline secondary cell than high discharge capacity and better cycle performance; In electrolyte, add at least a in aluminum oxide, aluminium hydroxide, the aluminate and also can reach identical purpose.
The addition of above-mentioned additive is eligible to be: the weight ratio of aluminium and nickel hydroxide is 0.1-5: 100, and the weight ratio of aluminium and nickel hydroxide is big more, and battery high-temperature charging efficient is also good more; But the weight ratio of aluminium and nickel hydroxide is excessive, and the nickel hydroxide activity substance content reduces, and the battery actual capacity also reduces.The weight ratio of aluminium and nickel hydroxide is less than 0.1%, and then too small because of the relative nickel hydroxide active material of aluminium weight ratio, additive containing aluminium works hardly.Take all factors into consideration, the inventor thinks that the weight ratio of aluminium and nickel hydroxide is 0.1-5: the 100th, and proper.
With the nickel-cadmium cell be below example the present invention is described in detail, wherein, nickel hydroxide active material and additive are all by weight.
[embodiment one]
The making of nickel positive pole: with 100 parts of ball-shape nickel hydroxides, 9 parts of nickel powders, 6 parts of cobalt protoxides and to contain aluminium weight be that 0.1 part aluminium hydroxide and CMC solution is mixed into pasty slurry, be filled in the foaming Ni substrate, drying, roll-in, cut into and be of a size of 365mm * 47mm * 0.7mm, make the positive plate that rated capacity is 4500mAh.
The making of cadmium cathode: the cadmium oxide powder is mixed together into pasty slurry with CMC solution and water, being applied to thickness is on the perforation nickel plated steel strip of 0.10mm, drying, scraper, roll-in, cut into and be of a size of 445mm * 47.8mm * 0.68mm, make corresponding negative plate.
Battery is made: anodal and cadmium cathode therebetween is wound into scroll pole piece group then with barrier film at nickel, and this pole piece is assembled into the circular metal shell, and through fluid injection, seal, making nominal capacity is the D type nickel-cadmium cell of 4500mAh.
[embodiment two]
The making of nickel positive pole: with 100 parts of ball-shape nickel hydroxides, 9 parts of nickel powders, 6 parts of cobalt protoxides and to contain aluminium weight be that 1 part aluminium hydroxide and CMC solution is mixed into pasty slurry, be filled in the foaming Ni substrate, drying, roll-in, cut into and be of a size of 365mm * 47mm * 0.7mm, make the positive plate that rated capacity is 4500mAh.
The making of cadmium cathode: identical with embodiment one.
Battery is made: with embodiment one, battery is designated as A1.
[embodiment three]
Basic identical with embodiment two, but aluminium hydroxide is to add with the form that is present in the electrolyte, addition is identical with embodiment two, and the gained battery is designated as A2.
[embodiment four]
The making of nickel positive pole: with 100 parts of ball-shape nickel hydroxides, 10 parts of nickel powders, 6 parts of cobalt protoxides and to contain aluminium weight be that 5 parts aluminium hydroxide and CMC solution is mixed into pasty slurry, be filled in the foaming Ni substrate, drying, roll-in, cut into and be of a size of 365mm * 47mm * 0.7mm, make the positive plate that rated capacity is 4500mAh.
The making of cadmium cathode: identical with embodiment one.
Battery is made: with embodiment one.
[comparative example]
The making of nickel positive pole: 100 parts of ball-shape nickel hydroxides, 9 parts of nickel powders, 6 parts of cobalt protoxides and 1 part of cadmium oxide and CMC solution are mixed into pasty slurry, be filled in the foaming Ni substrate, drying, roll-in, cut into and be of a size of 365mm * 47mm * 0.7mm, make the positive plate that rated capacity is 4500mAh.
The making of cadmium cathode: with embodiment one.
Battery is made: with embodiment one, battery is designated as B.
[Performance Detection]
The foregoing description, comparative example battery carry out following performance test after charge and discharge change into:
High-temperature charging efficiency test: at first under 20 ℃ ambient temperature, embodiment and comparative example battery with 1/17C multiplying power current charges 16 hours, were shelved 30 minutes; Then with 0.2C multiplying power current discharge to 1.0V, record discharge time is t
20Respectively under 45 ℃, 65 ℃ ambient temperature, adopt the system of discharging and recharging same as described above to test then, be designated as t discharge time respectively
45, t
65
Charge efficiency E at high temperature is calculated as follows:
E
45＝t
45×100％/t
20
E
65＝t
65×100％/t
20
Embodiment and comparative example battery high-temperature charging efficient comparative result see the following form:
| Ambient temperature | Embodiment one | Embodiment two | Embodiment three | Embodiment four | Comparative example |
| 45℃ | 83％ | 92％ | 93％ | 94％ | 81％ |
| 65℃ | 64％ | 78％ | 80％ | 79％ | 62％ |
Cycle life test: under 50 ℃ of ambient temperatures, embodiment and comparative example battery with 1/17C multiplying power current charges 24 hours, were shelved 30 minutes; Then with 0.5C multiplying power current discharge to 1.0V.Repeat said process, the record discharge capacity relatively.Fig. 1 is embodiment two, three and the cycle performance comparison diagram of comparative example under 50 ℃ of environment.
As can be seen from Table 1, alkaline secondary cell of the present invention at high temperature has higher charge efficiency; Fig. 1 shows, alkaline secondary cell of the present invention at high temperature has higher discharge capacity, and the high temperature cyclic performance of battery has clear improvement.
Claims (8)
1. alkaline secondary cell, comprise positive pole, barrier film, negative pole and electrolyte, be accommodated in the metal shell, wherein, the anodal mode that adopts the nickel hydroxide active material to be coated on the electrode matrix forms nickel hydroxide electrode, it is characterized in that: also contain at least a as additive in aluminum oxide, aluminium hydroxide, the aluminate in the described nickel hydroxide electrode, wherein the weight ratio of aluminium and nickel hydroxide is 0.1-5: 100.
2. according to the alkaline secondary cell described in the claim 1, it is characterized in that: described additive is to add in the mode with the blend of nickel hydroxide active material.
3. according to the alkaline secondary cell described in the claim 1, it is characterized in that: described additive is to inject metal shell by the form that is dissolved in the electrolyte, and deposition covers the nickel hydroxide particle surface.
4. according to the alkaline secondary cell described in claim 1 or 2 or 3, it is characterized in that: described additive also comprises cobalt/cobalt oxide or cobalt hydroxide.
5. according to the alkaline secondary cell described in the claim 4, it is characterized in that: also comprise at least a in nickel powder, cadmium powder, carbon black, the graphite in the described additive as conductive agent.
6. alkaline secondary cell according to claim 1 is characterized in that: described nickel hydroxide electrode, its matrix are any in nickel foam, nickel fibre felt, the nickel plating perforated steel ribbon.
7. alkaline secondary cell according to claim 1 is characterized in that: described negative pole is any in cadmium oxide electrode, the hydrogen-occlussion alloy electrode.
8. according to claim 1 or 7 described alkaline secondary cells, it is characterized in that: described negative pole is to be matrix with in nickel foam, nickel fibre felt, the nickel plating perforated steel ribbon any, coating negative electrode active material mode and the bonded electrode that forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031400450A CN1270396C (en) | 2003-08-02 | 2003-08-02 | Alkaline secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031400450A CN1270396C (en) | 2003-08-02 | 2003-08-02 | Alkaline secondary cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1581541A CN1581541A (en) | 2005-02-16 |
| CN1270396C true CN1270396C (en) | 2006-08-16 |
Family
ID=34579204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031400450A Expired - Fee Related CN1270396C (en) | 2003-08-02 | 2003-08-02 | Alkaline secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1270396C (en) |
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2003
- 2003-08-02 CN CNB031400450A patent/CN1270396C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1581541A (en) | 2005-02-16 |
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