CN102082302A - Nickel hydrogen secondary battery - Google Patents
Nickel hydrogen secondary battery Download PDFInfo
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- CN102082302A CN102082302A CN2009101884460A CN200910188446A CN102082302A CN 102082302 A CN102082302 A CN 102082302A CN 2009101884460 A CN2009101884460 A CN 2009101884460A CN 200910188446 A CN200910188446 A CN 200910188446A CN 102082302 A CN102082302 A CN 102082302A
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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 invention provides a nickel hydrogen secondary battery, and belongs to the field of nickel hydrogen batteries. The battery comprises a battery shell, an electrode group and an alkaline electrolyte, wherein the electrode group and the alkaline electrolyte are sealed in the battery shell, and the electrode group comprises a positive electrode, a negative electrode and a clapboard. The nickel hydrogen secondary battery is characterized in that the alkaline electrolyte is a gel electrolyte, and the gel electrolyte comprises carboxymethyl cellulose, hydroxides of alkali metal and water. The nickel hydrogen battery electrolyte provided by the invention is difficult to freeze up, the loss of the electrolyte is less in long-term usage, the electrolyte does not leak under the condition of high current, and the low temperature discharge performance is good.
Description
Technical field
The present invention relates to a kind of secondary cell, relate in particular to a kind of nickel-hydrogen secondary cell.
Background technology
In recent years, because the development of mobile electronic device and the revolution of traffic power source, the research and development of the high-energy battery energy have become the focus of countries in the world academia and Industrial Revolution.Nickel-hydrogen secondary cell is subjected to extensive attention because of advantage such as energy height, fail safe are good, pollution-free, memory-less effect, is one of main supplying cell type of electronic equipment.
At present, the electrolyte of nickel-hydrogen secondary cell mainly is the dense KOH aqueous solution, but electrolyte can freeze when being to use the dense KOH aqueous solution to use at a lower temperature as the electrolyte of Ni-MH battery, can't discharge and recharge again, causes the low temperature discharge efficient of Ni-MH battery lower.
Summary of the invention
The technical problem to be solved in the present invention is the inefficient defective of electrolyte low temperature discharge of existing nickel-hydrogen secondary cell, thereby provides a kind of low temperature discharge efficient high nickel-hydrogen secondary cell.
The invention provides a kind of nickel-hydrogen secondary cell, this battery comprises battery container, electrode group and alkaline electrolyte, described electrode group and alkaline electrolyte are sealed in the battery container, described electrode group comprises positive pole, negative pole and dividing plate, wherein, described alkaline electrolyte is for being gel electrolyte, and this gel electrolyte comprises carboxymethyl cellulose, alkali-metal hydroxide and water.
Nickel-hydrogen secondary cell of the present invention, contain carboxymethyl cellulose in the electrolyte of this battery, because carboxymethyl cellulose have good water absorption, when having absorbed a large amount of water in the electrolyte, carboxymethyl cellulose will form gel electrolyte, because alkali metal hydroxide is dissolved in the water, so can be well-proportioned in the gel that forms of dispersion carboxymethyl cellulose, nickel-hydrogen secondary cell of the present invention has overcome the liquid electrolyte frozen problem that dense potassium hydroxide produces as electrolyte, the easy dry leakage etc. that reaches of electrolyte when having solved dense potassium hydroxide as electrolyte simultaneously.Thereby further improve fail safe, reliability and the durable wear-resistant of the low temperature performance and the Ni-MH battery of battery.
Embodiment
The invention provides a kind of nickel-hydrogen secondary cell, this battery comprises battery container, electrode group and alkaline electrolyte, described electrode group and alkaline electrolyte are sealed in the battery container, described electrode group comprises positive pole, negative pole and dividing plate, wherein, described alkaline electrolyte is for being gel electrolyte, and this gel electrolyte comprises carboxymethyl cellulose, alkali-metal hydroxide and water.
Because carboxymethyl cellulose have good water absorption, when having absorbed a large amount of water in the electrolyte, carboxymethyl cellulose will form gel electrolyte, because alkali metal hydroxide is dissolved in the water, so in the gel that can well-proportioned dispersion carboxymethyl cellulose forms.Overcome concentrated sodium hydroxide as the liquid electrolyte that electrolyte produces freeze, problem such as dry and leakage, thereby further improve low temperature performance and fail safe, reliability and the durable wear-resistant of Ni-MH battery.Simultaneously, the raw material of electrolyte of the present invention are simple and cheap, can reduce the expense that Ni-MH battery is produced.After using electrolyte of the present invention,, can adopt cheap barrier film, reduce cost the requirement reduction of barrier film.
According to nickel-hydrogen secondary cell provided by the present invention, preferably, be benchmark with the weight of described electrolyte, the content of described carboxymethyl cellulose is 1.0-4.0wt%, the content of described alkali-metal hydroxide is 35-45wt%.
According to nickel-hydrogen secondary cell provided by the present invention, described alkali-metal hydroxide can be preferably NaOH and/or potassium hydroxide for various alkali-metal hydroxide known in those skilled in the art.
According to nickel-hydrogen secondary cell provided by the present invention, in order to improve the conductivity of electrolyte, preferably, described electrolyte also comprises zinc oxide.
According to nickel-hydrogen secondary cell provided by the present invention, the content of described zinc oxide has no particular limits, as long as can mention the conductivity of electrolyte, for the conductivity that makes electrolyte has good raising, trying one's best not simultaneously, waste material reaches the capacity that does not influence battery, preferably, be benchmark with the weight of described electrolyte, the content of described zinc oxide is 0.5-1.5wt%.
According to nickel-hydrogen secondary cell of the present invention, wherein, described electrolyte can form gel before injecting battery, also can form gel after injecting battery, for the ease of assembled battery, was preferably the injection battery and formed gel afterwards.The method that forms gel is to make the electrolyte that contains above-mentioned described composition leave standstill a period of time, be carboxymethyl cellulose fully the water in the Electolyte-absorptive get final product.
According to nickel-hydrogen secondary cell provided by the present invention, wherein, the preparation method of gel electrolyte is, carboxymethyl cellulose is soluble in water, slowly add alkaline hydrated oxide then, do not stop to be stirred to dissolving back injection Ni-MH battery fully, electrolyte forms gel electrolyte in battery.
Nickel-hydrogen secondary cell of the present invention is except electrolyte, and other structure can be to well known to a person skilled in the art the structure that is used for nickel-hydrogen secondary cell.
According to nickel-hydrogen secondary cell provided by the present invention, described dividing plate is arranged between positive pole and the negative pole, and it has electrical insulation capability and electrolyte keeps performance, and described electrode group and alkaline electrolyte are contained in the battery case together.Described dividing plate can be selected from various dividing plates used in the alkaline secondary cell, as polyolefine fiber nonwoven fabrics and the surperficial chip component of introducing hydrophilic fibre or handling through sulfonation.The position of described dividing plate, character and kind are conventionally known to one of skill in the art.
Described positive pole can be selected from the used positive pole of various nickel-hydrogen secondary cells, and it can commercially obtain, and also can adopt existing method preparation.Described anodal conducting base is a nickel-hydrogen secondary cell anodal conducting base commonly used, as matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
The described positive electrode of nickel-hydrogen secondary cell contains nickel hydroxide and adhesive, and described adhesive can adopt adhesive used in the negative pole.For example, be used for anodal described adhesive can be selected from carboxymethyl cellulose, hydroxypropyl methylcellulose, methylcellulose, Sodium Polyacrylate, polytetrafluoroethylene and polyvinyl alcohol one or more.The content of adhesive is conventionally known to one of skill in the art, is benchmark with the positive active material nickel hydroxide generally, and the content of described anodal adhesive is 0.01-5 weight %, is preferably 0.02-3 weight %.
The preparation method of described positive pole can adopt conventional preparation method.For example, described nickel hydroxide, adhesive and solvent are blended into pasty state, apply and/or be filled on the described conducting base, drying, pressing mold or pressing mold not can obtain described positive pole.Wherein, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described pastel have viscosity, can be coated on the described conducting base to get final product.In general, the content of described solvent is the 15-40 weight % of nickel hydroxide, is preferably 20-35 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
Described negative pole can be selected from the used negative pole of various nickel-hydrogen secondary cells, and it can commercially obtain, and also can adopt existing method preparation.The composition of described negative material has been conventionally known to one of skill in the art.In general, described negative material contains major constituent and adhesive, and major constituent is a hydrogen bearing alloy.Described hydrogen bearing alloy can be selected from can be as any hydrogen bearing alloy of alkaline secondary cell negative electrode key component, and this hydrogen bearing alloy can produce alkaline electrolyte in electrochemical reaction hydrogen absorbs, and, the reversible hydrogen ground of absorption is resolved.Hydrogen-storage alloy commonly used is AB
5
The kind of described adhesive and content are conventionally known to one of skill in the art, and for example, described adhesive can be selected from carboxymethyl cellulose, hydroxypropyl methylcellulose, methylcellulose, Sodium Polyacrylate, the polytetrafluoroethylene one or more; In general, according to the difference of adhesive therefor kind, the content of adhesive is the 0.01-5 weight % of major constituent, is preferably 0.02-3 weight %.
Described negative material can also contain additive, and the kind of additive and content are conventionally known to one of skill in the art.For example, described additive is selected from one or more in graphite, carbon black, nickel powder, the cobalt powder etc.In general, described content of additive is the 0.1-15 weight % of major constituent, is preferably 0.5-10 weight %.
Described negative plate can adopt preparation method well known in the art to be prepared.For example, negative material and solvent are obtained cathode size, then cathode size is applied and/or is filled on the negative pole conducting base, drying, pressing mold or pressing mold not can obtain described negative plate.Wherein, described solvent is preferably water.The consumption of solvent can make described cathode size have viscosity and flowability, can be coated on the negative pole conducting base to get final product.In general, the content of described solvent is the 10-30 weight % of major constituent, is preferably 15-25 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
According to the preparation method of nickel-hydrogen secondary cell provided by the invention, except described alkaline electrolyte was Ni-MH battery electrolyte provided by the invention, other step was conventionally known to one of skill in the art.In general, will between described positive pole for preparing and the negative pole dividing plate be set, constitute an electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, can obtain alkaline secondary cell provided by the invention.
Below by embodiment the present invention is illustrated in greater detail.
Embodiment 1
(1) makes positive pole
With weight ratio is 60: 4: 8: 3: 25 nickel hydroxide, CoO, Ni, carboxymethyl cellulose and water mixing and stirring are made anode sizing agent, and this slurry is coated on the nickel screen that is of a size of 184 millimeters * 24 millimeters * 1.5 millimeters.The slurry in the place of 40 millimeters at one end of distance on the nickel screen length direction is wiped off, and be pressed into the positive plate of 184 millimeters * 24.5 millimeters * 0.6 mm size.Behind the nickel screen compressing tablet, at the local spot welding positive pole ear of scraper.Positive pole ear is a nickel plated steel strip, is shaped as rectangle, is of a size of long 28.5 millimeters, and is wide 7.0 millimeters, 0.12 millimeter of thickness.Wherein, contain 8.8 gram nickel hydroxides in this positive pole.
(2) make negative pole
With weight ratio is that 85: 6: 9 hydrogen storing alloy powder, hydroxypropyl methylcellulose and water mixing and stirring made cathode size, this slurry is coated on 240 millimeters * 24.8 millimeters * 0.6 millimeter the steel band.The slurry in the place of 40 millimeters at one end of distance on the steel band length direction is wiped off, and be pressed into the negative plate of 242 millimeters * 24.8 millimeters * 0.3 mm size.Behind the steel band compressing tablet, in the local spot welding negative lug of scraper.Negative lug is a nickel plated steel strip, comprises rectangular welding portion 1 and circular contact portion 2, and the length of welding portion 1 is 8 millimeters, and width is 7 millimeters, and the diameter of contact portion 2 is 20.5 millimeters, and the thickness of negative lug is 0.12 millimeter.Wherein, contain 9.6 gram hydrogen storing alloy powders in this negative pole.
(3) assembled battery
With positive pole, the negative pole of (1), (2) preparation and the polypropylene diaphragm of handling through oversulfonate (surface density be 60 grams/square metre, thickness is 0.12 millimeter) reel after, put into battery case.
(4) electrolyte preparation
Carboxymethyl cellulose 2.4 gram and water 56.1 grams are put into beaker, stirs and restrain potassium hydroxide with 40 after 20 minutes and slowly add in the beaker, stirred 20 minutes, till the beaker temperature is cooled off; Under stirring condition, 1.5 gram zinc oxide are added in the electrolyte, stirred again 20 minutes after waiting to add, dissolve the electrolyte A1 that promptly obtains present embodiment fully until zinc oxide.
(5) encapsulation
In the battery in the electrolyte A1 implantation step (3), and seal, be made into Ni-MH battery B1.
Embodiment 2
Prepare Ni-MH battery B2 according to the method identical with embodiment 1, different is, preparation process at electrolyte is that carboxymethyl cellulose 4.0 grams and water 51 grams are put into beaker, stirring after 20 minutes slowly adds 45 gram potassium hydroxide in the beaker, stirred 20 minutes, and promptly obtained the electrolyte A2 of present embodiment until the cooling of beaker temperature.
Embodiment 3
Prepare Ni-MH battery B3 according to the method identical with embodiment 1, different is, preparation process at electrolyte is that carboxymethyl cellulose 1.0 grams and water 63.9 grams are put into beaker, stirring after 20 minutes slowly adds 35 gram potassium hydroxide in the beaker, stirred 20 minutes,, till the cooling of beaker temperature; Under stirring condition, 0.1 gram zinc oxide is added in the electrolyte, stirred again 20 minutes after waiting to add, dissolve the electrolyte A3 that promptly obtains present embodiment fully until zinc oxide.
Embodiment 4
Prepare Ni-MH battery B4 according to the method identical with embodiment 1, different is, preparation process at electrolyte is that carboxymethyl cellulose 3.0 grams and water 58 grams are put into beaker, stirring after 20 minutes slowly adds 38 gram potassium hydroxide in the beaker, stirred 20 minutes,, till the cooling of beaker temperature; Under stirring condition, 1.0 gram zinc oxide are added in the electrolyte, stirred again 20 minutes after waiting to add, dissolve the electrolyte A4 that promptly obtains present embodiment fully until zinc oxide.
Comparative Examples 1
Prepare battery according to the method identical with embodiment 1, different is that electrolyte is the KOH of 7mol/L, makes Ni-MH battery C1.
Method of testing
1, battery B1-B4 and C1 in embodiment 1-4 and the Comparative Examples 1 are existed respectively :-10 ℃ ,-20 ℃ ,-30 ℃ of following 0.2C discharges the results are shown in Table 1.
Table 1
| The electrolyte type | -10 ℃ of discharging efficiencies (%) | -20 ℃ of discharging efficiencies (%) | -30 ℃ of discharging efficiencies (%) |
| B1? | 93? | 74? | 31? |
| B2? | 94? | 74? | 33? |
| B3? | 93.5? | 72? | 30? |
| B4? | 94? | 73? | 31? |
| C1? | 84? | 68? | 22? |
2, battery B1-B4 in test implementation example 1-4 and the Comparative Examples 1 and the internal resistance of C1 the results are shown in Table 2.
Table 2
| The electrolyte type | Battery 1 internal resistance (milliohm) | Battery 2 internal resistances (milliohm) | Battery 3 internal resistances (milliohm) | Average internal resistance (milliohm) |
| B1? | 16? | 16.2? | 16.1? | 16.1? |
| B2? | 15.8? | 15.7? | 15.8? | 15.8? |
| B3? | 15.5? | 15.7? | 15.6? | 15.6? |
| B4? | 15.4? | 15.2? | 15.6? | 15.4? |
| C1? | 15.4? | 15.7? | 15.5? | 15.5? |
As can be seen from Table 1, the Ni-MH battery of using Ni-MH battery electrolyte of the present invention at-10 ℃ discharging efficiency greater than 93%,-20 ℃ discharging efficiency is greater than 72%,-30 ℃ discharging efficiency is greater than 30%, and the discharging efficiency of Comparative Examples is respectively 84%, 68% and 22%, and the Ni-MH battery of using electrolyte of the present invention thus has good low temperature performance.As can be seen from Table 2, do not add in the electrolyte zinc oxide the Ni-MH battery that is assembled into of electrolyte average internal resistance obviously than add in the electrolyte zinc oxide the average internal resistance of the Ni-MH battery that is assembled into of electrolyte big, zinc oxide can increase the conductivity of battery thus.
Claims (6)
1. nickel-hydrogen secondary cell, this battery comprises battery container, electrode group and alkaline electrolyte, described electrode group and alkaline electrolyte are sealed in the battery container, described electrode group comprises positive pole, negative pole and dividing plate, it is characterized in that, described alkaline electrolyte is for being gel electrolyte, and this gel electrolyte comprises carboxymethyl cellulose, alkali-metal hydroxide and water.
2. nickel-hydrogen secondary cell according to claim 1 is characterized in that, is benchmark with the weight of described gel electrolyte, and the content of described carboxymethyl cellulose is 1.0-4.0wt%.
3. nickel-hydrogen secondary cell according to claim 1 is characterized in that, is benchmark with the weight of described gel electrolyte, and the content of described alkali-metal hydroxide is 35-45wt%.
4. nickel-hydrogen secondary cell according to claim 1, wherein, described alkali-metal hydroxide is NaOH and/or potassium hydroxide.
5. according to any described nickel-hydrogen secondary cell of claim 1-4, wherein, also comprise zinc oxide.
6. nickel-hydrogen secondary cell according to claim 5 wherein, is a benchmark with the weight of described electrolyte, and the content of described zinc oxide is 0.5-1.5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101884460A CN102082302A (en) | 2009-11-27 | 2009-11-27 | Nickel hydrogen secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101884460A CN102082302A (en) | 2009-11-27 | 2009-11-27 | Nickel hydrogen secondary battery |
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| CN102082302A true CN102082302A (en) | 2011-06-01 |
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| CN2009101884460A Pending CN102082302A (en) | 2009-11-27 | 2009-11-27 | Nickel hydrogen secondary battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789567A (en) * | 2014-12-25 | 2016-07-20 | 深圳市豪鹏科技有限公司 | Preparation method for positive electrode of nickel power supply, positive electrode of nickel power supply and application of positive electrode |
| CN109698078A (en) * | 2017-10-20 | 2019-04-30 | 天津大学 | Reversible overheating protection aqueous electrolyte and its preparation method and application based on Thermo-sensitive cellulose ethers hydrogel |
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|---|---|---|---|---|
| JPH05258767A (en) * | 1992-03-13 | 1993-10-08 | Hitachi Maxell Ltd | Alkaline storage battery |
| US5541019A (en) * | 1995-11-06 | 1996-07-30 | Motorola, Inc. | Metal hydride electrochemical cell having a polymer electrolyte |
| CN1330104A (en) * | 2001-06-06 | 2002-01-09 | 东华大学 | Electrolyte film of modified polymer gel and its preparing process and application |
| CN1411090A (en) * | 2001-10-04 | 2003-04-16 | 松下电器产业株式会社 | Alkaline battery |
| CN1443381A (en) * | 2000-07-17 | 2003-09-17 | 松下电器产业株式会社 | Nickel-hydrogen storage battery and method for mfg. thereof |
-
2009
- 2009-11-27 CN CN2009101884460A patent/CN102082302A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05258767A (en) * | 1992-03-13 | 1993-10-08 | Hitachi Maxell Ltd | Alkaline storage battery |
| US5541019A (en) * | 1995-11-06 | 1996-07-30 | Motorola, Inc. | Metal hydride electrochemical cell having a polymer electrolyte |
| CN1443381A (en) * | 2000-07-17 | 2003-09-17 | 松下电器产业株式会社 | Nickel-hydrogen storage battery and method for mfg. thereof |
| CN1330104A (en) * | 2001-06-06 | 2002-01-09 | 东华大学 | Electrolyte film of modified polymer gel and its preparing process and application |
| CN1411090A (en) * | 2001-10-04 | 2003-04-16 | 松下电器产业株式会社 | Alkaline battery |
Non-Patent Citations (1)
| Title |
|---|
| 袁安保: "PVA-CMC-KOH-H2O碱性聚合物电解质研究", 《电化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789567A (en) * | 2014-12-25 | 2016-07-20 | 深圳市豪鹏科技有限公司 | Preparation method for positive electrode of nickel power supply, positive electrode of nickel power supply and application of positive electrode |
| CN105789567B (en) * | 2014-12-25 | 2019-07-02 | 深圳市豪鹏科技有限公司 | A kind of nickel positive pole preparation method, nickel positive pole and its application |
| CN109698078A (en) * | 2017-10-20 | 2019-04-30 | 天津大学 | Reversible overheating protection aqueous electrolyte and its preparation method and application based on Thermo-sensitive cellulose ethers hydrogel |
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Application publication date: 20110601 |