CN101332509B - Method for evenly cladding CoOOH on powdery nickel hydroxide electrode material surface - Google Patents
Method for evenly cladding CoOOH on powdery nickel hydroxide electrode material surface Download PDFInfo
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- CN101332509B CN101332509B CN2008100482600A CN200810048260A CN101332509B CN 101332509 B CN101332509 B CN 101332509B CN 2008100482600 A CN2008100482600 A CN 2008100482600A CN 200810048260 A CN200810048260 A CN 200810048260A CN 101332509 B CN101332509 B CN 101332509B
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- nickel hydroxide
- coooh
- cobalt
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- powdery nickel
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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
Abstract
The invention relates to a method for uniformly, closely and tightly coating a layer of CoOOH which plays a role in improving electrical conductivity on the surface of a powdered nickel hydroxide particle which is taken as a positive electrode active material for an alkaline storage battery. The method is that: in neutral aqueous solution, hydrogen peroxide is taken as an oxidizing agent, a thin layer of uniform and stable CoOOH is formed on the surface of the nickel hydroxide particle by virtue of the ion exchange between bivalent soluble cobalt salt and the surface of the solid nickel hydroxide particle, thus obtaining a powdered nickel hydroxide electrode material coated with cobalt. The method of the invention has the advantages of simple operation, high efficiency, low cost and environment protection; and the prepared powdered nickel hydroxide electrode material coated with cobalt has good electrical conductivity, strong heavy-current charge-discharge capacity and good cycle performance.
Description
Technical field
The present invention relates to a kind ofly, further refer to form at the powdery nickel hydroxide particle surface method of the CoOOH clad of the even and close and firm of one deck according to the ion-exchange reactions principle in the method that evenly coats CoOOH as the powdery nickel hydroxide particle surface of alkaline battery positive active material.
Background technology
(the nickel hydroxide chemical formula is Ni (OH) to the powdery nickel hydroxide material
2) be the positive electrode active materials that extensively adopts in the present business-like nickel-base alkaline battery.Because nickel hydroxide itself is a kind of semiconductor, when it was used for the high power applications occasion, during electrical source of power on hybrid-power electric vehicle, the relatively poor characteristic of its electric conductivity was directly limiting its high rate during charging-discharging.So in order to improve the electric conductivity of powdery nickel hydroxide, the auxiliary material that need when the preparation electrode, in proportion scheme, add the effect of intensifier electrode electric conductivity usually, as except the adding raw material of wood-charcoal material of routine, more be to need to add a large amount of solid metallic cobalts or the oxide of cobalt.Wherein, the mechanism of action of cobalt and various oxides thereof mainly is, under alkali condition, the chemical process complicated by dissolving, deposition, oxidation etc. forms the CoOOH adhesion layer on the surface of powdery nickel hydroxide particle, and that CoOOH is a kind of electric conductivity is more much better and keep the material of stable existence in can the charge and discharge process at battery after the formation than nickel hydroxide, thereby can form a kind of conductive network on the nickel hydroxide particle surface, improve the electric conductivity on nickel hydroxide particle surface effectively.The deficiency that this kind method exists is, formed CoOOH skewness in electrode structure, and also good inadequately with contacting of nickel hydroxide particle, the effect of CoOOH can not well be brought into play.Also the service efficiency owing to cobalt in this method is low simultaneously, in order to reach significant effect, needs to use relatively large cobalt material, causes the waste of cobalt.Therefore, the coating of carrying out the hydroxide of the oxide of cobalt, cobalt or cobalt at the powdery nickel hydroxide particle surface in advance before batching is a kind of more efficient methods that addresses the above problem.Traditional method that coats CoOOH on the nickel hydroxide particle surface is electroless plating method and solution-deposition method.But, common employed electroless plating method is to the conditional request harshness, and bring pollution easily, though and solution-deposition method is simpler relatively, but clad and product combine that but defective tightness is firm, cause clad to come off easily, and further cause the electrochemistry cycle performance of material to fail too early.So it is necessary developing a kind of more effective method for coating.
Summary of the invention
The object of the present invention is to provide the method that coats CoOOH on powdery nickel hydroxide electrode material granules surface equably of a kind of simple, environmental protection, efficient height, easy operating, adopt the specific capacity, fast charging and discharging ability, cycle performance etc. of the resulting material of the method all can be significantly improved.
The coating of indication of the present invention in the powdery nickel hydroxide electrode material of CoOOH, the molar content of cobalt can be adjusted between 0.1% to 10%, wherein, it is outer that cobalt is that the form with CoOOH is created on the surface of powdery nickel hydroxide particle.
The present invention by solid state powder shape nickel hydroxide particle surface nickel ion and the cobalt ions of water-soluble liquid phase between carry out cation exchange and be implemented in the nickel hydroxide particle surface and coat CoOOH.
The powdery nickel hydroxide preparation methods of the coating CoOOH of indication of the present invention comprises the steps: powdery nickel hydroxide is joined in the middle of the aqueous solution of solubility cobalt salt, under the condition that hydrogen peroxide exists, under 40 ℃ of-100 ℃ of temperature stirring reaction 0.5-10 hour, after the isolated by filtration under 40 ℃ of-200 ℃ of temperature dry 1 hour--48 hours, promptly be implemented in the nickel hydroxide particle surface and coat CoOOH.
Described solubility cobalt salt is a kind of in cobaltous sulfate, cobalt nitrate or the cobalt chloride, and the concentration of its aqueous solution is 0.01mol/L--5mol/L.
The molar ratio of the cobalt in the aqueous solution of nickel that described powdery nickel hydroxide comprised and solubility cobalt salt is 1: 0.01 to 1: 0.5.
The concentration of hydrogen peroxide is 5wt%-30wt% in the described aqueous hydrogen peroxide solution, and the used hydrogen peroxide and the molar ratio of cobalt salt are 1: 1 to 5: 1.
The particle diameter of described powdery nickel hydroxide is between 0.1 micron to 30 microns.
Described method at powdery nickel hydroxide particle surface layer coating CoOOH is the Co that utilizes in the solution
3+Ni with powdery nickel hydroxide particle top layer
2+Between ion-exchange reactions produce, so resulting CoOOH clad combines closely with the internal structure of nickel hydroxide particle and firmly, do not have new contact interface, help mentioning the electric conductivity and the service life of material.
The electrochemical property test of the nickel hydroxide electrode material of Powdered coating cobalt of the present invention adopts to discharge and recharge and tests, and working electrode adopts bonded electrode, is commercialization hydrogen bearing alloy pole plate to electrode, and electrolyte is the KOH solution of 6mol/L.
The invention has the advantages that and adopt simple, easy method capable, inexpensive, environmental protection to prepare the nickel hydroxide electrode material that clad is even, tight, clad combines firm Powdered coating cobalt with the nickel hydroxide particle surface.This kind preparation method is suitable for large-scale operation.Electrochemical results shows, the nickel hydroxide electrode material of this coating cobalt discharge and recharge good reversibility, cycle performance is good, and electric conductivity is significantly increased than common powdery nickel hydroxide active material.When the nickel hydroxide material of Powdered coating cobalt was used for the nickel electrode of alkaline storage battery, the specific capacity of nickel electrode and high current charge-discharge ability all were significantly improved.
Description of drawings
Fig. 1 a, 1b are respectively the stereoscan photographs of nickel hydroxide particle of CoOOH that do not carried out coated with uniform that powdery nickel hydroxide particle that CoOOH coat to handle and the present invention obtained.
Fig. 2 be adopt coated with uniform that the present invention prepares respectively CoOOH the powdery nickel hydroxide material and do not carry out the charging and discharging curve comparison diagram that CoOOH coats the electrode that the powdery nickel hydroxide material handled makes.
Fig. 3 be adopt coated with uniform that the present invention prepares respectively CoOOH the powdery nickel hydroxide material and do not carry out the specific discharge capacity cycle performance comparison diagram that CoOOH coats the electrode that the powdery nickel hydroxide handled makes.
The specific embodiment
Embodiment one: at first in reactor, the 0.65g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while the H of 8mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered uses pure water and ethanol washing back promptly to get the described even powdery nickel hydroxide material that has coated CoOOH in 6 hours in 80 ℃ of dryings.The average quality percentage composition of the cobalt in the powdery nickel hydroxide material of the coating CoOOH that employing plasma emission spectrometry (ICP) is measured is 3.6%, and the mol ratio of nickel and cobalt is 15.33: 1.And the quality percentage composition that coats the cobalt in the CoOOH powdery nickel hydroxide raw material before is 1.38%, and the mol ratio of nickel and cobalt is 38.44: 1.Here it should be noted that business-like nickel hydroxide material is the composite that contains a certain proportion of Co in a kind of internal structure.ESEM (SEM) photo of the nickel hydroxide particle before and after the coating CoOOH is shown in Fig. 1 a and 1b.Fig. 1 b result shows, has coated the nickel hydroxide particle smooth surface of CoOOH, and the surface appearance of not carrying out nickel hydroxide that CoOOH coat given with Fig. 1 a is similar, illustrates that clad is coated on the nickel hydroxide particle surface evenly, closely, securely.X-ray quantum power spectrum (EDX) test result shows, coated that the mol ratio of nickel and cobalt is 12.95: 1 in the nickel hydroxide particle superficial layer of CoOOH, promptly in the degree of depth that X ray can detect, the content of cobalt is than the height of whole particle body phase, and the cobalt in this explanation nickel hydroxide particle mainly is enriched in the surface of particle.Resulting material is made into adhered electrode carries out charge-discharge test, its 2C charging and discharging curve is seen Fig. 2.The result shows that the 2C multiplying power discharging specific capacity of the powdery nickel hydroxide of prepared coating CoOOH reaches 320mAh/g, and any decay (Fig. 3) does not appear in capacity after carrying out 200 all charge and discharge cycles with the 2C multiplying power.
Embodiment two: at first in reactor, the 0.98g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while the H of 12mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered is with the powdery nickel hydroxide material that promptly got described even coating CoOOH after pure water and the ethanol washing in 80 ℃ of dryings in 6 hours.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 336mAh/g.
Embodiment three: at first in reactor, the 0.33g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while the H of 12mL 10%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 341mAh/g, any decay do not occur with capacity after 200 weeks of 2C rate charge-discharge circulation.
Embodiment four: at first in reactor, the 0.16g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while the H of 2mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 330mAh/g, carries out charge and discharge cycles 200 all backs capacity with the 2C multiplying power and any decay do not occur.
Embodiment five: at first in reactor the 0.65g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 70 ℃, the churned mechanically while is the H of 8mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 317mAh/g.
Embodiment six: at first in reactor, the 0.65g cobalt nitrate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 0 ℃, when tool stirs the H of 8mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 302mAh/g.
Embodiment seven: at first in reactor the 0.65g cobaltous sulfate is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while is the H of 8mL 30%
2O
2Aqueous solution compartment of terrain adds in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 318mAh/g.
Embodiment eight: at first in reactor the 0.65g cobalt chloride is dissolved in the 50mL distilled water, adds behind the 1g powdery nickel hydroxide water-bath that reactor is placed 90 ℃, the churned mechanically while is the H of 8mL 30%
2O
2Aqueous solution compartment of terrain is added in the reactor, insulated and stirred 2 hours.The nature cooled and filtered in 80 ℃ of dryings 6 hours, promptly get the powdery nickel hydroxide material of the described even CoOOH of coating with pure water and ethanol washing back.Resulting material is made into adhered electrode carries out charge-discharge test, the result shows that the 2C specific discharge capacity of the powdery nickel hydroxide of prepared coating CoOOH is 330mAh/g.
Comparing embodiment: will be not do not use to be made into adhered electrode with the identical method of the foregoing description and to carry out the charge-discharge test identical all test conditions identical with embodiment one as active material with embodiment one through the powdery nickel hydroxide that coats.The result shows that the 2C specific discharge capacity of the powdery nickel hydroxide that does not coat only is 259mAh/g.
Comparing (Fig. 2) by the charging and discharging curve to the powdery nickel hydroxide material of the coated with uniform CoOOH that adopts the preparation of this patent method and the electrode of the powdery nickel hydroxide material made that does not coat CoOOH finds out, the surface has coated the powdery nickel hydroxide of CoOOH except having tangible specific discharge capacity advantage, also demonstrate lower charging voltage platform and higher discharge voltage plateau, show that the powdery nickel hydroxide that coats CoOOH has higher capacity usage ratio in charge and discharge process.
Employing by the powdery nickel hydroxide material of the coated with uniform CoOOH of this patent method preparation and the high current charge-discharge circulation that does not coat the nickel electrode that the powdery nickel hydroxide of CoOOH makes the results are shown in Fig. 3 (carry out before the cycle performance test, to this two Battery packs employing is identical activate mechanism).The result shows, adopt the powdery nickel hydroxide material of the coated with uniform CoOOH of this patent method preparation not only to show bigger specific capacity, also demonstrate good cycle performance, in the middle of the charge and discharge cycles in 200 weeks, specific discharge capacity is almost without any decay.And the specific discharge capacity of powdery nickel hydroxide that does not coat CoOOH is less relatively, and difference can reach 70mAh/g.In addition, the electrode of powdery nickel hydroxide material that does not coat CoOOH is the activation process that also has active material early stage of charge and discharge cycles (being that capacity increases the process that improves with the charge and discharge cycles number of times), and there is not activation process in the electrode of the powdery nickel hydroxide material of the coated with uniform CoOOH of employing this patent method preparation, the powdery nickel hydroxide electrode material that the coated with uniform CoOOH that the described method of employing this patent makes is described has good conductivity, the characteristic that is easy to activate.
The intact cobalt of unreacted can reclaim and reintegrate in the body series and use by simple method in the reactant liquor that this patent method relates to.
In sum, this patent is described to have characteristics such as simple, inexpensive, environmental protection in the method as the powdery nickel hydroxide coated with uniform CoOOH of alkaline battery positive active material, the material that makes with the method has good conductivity, discharges and recharges the reaction good reversibility, high rate during charging-discharging is good, the characteristic of good cycle.
Claims (5)
1. method that evenly coats CoOOH at the particle surface of powdery nickel hydroxide electrode material, it is characterized in that: powdery nickel hydroxide is joined in the middle of the aqueous solution of solubility cobalt salt, under the condition that hydrogen peroxide exists, under 40 ℃ of-100 ℃ of temperature stirring reaction 0.5-10 hour, after the isolated by filtration under 40 ℃ of-200 ℃ of temperature dry 1 hour--48 hours, the particle surface that promptly is implemented in nickel hydroxide electrode material coated CoOOH.
2. method according to claim 1 is characterized in that: described solubility cobalt salt is a kind of in cobaltous sulfate, cobalt nitrate or the cobalt chloride, and the concentration of the aqueous solution of solubility cobalt salt is 0.01mol/L--5mol/L.
3. method according to claim 1 and 2 is characterized in that: the nickel that described powdery nickel hydroxide comprised and the molar ratio of the cobalt in the cobalt saline solution are 1: 0.01 to 1: 0.5.
4. method according to claim 1 and 2 is characterized in that: the concentration of hydrogen peroxide is 5wt%-30wt% in the described aqueous hydrogen peroxide solution, and the used hydrogen peroxide and the molar ratio of cobalt salt are 1: 1 to 5: 1.
5. method according to claim 1 and 2 is characterized in that: the particle diameter of described powdery nickel hydroxide electrode material is between 0.1 micron to 30 microns.
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| CN2008100482600A CN101332509B (en) | 2008-07-02 | 2008-07-02 | Method for evenly cladding CoOOH on powdery nickel hydroxide electrode material surface |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101794913A (en) * | 2010-03-23 | 2010-08-04 | 欧阳宁 | Maintenance-free nickel/metal hydride (MH-Ni) battery and manufacturing method thereof |
| CN102760875B (en) * | 2011-12-08 | 2015-08-12 | 郑州大学 | The preparation method of a kind of ball-shaped lithium-ion battery anode material and presoma thereof |
| JP5626387B2 (en) * | 2012-10-25 | 2014-11-19 | 住友金属鉱山株式会社 | The evaluation method of the coating adhesiveness of the coating nickel hydroxide powder for alkaline secondary battery positive electrode active materials and a coating nickel hydroxide powder. |
| CN103367817B (en) * | 2013-07-12 | 2016-05-18 | 深圳市量能科技有限公司 | A kind of Ni-MH battery and manufacture method thereof of exempting from formation process |
| JP6643054B2 (en) * | 2015-11-16 | 2020-02-12 | Fdk株式会社 | Evaluation method of positive electrode active material for nickel-metal hydride secondary battery |
| CN107068421A (en) * | 2017-03-13 | 2017-08-18 | 黄冈师范学院 | A kind of calcium analysis cobalt hydroxide nanometer sheet electrode material and its preparation method and the application in ultracapacitor is prepared |
| CN108565415A (en) * | 2018-03-29 | 2018-09-21 | 武汉倍特利科技有限公司 | A method of improving nickel hydroxide surface electric conductivity |
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