CN116169258A - Nickel-hydrogen battery negative electrode material and preparation method thereof - Google Patents
Nickel-hydrogen battery negative electrode material and preparation method thereof Download PDFInfo
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- CN116169258A CN116169258A CN202211580862.7A CN202211580862A CN116169258A CN 116169258 A CN116169258 A CN 116169258A CN 202211580862 A CN202211580862 A CN 202211580862A CN 116169258 A CN116169258 A CN 116169258A
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- H01M4/24—Electrodes for alkaline accumulators
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
本发明公开了一种镍氢电池负极材料及其制备方法，包括以下重量份的组分：储氢合金100份，导电剂1~2份，添加剂0.5~1.5份，增稠剂0.1~0.4份，粘结剂1~3份，水25~35份；所述添加剂为无机压电材料；制备方法包括：将储氢合金、导电剂、添加剂、增稠剂、粘结剂和水按重量份配比混合搅拌成均匀浆料；将所述浆料涂覆于泡沫镍集流体上，经烘干、辊压、剪裁和焊接极耳，制得负极极片。本发明所制得的负极材料能够有效消除电极表面的尖端放电现象，减少铜沉积及铜枝晶的产生，进而减少镍氢电池因铜枝晶导致的短路和微断路现象。
The invention discloses a nickel-hydrogen battery negative electrode material and a preparation method thereof, comprising the following components in parts by weight: 100 parts of a hydrogen storage alloy, 1-2 parts of a conductive agent, 0.5-1.5 parts of an additive, and 0.1-0.4 parts of a thickener , 1-3 parts of binder, 25-35 parts of water; the additive is an inorganic piezoelectric material; the preparation method comprises: mixing hydrogen storage alloy, conductive agent, additive, thickener, binder and water in parts by weight Proportional mixing and stirring to form a uniform slurry; coating the slurry on a nickel foam current collector, drying, rolling, cutting and welding tabs to obtain a negative pole piece. The negative electrode material prepared by the invention can effectively eliminate the tip discharge phenomenon on the electrode surface, reduce copper deposition and the generation of copper dendrites, and further reduce the phenomenon of short circuit and micro-opening caused by copper dendrites in nickel-hydrogen batteries.
Description
Technical Field
The invention belongs to the technical field of nickel-hydrogen batteries, and particularly relates to a nickel-hydrogen battery negative electrode material and a preparation method thereof.
Background
The nickel-hydrogen battery is a new energy secondary battery with mature technology and wide application, and is applied to more subdivision fields along with the rapid development of new energy markets.
Copper is an impurity which is strictly prevented in the production process of the nickel-metal hydride battery, if the copper is mixed into an anode or electrolyte, oxidation-reduction reaction occurs in the charge-discharge process, electrons are lost to become copper ions, the copper ions are dissolved in the electrolyte, and then after a plurality of charge-discharge cycles, the copper ions obtain electrons on a cathode and are reduced to metallic copper. From the microscopic view, the electrode surface is always uneven, so that a point discharge phenomenon can occur, copper ions in the electrolyte are reduced to metallic copper and then deposited at a position easy to discharge, after copper is deposited on the negative electrode, reverse reversible reaction can not occur, the copper ions always exist on the negative electrode in the form of metallic copper, copper dendrites can be formed after accumulation for a certain time, and the copper dendrites easily puncture the diaphragm to cause short circuit of the battery.
In actual nickel-metal hydride battery production, copper parts are often used for production equipment and processing tools. Copper is present in the working environment due to welding and friction of parts, so that the battery is polluted, and micro short circuit and short circuit of the battery are finally caused.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a nickel-metal hydride battery negative electrode material and a preparation method thereof, and the prepared negative electrode material can reduce the phenomena of short circuit and micro-disconnection of the nickel-metal hydride battery caused by copper dendrites.
The invention provides the following technical scheme:
in a first aspect, a nickel-metal hydride battery anode material is provided, which comprises the following components in parts by weight:
100 parts of a hydrogen storage alloy,
1-2 parts of a conductive agent,
0.5 to 1.5 portions of additive,
0.1 to 0.4 part of thickener,
1-3 parts of a bonding agent,
25-35 parts of water;
the additive is an inorganic piezoelectric material.
Further, the hydrogen storage alloy is AB 5 Rare earth hydrogen storage alloy.
Furthermore, the conductive agent is carbonyl nickel powder, and compared with graphite conductive agents, the carbonyl nickel powder has strong adhesive force in the polar plate after being compacted and has stable structure.
Further, the additive is one or more of barium titanate, sodium tungstate, ytterbium oxide and lead titanate.
Further, the thickener is sodium carboxymethyl cellulose.
Further, the binder is styrene-butadiene rubber emulsion and polyvinylidene fluoride emulsion, the weight portion of the styrene-butadiene rubber emulsion is 0.5-1.5, and the weight portion of the polyvinylidene fluoride emulsion is 0.5-1.5.
In a second aspect, a method for preparing the nickel-metal hydride battery anode material according to the first aspect is provided, including:
mixing and stirring hydrogen storage alloy, a conductive agent, an additive, a thickening agent, a binder and water according to the weight part ratio to form uniform slurry;
and (3) coating the slurry on a foam nickel current collector, and drying, rolling, cutting and welding the tab to obtain the negative electrode plate.
Further, the concrete preparation method of the slurry comprises the following steps: weighing thickener according to weight proportion, adding purified water to prepare colloidal thickener aqueous solution, sequentially adding conductive agent, additive and hydrogen storage alloy, stirring uniformly, adding binder, and stirring to obtain uniform slurry.
Further, the drying adopts a vertical infrared heating oven, the drying temperature is 150 ℃, and the drying time is 5min.
Further, the rolling adopts a 800mm diameter roll squeezer, the pressure is 15-20 t (ton), and the rolling speed is 2m/s.
Compared with the prior art, the invention has the beneficial effects that:
(1) The additive in the negative electrode material of the nickel-metal hydride battery provided by the invention is an inorganic piezoelectric material, has a piezoelectric effect, and is influenced by positive voltage generated between pressure and negative active substances in the process of changing the internal pressure of the battery, so that complex, multidirectional and disordered voltage can be generated in the whole negative electrode, thereby effectively eliminating the point discharge phenomenon on the surface of the electrode, reducing the self-discharge of the battery, reducing the copper deposition and the generation of copper dendrites, and further reducing the short circuit and micro-circuit phenomenon of the nickel-metal hydride battery caused by the copper dendrites;
(2) The preparation method of the nickel-metal hydride battery cathode material provided by the invention is simple and feasible, is convenient to operate, and can be applied to actual production.
Drawings
FIG. 1 is an SEM photograph of the surface of a negative electrode after 20 charge-discharge cycles of the nickel-metal hydride battery prepared in example 1 of the present invention;
fig. 2 is an SEM photograph of the surface of the negative electrode of the nickel-hydrogen battery manufactured in comparative example 1 according to the present invention after 20 charge and discharge cycles.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
(1) Weighing LaNi according to parts by weight 5 100 parts of hydrogen storage alloy powder, 2 parts of nickel carbonyl powder, 1 part of additive (barium titanate, sodium tungstate, ytterbium oxide and lead titanate are mixed according to the weight ratio of 1:1:1), 0.4 part of sodium carboxymethyl cellulose, 1 part of styrene-butadiene rubber emulsion, 0.5 part of polyvinylidene fluoride emulsion and 31 parts of purified water.
Adding sodium carboxymethylcellulose into purified water according to a proportion to prepare a colloidal aqueous solution; and then sequentially adding nickel carbonyl powder, additives and hydrogen storage alloy powder, stirring uniformly, and finally adding styrene butadiene rubber emulsion and polyvinylidene fluoride emulsion, and stirring to obtain uniform slurry.
Coating the slurry on a foam nickel current collector, adopting a vertical infrared heating oven, and preserving heat for 5min at 150 ℃ for drying; then rolling by adopting a roll squeezer with the diameter of 800mm, wherein the pressure is 15t, and the rolling speed is 2m/s; cutting into 150mm long and 150mm wide, and welding the tab to obtain the negative electrode plate.
(2) The cathode active material nickel hydroxide 100 parts, yttrium oxide 1.5 parts, cobalt oxide 2 parts, sodium carboxymethyl cellulose 0.05 parts, polytetrafluoroethylene 1 part and pure water 33 parts are weighed according to the weight parts. Adding pure water into sodium carboxymethylcellulose in proportion to prepare aqueous solution, wherein the aqueous solution is gelatinous; then yttrium oxide, cobalt oxide and nickel hydroxide are added in sequence and stirred uniformly, and finally polytetrafluoroethylene emulsion is added and stirred into uniform slurry. And (3) coating the slurry on a foam nickel current collector, and drying, rolling, cutting and welding the tab to prepare the positive electrode plate.
(3) As an electrolyte, 5.5mol/L of potassium hydroxide solution, 0.5mol/L of sodium hydroxide solution, and 0.5mol/L of lithium hydroxide solution were uniformly mixed.
(4) Adding a small amount of copper powder on the surface of the positive electrode plate manufactured in the step (2), respectively laminating the positive electrode plate added with the copper powder, the negative electrode plate in the step (1) and the polypropylene diaphragm, then placing the laminated positive electrode plate and the laminated polypropylene diaphragm into a square stainless steel shell, adding electrolyte, welding and sealing, and then forming to finish the manufacturing of the square nickel-hydrogen battery.
Example 2
Weighing LaNi according to parts by weight 5 100 parts of hydrogen storage alloy, 1 part of nickel carbonyl powder, 0.5 part of additive (barium titanate, sodium tungstate, ytterbium oxide and lead titanate are mixed according to the weight ratio of 1:1:1), 0.1 part of sodium carboxymethyl cellulose, 1.5 parts of styrene-butadiene rubber emulsion, 0.7 part of polyvinylidene fluoride emulsion and 25 parts of water, and preparing the negative electrode plate according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Example 3
Weighing LaNi according to parts by weight 5 100 parts of hydrogen storage alloy, 1.5 parts of nickel carbonyl powder, 1.5 parts of additive (barium titanate, sodium tungstate and ytterbium oxide are mixed according to the weight ratio of 1:1:1), 0.2 part of sodium carboxymethyl cellulose, 0.5 part of styrene-butadiene rubber emulsion, 1.5 parts of polyvinylidene fluoride emulsion and 35 parts of water, and preparing the negative electrode plate according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Example 4
Weighing LaNi according to parts by weight 5 100 parts of hydrogen storage alloy, 1.5 parts of nickel carbonyl powder, 1.2 parts of additive (barium titanate and sodium tungstate are mixed according to the weight ratio of 1:1), 0.3 part of sodium carboxymethyl cellulose, 1 part of styrene-butadiene rubber emulsion, 1 part of polyvinylidene fluoride emulsion and 30 parts of water, and preparing the negative electrode plate according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Example 5
Weighing LaNi according to parts by weight 5 100 parts of hydrogen storage alloy, 1.7 parts of nickel carbonyl powder, 0.8 part of additive barium titanate, 0.4 part of sodium carboxymethyl cellulose, 1 part of styrene-butadiene rubber emulsion, 1.2 parts of polyvinylidene fluoride emulsion and 32 parts of water, and preparing a negative electrode plate according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Comparative example 1
The LaNi is prepared by the following steps in parts by weight 5 100 parts of hydrogen storage alloy, 2 parts of nickel carbonyl powder, 0.4 part of sodium carboxymethylcellulose, 1 part of styrene-butadiene rubber emulsion, 0.5 part of polyvinylidene fluoride emulsion and 31 parts of water are mixed and stirred into uniform slurry, and a negative electrode plate is prepared according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Comparative example 2
The LaNi is prepared by the following steps in parts by weight 5 100 parts of hydrogen storage alloy, 2 parts of nickel carbonyl powder, 0.4 part of sodium carboxymethylcellulose, 1.5 parts of styrene-butadiene rubber emulsion and 31 parts of water are mixed and stirred into uniform slurry, and a negative electrode plate is prepared according to the method of the step (1) of the example 1.
Nickel-hydrogen batteries were produced in the same manner as in step (2) to step (4) of example 1.
Performance comparison
1. Fig. 1 is an SEM photograph of the surface of the negative electrode after 20 charge and discharge cycles of the 120Ah nickel-hydrogen battery prepared in example 1, and it can be seen that the surface of the negative electrode forms few crystals; fig. 2 is an SEM photograph of the surface of the negative electrode after 20 charge and discharge cycles of the nickel-metal hydride battery prepared in comparative example 1, and it can be seen that the crystal form formed on the surface of the negative electrode is obvious; it is explained that the addition of the additive inorganic piezoelectric material can significantly reduce copper deposition and copper dendrite generation.
2. The batteries of examples 1 to 5 and comparative examples 1 to 2 were subjected to a self-discharge test, after 20 charge and discharge cycles, the 120Ah nickel-hydrogen battery was charged with 1C current for 1h, and after 1h of charging with 0.1C current, the battery was left open-circuited in an environment at 25 ℃ for 28 days, and after the rest, the battery was discharged to 1V with 1C current, the discharge capacity of the battery was recorded, the self-discharge rate of the battery was calculated, and the self-discharge condition of the battery was examined. The test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the self-discharge rate of the nickel-hydrogen battery using the inorganic piezoelectric material as the additive according to the present invention was lower than that of the nickel-hydrogen battery produced by the conventional formulation, which indicates that the nickel-hydrogen battery using the inorganic piezoelectric material as the additive according to the present invention can effectively reduce the self-discharge of the battery.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (10)
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202015A (en) * | 1997-06-05 | 1998-12-16 | 三星电管株式会社 | Negative electrode for nickel-hydrogen cell and method of preparing the same |
| JP2005251439A (en) * | 2004-03-02 | 2005-09-15 | Yuasa Corp | Nickel metal hydride battery |
| CN101027802A (en) * | 2004-08-26 | 2007-08-29 | 株式会社杰士汤浅 | Hydrogen storage electrodes and nickel metal hydride batteries |
| CN103782441A (en) * | 2011-09-08 | 2014-05-07 | 丰田自动车株式会社 | Lithium secondary battery manufacturing method |
| US20170125814A1 (en) * | 2015-10-30 | 2017-05-04 | Nissan North America, Inc. | Electrode having an actuating binder |
| CN107799735A (en) * | 2017-09-20 | 2018-03-13 | 四会市达博文实业有限公司 | One kind uses for nickel-hydrogen battery AB5Type hydrogen storage alloy and preparation method thereof |
| JP2019106284A (en) * | 2017-12-12 | 2019-06-27 | 日立化成株式会社 | Zinc battery negative electrode and zinc battery |
| CN112072105A (en) * | 2020-08-24 | 2020-12-11 | 湖南科技大学 | A kind of coating for electrode and preparation method and application thereof |
| CN113903893A (en) * | 2021-09-26 | 2022-01-07 | 深圳市豪鹏科技股份有限公司 | Nickel-hydrogen battery cathode, material formula, preparation method, electrode material and application |
-
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- 2022-12-09 CN CN202211580862.7A patent/CN116169258A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202015A (en) * | 1997-06-05 | 1998-12-16 | 三星电管株式会社 | Negative electrode for nickel-hydrogen cell and method of preparing the same |
| JP2005251439A (en) * | 2004-03-02 | 2005-09-15 | Yuasa Corp | Nickel metal hydride battery |
| CN101027802A (en) * | 2004-08-26 | 2007-08-29 | 株式会社杰士汤浅 | Hydrogen storage electrodes and nickel metal hydride batteries |
| CN103782441A (en) * | 2011-09-08 | 2014-05-07 | 丰田自动车株式会社 | Lithium secondary battery manufacturing method |
| US20170125814A1 (en) * | 2015-10-30 | 2017-05-04 | Nissan North America, Inc. | Electrode having an actuating binder |
| CN107799735A (en) * | 2017-09-20 | 2018-03-13 | 四会市达博文实业有限公司 | One kind uses for nickel-hydrogen battery AB5Type hydrogen storage alloy and preparation method thereof |
| JP2019106284A (en) * | 2017-12-12 | 2019-06-27 | 日立化成株式会社 | Zinc battery negative electrode and zinc battery |
| CN112072105A (en) * | 2020-08-24 | 2020-12-11 | 湖南科技大学 | A kind of coating for electrode and preparation method and application thereof |
| CN113903893A (en) * | 2021-09-26 | 2022-01-07 | 深圳市豪鹏科技股份有限公司 | Nickel-hydrogen battery cathode, material formula, preparation method, electrode material and application |
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