CN111261853B - Preparation method of zinc-nickel battery cathode coating material - Google Patents
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- CN111261853B CN111261853B CN201911229194.1A CN201911229194A CN111261853B CN 111261853 B CN111261853 B CN 111261853B CN 201911229194 A CN201911229194 A CN 201911229194A CN 111261853 B CN111261853 B CN 111261853B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 the technical field of lead-acid storage batteries, in particular to a preparation method of a zinc-nickel battery cathode coating material, which comprises the following steps: (1) adding a first catalyst into pure water, stirring until the first catalyst is dissolved, continuously adding a second catalyst during stirring, and dissolving to obtain a first mixed solution; (2) taking bismuth nitrate, adding water and nitric acid, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution; (3) slowly dripping the bismuth nitrate/nitric acid mixed solution into the first mixed solution to obtain a second mixed solution; (4) and adding alkali liquor into the second mixed solution, stirring, filtering, washing, filtering, and drying. The invention adopts the dispersing material to dissolve the coating and evenly distributes the coating on the surface layer of the zinc oxide, a good conductive network is formed on the surface layer of the zinc oxide, and the coating layer is attached to the surface of the zinc oxide, so that the hydrogen evolution overpotential of the zinc oxide can be effectively improved; the cathode coating material prepared by the method can effectively improve the binding force between the active substance and the matrix of the zinc-nickel battery.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a preparation method of a zinc-nickel battery cathode coating material.
Background
The lead-acid storage battery has been invented for over 150 years, and is widely applied to national economy and life of people due to the characteristics of high safety, stable performance, low manufacturing cost and high recycling value. However, lead-acid batteries also have a series of problems of low cycle life, low energy density utilization rate, capacity attenuation caused by incomplete conversion of active substances and the like, and become important factors for restricting the lead-acid batteries to occupy larger markets. As the contribution of electric vehicles to vehicle driving increases, the demand for battery energy increases greatly, and especially, the fully hybrid and plug-in hybrid vehicles impose more strict standards on the energy of the battery, so the development of other novel energy batteries is urgent.
The zinc-nickel battery has the obvious advantages of high working voltage, high energy density, no environmental pollution, high safety index, low production cost and the like, and is a secondary battery capable of being recycled. The charge-discharge cycle life of the zinc-nickel battery is short because the zinc cathode has high solubility in a discharge product of a potassium hydroxide electrolyte, and uneven zinc deposition occurs during charging. The zinc negative electrode changes its shape after a plurality of times of charge and discharge, and the periphery of the electrode becomes thinner and the middle part becomes thicker, sometimes the upper part becomes thinner and the lower part becomes thicker. The active surface area of the electrode is reduced, the capacity of the electrode is reduced, and the zinc electrode also generates dendritic-like deposits at the later stage of charging, and the dendritic-like deposits can sometimes puncture the separator to cause short circuit inside the battery, so that the service life of the battery is terminated.
In order to improve the charge-discharge cycle life of a zinc-nickel battery, it is necessary to prevent deformation of a zinc electrode, suppress growth of zinc dendrites, and suppress hydrogen gas generated by self-discharge and migration of zinc from a negative electrode to a positive electrode.
Disclosure of Invention
The invention provides a preparation method of a zinc-nickel battery cathode coating material, aiming at overcoming the problems of low hydrogen evolution overpotential and obvious self-discharge of a zinc cathode caused by adding a carbon material in the zinc cathode of the conventional zinc-nickel battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a zinc-nickel battery cathode coating material comprises the following steps:
(1) adding the first catalyst into pure water at the temperature of 50-75 ℃, stirring until the first catalyst is dissolved, continuously adding the second catalyst in the stirring process, and dissolving to obtain a first mixed solution;
(2) adding a small amount of water into bismuth nitrate, adding nitric acid, supplementing water, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution;
(3) slowly dripping the bismuth nitrate/nitric acid mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), and uniformly stirring to obtain a second mixed solution;
(4) and adding alkali liquor into the second mixed solution, stirring, filtering, washing with pure water, performing suction filtration, and drying the obtained product to obtain the zinc-nickel battery cathode coating material. The lye is preferably a sodium hydroxide solution.
The coating layer avoids direct contact between zinc oxide and electrolyte, so that the solubility of the zinc oxide in the electrolyte is reduced, and the coating layer has good conductivity and higher hydrogen evolution overpotential, so that a conductive network can be formed among zinc oxide particles, hydrogen evolution reaction and self-discharge can be obviously inhibited, and the preservation rate of self-discharge capacity is improved by 5-8%.
Preferably, in the step (1), the first catalyst is one or more selected from polyethylene glycol, naphthalene sulfonic acid formaldehyde condensate, methyl cellulose and iridium acetylacetonate.
Preferably, in the step (1), the second catalyst is one or more selected from phosphate, antimony trioxide and bismuth trioxide.
Preferably, in the step (1), the mass ratio of the first catalyst to the second catalyst is 1: (0.5-0.8).
Preferably, in the step (3), the dropping time of the bismuth nitrate/nitric acid mixed solution is controlled to be 10-20 min; the stirring rate is controlled to be 120-200 rmp. The reaction of nitric acid and catalytic reactant should be as full as possible, the addition speed is too fast, the reaction is easy to be insufficient, a large amount of heat energy is generated, meanwhile, the time is controlled within a reasonable interval range, and the process efficiency is improved.
Preferably, in the step (4), the suction filtration process comprises the following steps: pouring out the clear liquid in the solution to the position where the solution surface is level to the precipitate, pouring pure water into the solution, placing the solution into the solution for water bath ultrasonic treatment, precipitating, continuously pouring out the clear liquid for filtration, stirring the solution in the process, performing suction filtration twice, pouring pure water into the solution when the liquid surface is close to the filter cake each time, continuously performing suction filtration, and washing with pure water.
Preferably, the temperature of the water bath ultrasound is 35-40 ℃, and the time of the water bath ultrasound is 2-3 h.
Preferably, in the step (4), the drying temperature is 50-90 ℃ and the drying time is 0.5-5 h.
Therefore, the invention has the following beneficial effects:
(1) the dispersed material is adopted to dissolve the coating and is uniformly distributed on the surface layer of the zinc oxide, a good conductive network is formed on the surface layer of the zinc oxide, and the coating layer is attached to the surface of the zinc oxide, so that the hydrogen evolution overpotential of the zinc oxide can be effectively improved;
(2) the cathode coating material prepared by the method can effectively improve the binding force between the active substance and the matrix of the zinc-nickel battery;
(3) the coating layer material prepared by the method is uniformly mixed, has strong adhesive force, can ensure the stress of the negative electrode material during shrinkage and expansion, and has long duration.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Adding a first catalyst (polyethylene glycol) into pure water at 50 ℃, stirring until the first catalyst is dissolved, continuously adding a second catalyst (phosphate) during stirring, and dissolving to obtain a first mixed solution; the mass ratio of the first catalyst to the second catalyst is 1: 0.5;
(2) adding a small amount of water into bismuth nitrate, adding nitric acid, supplementing water, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution;
(3) slowly dripping the bismuth nitrate/nitric acid mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), and uniformly stirring to obtain a second mixed solution; the dripping time is controlled to be 10 min; the stirring rate is controlled at 200 rmp;
(4) adding alkali liquor into the second mixed solution, stirring, filtering, washing with pure water, performing suction filtration, and drying the obtained product for 0.5h at 90 ℃ to obtain a zinc-nickel battery cathode coating material; pouring out the clear liquid in the solution to the position where the solution surface is level to the precipitate, pouring pure water, putting the solution into 50 ℃ water bath ultrasound for 5 hours, precipitating, continuously pouring out the clear liquid, filtering, stirring the solution in the process, performing suction filtration twice, pouring pure water when the liquid level is close to the filter cake each time, continuously performing suction filtration, and washing with pure water.
Example 2
(1) Adding a first catalyst (naphthalenesulfonic acid-formaldehyde condensate, methyl cellulose) into pure water at 75 ℃, stirring until the first catalyst is dissolved, continuously adding a second catalyst (antimony trioxide and bismuth trioxide) during stirring, and dissolving to obtain a first mixed solution; the mass ratio of the first catalyst to the second catalyst is 1: 0.8;
(2) adding a small amount of water into bismuth nitrate, adding nitric acid, supplementing water, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution;
(3) slowly dripping the bismuth nitrate/nitric acid mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), and uniformly stirring to obtain a second mixed solution; the dripping time is controlled to be 20 min; the stirring rate is controlled at 120 rmp;
(4) adding alkali liquor into the second mixed solution, stirring, filtering, washing with pure water, performing suction filtration, and drying the obtained product for 5 hours at 50 ℃ to obtain a zinc-nickel battery cathode coating material; pouring out the clear liquid in the solution to the position where the solution surface is level with the precipitate, pouring pure water, putting the pure water into the solution, performing water bath ultrasound at 90 ℃ for 0.5h, precipitating, continuously pouring out the clear liquid, filtering, stirring the solution in the process, performing suction filtration twice, pouring pure water when the liquid surface is close to the filter cake each time, continuously performing suction filtration, and washing with pure water.
Example 3
(1) Adding a first catalyst (naphthalene sulfonic acid formaldehyde condensate into pure water at 65 ℃, stirring until the naphthalene sulfonic acid formaldehyde condensate is dissolved, continuously adding a second catalyst (bismuth trioxide) during stirring, and dissolving to obtain a first mixed solution, wherein the mass ratio of the first catalyst to the second catalyst is 1: 0.7;
(2) adding a small amount of water into bismuth nitrate, adding nitric acid, supplementing water, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution;
(3) slowly dripping the bismuth nitrate/nitric acid mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), and uniformly stirring to obtain a second mixed solution; the dripping time is controlled to be 15 min; the stirring rate is controlled at 180 rmp;
(4) adding alkali liquor into the second mixed solution, stirring, filtering, washing with pure water, performing suction filtration, and drying the obtained product for 0.5-5 h at 50-90 ℃ to obtain a zinc-nickel battery cathode coating material; pouring out the clear liquid in the solution to the position where the solution surface is level to the precipitate, pouring pure water, putting the pure water into the solution, performing water bath ultrasound at 80 ℃ for 4 hours, precipitating, continuously pouring out the clear liquid, filtering, stirring the solution in the process, performing suction filtration twice, pouring pure water when the liquid level is close to the filter cake each time, continuously performing suction filtration, and washing with pure water.
The zinc-nickel battery negative electrode coating materials prepared in examples 1 to 3 were prepared into a zinc-nickel battery together with a positive electrode, a positive electrode coating material, a negative electrode and an electrolyte, and the battery cycle performance of the obtained zinc-nickel battery and a commercially available zinc-nickel battery was measured, and the results are shown in table 1:
TABLE 1 Battery cycling Performance results for Zinc-Nickel batteries
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the scope of the present invention as set forth in the claims.
Claims (6)
1. The preparation method of the zinc-nickel battery cathode coating material is characterized by comprising the following steps of:
(1) adding the first catalyst into pure water at the temperature of 50-75 ℃, stirring until the first catalyst is dissolved, continuously adding the second catalyst in the stirring process, and dissolving to obtain a first mixed solution;
(2) adding a small amount of water into bismuth nitrate, adding nitric acid, supplementing water, and fixing the volume to obtain a bismuth nitrate/nitric acid mixed solution;
(3) slowly dripping the bismuth nitrate/nitric acid mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), and uniformly stirring to obtain a second mixed solution;
(4) adding alkali liquor into the second mixed solution, stirring, filtering, washing with pure water, performing suction filtration, and drying the obtained product to obtain a zinc-nickel battery cathode coating material;
in the step (1), the first catalyst is selected from one or more of polyethylene glycol, naphthalene sulfonic acid formaldehyde condensate, methyl cellulose and iridium acetylacetonate, and the second catalyst is selected from one or more of phosphate, antimony trioxide and bismuth trioxide;
in the step (4), the alkali liquor is sodium hydroxide solution.
2. The preparation method of the coating material for the negative electrode of the zinc-nickel battery as claimed in claim 1, wherein in the step (1), the mass ratio of the first catalyst to the second catalyst is 1: (0.5-0.8).
3. The method for preparing the coating material for the cathode of the zinc-nickel battery as claimed in claim 1, wherein in the step (3), the dropping time of the bismuth nitrate/nitric acid mixed solution is controlled within 10-20 min; the stirring speed is controlled to be 120-200 rmp.
4. The preparation method of the zinc-nickel battery cathode coating material according to claim 1, wherein in the step (4), the suction filtration process comprises the following steps: pouring out the clear liquid in the solution to the position where the solution surface is level to the precipitate, pouring pure water into the solution, placing the solution into the solution for water bath ultrasonic treatment, precipitating, continuously pouring out the clear liquid for filtration, stirring the solution in the process, performing suction filtration twice, pouring pure water into the solution when the liquid surface is close to the filter cake each time, continuously performing suction filtration, and washing with pure water.
5. The preparation method of the zinc-nickel battery negative electrode coating material according to claim 4, characterized in that the temperature of the water bath ultrasound is 35-40 ℃, and the time of the water bath ultrasound is 2-3 h.
6. The preparation method of the zinc-nickel battery negative electrode coating material according to claim 1, wherein in the step (4), the drying temperature is 50-90 ℃ and the drying time is 0.5-5 h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086340A (en) * | 2011-11-01 | 2013-05-08 | 中国科学院福建物质结构研究所 | Polycrystalline-phase bismuth phosphate nano-powder and preparation method thereof |
| CN106848315A (en) * | 2017-03-09 | 2017-06-13 | 河南师范大学 | Zinc-nickel battery anode material and preparation method thereof and the battery using the negative material |
| CN107403967A (en) * | 2017-07-25 | 2017-11-28 | 中南大学 | A kind of method of inorganic matter modification zinc oxide nano composite material |
| CN108539169A (en) * | 2018-04-16 | 2018-09-14 | 西北工业大学 | A kind of self-assembled structures Bi2O3Zinc-base battery anode material and preparation method |
| BG111775A (en) * | 2014-06-16 | 2018-11-15 | Институт По Електрохимия И Енергийни Системи При Бан | Alkaline rechargeable nickel-zincbattery |
| CN110289395A (en) * | 2019-07-01 | 2019-09-27 | 超威电源有限公司 | A kind of lotion and preparation method thereof for Zinc-nickel battery negative |
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- 2019-12-04 CN CN201911229194.1A patent/CN111261853B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086340A (en) * | 2011-11-01 | 2013-05-08 | 中国科学院福建物质结构研究所 | Polycrystalline-phase bismuth phosphate nano-powder and preparation method thereof |
| BG111775A (en) * | 2014-06-16 | 2018-11-15 | Институт По Електрохимия И Енергийни Системи При Бан | Alkaline rechargeable nickel-zincbattery |
| CN106848315A (en) * | 2017-03-09 | 2017-06-13 | 河南师范大学 | Zinc-nickel battery anode material and preparation method thereof and the battery using the negative material |
| CN107403967A (en) * | 2017-07-25 | 2017-11-28 | 中南大学 | A kind of method of inorganic matter modification zinc oxide nano composite material |
| CN108539169A (en) * | 2018-04-16 | 2018-09-14 | 西北工业大学 | A kind of self-assembled structures Bi2O3Zinc-base battery anode material and preparation method |
| CN110289395A (en) * | 2019-07-01 | 2019-09-27 | 超威电源有限公司 | A kind of lotion and preparation method thereof for Zinc-nickel battery negative |
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