CN111509196A - Novel nickel-metal hydride battery negative plate and manufacturing method thereof - Google Patents
Novel nickel-metal hydride battery negative plate and manufacturing method thereof Download PDFInfo
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- CN111509196A CN111509196A CN202010311979.XA CN202010311979A CN111509196A CN 111509196 A CN111509196 A CN 111509196A CN 202010311979 A CN202010311979 A CN 202010311979A CN 111509196 A CN111509196 A CN 111509196A
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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
- H01M4/24—Electrodes for alkaline 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
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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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Abstract
The invention discloses a novel nickel-metal hydride battery negative plate and a manufacturing method thereof, belonging to the field of nickel-metal hydride batteries. The novel nickel-hydrogen battery negative plate comprises a negative substrate and a coating layer, wherein the negative substrate comprises any one of a steel belt, a copper net and a copper foil, and the coating layer comprises the following raw materials: alloy powder, deionized water, a binder and a conductive agent. The alloy powder used is AB5 alloy powder and AB3 alloy powder. The novel nickel-hydrogen cathode manufacturing method mainly comprises the steps of preparing slurry, coating AB5 alloy powder slurry on one surface, drying and cutting, coating AB3 alloy powder slurry on the other surface, and finally drying and cutting. The prepared novel nickel-metal hydride battery cathode piece is applied to the secondary battery, so that the secondary battery has stronger corrosion resistance, longer cycle life and larger rate performance.
Description
Technical Field
The invention belongs to the field of nickel-metal hydride batteries, and particularly relates to a novel nickel-metal hydride battery negative plate and a manufacturing method thereof.
Background
In recent years, with the rapid development of industries such as mining industry, transportation, electronic technology and the like, people have gradually raised awareness of environmental protection, wherein the use of batteries has penetrated into various fields of people's lives, people have further raised requirements on the performance of secondary rechargeable batteries, and nickel-hydrogen batteries are trusted by consumers due to outstanding safety performance.
A nickel-metal hydride battery generally includes a positive electrode, a negative electrode, a separator, an electrolyte solution, and the like. The positive electrode is a nickel electrode, the active material of the positive electrode is nickel hydroxide, the active material of the negative electrode is metal oxide, the diaphragm is a material for separating the positive electrode from the negative electrode, and the electrolyte is potassium hydroxide and mainly plays a role in electric conduction. At present, the negative electrode of the nickel-hydrogen battery is mainly divided into two types, which mainly comprise AB3 alloy powder and AB5 alloy powder. The AB3 alloy powder has low self-discharge and good wide-temperature discharge performance, but has poor corrosion resistance, short cycle life and low rate performance; the AB5 alloy powder has good corrosion resistance, long cycle life and good rate capability, but has large self-discharge and poor wide-temperature discharge performance.
CN106531974B discloses a method for manufacturing a nickel-hydrogen battery negative plate, which is prepared by coating a powder mixture containing metallic nickel or a powder mixture containing hydrogen storage alloy on the surface of a porous nickel-plated steel strip, filling active substances by a dry method, carrying out surface treatment, drying, rolling and slicing, wherein the step of coating the powder mixture on the surface in the first step is to pull and dry the porous nickel-plated steel strip by mixed slurry, and the mixed slurry is prepared by mixing metallic nickel powder or hydrogen storage alloy powder, SBR, CMC and water according to a certain mass ratio. The cycle performance test of the battery prepared from the prepared negative plate and the battery prepared from the negative plate prepared by the conventional process shows that the 1C cycle life of the battery prepared in the embodiment is about 27% longer than that of the battery prepared by the conventional process, which indicates that the performance of the modified negative plate is improved to a certain extent, but the test of other performances needs further research.
CN108199010A discloses a nickel-hydrogen battery cathode and a method for making the same, the nickel-hydrogen battery cathode includes a cathode substrate, a cathode coating layer is provided on the surface of the cathode substrate, and the alloy powder material in the coating layer includes nickel, cobalt, manganese, aluminum and mixed lanthanide. Wherein the mixed lanthanide comprises lanthanum, cerium, praseodymium, and neodymium. The manufacturing method of the nickel-hydrogen battery cathode mainly comprises the steps of mixing the alloy powder materials according to a certain proportion, putting the mixture into a smelting furnace for smelting to obtain molten alloy slurry, cooling and grinding to obtain cathode alloy powder; and then adding the binder into the alloy powder material and diluting to obtain negative electrode slurry, finally soaking the negative electrode substrate in the negative electrode slurry, and drying. The performance test of the prepared nickel-metal hydride battery cathode shows that the capacity retention rate of the nickel-metal hydride battery cathode prepared in the embodiment is about 77-82% after the cycle is performed for 300 times, and the cycle stability of the nickel-metal hydride battery cathode is to be improved.
CN109742331A discloses a negative plate of a secondary nickel-metal hydride battery and a manufacturing method thereof, the negative plate of the nickel-metal hydride battery uses rare earth hydrogen storage alloy powder as an active substance, ferroferric oxide, graphite, nickel hydroxide and ferrous sulfide as additives and a high polymer material binder, then the materials are mixed into slurry, the slurry is coated on a negative plate substrate, and the negative plate is manufactured after drying, rolling and cutting. The negative plate prepared by the material is applied to a secondary nickel-metal hydride battery to prepare the battery. The internal resistance, the 0.2C capacity, the 5C capacity, the 28-day charge retention rate at 45 ℃ and the 1C cycle life of the battery are respectively tested, compared with a comparative example, various performances are greatly improved, and a proper amount of additive is added to have an effective synergistic effect.
In order to research a nickel-metal hydride battery negative plate with excellent performance, researchers have conducted a lot of research, and the problems of poor corrosion resistance, short cycle life, low rate capability, large self-discharge, poor wide-temperature discharge performance and the like still exist in the conventional nickel-metal hydride battery negative plate, so that the nickel-metal hydride battery negative plate with excellent performance needs to be provided.
Disclosure of Invention
In view of the defects indicated by the background art, the invention aims to provide a novel nickel-metal hydride battery negative plate and a manufacturing method thereof, the negative plate is manufactured by combining AB5 alloy powder and AB3 alloy powder, the manufactured negative plate has the advantages of the two alloy powders, and the manufactured novel negative plate has stronger corrosion resistance, circulation stability and higher rate performance when being applied to a nickel-metal hydride secondary battery.
In order to achieve the above object, the present invention adopts the following techniques:
the novel nickel-metal hydride battery negative plate comprises a negative electrode substrate and a coating layer, wherein the coating layer comprises the following raw materials: alloy powder, deionized water, a binder and a conductive agent.
Further, the coating layer comprises the following raw materials in percentage by weight: 87-92% of alloy powder, 6-11% of deionized water, 0.6-0.8% of binder and 1.2-1.4% of conductive agent.
Further preferably, the nickel-metal hydride battery negative electrode sheet comprises the following raw materials in percentage by weight: 88% of alloy powder, 10% of deionized water, 0.7% of binder and 1.3% of conductive agent.
Further, the negative electrode substrate comprises any one of a steel belt, a copper net and a copper foil.
Furthermore, the thickness of the steel belt is 0.035-0.08mm, the thickness of the copper net is 0.20-0.30mm, and the thickness of the copper foil is 0.010-0.015 mm.
Further, the alloy powder is AB5 alloy powder and AB3 alloy powder.
Further, the binder is one or more of sodium polyacrylate, styrene butadiene rubber, a cross-linked high molecular polymer and hydroxypropyl methyl cellulose.
Further, the conductive agent is one or more of nickel powder, graphite, yttrium oxide and ytterbium oxide.
The invention also provides a manufacturing method of the novel nickel-metal hydride battery negative plate, which comprises the following steps:
(1) mixing AB3 alloy powder, deionized water, a binder and a conductive agent to obtain slurry 1, coating the slurry 1 on one surface of a negative electrode substrate, drying and cutting to obtain the negative electrode substrate coated on one surface;
(2) mixing the AB5 alloy powder, deionized water, a binder and a conductive agent to obtain slurry 2, then coating the slurry 2 on the other side of the negative electrode substrate, drying and cutting to obtain the negative electrode substrate with two coated sides, namely the novel nickel-hydrogen battery negative electrode sheet.
Further, the thickness of the single-side coated negative electrode substrate in the step (1) is 0.22-0.24 mm.
Further, the drying temperature in the step (1) is 90-110 ℃, and the drying time is 8-12 min.
Further, the slurry 2 in the step (2) is coated on the other side of the negative electrode substrate, and the coating thickness is the same as the coating thickness of the slurry 1 in the step (1).
Further, the drying temperature in the step (2) is 90-110 ℃, and the drying time is 8-12 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the novel nickel-metal hydride battery negative plate prepared by the application combines the advantages of AB5 alloy powder and AB3 alloy powder, overcomes the defects of poor corrosion resistance, short cycle life, low multiplying power performance and the like of the AB3 alloy powder used alone, and overcomes the defects of large self-discharge and poor wide-temperature discharge performance of the AB5 alloy powder used alone.
(2) The novel nickel-metal hydride battery negative plate prepared by the application is applied to the secondary battery, so that the secondary battery has stronger corrosion resistance, longer cycle life and larger rate performance.
Drawings
FIG. 1 initial voltage and end voltage profiles at 45 deg.C for × 28 days for example 1, comparative 1 and comparative 2;
FIG. 2 initial voltage and end voltage profiles at 60 deg.C for × 28 days for example 1, comparative 1 and comparative 2;
FIG. 3 cycle life plots for example 1, comparative 1 and comparative 2 cycled to 80% capacity at 1C.
Detailed Description
For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The raw material sources are as follows:
the AB3 alloy powder is available from Baotou Sande battery materials Co., Ltd, product No. 19050019;
the AB5 alloy powder is available from Baotou Sande battery materials Co., Ltd, product No. 19050033;
other raw materials are common commercial products, so that the source of the raw materials is not particularly limited.
Example 1
The novel nickel-metal hydride battery negative plate comprises a negative substrate steel belt (the thickness is 0.05mm) and a coating layer, wherein the coating layer comprises the following raw materials: alloy powder (including AB5 alloy powder and AB3 alloy powder), deionized water, a binder and a conductive agent.
The manufacturing method of the novel nickel-metal hydride battery negative plate comprises the following steps:
(1) mixing 88% of AB3 alloy powder, 10% of deionized water, 0.7% of sodium polyacrylate and 1.3% of graphite according to weight percentage to obtain slurry 1, then coating the slurry 1 on one surface of a negative electrode substrate, drying for 10min at the temperature of 100 ℃, and cutting to obtain a negative electrode substrate with a single-side coating, wherein the thickness of the negative electrode substrate is 0.23 mm;
(2) mixing 88% of AB5 alloy powder, 10% of deionized water, 0.7% of sodium polyacrylate and 1.3% of graphite according to the weight percentage to obtain slurry 2, then coating the slurry 2 on the other side of the negative electrode substrate, wherein the coating thickness is the same as that of the slurry 1 in the step (1), drying for 10min at the temperature of 100 ℃, and cutting to obtain the negative electrode substrate with double coated surfaces, namely the novel nickel-hydrogen battery negative electrode plate.
Example 2
The novel nickel-metal hydride battery negative plate comprises a negative substrate steel belt (the thickness is 0.05mm) and a coating layer, wherein the coating layer comprises the following raw materials: alloy powder (including AB5 alloy powder and AB3 alloy powder), deionized water, a binder and a conductive agent.
The manufacturing method of the novel nickel-metal hydride battery negative plate comprises the following steps:
(1) mixing 87% of AB3 alloy powder, 11% of deionized water, 0.6% of sodium polyacrylate and 1.4% of graphite according to weight percentage to obtain slurry 1, then coating the slurry 1 on one surface of a negative electrode substrate, drying for 10min at the temperature of 100 ℃, and cutting to obtain a negative electrode substrate with a single-surface coating, wherein the thickness of the negative electrode substrate is 0.24 mm;
(2) mixing 87% of AB5 alloy powder, 11% of deionized water, 0.6% of sodium polyacrylate and 1.4% of graphite according to the weight percentage to obtain slurry 2, then coating the slurry 2 on the other side of the negative electrode substrate, wherein the coating thickness is the same as that of the slurry 1 in the step (1), drying for 10min at the temperature of 100 ℃, and cutting to obtain the negative electrode substrate with double coated surfaces, namely the novel nickel-hydrogen battery negative electrode plate.
Example 3
The novel nickel-metal hydride battery negative plate comprises a negative substrate steel belt (the thickness is 0.05mm) and a coating layer, wherein the coating layer comprises the following raw materials: alloy powder (including AB5 alloy powder and AB3 alloy powder), deionized water, a binder and a conductive agent.
The manufacturing method of the novel nickel-metal hydride battery negative plate comprises the following steps:
(1) mixing 92% of AB3 alloy powder, 6% of deionized water, 0.8% of sodium polyacrylate and 1.2% of graphite according to weight percentage to obtain slurry 1, then coating the slurry 1 on one surface of a negative electrode substrate, drying for 10min at the temperature of 100 ℃, and cutting to obtain a negative electrode substrate with a single-side coating, wherein the thickness of the negative electrode substrate is 0.22 mm;
(2) mixing 92% of AB5 alloy powder, 6% of deionized water, 0.8% of sodium polyacrylate and 1.4% of graphite according to the weight percentage to obtain slurry 2, then coating the slurry 2 on the other side of the negative electrode substrate, wherein the coating thickness is the same as that of the slurry 1 in the step (1), drying for 10min at the temperature of 100 ℃, and cutting to obtain the negative electrode substrate with double coated surfaces, namely the novel nickel-hydrogen battery negative electrode plate.
The difference from example 1 is that both sides of the negative electrode substrate were coated with slurry prepared using AB3 alloy powder to obtain a nickel-hydrogen negative electrode;
the other raw material components and contents and the preparation method are the same as those of the example 1.
The difference from example 1 is that both sides of the negative electrode substrate were coated with slurry prepared using AB5 alloy powder to obtain a nickel-hydrogen negative electrode;
the other raw material components and contents and the preparation method are the same as those of the example 1.
Effect test experiment:
the novel nickel-hydrogen negative electrode piece prepared in the example 1 is used for preparing an AA600mAh negative electrode piece and an AA600mAh battery core, the nickel-hydrogen negative electrode prepared in the comparison group 2 is used for preparing an AA600mAh negative electrode piece and an AA600mAh battery core, the nickel-hydrogen negative electrodes prepared in the example 1 and the comparison groups 1-2 are combined with other materials to be assembled into a battery, wherein the positive electrode piece is cobalt-coated spherical nickel, the diaphragm is a PP material, the electrolyte is a potassium hydroxide solution, the concentration of the potassium hydroxide solution is 7-10.8 mol/L, and the self-discharge performance, the wide-temperature discharge performance, the cycle life performance and the.
1. Storage test at 45 ℃ for × 28 days:
the nickel-hydrogen cathode assembled batteries prepared in example 1 and comparative groups 1-2 were placed at a temperature of 45 ℃ for 28 days for internal resistance, voltage and charge retention rate testing, once every 7 days, and the relevant data were recorded in table 1 and fig. 1.
Table 1:
as can be seen from table 1 and fig. 1, the average charge retention rate of the battery prepared in example 1 at 45 ℃ for × 28 days was 76.03%, which is close to the average charge retention rate (82.2%) of the battery prepared in comparative group 1, but much higher than the average charge retention rate (67.2%) of the battery prepared in comparative group 2.
2. Storage test at 60 ℃ for × 28 days:
the nickel-hydrogen cathode assembled batteries prepared in example 1 and comparative groups 1-2 were placed at a temperature of 60 ℃ for 28 days for internal resistance, voltage and charge retention rate testing, once every 7 days, and the relevant data were recorded in table 2 and fig. 2.
Table 2:
as can be seen from table 2 and fig. 2, the average charge retention rate of the battery prepared in example 1 at 60 ℃ for × 28 days was 60.8%, which is close to the average charge retention rate (64.6%) of the battery prepared in comparative group 1, but much higher than the average charge retention rate (54.3%) of the battery prepared in comparative group 2.
3. Testing wide-temperature discharge performance:
the batteries assembled with the nickel-hydrogen cathodes prepared in example 1 and comparative groups 1-2 were subjected to a wide temperature discharge performance test, and the test items and related data are recorded in table 3.
Table 3:
as can be seen from Table 3, the average terminal capacity at-30 ℃ is: 676.5mAh for example 1, 706mAh for comparative 1, 583.5mAh for comparative 2; the high temperature 85 ℃ end capacity averages: example 1 was 309mAh, comparative 1 was 319mAh, and comparative 2 was 214 mAh. It can be seen that the wide temperature performance of example 1 is closer to that of comparative group 1 and better than that of comparative group 2 in the wide temperature test.
4. And (3) testing the cycle life:
the nickel-hydrogen cathode assembled batteries prepared in example 1 and comparative groups 1-2 were subjected to cycle life test under the condition of cycle life test at 1C to 80% of capacity, and the test results are shown in fig. 3.
As can be seen from fig. 3, the 1C cycle-to-80% capacity life test showed that the 1C cycle life of example 1 was 38 weeks less than 891 weeks for comparative group 2 and 351 weeks more than 502 weeks for comparative group 1 for 853 weeks.
5. And (3) rate performance test:
the rate capability test was performed on the nickel-hydrogen cathode assembled batteries prepared in example 1 and comparative groups 1 to 2, and the test results are shown in table 4.
Table 4:
as can be seen from Table 4, the average discharge time of example 1 at 10C discharge was 7.75min, which was close to 8.15min for comparative group 2 and significantly better than 6.95min for comparative group 1.
In conclusion, the comparison of the data shows that the test result of the novel nickel-metal hydride battery cathode prepared by the method is obviously superior to that of the cathode made of the traditional single material, and the data of the battery produced by the embodiment of the invention is better than that of the battery produced normally, so that the purposes of improving the product capacity, improving the high-rate discharge and prolonging the cycle life can be achieved by using the embodiment of the invention.
The above disclosure is only one preferred embodiment of the present invention, and certainly should not be construed as limiting the scope of the invention, which is defined by the claims and their equivalents.
Claims (10)
1. The novel nickel-metal hydride battery negative plate is characterized by comprising a negative substrate and a coating layer, wherein the coating layer comprises the following raw materials in percentage by weight: 87-92% of alloy powder, 6-11% of deionized water, 0.6-0.8% of binder and 1.2-1.4% of conductive agent.
2. The negative electrode sheet according to claim 1, wherein the negative electrode substrate comprises any one of a steel strip, a copper mesh and a copper foil, wherein the steel strip has a thickness of 0.035-0.08mm, the copper mesh has a thickness of 0.20-0.30mm, and the copper foil has a thickness of 0.010-0.015 mm.
3. The negative plate of claim 1, wherein said alloy powders are AB5 alloy powder and AB3 alloy powder.
4. The negative electrode sheet according to claim 1, wherein the binder is one or more of sodium polyacrylate, styrene-butadiene rubber, a cross-linked high molecular polymer and hydroxypropyl methyl cellulose.
5. The negative electrode sheet according to claim 1, wherein said conductive agent is one or more of nickel powder, graphite, yttrium oxide, and ytterbium oxide.
6. The method for manufacturing the novel nickel-metal hydride battery negative plate as claimed in any one of claims 1 to 5, comprising the following steps:
(1) mixing AB3 alloy powder, deionized water, a binder and a conductive agent to obtain slurry 1, coating the slurry 1 on one surface of a negative electrode substrate, drying and cutting to obtain the negative electrode substrate coated on one surface;
(2) mixing the AB5 alloy powder, deionized water, a binder and a conductive agent to obtain slurry 2, then coating the slurry 2 on the other side of the negative electrode substrate, drying and cutting to obtain the negative electrode substrate with two coated sides, namely the novel nickel-hydrogen battery negative electrode sheet.
7. The method according to claim 6, wherein the thickness of the single-coated negative electrode substrate in the step (1) is 0.22-0.24 mm.
8. The method according to claim 6, wherein the drying temperature in step (1) is 90-110 ℃ and the drying time is 8-12 min.
9. The manufacturing method according to claim 6, wherein the slurry 2 in the step (2) is coated on the other surface of the negative electrode substrate to the same thickness as the slurry 1 in the step (1).
10. The method according to claim 6, wherein the drying temperature in step (2) is 90-110 ℃ and the drying time is 8-12 min.
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