CN111342033A - Cathode of alkaline battery and preparation method thereof - Google Patents
Cathode of alkaline battery and preparation method thereof Download PDFInfo
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- CN111342033A CN111342033A CN202010347354.9A CN202010347354A CN111342033A CN 111342033 A CN111342033 A CN 111342033A CN 202010347354 A CN202010347354 A CN 202010347354A CN 111342033 A CN111342033 A CN 111342033A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
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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
- H01M4/06—Electrodes for primary cells
- H01M4/08—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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/621—Binders
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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
- H01M4/625—Carbon or graphite
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
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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 relates to the technical field of batteries, in particular to an alkaline battery cathode and a preparation method thereof, wherein the alkaline battery cathode comprises the following raw materials in parts by weight: 85-91 parts of manganese dioxide, 6-7.2 parts of graphite, 0.3-0.5 part of binder, 2-3 parts of additive and 2.6-3.0 parts of cathode electrolyte. The cathode material of the alkaline battery can improve the discharge performance of large current and medium current of the alkaline battery, improve the utilization rate of the anode, promote the forming of the cathode ring of the battery and reduce the risks of the breakage and the cracking of the cathode ring; the consistency of the discharge performance of the battery is improved; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low cost, is beneficial to industrial production, and can be suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an alkaline battery cathode and a preparation method thereof.
Background
The alkaline battery is also called alkaline dry battery, alkaline zinc-manganese battery, alkaline manganese battery, it is the more excellent variety of performance in the zinc-manganese battery series, in each battery variety, it has the advantages of large discharge capacity and long service life, generally, the alkaline battery of the same model is 3-7 times of capacity and discharge time of the ordinary battery, the difference between the two low-temperature performance is bigger, the alkaline battery is more suitable for the heavy current continuous discharge and the power utilization occasion that requires high operating voltage, especially suitable for camera, flash light, razor, electronic toy, CD machine, high-power remote controller, wireless mouse, keyboard, etc., have been increasingly and widely used. However, the discharge performance of the existing alkaline battery material in high current and medium current is not good, the utilization rate of the positive electrode is not high, and the molding of the cathode ring of the battery is not good, so that further improvement is awaited.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the cathode material of the alkaline battery, which can improve the discharge performance of large current and medium current of the alkaline battery, improve the utilization rate of a positive electrode, promote the forming of a cathode ring of the battery, reduce the risks of crushing and cracking of the cathode ring and improve the consistency of the discharge performance of the battery.
Another object of the present invention is to provide a method of making a cathode for an alkaline battery. The preparation method has the advantages of simple operation, convenient control, high production efficiency and low cost, and can be suitable for industrial production.
The purpose of the invention is realized by the following technical scheme: the cathode material of the alkaline battery comprises the following raw materials in parts by weight:
85-91 parts of manganese dioxide
6-7.2 parts of graphite
0.3 to 0.5 portion of adhesive
2-3 parts of additive
2.6-3.0 parts of cathode electrolyte.
Further, the manganese dioxide is electrolytic manganese dioxide. Further, the particle size of the electrolytic manganese dioxide is 10-30 μm.
Further, the preparation method of the electrolytic manganese dioxide comprises the following steps:
s1, heating anatase crystal form titanium dioxide to 700-900 ℃ under the condition of inert gas, and carrying out heat treatment for 20-45min to obtain modified titanium dioxide powder;
and S2, suspending the modified titanium dioxide powder prepared in the step S1 in a bath solution of an electrolytic bath to be used as a suspending agent, and preparing electrolytic manganese dioxide by adopting a suspension electrolysis process.
Further, in the step S2, the bath solution is a barium sulfate solution, and the concentration of the modified titanium dioxide in the bath solution is 0.2-0.4g/L.
Further, the content of barium sulfate in the modified electrolytic manganese dioxide prepared in the step S2 is 4-8%.
The preparation method of the electrolytic manganese dioxide has the advantages of simple and efficient process, convenient control, low impurity content, high product quality, excellent performance, large discharge capacity, strong activity, small volume, long service life and the like, can be uniformly distributed on a cathode material of an alkaline battery, can improve the discharge performance of large current and medium current of the alkaline battery, improve the utilization rate of a positive electrode, promote the discharge time of an effective low-voltage area and prolong the storage life of the battery.
Further, the binder is binder HA1681. Through adopting binder HA1681 can lubricate system ring mould at anodal powder pressure ring in-process, be favorable to the shaping of negative pole ring, reduce the broken, the cracked risk of negative pole ring.
Further, the additive is barium sulfate. The alkaline battery cathode material can improve the discharge performance of heavy current and medium current of the alkaline battery, improve the utilization rate of the anode, promote the discharge time of an effective low-pressure area, promote the forming of the cathode ring of the battery, reduce the risk of crushing and cracking of the cathode ring and improve the consistency of the discharge performance of the battery by matching barium sulfate, electrolytic manganese dioxide, graphite powder and sodium hydroxide, and can reduce the cost of the alkaline battery due to the price difference of the barium sulfate and the main material of the alkaline battery cathode material.
Furthermore, each part of the cathode electrolyte comprises the following raw materials in parts by weight: 51-57 parts of potassium hydroxide and 43-49 parts of deionized water. The invention adopts the potassium hydroxide to play an electrolysis role, so that the cathode ring prepared from the cathode material of the alkaline battery can obtain good activity and stable performance.
The invention also provides a preparation method of the alkaline battery cathode, which comprises the following steps:
(1) Weighing manganese dioxide, barium sulfate, graphite powder, a binder and an additive according to a proportion, and uniformly mixing to obtain a mixture I;
(2) And (2) adding a cathode electrolyte into the mixture I in the step (1), uniformly mixing, uniformly stirring, tabletting, granulating and sieving to obtain cathode material granular powder.
The invention has the beneficial effects that: the cathode material of the alkaline battery can improve the discharge performance of large current and medium current of the alkaline battery, improve the utilization rate of the anode, promote the forming of the cathode ring of the battery and reduce the risks of the breakage and the cracking of the cathode ring; the consistency of the discharge performance of the battery is improved; the preparation method has the advantages of simple and convenient operation, convenient control, high production efficiency and low cost, and the prepared product has stable performance and can be suitable for industrial production.
Drawings
FIG. 1 is a graph comparing 3.9 ohm continuous discharge to 0.8V for the cells of example 1 of the present invention and comparative example 1.
Figure 2 is a graph comparing 250 milliamps per day discharge from one hour to 0.9V for a cell of example 1 of the present invention and comparative example 1.
Figure 3 is a graph comparing the 1000 milliamp pulse discharge to 0.9V for the cells of example 1 of the present invention and comparative example 1.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1-3, which are not intended to limit the present invention.
Example 1
In this embodiment, an alkaline battery cathode material includes the following raw materials in parts by weight:
88 parts of manganese dioxide
6.6 parts of graphite
0.4 part of binder
2.8 parts of additive
And 2.8 parts of cathode electrolyte.
Further, the manganese dioxide is electrolytic manganese dioxide.
Further, the particle size of the electrolytic manganese dioxide is 200-500 μm.
Further, the additive is barium sulfate.
Further, the binder is binder HA1681.
Furthermore, each part of the cathode electrolyte comprises the following raw materials in parts by weight: 54 parts of potassium hydroxide and 46 parts of deionized water.
Further, the preparation method of the electrolytic manganese dioxide comprises the following steps:
s1, heating anatase crystal form titanium dioxide to 800 ℃ under the condition of inert gas, and carrying out heat treatment for 30min to obtain modified titanium dioxide powder;
and S2, suspending the modified titanium dioxide powder prepared in the step S1 in a bath solution of an electrolytic bath to be used as a suspending agent, and preparing electrolytic manganese dioxide by adopting a suspension electrolysis process.
Further, in the step S2, the bath solution is a barium sulfate solution, and the concentration of the modified titanium dioxide in the bath solution is 0.24g/L.
Further, the content of barium sulfate in the modified electrolytic manganese dioxide prepared in the step S2 is 4.7%.
The present invention also provides a method for preparing the cathode of the alkaline battery, comprising the following steps:
(1) Weighing manganese dioxide, barium sulfate, graphite powder, a binder and an additive according to a ratio, and uniformly mixing to obtain a mixture I;
(2) And (2) adding a cathode electrolyte into the mixture I in the step (1), uniformly mixing, uniformly stirring, tabletting, granulating and sieving to obtain cathode material particle powder.
Example 2
In this embodiment, the cathode material for the alkaline battery comprises the following raw materials in parts by weight:
85 parts of manganese dioxide
6 parts of graphite
0.3 part of binder
2.6 parts of cathode electrolyte.
Further, the manganese dioxide is electrolytic manganese dioxide.
Further, the particle size of the electrolytic manganese dioxide is 200-500 μm.
Further, the additive is barium sulfate.
Further, the binder is binder HA1681.
Furthermore, each part of the cathode electrolyte comprises the following raw materials in parts by weight: 51-57 parts of potassium hydroxide and 43-49 parts of deionized water.
Further, the preparation method of the electrolytic manganese dioxide comprises the following steps:
s1, heating anatase crystal form titanium dioxide to 700 ℃ under the condition of inert gas, and carrying out heat treatment for 45min to obtain modified titanium dioxide powder;
and S2, suspending the modified titanium dioxide powder obtained in the step S1 in bath solution of an electrolytic bath to be used as a suspending agent, and preparing electrolytic manganese dioxide by adopting a suspension electrolysis process.
Further, in the step S2, the bath solution is a barium sulfate solution, and the concentration of the modified titanium dioxide in the bath solution is 0.2g/L.
Further, the content of barium sulfate in the modified electrolytic manganese dioxide prepared in the step S2 is 4%.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Example 3
In this embodiment, an alkaline battery cathode material includes the following raw materials in parts by weight:
91 parts of manganese dioxide
7.2 parts of graphite
0.5 part of binder
3.0 parts of cathode electrolyte.
Further, the particle size of the electrolytic manganese dioxide is 200-500 μm.
Furthermore, each part of the cathode electrolyte comprises the following raw materials in parts by weight: 57 parts of potassium hydroxide and 49 parts of deionized water.
Further, the preparation method of the electrolytic manganese dioxide comprises the following steps:
s1, heating anatase crystal form titanium dioxide to 900 ℃ under the condition of inert gas, and carrying out heat treatment for 20min to obtain modified titanium dioxide powder;
and S2, suspending the modified titanium dioxide powder prepared in the step S1 in a bath solution of an electrolytic bath to be used as a suspending agent, and preparing electrolytic manganese dioxide by adopting a suspension electrolysis process.
Further, in the step S2, the bath solution is a barium sulfate solution, and the concentration of the modified titanium dioxide in the bath solution is 0.4g/L.
Further, the content of barium sulfate in the modified electrolytic manganese dioxide prepared in the step S2 is 8%.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Example 4
In this embodiment, the cathode material for the alkaline battery comprises the following raw materials in parts by weight:
86 parts of manganese dioxide
6.5 parts of graphite
0.4 part of binder
2.5 parts of additive
2.9 parts of cathode electrolyte.
Further, the manganese dioxide is electrolytic manganese dioxide.
Further, the particle size of the electrolytic manganese dioxide is 200-500 μm.
Furthermore, each part of the cathode electrolyte comprises the following raw materials in parts by weight: 55 parts of potassium hydroxide and 45 parts of deionized water.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Comparative example 1
This comparative example differs from example 1 above in that: the cathode material of the alkaline battery comprises the following raw materials in parts by weight: 88 parts of manganese dioxide, 6.6 parts of graphite, 0.4 part of binder and 2.8 parts of cathode electrolyte. The rest of the present comparative example is similar to that of comparative document 1, and is not described in detail here.
Comparative example 2
This comparative example differs from example 1 above in that: this comparative example uses conventional electrolytic manganese dioxide instead of the electrolytic manganese dioxide of example 1.
Comparative example 3
This comparative example differs from example 3 above in that:
LR6 cells were fabricated using examples 1-4 and comparative examples 1-2. Performance parameters were determined for the alkaline cell anode materials of example 1 and comparative example 1, respectively, with the cells of example 1 and comparative example 1 being discharged continuously to 0.8V at 3.9 ohms, the cells of example 1 and comparative example 1 being discharged at 250 milliamps for one hour per day to 0.9V, and the cells of example 1 and comparative example 1 being discharged at 1000 milliamps to 0.9V, as shown in figures 1-3, respectively (example 1 being referred to as an experimental group). As can be seen from fig. 1 to 3, the discharge time was longer with the cathode material for alkaline batteries of example 1. Compared with comparative example 1, the battery cathode adopted in example 1 can improve the discharge performance of the alkaline battery with high current and medium current, which can be improved by about 5%, improve the utilization rate of the positive electrode, and promote the discharge time of the effective low-voltage area to be increased by 30%.
In comparison with comparative example 2, the 3.9 ohm continuous discharge time to 0.8V for the cell used in example 1 was 8.5h, while that for comparative example 2 was 8.1h; the cell used in example 1 was discharged one hour per day at 250 milliamps to a discharge time of 0.9V of 8.5 hours versus 8.2 hours for comparative example 2; the 1000 milliamp pulse discharge to 0.9V discharge time for the 1000 milliamp cell used in example 1 was 500 times or more compared to less than 450 times for comparative example 2.
The cathode material of the alkaline battery can improve the discharge performance of large current and medium current of the alkaline battery, improve the utilization rate of the anode, promote the forming of the cathode ring of the battery and reduce the risks of the breakage and the cracking of the cathode ring; the consistency of the discharge performance of the battery is improved; the preparation method has the advantages of simple and convenient operation, convenient control, high production efficiency and low cost, and the prepared product has stable performance and can be suitable for industrial production.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. An alkaline battery cathode material, characterized by: the feed comprises the following raw materials in parts by weight:
85-91 parts of manganese dioxide
6-7.2 parts of graphite
0.3 to 0.5 portion of adhesive
2-3 parts of additive
2.6-3.0 parts of cathode electrolyte.
2. The alkaline battery cathode material of claim 1, wherein: the additive is barium sulfate.
3. The alkaline battery cathode material of claim 1, wherein: the binder is binder HA1681.
4. The alkaline battery cathode material of claim 1, wherein: the manganese dioxide is electrolytic manganese dioxide.
5. The alkaline battery cathode material according to claim 4, wherein: the particle size of the electrolytic manganese dioxide is 10-30 mu m.
6. The alkaline battery cathode material of claim 1, wherein: each part of the cathode electrolyte comprises the following raw materials in parts by weight: 51-57 parts of potassium hydroxide and 43-49 parts of deionized water.
7. The method for preparing the cathode material for alkaline batteries according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) Weighing manganese dioxide, barium sulfate, graphite powder, a binder and an additive according to a proportion, and uniformly mixing to obtain a mixture I;
(2) And (2) adding a cathode electrolyte into the mixture I in the step (1), uniformly mixing, uniformly stirring, tabletting, granulating and sieving to obtain cathode material particle powder.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615907A (en) * | 2018-03-28 | 2018-10-02 | 连州市凌力电池配件有限公司 | A kind of preparation process of primary alkaline battery |
| CN109273708A (en) * | 2018-10-10 | 2019-01-25 | 嘉兴华荣电池有限公司 | Alkaline battery positive electrode powder |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615907A (en) * | 2018-03-28 | 2018-10-02 | 连州市凌力电池配件有限公司 | A kind of preparation process of primary alkaline battery |
| CN109273708A (en) * | 2018-10-10 | 2019-01-25 | 嘉兴华荣电池有限公司 | Alkaline battery positive electrode powder |
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