CN103071787A - Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery - Google Patents
Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery Download PDFInfo
- Publication number
- CN103071787A CN103071787A CN2012105922247A CN201210592224A CN103071787A CN 103071787 A CN103071787 A CN 103071787A CN 2012105922247 A CN2012105922247 A CN 2012105922247A CN 201210592224 A CN201210592224 A CN 201210592224A CN 103071787 A CN103071787 A CN 103071787A
- Authority
- CN
- China
- Prior art keywords
- mercury
- zinc powder
- battery
- free zinc
- alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention provides a treatment method of mercury-free zinc powder, which comprises the following steps: and carrying out annealing treatment on the mercury-free zinc powder. Compared with the untreated mercury-free zinc powder obtained by the atomization technology in the prior art, the method has the advantages that the mercury-free zinc powder is subjected to annealing treatment, the mercury-free zinc powder is heated to a certain temperature and kept for a certain time through annealing, and then the mercury-free zinc powder is slowly cooled to further diffuse trace elements in the mercury-free zinc powder, so that the internal components of the mercury-free zinc powder are uniformly distributed, impurities in the mercury-free zinc powder can be dispersed, the mercury-free zinc powder is difficult to form a microcell structure in alkali liquor, the gas evolution amount of the mercury-free zinc powder can be reduced, and the electrical property, the safety and the leak resistance of a battery can be improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a mercury-free zinc powder treatment method, battery zinc paste and an alkaline battery.
Background
The alkaline zinc-manganese battery has excellent performances of large capacity, heavy current discharge, long storage life and the like, and is relatively low in price, so that the alkaline zinc-manganese battery is still the battery with the widest application and the largest output. The alkaline Zn-Mn battery is a new chemical power source with Electrolytic Manganese Dioxide (EMD) as positive active material, special metal zinc powder as negative active material and potassium hydroxide as electrolyte.
Because zinc is thermodynamically unstable in alkaline solution and can react with alkaline liquor to release hydrogen, the capacity of the battery is reduced in the processes of storage and use, and the released hydrogen can also cause the battery to deform, leak electrolyte and even explode, so that the traditional alkaline battery adopts a zinc powder amalgamation method to form an amalgamation film to uniformly and flatly cover the surface of zinc powder, change the surface condition of zinc particles and activate the zinc battery, thereby improving the electrical property of the battery, reducing the corrosion speed of zinc and reducing the leakage rate of the battery. However, mercury belongs to a first-level poison, which can cause serious environmental pollution, so that the development of mercury-free batteries is needed, and mercury-free zinc powder is researched to meet the requirement of manufacturing green environment-friendly alkaline batteries.
In order to inhibit the gassing amount of mercury-free zinc powder and improve the leak-proof performance of a battery, at present, a common method at home and abroad is to add trace elements such as indium, bismuth, aluminum or calcium and the like which can improve the hydrogen evolution potential of the zinc powder in the zinc powder smelting process. For example, chinese patent publication No. CN102274964a discloses a mercury-free alkaline zinc powder, which comprises zinc powder and metal additives, wherein the metal additives comprise indium, bismuth and cerium in rare earth metals and calcium, magnesium and aluminum in non-rare earth metals.
The preparation method of the mercury-free zinc powder mainly comprises an atomization blowing method, a chemical displacement method and an electrolytic codeposition method, wherein the atomization process is mature, and the chemical displacement method and the electrolytic codeposition method are still in experimental research stages, so that the existing mercury-free zinc powder preparation adopts the atomization process, namely, zinc solution is rapidly cooled in a short time to prepare the zinc powder. However, the atomization cooling time is very short, and after indium, bismuth, aluminum, calcium and other elements are added into zinc liquid to form zinc powder alloy, segregation phenomenon is easily generated in zinc powder crystals, so that the elements are unevenly distributed in the zinc powder, potential difference exists, and a zinc cathode micro-battery is easily generated. In addition, in the rapid cooling process, most impurities are distributed on the surfaces of the particles, and zinc is easy to form a microcell structure, so that the zinc powder is easy to generate hydrogen evolution reaction in the environment, active substances are consumed, and the electrical property and the safety and leakage-proof performance of the battery are deteriorated. Therefore, the problem that the mercury-free zinc powder is easy to generate gas in the alkaline electrolyte cannot be completely solved after the inorganic corrosion inhibitor is added to the mercury-free zinc powder prepared by the atomization process.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for treating mercury-free zinc powder, a battery zinc paste and an alkaline battery, wherein the amount of gas evolved from the mercury-free zinc powder treated by the method is small.
The invention provides a treatment method of mercury-free zinc powder, which comprises the following steps:
a) And carrying out annealing treatment on the mercury-free zinc powder.
Preferably, the mercury-free zinc powder is prepared by an atomization process.
Preferably, the step a) is specifically:
heating the mercury-free zinc powder, preserving the heat, and then cooling to room temperature.
Preferably, the heating rate is 5 to 40 ℃/min.
Preferably, the temperature of the heat preservation is 50-350 ℃.
Preferably, the temperature of the heat preservation is 60-250 ℃.
Preferably, the heat preservation time is 1 to 7h.
Preferably, the heat preservation time is 1 to 5h.
The invention also provides battery zinc paste which comprises the mercury-free zinc powder obtained by treatment.
The invention also provides an alkaline battery which comprises the mercury-free zinc powder obtained by the treatment.
The invention provides a treatment method of mercury-free zinc powder, which comprises the following steps: and (4) annealing the mercury-free zinc powder. Compared with the untreated mercury-free zinc powder obtained by the atomization technology in the prior art, the method has the advantages that the mercury-free zinc powder is subjected to annealing treatment, the mercury-free zinc powder is heated to a certain temperature and kept for a certain time through annealing, and then the mercury-free zinc powder is slowly cooled to further diffuse trace elements in the mercury-free zinc powder, so that the internal components of the mercury-free zinc powder are uniformly distributed, impurities in the mercury-free zinc powder can be dispersed, the mercury-free zinc powder is difficult to form a microcell structure in alkali liquor, the gas evolution amount of the mercury-free zinc powder can be reduced, and the electrical property, the safety and the leak resistance of a battery can be improved.
Experimental results show that the gas evolution amount of the mercury-free zinc powder obtained by the treatment of the invention can be as low as 0.01ml/g day.
Drawings
FIG. 1 is a graph of the relationship between the gassing amount of mercury-free zinc powder and the annealing temperature after treatment in comparative example 1 and example 1~5;
FIG. 2 is a line graph showing the relationship between the expansion rate and the annealing temperature of the cell pastes obtained in comparative example 1 and example 1~5;
FIG. 3 is a line graph showing the relationship between the leakage rate and the annealing temperature of the alkaline batteries obtained in comparative example 1 and example 1~5 of the present invention;
FIG. 4 is a line graph showing the relationship between the expansion rate and the annealing time of the battery calamine cream obtained in example 4 and example 6~9 of the present invention;
fig. 5 is a line graph showing the relationship between the leakage rate and the annealing time of the alkaline batteries obtained in example 4 and example 6~9 of the present invention.
Detailed Description
The invention provides a treatment method of mercury-free zinc powder, which comprises the following steps: a) And carrying out annealing treatment on the mercury-free zinc powder.
The mercury-free zinc powder is not particularly limited, as long as it is known to those skilled in the art. The mercury-free zinc powder is added with trace elements for improving hydrogen evolution overpotential of the zinc powder, and is preferably prepared by an atomization process. The source of the mercury-free zinc powder is not particularly limited, and the mercury-free zinc powder can be commercially available or self-made.
According to the invention, the step A) is specifically as follows: heating the mercury-free zinc powder, preserving the heat for a certain time, and then cooling to room temperature.
The temperature of the annealing treatment, i.e. the temperature of the heat preservation, is preferably 50 ℃ to 350 ℃ in the invention, and more preferably 60 ℃ to 250 ℃.
The temperature increase rate of the annealing treatment is not particularly limited as long as it is a temperature increase rate known to those skilled in the art. In the present invention, the temperature increase rate of the annealing treatment is preferably 5 to 40 ℃/min, more preferably 10 to 30 ℃/min.
The annealing time, i.e., the constant heat-insulating time, is preferably 1 to 7 hours, and more preferably 1 to 5 hours in the present invention.
The mercury-free zinc powder obtained by the atomization process has short atomization cooling time, and after trace elements added in the zinc liquid and used for reducing hydrogen evolution overpotential of the zinc powder form a zinc powder alloy, segregation phenomenon is easily generated in a crystal, so that different components in the zinc powder are unevenly distributed, and a microcell is easily formed in electrolyte due to potential difference. After atomization forming, annealing the formed zinc powder, heating the mercury-free zinc powder to a certain temperature and keeping the temperature for a certain time through annealing, and then slowly cooling to further diffuse trace elements in the mercury-free zinc powder, so that the internal components of the mercury-free zinc powder particles are uniformly distributed, and impurities in the mercury-free zinc powder particles can be dispersed, so that the mercury-free zinc powder is difficult to form a microcell structure in alkali liquor, the gas evolution amount of the mercury-free zinc powder can be reduced, and the electrical performance and the safety leakage-proof performance of a battery can be improved.
The invention also provides battery zinc paste which contains mercury-free zinc powder subjected to annealing treatment.
The battery zinc paste is well known to those skilled in the art, and includes mercury-free zinc powder subjected to the above annealing treatment, and others are not particularly limited. The battery zinc paste preferably comprises mercury-free zinc powder subjected to annealing treatment, a gelling agent and electrolyte. The gelling agent and the electrolyte are well known to those skilled in the art, and there is no particular limitation.
The invention also provides an alkaline battery, which comprises the mercury-free zinc powder subjected to the annealing treatment.
The alkaline cell is well known to those skilled in the art, and may include mercury-free zinc powder subjected to the above-described annealing treatment, and others are not particularly limited.
In order to further illustrate the invention, the following examples are provided to describe the method of treating mercury-free zinc powder, the cell paste and the alkaline cell.
The reagents used in the following examples are commercially available and the mercury-free zinc powder used is IBA mercury-free zinc powder with added indium, bismuth and aluminum elements, available from south-of-the-gulch technologies, inc.
Example 1
1.1 putting 50g mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 60 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and naturally cooling to room temperature.
1.2 mixing 50 weight portions of the mercury-free zinc powder treated in the step 1.1, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery calamine cream, wherein the electrolyte is 10mol/L KOH solution.
1.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 1.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (3) testing the gas evolution quantity of the zinc powder treated in the step (1.1) according to QB/T2576-2002 to obtain the gas evolution quantity (5 days at 60 ℃) of 0.02 ml/g-day.
And (2) pouring the battery calamine cream obtained in 25ml1.2 into a measuring cylinder, tamping, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 20.1%.
The alkaline battery obtained in 1.3 was subjected to a battery internal resistance test four times, and the results are shown in table 1.
The alkaline battery obtained in 1.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (3) storing the alkaline battery obtained in the step (1.3) at a high temperature of 90 ℃, and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 11%.
The alkaline cell obtained in 1.3 was subjected to an electrical property test, and the results are shown in table 2.
Example 2
2.1 putting 50g mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and naturally cooling to room temperature.
2.2 mixing 50 weight portions of the mercury-free zinc powder treated in the step 2.1, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery calamine cream, wherein the electrolyte is 10mol/L KOH solution.
2.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 2.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (3) testing the gas evolution quantity of the zinc powder treated in the step (2.1) according to QB/T2576-2002 to obtain the gas evolution quantity (5 days at 60 ℃) of 0.02 ml/g-day.
And pouring the battery calamine cream obtained in 25ml2.2 into a measuring cylinder, tamping, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then preserving the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 19.2%.
The alkaline battery obtained in 2.3 was subjected to a battery internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 2.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain the results shown in table 1.
And (4) storing the alkaline battery obtained in the step (2.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 9%.
The alkaline cell obtained in 2.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 3
3.1 placing 50g of mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 150 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and naturally cooling to room temperature.
3.2 mixing 50 weight portions of 3.1 treated mercury-free zinc powder, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery zinc paste, wherein the electrolyte is 10mol/L KOH solution.
3.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 3.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
The mercury-free zinc powder treated in 3.1 is subjected to a zinc powder gassing test according to QB/T2576-2002, and the gassing amount (5 days at 60 ℃) is 0.02ml/g day.
And (3) pouring the battery calamine cream obtained in 25ml3.2 into a measuring cylinder, compacting, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 18.3%.
The alkaline cell obtained in 3.3 was subjected to cell internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 3.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (3) storing the alkaline battery obtained in the step (3.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the liquid leakage rate of 6%.
The alkaline cell obtained in 3.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 4
4.1 putting 50g of mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 200 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2h, and naturally cooling to the room temperature.
4.2 mixing 50 weight parts of the mercury-free zinc powder treated in the step 4.1, 0.3 weight part of polyacrylic acid, 0.3 weight part of sodium polyacrylate and 30 weight parts of electrolyte to prepare the battery calamine cream, wherein the electrolyte is KOH solution of 10 mol/L.
4.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 4.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (3) testing the gas evolution quantity of the zinc powder treated in the step (4.1) according to QB/T2576-2002 to obtain the gas evolution quantity (5 days at 60 ℃) of 0.01 ml/g.day.
And (3) pouring the battery calamine cream obtained in 25ml4.2 into a measuring cylinder, compacting, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 15.8%.
The alkaline battery obtained in 4.3 was subjected to a battery internal resistance test four times, and the results are shown in table 1.
The alkaline battery obtained in 4.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (4) storing the alkaline battery obtained in the step (4.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 0%.
The alkaline cell obtained in 4.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 5
5.1 putting 50g of mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant-force furnace industry), heating to 250 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and naturally cooling to room temperature.
5.2 mixing 50 weight portions of the mercury-free zinc powder treated in the step 5.1, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery calamine cream, wherein the electrolyte is 10mol/L KOH solution.
And 5.3, preparing the battery zinc paste obtained in the step 5.2, electrolytic manganese dioxide, graphite powder and diaphragm paper into the alkaline battery.
The mercury-free zinc powder treated in the step 5.1 is subjected to a zinc powder gassing test according to QB/T2576-2002, and the gassing amount (5 days at 60 ℃) is 0.02ml/g day.
And (2) pouring 25ml of the battery zinc paste obtained in 5.2 into a measuring cylinder, compacting, discharging gas among the battery zinc pastes until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording original data, then keeping the temperature of the measuring cylinder filled with the battery zinc paste for 24 hours under the condition of constant temperature of 90 ℃, reading scales and calculating the rising percentage of the battery zinc paste to obtain the expansion rate of the battery zinc paste of 17.2%.
The alkaline cell obtained in 5.3 was subjected to cell internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 5.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (3) storing the alkaline battery obtained in the step (5.3) at a high temperature of 90 ℃, and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 2%.
The alkaline cell obtained in 5.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 6
6.1 putting 50g mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 200 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature.
6.2 mixing 50 weight parts of mercury-free zinc powder treated in 6.1, 0.3 weight part of polyacrylic acid, 0.3 weight part of sodium polyacrylate and 30 weight parts of electrolyte to prepare the battery calamine cream, wherein the electrolyte is KOH solution of 10 mol/L.
6.3 preparing the alkaline battery by mixing the battery zinc paste obtained in the step 6.2 with electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (2) pouring 25ml of the battery zinc paste obtained in the step (6.2) into a measuring cylinder, compacting, discharging gas among the battery zinc pastes until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording original data, then keeping the temperature of the measuring cylinder filled with the battery zinc paste for 24 hours at the constant temperature of 90 ℃, reading scales and calculating the rising percentage of the battery zinc paste to obtain the expansion rate of the battery zinc paste of 16.5%.
The alkaline battery obtained in 6.3 was subjected to a battery internal resistance test four times, and the results are shown in table 1.
The alkaline battery obtained in 6.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (3) storing the alkaline battery obtained in the step (6.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 3%.
The alkaline cell obtained in 6.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 7
7.1 putting 50g of mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant-force furnace industry), heating to 200 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, and naturally cooling to room temperature.
7.2 mixing 50 weight portions of the mercury-free zinc powder treated in the step 7.1, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery calamine cream, wherein the electrolyte is KOH solution of 10 mol/L.
7.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 7.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (3) pouring the battery calamine cream obtained in 25ml7.2 into a measuring cylinder, compacting, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 15.7%.
The alkaline cell obtained in 7.3 was subjected to cell internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 7.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain the results shown in Table 1.
And (4) storing the alkaline battery obtained in the step (7.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 0%.
The alkaline cell obtained in 7.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 8
8.1 putting 50g mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 200 ℃ at the heating rate of 10 ℃/min, preserving the heat for 4h, and naturally cooling to the room temperature.
8.2 mixing 50 weight parts of mercury-free zinc powder treated in 8.1, 0.3 weight part of polyacrylic acid, 0.3 weight part of sodium polyacrylate and 30 weight parts of electrolyte to prepare the battery calamine cream, wherein the electrolyte is KOH solution of 10 mol/L.
8.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 8.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (2) pouring 25ml of the battery zinc paste obtained in the step (8.2) into a measuring cylinder, compacting, discharging gas among the battery zinc pastes until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording original data, then keeping the temperature of the measuring cylinder filled with the battery zinc paste for 24 hours at the constant temperature of 90 ℃, reading scales and calculating the rising percentage of the battery zinc paste to obtain the expansion rate of the battery zinc paste of 15.7%.
The alkaline cell obtained in 8.3 was subjected to cell internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 8.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain results shown in table 1.
And (3) storing the alkaline battery obtained in the step (8.3) at a high temperature of 90 ℃ and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 0%.
The alkaline cell obtained in 8.3 was subjected to electrical property tests, and the results are shown in table 2.
Example 9
9.1 putting 50g of mercury-free zinc powder into an RJ2-125-9 type annealing furnace (Jiangsu constant force furnace industry), heating to 200 ℃ at the heating rate of 10 ℃/min, preserving the heat for 5h, and naturally cooling to room temperature.
9.2 mixing 50 weight portions of the mercury-free zinc powder treated in the step 9.1, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery zinc paste, wherein the electrolyte is 10mol/L KOH solution.
9.3 preparing the alkaline battery by using the battery zinc paste obtained in the step 9.2, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (2) pouring the battery calamine cream obtained in 25ml9.2 into a measuring cylinder, compacting, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the temperature of the measuring cylinder filled with the battery calamine cream for 24 hours under the condition of constant temperature of 90 ℃, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 15.6%.
The alkaline cell obtained in 9.3 was subjected to cell internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 9.3 was stored at 70 ℃ for 5 days, and subjected to a gas evolution test four times, to obtain the results shown in table 1.
And (3) storing the alkaline battery obtained in the step (9.3) at a high temperature of 90 ℃, and testing the high-temperature leakage-proof performance of the alkaline battery to obtain the alkaline battery with the leakage rate of 0%.
The alkaline cell obtained in 9.3 was subjected to electrical property tests and the results are shown in table 2.
The expansion of the cell pastes obtained in examples 4 and 6~9 was plotted against the annealing time to obtain a line graph, as shown in fig. 4.
The leakage rate of the alkaline batteries obtained in examples 4 and 6~9 was plotted against the annealing treatment time to obtain a line graph as shown in fig. 5.
Comparative example 1
1.1 mixing 50 weight portions of untreated mercury-free zinc powder, 0.3 weight portion of polyacrylic acid, 0.3 weight portion of sodium polyacrylate and 30 weight portions of electrolyte to prepare the battery zinc paste, wherein the electrolyte is 10mol/L KOH solution.
1.2 preparing the alkaline battery by using the battery zinc paste obtained in the step 1.1, electrolytic manganese dioxide, graphite powder and diaphragm paper.
And (4) testing the gas evolution quantity of the zinc powder according to QB/T2576-2002 to obtain the gas evolution quantity of 0.03ml/g day.
Pouring the battery calamine cream obtained in 25ml1.1 into a measuring cylinder, tamping, discharging gas among the battery calamine creams until no obvious bubbles exist, covering 5ml of liquid paraffin on the surface layer, recording the original data, then keeping the measuring cylinder filled with the battery calamine cream at the constant temperature of 90 ℃ for 24h, reading the scales and calculating the rising percentage of the battery calamine cream to obtain the expansion rate of the battery calamine cream of 25.0%.
The alkaline battery obtained in 1.3 was subjected to a battery internal resistance test four times, and the results are shown in table 1.
The alkaline cell obtained in 1.3 was stored at 70 ℃ for 5 days, and the gassing amount was measured four times to obtain the results shown in Table 1.
The alkaline battery obtained in the step 1.3 is stored at a high temperature of 90 ℃ and is subjected to a high-temperature leakage-proof performance test, and the leakage rate of the alkaline battery is 29 percent.
The alkaline cell obtained in 1.3 was subjected to an electrical property test, and the results are shown in table 2.
The gassing amount of the mercury-free zinc powders treated in comparative example 1 and example 1~5 was plotted against the annealing temperature to obtain a line graph as shown in fig. 1.
The expansion rates of the cell pastes obtained in comparative example 1 and example 1~5 were plotted against the annealing temperature to obtain a line graph as shown in fig. 2.
The cell leakage rates obtained in comparative example 1 and example 1~5 were plotted against the annealing temperature to obtain a line graph as shown in fig. 3.
TABLE 1 internal resistance and gassing of alkaline cells
TABLE 2 alkaline cell Electrical Properties
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The method for treating mercury-free zinc powder is characterized by comprising the following steps:
a) And carrying out annealing treatment on the mercury-free zinc powder.
2. The treatment method as claimed in claim 1, characterized in that the mercury-free zinc powder is prepared by an atomization process.
3. The processing method according to claim 1, characterized in that said step a) is in particular:
heating the mercury-free zinc powder, preserving the heat, and then cooling to room temperature.
4. The method of claim 1, wherein the heating is performed at a temperature rise rate of 5 to 40 ℃/min.
5. The process of claim 2, wherein the temperature of said incubation is between 50 ℃ and 350 ℃.
6. The process of claim 2, wherein the temperature of the incubation is in the range of 60 ℃ to 250 ℃.
7. The process according to claim 2, characterized in that the holding time is from 1 to 7h.
8. The process according to claim 2, characterized in that the incubation time is from 1 to 5 hours.
9. A battery zincpaste comprising mercury-free zinc powder treated according to any one of claims 1~8.
10. An alkaline cell comprising mercury-free zinc dust treated according to any one of claims 1~8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105922247A CN103071787A (en) | 2012-12-30 | 2012-12-30 | Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105922247A CN103071787A (en) | 2012-12-30 | 2012-12-30 | Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103071787A true CN103071787A (en) | 2013-05-01 |
Family
ID=48148595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105922247A Pending CN103071787A (en) | 2012-12-30 | 2012-12-30 | Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103071787A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597388A (en) * | 2022-03-16 | 2022-06-07 | 宁波双鹿新能源科技有限公司 | Zinc material special for battery and production process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452378A (en) * | 1987-08-24 | 1989-02-28 | Mitsui Mining & Smelting Co | Manufacture of amalgamated zinc alloy powder |
| CN1075670A (en) * | 1992-08-07 | 1993-09-01 | 沈阳市葫锌新产品技术开发公司 | Produce the method for alkaline cell zinc dust |
| CN1311573A (en) * | 2000-03-03 | 2001-09-05 | 朗迅科技公司 | Method and device for proceeding analog operation during transmitting audio frequency and data |
| JP2001273893A (en) * | 2000-03-27 | 2001-10-05 | Dowa Mining Co Ltd | Zinc alloy powder for alkaline battery with less gas generation amount and method of manufacturing the same |
| CN1713427A (en) * | 2004-06-23 | 2005-12-28 | 同和矿业株式会社 | Zinc alloy powder for alkaline cell and method for producing same |
-
2012
- 2012-12-30 CN CN2012105922247A patent/CN103071787A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452378A (en) * | 1987-08-24 | 1989-02-28 | Mitsui Mining & Smelting Co | Manufacture of amalgamated zinc alloy powder |
| CN1075670A (en) * | 1992-08-07 | 1993-09-01 | 沈阳市葫锌新产品技术开发公司 | Produce the method for alkaline cell zinc dust |
| CN1311573A (en) * | 2000-03-03 | 2001-09-05 | 朗迅科技公司 | Method and device for proceeding analog operation during transmitting audio frequency and data |
| JP2001273893A (en) * | 2000-03-27 | 2001-10-05 | Dowa Mining Co Ltd | Zinc alloy powder for alkaline battery with less gas generation amount and method of manufacturing the same |
| CN1713427A (en) * | 2004-06-23 | 2005-12-28 | 同和矿业株式会社 | Zinc alloy powder for alkaline cell and method for producing same |
Non-Patent Citations (1)
| Title |
|---|
| 周美玲等: "《材料工程基础》", 30 April 2001, 北京工业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597388A (en) * | 2022-03-16 | 2022-06-07 | 宁波双鹿新能源科技有限公司 | Zinc material special for battery and production process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104532095B (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN104561673B (en) | A kind of rare earth modified aluminum alloy anode sheet and preparation method thereof | |
| CN105244492A (en) | Cathode material for boracic lithium ion battery and preparation method thereof | |
| CN104513925B (en) | Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy | |
| CN104518204A (en) | Rare earth-yttrium-nickel family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy | |
| CN109585837A (en) | A kind of preparation method and applications of the carbon-coated cobaltous selenide nano material in original position | |
| CN104532062A (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN104513916B (en) | Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy | |
| CN106917010B (en) | A kind of aluminum alloy anode material and its casting method and application | |
| CN111293284A (en) | Negative electrode material, preparation method and application thereof | |
| CN106784705B (en) | A kind of hydrogen storing alloy powder and its surface treatment method | |
| CN103280565A (en) | Aluminium alloy anode material and preparation method thereof | |
| CN110391412A (en) | A kind of negative electrode material and preparation method thereof and lithium ion battery | |
| CN113881872A (en) | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof | |
| CN103894602B (en) | Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy | |
| WO2016029861A1 (en) | Rare-earth based hydrogen storage alloy and application thereof | |
| CN111705337B (en) | Method for preparing lead-calcium master alloy by molten salt galvanic cell method | |
| CN103456927B (en) | Containing vanadyl titanio hydrogen-storing alloy as electrode and preparation method thereof | |
| CN106544535B (en) | Preparation method of hydrogen storage alloy containing yttrium and nickel elements | |
| CN115117360B (en) | Mercury-free active negative electrode material and preparation method thereof | |
| CN103071787A (en) | Mercury-free zinc powder treatment method, battery zinc paste and alkaline battery | |
| CN104953114B (en) | Cobaltosic oxide-stannic disulfide nano-complex preparation method | |
| CN103137956B (en) | The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic | |
| CN103078119B (en) | Mercury-free alkaline battery cathode material and preparation method thereof | |
| CN103236552B (en) | high-capacity alkaline zinc-manganese battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130501 |