CN114671455A - Method for industrially producing silver oxide for battery - Google Patents
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Abstract
The invention discloses a method for industrially producing silver oxide for a battery, belonging to the field of battery materials. The method comprises the following steps: (1) injecting silver nitrate aqueous solution and sodium hydroxide aqueous solution into a reaction kettle containing pure water simultaneously under stirring at 25-50 ℃, controlling the pH of the reaction solution to be 9-12, stopping adding the silver nitrate when the volume of the reaction solution reaches 80% of the reaction kettle, continuously adding the sodium hydroxide, keeping the pH to be 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant to obtain first silver oxide slurry; (2) repeating the step (1) for 1-3 times, and finally washing and drying the obtained silver oxide slurry to obtain silver oxide particles with the average particle size of 5-30 mu m. The method solves the problem that the traditional method for producing the silver oxide powder contains fine particles, is simple, and is easy for mass production.
Description
Technical Field
The invention relates to a method for industrially producing silver oxide for a battery, belonging to the field of battery material preparation.
Background
The silver oxide battery has the characteristics of high specific energy, high specific power and capability of discharging at a large multiplying power, and has important application in the fields of military industry, standby power supplies, portable devices, high-end clocks and watches and the like. Therefore, it is of great significance to research and improve the performance of the silver oxide battery by enterprises, colleges and universities and the like. According to the current domestic and foreign patents and documents, it can be found that domestic researchers mainly carry out modification research on silver oxide electrodes, for example, the silver oxide electrodes are prepared by adopting a smelting method, an electroplating synthesis method, a liquid phase deposition method, a method for preparing porous electrodes and the like, and the activation performance, the service life and the diaphragm of the silver oxide electrodes are respectively researched; foreign researchers mainly focus on the structural research of the silver oxide, synthesize the silver oxide by a chemical synthesis method, research the crystal structure of the silver oxide, research the decomposition kinetics of the silver oxide and the like.
The production method of silver oxide powder applied to a silver oxide battery in the market at present mainly takes silver nitrate as a raw material and then reacts with a precipitator, wherein common precipitants comprise sodium carbonate, sodium citrate, potassium carbonate, potassium bicarbonate, ammonia water, sodium hydroxide and the like. Although the conventional silver oxide specification is not clearly specified in terms of the primary particle size, a large secondary particle size ratio is generally required. If the silver oxide powder for the battery contains fine particles (less than or equal to 5 mu m), the fine particles are adhered to the male die in the forming process, so that the tabletting die needs to be cleaned, and the mass production efficiency of the silver oxide battery is directly influenced. The invention patent CN1148820C discloses a preparation method of silver oxide, sodium carbonate is dripped into silver nitrate solution under stirring, pH is adjusted to 5.5-6.5, and the obtained silver carbonate is calcined at 250 ℃ to obtain the silver oxide. However, the activity of the silver oxide for the battery is reduced after the silver oxide is calcined at a high temperature, so that the specific energy, the specific power and other performances of the silver oxide battery are influenced. The invention patent CN104787795B discloses a method for preparing micron-sized silver oxide in a laboratory, which comprises the steps of sealing a test tube filled with sodium hydroxide by using a micro-filtration membrane, then inserting the test tube into a silver nitrate solution, and preparing the micron-sized silver oxide by using a common device in the laboratory. However, the method disclosed in the patent is not suitable for mass production on a production line, and if experimental parameters are amplified in the same proportion, the precipitation rate of the silver oxide is difficult to control, so that the mass production is difficult.
Therefore, under the condition of not influencing the activity of the silver oxide for the battery, the silver oxide powder is prepared by the method for improving the synthesis process of the silver oxide, so that the secondary particle size of the silver oxide powder is effectively improved, the particle size distribution range is 5-30 mu m, the mass production can be simply realized, and the use requirements of silver oxide battery enterprises can be completely met.
Disclosure of Invention
During research and development and production of the silver oxide for the battery, silver oxide parameters influencing the performance of the battery need to be comprehensively considered, and mainly the impurity element content, the silver oxide content, the nitrate content, nitric acid insoluble substances, the apparent density, the particle size distribution and the like of silver oxide powder. These parameters of silver oxide directly affect the water absorption, fluidity, adhesion, etc. of the discharge performance. The silver oxide prepared by the chemical synthesis method has higher activity, but the activity is reduced after high-temperature sintering, the invention aims to overcome the defects of the prior art, and provides the method for industrially producing the silver oxide for the battery.
In order to realize the purpose, the invention adopts the technical scheme that: a method for industrially producing silver oxide for batteries comprises the following steps:
(1) injecting silver nitrate aqueous solution and sodium hydroxide aqueous solution into a reaction kettle containing pure water simultaneously under stirring at 25-50 ℃, controlling the pH of the reaction solution to be 9-12, stopping adding the silver nitrate when the volume of the reaction solution reaches 80% of the reaction kettle, continuously adding the sodium hydroxide, keeping the pH to be 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant to obtain first silver oxide slurry;
(2) and (2) repeating the step (1) for 1-3 times, and finally washing and drying the obtained silver oxide slurry to obtain silver oxide particles with the average particle size of 5-30 mu m.
Silver oxide prepared by the traditional industrial process often contains fine powder with the diameter less than 5 mu m, and the production process and the discharge performance of the silver oxide battery are influenced. The invention takes silver nitrate and sodium hydroxide as raw materials, can industrially produce micron-sized silver oxide by adopting a wet synthesis process, does not contain fine powder less than 5 mu m, does not need high-temperature sintering, and has better activity.
Under the rotation action of stirring, the silver nitrate aqueous solution and the sodium hydroxide aqueous solution are simultaneously injected into a reaction kettle containing water to generate rapid instant precipitation reaction, and the silver oxide has a longer nucleation period by continuously stirring under the condition that the pH value is 12, so that the particle size of the silver oxide is increased, and the yield of the silver oxide is improved. In addition, in the process of repeating the wet synthesis, the silver oxide synthesized in the previous time is taken as a crystal nucleus, the production is continued, the grain size of the silver oxide is increased, and the content of small silver oxide grains is reduced.
The pH value of the reaction liquid can influence the precipitation, growth and granulation of oxidation, and when the pH value of the reaction liquid is less than 9 or more than 12, the concentration of silver in the solution can be improved, the yield of silver oxide is reduced, and the production efficiency of the silver oxide is reduced.
Preferably, the concentration of the silver nitrate aqueous solution is 1-2 mol/L.
Preferably, the concentration of the silver nitrate aqueous solution is 2 mol/L.
Preferably, the concentration of the sodium hydroxide aqueous solution is 1-2 mol/L.
Preferably, the concentration of the sodium hydroxide aqueous solution is 2 mol/L.
The silver nitrate and the sodium hydroxide can react with each other, so that the concentration of a silver nitrate aqueous solution and the concentration of a sodium hydroxide aqueous solution need to be controlled, and the appropriate concentration can improve the reaction speed of the silver nitrate and the sodium hydroxide and improve the production efficiency of the silver oxide; when the concentration of the silver nitrate aqueous solution is 2mol/L and the concentration of the sodium hydroxide aqueous solution is 2mol/L, the silver oxide with better performance can be obtained.
Preferably, the conductivity of the silver oxide solution obtained by washing is less than 20 mu s/cm.
Preferably the pH of the reaction solution varies by less than ± 0.25. If the variation range of the pH of the reaction solution fluctuates too much, the silver oxide will dissolve and crystallize, thereby reducing the performance of the silver oxide and the production efficiency of the silver oxide.
Preferably, the stirring reaction time is 2 h. In the above time, the Ag which is not precipitated in the reaction solution continues to precipitate, and the yield of the silver oxide is improved.
Compared with the prior art, the invention has the beneficial effects that: under the condition of not influencing the activity of the silver oxide for the battery, the invention aims to solve the problem that the traditional silver oxide powder production contains fine particles, improve the synthesis process of the silver oxide, effectively improve the size of the secondary particle diameter of the silver oxide powder, ensure the particle size distribution range to be 5-30 mu m, simply realize batch production and completely meet the use requirements of silver oxide battery enterprises.
Drawings
FIG. 1 is a flow chart of the industrial production of silver oxide according to example 2 of the present invention;
FIG. 2 is a graph showing a particle size distribution of silver oxide obtained in example 1;
FIG. 3 is a graph showing a distribution of the particle size of silver oxide obtained in example 2;
FIG. 4 is a graph showing a distribution of the particle size of silver oxide obtained in example 3;
Fig. 5 is a distribution diagram of the particle size of the silver oxide obtained in comparative example 1.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific embodiments and the accompanying drawings.
Example 1
The embodiment provides a method for industrially producing silver oxide for batteries, which comprises the following steps:
(1) the first synthesis: firstly, preparing silver nitrate aqueous solution with the concentration of 2mol/L and sodium hydroxide aqueous solution with the concentration of 2 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(2) and (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction liquid just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction liquid to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, and continuing adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12 and continuing stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and the solution is kept unchanged, and fully drying the silver oxide slurry at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was measured, and the results are shown in fig. 2 and table 1.
Example 2
The embodiment provides a method for industrially producing silver oxide for batteries, the production flow of which is shown in fig. 2, and the method specifically comprises the following steps:
(1) the first synthesis: firstly, preparing a silver nitrate aqueous solution with the concentration of 2mol/L and a sodium hydroxide aqueous solution with the concentration of 2 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(2) and (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction liquid just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction liquid to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) And (3) third synthesis: adding a proper amount of pure water into the reaction kettle for the second synthesis to ensure that the reaction liquid just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction liquid to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and the solution is kept unchanged, and fully drying the silver oxide slurry at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was examined, and the results are shown in FIG. 3 and Table 1.
Example 3
The embodiment provides a method for industrially producing silver oxide for batteries, which comprises the following steps:
(1) the first synthesis: firstly, preparing a silver nitrate aqueous solution with the concentration of 2mol/L and a sodium hydroxide aqueous solution with the concentration of 2 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(2) And (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(3) and (3) third synthesis: adding a proper amount of pure water into the reaction kettle for the second synthesis to ensure that the reaction liquid just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction liquid to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(4) fourth synthesis: adding a proper amount of pure water into the reaction kettle for the third synthesis to ensure that the reaction liquid just submerges the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction liquid to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and the solution is kept unchanged, and fully drying the silver oxide slurry at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was examined, and the results are shown in FIG. 4 and Table 1.
Example 4
The embodiment provides a method for industrially producing silver oxide for batteries, which comprises the following steps:
(1) the first synthesis: firstly, preparing silver nitrate aqueous solution with the concentration of 2mol/L and sodium hydroxide aqueous solution with the concentration of 2 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 25 ℃, and controlling the pH value of the reaction solution to be 9; when the volume of the reaction solution reaches 80 percent of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1.5 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(2) and (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 25 ℃, and controlling the pH value of the reaction solution to be 9; when the volume of the reaction solution reaches 80 percent of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1.5 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(3) And (3) third synthesis: adding a proper amount of pure water into the reaction kettle for the second synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 25 ℃, and controlling the pH value of the reaction solution to be 9; when the volume of the reaction solution reaches 80 percent of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1.5 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and is kept unchanged, and fully drying at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was measured, and the results are shown in table 1.
Example 5
The embodiment provides a method for industrially producing silver oxide for batteries, which comprises the following steps:
(1) the first synthesis: firstly, preparing a silver nitrate water solution with the concentration of 1.5mol/L and a sodium hydroxide water solution with the concentration of 1.5 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(2) And (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(3) and (3) third synthesis: adding a proper amount of pure water into the reaction kettle for the second synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and is kept unchanged, and fully drying at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was measured, and the results are shown in Table 1.
Example 6
The embodiment provides a method for industrially producing silver oxide for batteries, which comprises the following steps:
(1) the first synthesis: firstly, preparing a silver nitrate aqueous solution with the concentration of 1mol/L and a sodium hydroxide aqueous solution with the concentration of 1 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant;
(2) and (3) second synthesis: adding a proper amount of pure water into the reaction kettle for the first synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) And (3) third synthesis: adding a proper amount of pure water into the reaction kettle for the second synthesis to ensure that the reaction solution just submerges the stirring paddle, starting stirring, simultaneously adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution at 50 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring for reaction for 1 hour; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and the solution is kept unchanged, and fully drying the silver oxide slurry at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was measured, and the results are shown in table 1.
Comparative example 1
The present comparative example provides a method for the industrial production of silver oxide for batteries, comprising the steps of:
firstly, preparing a silver nitrate aqueous solution with the concentration of 2mol/L and a sodium hydroxide aqueous solution with the concentration of 2 mol/L; secondly, adding a proper amount of pure water into the reaction kettle to just submerge the stirring paddle, starting stirring and heating, adding a silver nitrate aqueous solution and a sodium hydroxide aqueous solution when the temperature is stabilized at 40 ℃, and controlling the pH value of the reaction solution to be 10; when the volume of the reaction solution reaches 80% of that of the reaction kettle, stopping adding the silver nitrate aqueous solution, continuously adding the sodium hydroxide aqueous solution to enable the pH of the reaction solution to be 12, and continuously stirring for reaction for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant; and finally, fully washing the obtained silver oxide slurry to ensure that the conductivity of the solution is less than 20 mu s/cm and the solution is kept unchanged, and fully drying the silver oxide slurry at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was examined, and the results are shown in FIG. 5 and Table 1.
Comparative example 2
The comparative example provides a method for industrially producing silver oxide for batteries, comprising the steps of:
firstly, preparing silver nitrate aqueous solution with the concentration of 2mol/L and sodium hydroxide aqueous solution with the concentration of 2 mol/L;
secondly, adding a silver nitrate aqueous solution into the reaction kettle, starting stirring and heating, starting slowly adding a sodium hydroxide aqueous solution when the temperature is stabilized below 40 ℃ until the pH value of the reaction solution is 12, continuously stirring for reacting for 2 hours, stopping stirring, standing and layering the reaction solution, extracting a supernatant, fully washing the obtained silver oxide slurry to enable the conductivity of the solution to be less than 20 mus/cm and keep the conductivity unchanged, and fully drying at 100 ℃ to obtain a micron-sized silver oxide product. The particle size distribution of the obtained silver oxide was measured, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1 and FIGS. 2-5, the method of the present invention uses silver nitrate and sodium hydroxide as raw materials, and adopts a wet synthesis process to industrially produce micron-sized silver oxide without fine particles, and the silver oxide does not need to be sintered at high temperature, and has high activity. It can be known from the test data of comparative example 2 that the slow addition of the aqueous solution of sodium hydroxide to the aqueous solution of silver nitrate by the conventional chemical synthesis method results in the silver oxide powder having a wide particle size distribution range, containing a lot of fine particles, being unsuitable for large-scale continuous production, and affecting the male molding of silver oxide.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for industrially producing silver oxide for batteries is characterized by comprising the following steps:
(1) injecting a silver nitrate aqueous solution and a sodium hydroxide aqueous solution into a reaction kettle containing pure water simultaneously under stirring at the temperature of 25-50 ℃, controlling the pH of the reaction solution to be 9-12, stopping adding the silver nitrate when the volume of the reaction solution reaches 80% of the reaction kettle, continuously adding the sodium hydroxide, keeping the pH to be 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction solution, and pumping out the supernatant to obtain first silver oxide slurry;
(2) and (2) repeating the step (1) for 1-3 times, and finally washing and drying the obtained silver oxide slurry to obtain silver oxide particles with the average particle size of 5-30 mu m.
2. The method of claim 1, wherein the concentration of the aqueous silver nitrate solution is 1 to 2 mol/L.
3. The method of claim 2, wherein the concentration of the aqueous silver nitrate solution is 2 mol/L.
4. The method of claim 1, wherein the aqueous sodium hydroxide solution has a concentration of 1 to 2 mol/L.
5. The method of claim 4, wherein the aqueous sodium hydroxide solution has a concentration of 2 mol/L.
6. The method of claim 1, wherein the washed silver oxide solution has a conductivity of < 20 μ s/cm.
7. The method of claim 1, wherein the pH of the reaction solution varies by less than ± 0.25.
8. The method of claim 1, wherein the stirring reaction time is 2 hours.
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