CN114671455B - Method for industrially producing silver oxide for battery - Google Patents
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- C01G5/00—Compounds of silver
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a method for industrially producing silver oxide for a battery, and belongs to the field of battery materials. The method comprises the following steps: (1) Simultaneously injecting a silver nitrate aqueous solution and a sodium hydroxide aqueous solution into a reaction kettle containing pure water at the temperature of 25-50 ℃ under stirring, controlling the pH of the reaction liquid to be 9-12, stopping adding silver nitrate when the volume of the reaction liquid reaches 80% of the reaction kettle, continuously adding sodium hydroxide, keeping the pH at 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction liquid, and extracting 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 diameter of 5-30 mu m. The method solves the problem that the traditional silver oxide powder contains fine particles, and is simple and easy for mass production.
Description
Technical Field
The invention relates to a method for industrially producing silver oxide for a battery, and belongs 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 large-rate discharge, and has important application in the fields of military industry, standby power supplies, portable devices, high-end clocks and the like. Therefore, it is of great significance to research and improve the performance of silver oxide batteries in enterprises, universities and the like. According to the current domestic and foreign patents and documents, domestic researchers mainly carry out modification research on silver oxide electrodes, such as modification research on silver oxide electrodes prepared by a smelting method, an electroplating synthesis method, a liquid phase deposition method, a method for preparing a porous electrode and the like, and research on the activation performance, the service life and a diaphragm of the silver oxide electrodes respectively; foreign researchers are mainly focused on structural research of silver oxide, synthesis of silver oxide by a chemical synthesis method, research of crystal structure of silver oxide, research of decomposition kinetics of silver oxide and the like.
The silver oxide powder used in silver oxide battery in the market is produced by using silver nitrate as material and through reaction with precipitant, including sodium carbonate, sodium citrate, potassium carbonate, potassium bicarbonate, ammonia water, sodium hydroxide, etc. Although the conventional silver oxide specification is not clearly defined in terms of primary particle diameter, a relatively large secondary particle diameter is generally required. If the silver oxide powder for the battery contains fine particles (less than or equal to 5 mu m), the silver oxide powder can adhere to a male die in the forming process, so that a tabletting die needs to be cleaned, and the mass production efficiency of the silver oxide battery is directly affected. The invention patent CN1148820C discloses a preparation method of silver oxide, sodium carbonate is dropwise added into a silver nitrate solution under stirring, the pH value is regulated to 5.5-6.5, and the obtained silver carbonate is calcined at 250 ℃ to obtain the silver oxide. However, the activity of silver oxide for a battery is reduced after high-temperature calcination, so that the specific energy, specific power and other performances of the silver oxide battery are affected. The invention patent CN104787795B discloses a method for preparing micron silver oxide in a laboratory, wherein a test tube filled with sodium hydroxide is sealed by a microfiltration membrane and then is inserted into a silver nitrate solution, and the micron silver oxide can be prepared by using a common device in the laboratory. However, the method is not suitable for mass production on a production line, and if experimental parameters are amplified in the same proportion, the precipitation speed of silver oxide is difficult to control, so that the mass production is difficult.
Therefore, under the condition that the activity of silver oxide for a battery is not influenced, the silver oxide powder is prepared by improving the synthesis process of silver oxide in order to solve the problem that the silver oxide powder is prepared by the traditional method, the size of the secondary particle size of the silver oxide powder is effectively improved, the particle size distribution range is 5-30 mu m, the batch production can be simply realized, and the use requirement of silver oxide battery enterprises can be completely met.
Disclosure of Invention
During research and development of silver oxide for battery, the parameters of silver oxide, such as impurity element content, silver oxide content, nitrate content, nitric acid insoluble matter, apparent density, particle size distribution, etc. of silver oxide powder need to be comprehensively considered to influence the battery performance. These parameters of silver oxide directly affect the water absorption, fluidity, adhesion, etc. of discharge performance. The silver oxide prepared by adopting the chemical synthesis method has higher activity, but the activity is reduced after high-temperature sintering, and 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 achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for industrially producing silver oxide for a battery, comprising the following steps:
(1) Simultaneously injecting a silver nitrate aqueous solution and a sodium hydroxide aqueous solution into a reaction kettle containing pure water at the temperature of 25-50 ℃ under stirring, controlling the pH of the reaction liquid to be 9-12, stopping adding silver nitrate when the volume of the reaction liquid reaches 80% of the reaction kettle, continuously adding sodium hydroxide, keeping the pH at 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction liquid, and extracting 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 diameter of 5-30 mu m.
Silver oxide prepared by the traditional industrial process often contains fine powder smaller than 5 mu m, which can affect the production process and discharge performance of the silver oxide battery. The invention uses 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 smaller than 5 mu m, and the silver oxide prepared by the method does not need to be sintered at high temperature 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 perform rapid instant precipitation reaction, and the stirring is continued under the condition of pH=12 to ensure that the silver oxide has a longer nucleation period, 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 repeated wet synthesis, the silver oxide synthesized in the previous time is used as a crystal nucleus to continue production, so that the particle size of the silver oxide is increased, and the content of silver oxide small particles is reduced.
The pH value of the reaction liquid can influence precipitation, growth and granulation of oxidation, and when the pH value of the reaction liquid is smaller than 9 or larger than 12, the concentration of silver in the solution can be improved, the yield of silver oxide is reduced, and the production efficiency of silver oxide is reduced.
Preferably, the concentration of the silver nitrate aqueous solution is 1-2mol/L.
Preferably, the concentration of the silver nitrate aqueous solution is 2mol/L.
Preferably, the concentration of the sodium hydroxide aqueous solution is 1-2mol/L.
Preferably, the concentration of the sodium hydroxide aqueous solution is 2mol/L.
The silver nitrate and the sodium hydroxide react, so that the concentration of the silver nitrate aqueous solution and the concentration of the sodium hydroxide aqueous solution need to be controlled, and the proper concentration can improve the reaction speed of the silver nitrate and the sodium hydroxide and 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, silver oxide having good performance can be obtained.
Preferably, the conductivity of the silver oxide solution obtained by said washing is < 20. Mu.s/cm.
Preferably the reaction solution has a pH that varies within a range of less than + -0.25. If the fluctuation of the pH range of the reaction liquid is too large, the silver oxide can be dissolved and crystallized, so that the performance of the silver oxide is reduced, and the production efficiency of the silver oxide is reduced.
Preferably, the stirring reaction is carried out for a period of 2 hours. Under the above time, the Ag not precipitated in the reaction solution continues to precipitate, thereby improving the yield of silver oxide.
Compared with the prior art, the invention has the beneficial effects that: under the condition that the activity of silver oxide for a battery is not affected, the invention aims to solve the problem that the traditional silver oxide powder is produced to contain fine particles, improves the synthesis process of silver oxide, effectively improves the secondary particle size of the silver oxide powder, has the particle size distribution range of 5-30 mu m, can simply realize batch production, and can 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 the particle size distribution of silver oxide obtained in example 1;
FIG. 3 is a graph showing the particle size distribution of silver oxide obtained in example 2;
FIG. 4 is a graph showing the particle size distribution of silver oxide obtained in example 3;
FIG. 5 is a graph showing the particle diameter distribution of silver oxide obtained in comparative example 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings.
Example 1
The embodiment provides a method for industrially producing silver oxide for a battery, which comprises the following steps:
(1) 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, and simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 a reaction kettle for the first synthesis to enable a reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, and continuing adding the sodium hydroxide aqueous solution to make the pH value of the reaction solution be 12, and continuing stirring and reacting 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 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 examined, 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, which specifically comprises the following steps:
(1) 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, and simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 a reaction kettle for the first synthesis to enable a reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) Third synthesis: adding a proper amount of pure water into a reaction kettle for the second synthesis to enable the reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 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 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 a battery, which comprises the following steps:
(1) 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, and simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 a reaction kettle for the first synthesis to enable a reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 2 hours; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) Third synthesis: adding a proper amount of pure water into a reaction kettle for the second synthesis to enable the reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 a reaction kettle for the third synthesis to enable the reaction liquid to just submerge a stirring paddle, starting stirring and heating, simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 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 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 a battery, which comprises the following steps:
(1) 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, 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1.5h; 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 a reaction kettle for the first synthesis to enable the reaction liquid to just submerge a 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 liquid to be 9; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1.5h; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) Third synthesis: adding a proper amount of pure water into a reaction kettle for the second synthesis to enable the reaction liquid to just submerge a 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 liquid to be 9; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1.5h; 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 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 examined, and the results are shown in Table 1.
Example 5
The embodiment provides a method for industrially producing silver oxide for a battery, which comprises the following steps:
(1) First synthesis: firstly, preparing a silver nitrate aqueous solution with the concentration of 1.5mol/L and a sodium hydroxide aqueous 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; 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 a reaction kettle for the first synthesis to enable the reaction liquid to just submerge a 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 liquid to be 10; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) Third synthesis: adding a proper amount of pure water into a reaction kettle for the second synthesis to enable the reaction liquid to just submerge a 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 liquid to be 10; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; 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 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 examined, and the results are shown in Table 1.
Example 6
The embodiment provides a method for industrially producing silver oxide for a battery, which comprises the following steps:
(1) 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; 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 a reaction kettle for the first synthesis to enable the reaction liquid to just submerge a 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 liquid to be 10; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; stopping stirring, standing and layering the reaction solution, and extracting the supernatant;
(3) Third synthesis: adding a proper amount of pure water into a reaction kettle for the second synthesis to enable the reaction liquid to just submerge a 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 liquid to be 10; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting for 1h; 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 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 examined, and the results are shown in Table 1.
Comparative example 1
The comparative example provides a method for industrially producing silver oxide for a battery, comprising the following steps:
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, and simultaneously 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; stopping adding the silver nitrate aqueous solution when the volume of the reaction solution reaches 80% of that of the reaction kettle, continuously adding the sodium hydroxide aqueous solution to ensure that the pH of the reaction solution is 12, and continuously stirring and reacting 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 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 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 a battery, comprising the following steps:
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;
and secondly, adding a silver nitrate aqueous solution into a reaction kettle, starting stirring and heating, starting to slowly add a sodium hydroxide aqueous solution until the temperature is stabilized at 40 ℃, continuously stirring and reacting for 2 hours until the pH value of the reaction solution is 12, stopping stirring, standing and layering the reaction solution, extracting 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 unchanged, and fully drying 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 Table 1.
TABLE 1
As can be seen from Table 1 and FIGS. 2-5, the present invention uses silver nitrate and sodium hydroxide as raw materials, and can industrially produce micron-sized silver oxide by adopting a wet synthesis process, without generating fine particles, and without high-temperature sintering, the silver oxide has higher activity. From the test data of comparative example 2, it is known that the slow addition of an aqueous sodium hydroxide solution to an aqueous silver nitrate solution by a conventional chemical synthesis method results in a wide particle size distribution range of silver oxide powder, contains a large number of fine particles, and is not suitable for large-scale continuous production, affecting the male die formation of silver oxide.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that the technical scheme of the invention may be modified or equally substituted without departing from the spirit and scope of the technical scheme of the invention.
Claims (8)
1. A method for industrially producing silver oxide for a battery, comprising the steps of:
(1) Simultaneously injecting a silver nitrate aqueous solution and a sodium hydroxide aqueous solution into a reaction kettle containing pure water at the temperature of 25-50 ℃ under stirring, controlling the pH of the reaction liquid to be 9-12, stopping adding silver nitrate when the volume of the reaction liquid reaches 80% of the reaction kettle, continuously adding sodium hydroxide, keeping the pH at 12, and continuously stirring for reacting for 1-2 hours; stopping stirring, standing and layering the reaction liquid, and extracting 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 diameter of 5-30 mu m; d of the silver oxide particles 90 >15μm。
2. The method of claim 1, wherein the aqueous silver nitrate solution has a concentration of 1 to 2mol/L.
3. The method of claim 2, wherein the aqueous silver nitrate solution has a concentration of 2mol/L.
4. The method of claim 1, wherein the aqueous sodium hydroxide solution has a concentration of 1 to 2mol/L.
5. The method according to claim 4, wherein the aqueous sodium hydroxide solution has a concentration of 2mol/L.
6. The method according to claim 1, wherein the washed silver oxide solution has a conductivity of < 20 μs/cm.
7. The method of claim 1, wherein the reaction solution has a pH that varies less than ± 0.25.
8. The method of claim 1, wherein the stirring reaction is for a period of 2 hours.
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