CN113871738A - Electrode charging method for improving capacity of zinc-silver reserve battery - Google Patents
Electrode charging method for improving capacity of zinc-silver reserve battery Download PDFInfo
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- CN113871738A CN113871738A CN202111122851.XA CN202111122851A CN113871738A CN 113871738 A CN113871738 A CN 113871738A CN 202111122851 A CN202111122851 A CN 202111122851A CN 113871738 A CN113871738 A CN 113871738A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of zinc-silver batteries, in particular to an electrode charging method for improving the capacity of a zinc-silver reserve battery, which inhibits the over-fast increase of charging voltage by adopting a charging mode of gradient charging and charge-discharge alternation, thereby achieving the purpose of maintaining the charging voltage below 2.10V for a long time, further improving the conversion rate of active material Ag powder, shortening the charging time and enabling the battery to output more capacity.
Description
Technical Field
The invention relates to the technical field of zinc-silver batteries, in particular to an electrode charging method for improving the capacity of a zinc-silver reserve battery.
Background
The zinc-silver reserve battery has stable discharge voltage, long working time and specific energyHigh volume, safety and reliability, and the like, and is widely applied to the field of strategic tactical missiles. During charging, the active material Ag powder of the positive electrode is firstly converted into Ag2O, the voltage is below 1.98V at the moment; continued charging of Ag2The O will gradually convert to AgO, and the voltage is about 2.10V. When Ag powder is completely converted into AgO, the electrode reaches a theoretical capacity value at the moment, and the highest active substance utilization rate is achieved.
In general, when an electrode is charged, due to the fastest reaction rate of the surface of the electrode, active material Ag powder on the surface is firstly converted into AgO, so that the charging voltage is rapidly increased to 2.10V. If the charging is continued, the voltage will be further increased, the electrochemical reaction of the electrolyzed water occurs in the formation tank, the charging efficiency is low, the electrode capacity is slowly increased, the conversion rate of the active material cannot be effectively improved even if the charging time is prolonged, and the output capacity is far smaller than the theoretical capacity of the active material during discharging.
Patent CN105098922A discloses a 28V/35Ah zinc-silver battery charging system and charging method thereof, which improves the charging efficiency of the zinc-silver battery by controlling the charging limit voltage to 40V, then charging with different charging currents, and detecting the voltage of the single battery, but the requirement of the scheme for current control and polling of the single battery by a polling control circuit is strict, and how to solve the problem that the actual output capacity is smaller than the theoretical capacity is not mentioned.
Disclosure of Invention
The invention provides an electrode charging method for improving the capacity of a zinc-silver reserve battery aiming at the defects of the prior art.
The method is realized by the following technical scheme:
an electrode charging method for improving the capacity of a zinc-silver reserve battery comprises the following steps:
first-step assembly: the sintered silver electrode and the pasted zinc cathode are assembled in pairs and then placed in a rectangular container, and the ratio of the thickness of the electrode pair to the length of the rectangular container is controlled to be 63-68%;
adding electrolyte in the second step: adding KOH aqueous solution into a rectangular container;
third step ladderAnd (3) charging at a certain degree: in a constant temperature environment, the temperature is firstly 1.8-2.2mA/cm2Charging to 57-63% of the theoretical capacity of the positive electrode with the current density of 0.9-1.1mA/cm2The current density of (a) is charged to 78-83% of the theoretical capacity of the positive electrode;
the fourth step is alternately charged: charging for at least 10h in a manner of charging for 5ms first and then discharging for 5ms, wherein the charging current density is greater than the discharging current density;
and a fifth step of washing and drying: and (4) washing the anode and the cathode to be neutral by using deionized water, and then respectively drying the anode and the cathode.
The density of the KOH aqueous solution is 1.10-1.30 g/ml. The constant temperature environment is 23-28 ℃; preferably 25 deg.c.
The charging current density in the fourth step is 0.9-1.1mA/cm2(ii) a Preferably 1mA/cm2。
The discharge current density in the fourth step is 0.45-0.55mA/cm2(ii) a Preferably 0.5mA/cm2。
The sum of the time of the gradient charging and the alternating charging is less than or equal to 40 h.
The drying temperature is not more than 60 ℃.
Has the advantages that:
the invention adopts a charging mode of gradient charging and charge-discharge alternation to inhibit the over-rapid increase of the charging voltage, thereby achieving the purpose of maintaining the charging voltage below 2.10V for a long time and further improving the conversion rate of the active material Ag powder; specifically, the method comprises the following steps:
according to the invention, different charging current densities are controlled at different charging stages, so that the charging voltage can be maintained below 2.10V for a long time, and the charging efficiency is improved; and the charging is carried out in an alternative charging and discharging mode at the final stage of charging, so that the charging voltage is maintained at the level of 2.10V, and the normal conversion of the positive active material is ensured.
The invention not only improves the charging efficiency, shortens the charging time from 40 h-70 h to no more than 40h, but also improves the conversion rate of the active substances of the electrode, and enables the battery to output more capacity, namely the difference between the theoretical output capacity and the actual output capacity to be reduced.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
An electrode charging method for improving the capacity of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.30g/ml into the chemosynthesis tank;
step three, gradient charging:
in a constant temperature environment of 25 ℃, the temperature is firstly controlled to be 5A (the current density is 2.05 mA/cm)2) Charging for 14h, then reaching the theoretical capacity of 58%, and further charging at 2.5A (current density of 1.02 mA/cm)2) Charging for 10h, wherein the theoretical capacity is 78%;
the fourth step is alternately charged:
firstly, the current density is 2.5A (the current density is 1.02 mA/cm)2) Charging for 5ms, and charging at 1.2A (current density 0.49 mA/cm)2) Discharging for 12h in an alternating mode of 5 ms;
and a fifth step of washing and drying:
washing the positive electrode and the negative electrode to be neutral by using deionized water, and respectively drying the positive electrode and the negative electrode in an environment at 50 ℃;
in this example, the total charging time was 36 hours, the charging capacity reached 110.6Ah, the apparent depth of charge reached 91%, and the monolithic positive electrode capacity was about 2.50 Ah. The electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 12.42Ah, and the utilization rate reaches 75%.
Comparative example 1
A method for charging an electrode of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.30g/ml into the chemosynthesis tank;
and step three, constant current charging:
charging at 25 deg.C under constant temperature for 20h at 4A, and charging at 2A for 18 h;
and fourthly, washing and drying:
washing the positive electrode and the negative electrode to be neutral by using deionized water, and respectively drying the positive electrode and the negative electrode in the environment of 50 ℃ and 260 ℃;
in the comparative example, the total charging time was 38 hours, the charging capacity reached 116Ah, the apparent depth of charge reached 96%, and the monolithic positive electrode capacity was about 2.64 Ah; the electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 10.74Ah, and the utilization rate reaches 65%.
Therefore, comparing example 1 with comparative example 1, the charging time was shortened, the output capacity was improved, and the electrode utilization rate was improved by about 11% in example 1.
Example 2
An electrode charging method for improving the capacity of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.10g/ml into the chemosynthesis tank;
step three, gradient charging:
at 25 deg.CIn a constant temperature environment, the temperature is controlled to be 4.5A (the current density is 1.84 mA/cm)2) Charging for 16h, wherein the theoretical capacity is 60%; then, the current density was adjusted to 2.2A (current density 0.90 mA/cm)2) Charging for 11h, wherein the theoretical capacity is 80%;
the fourth step is alternately charged:
firstly, 2.2A (current density 0.90 mA/cm)2) Charging for 5ms, and charging at 1.1A (current density 0.45 mA/cm)2) Discharging for 12h in an alternating mode of 5 ms;
and a fifth step of washing and drying:
and (4) washing the anode and the cathode to be neutral by using deionized water, and respectively drying the anode and the cathode in an environment at 50 ℃.
In this example, the total charging time was 39 hours, the charging capacity reached 111.6Ah, the apparent depth of charge reached 92%, and the monolithic positive electrode capacity was about 2.54 Ah. The electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 12.62Ah, and the utilization rate reaches 76.5%.
Comparative example 2
A method for charging an electrode of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.10g/ml into the chemosynthesis tank;
and step three, constant current charging:
charging at 25 deg.C under constant temperature for 18h at 4.5A, and charging at 2.2A for 18 h;
and fourthly, washing and drying:
washing the positive electrode and the negative electrode to be neutral by using deionized water, and respectively drying the positive electrode and the negative electrode in the environment of 50 ℃ and 260 ℃;
in this comparative example, the total charging time was 38 hours, the charging capacity reached 120.6Ah, the apparent depth of charge reached 100%, and the monolithic positive electrode capacity was about 2.75 Ah. The electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 10.92Ah, and the utilization rate reaches 66%.
Therefore, comparing example 2 with comparative example 2, the charging time was shortened, the output capacity was improved, and the electrode utilization was improved by about 10.5% in example 1.
Example 3
An electrode charging method for improving the capacity of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.10g/ml into the chemosynthesis tank;
step three, gradient charging:
in a constant temperature environment of 25 ℃, the temperature is controlled to be 5.4A (the current density is 2.21 mA/cm)2) Charging for 14h, wherein the theoretical capacity is 62%; then, the current density was adjusted to 2.7A (current density 1.10 mA/cm)2) Charging for 8h, wherein the theoretical capacity is 78%;
the fourth step is alternately charged:
firstly, the current density is 2.7A (the current density is 1.10 mA/cm)2) Charging for 5ms, and charging at 1.4A (current density 0.57 mA/cm)2) Discharging for 12h in an alternating mode of 5 ms;
and a fifth step of washing and drying:
and (4) washing the anode and the cathode to be neutral by using deionized water, and respectively drying the anode and the cathode in an environment at 50 ℃.
In this example, the total charging time was 34 hours, the charging capacity reached 112.8Ah, the apparent depth of charge reached 93%, and the monolithic positive electrode capacity was about 2.56 Ah. The electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 12.72Ah, and the utilization rate reaches 77%.
Comparative example 3
A method for charging an electrode of a zinc-silver reserve battery comprises the following steps:
first-step assembly:
44 sintered silver electrodes (the theoretical capacity of a single electrode is 2.75Ah) with the thickness of 0.45mm and 45 pasted zinc electrodes (the thickness is 55.08mm) with the thickness of 0.60mm are packaged and then put into a forming groove with the length of 85 mm;
adding electrolyte in the second step:
adding 0.45L of KOH aqueous solution with the density of 1.10g/ml into the chemosynthesis tank;
and step three, constant current charging:
charging at 25 deg.C under constant temperature for 14h at 5.5A, and charging at 2.5A for 18 h;
and fourthly, washing and drying:
washing the positive electrode and the negative electrode to be neutral by using deionized water, and respectively drying the positive electrode and the negative electrode in an environment at 50 ℃;
in this comparative example, the total charging time was 32 hours, the charging capacity reached 122Ah, the apparent depth of charge reached 101%, and the monolithic positive electrode capacity was about 2.75 Ah. The electrode prepared by the method is assembled into a single battery according to 6 positive electrodes and 6 negative electrodes, the single battery is discharged to cut-off voltage of 1.25V at the current of 30A, the total output capacity is 10.93Ah, and the utilization rate reaches 66%.
Therefore, comparing example 3 with comparative example 3, the charging time was shortened, the output capacity was improved, and the electrode utilization rate was improved by about 11% in example 3.
Claims (9)
1. An electrode charging method for improving the capacity of a zinc-silver reserve battery is characterized by comprising the following steps:
first-step assembly: the sintered silver electrode and the pasted zinc cathode are assembled in pairs and then placed in a rectangular container, and the ratio of the thickness of the electrode pair to the length of the rectangular container is controlled to be 63-68%;
adding electrolyte in the second step: adding KOH aqueous solution into a rectangular container;
step three, gradient charging: in a constant temperature environment, the temperature is firstly 1.8-2.2mA/cm2Charging to 57-63% of the theoretical capacity of the positive electrode with the current density of 0.9-1.1mA/cm2The current density of (a) is charged to 78-83% of the theoretical capacity of the positive electrode;
the fourth step is alternately charged: charging for at least 10h in a manner of charging for 5ms first and then discharging for 5ms, wherein the charging current density is greater than the discharging current density;
and a fifth step of washing and drying: and (4) washing the anode and the cathode to be neutral by using deionized water, and then respectively drying the anode and the cathode.
2. The method of claim 1, wherein the KOH aqueous solution has a density of 1.10 to 1.30 g/ml.
3. The method of charging an electrode for increasing the capacity of a zinc-silver reserve battery according to claim 1, characterized in that the constant temperature environment is 23-28 ℃.
4. A method of charging an electrode for increasing the capacity of a zinc-silver reserve battery according to claim 1 or 3, characterized in that the constant temperature environment is 25 ℃.
5. The method for charging an electrode for increasing the capacity of a zinc-silver reserve battery according to claim 1, wherein the charging current density in the fourth step is 0.9 to 1.1mA/cm2。
6. The method for charging an electrode for improving the capacity of a zinc-silver reserve battery according to claim 1 or 5, wherein the charging current density in the fourth step is 1mA/cm2。
7. The method for charging an electrode for increasing the capacity of a zinc-silver reserve battery according to claim 1, wherein the discharge current density in the fourth step is 0.45 to 0.55mA/cm2。
8. The method of claim 1 or 7 for increasing reserve power of zinc and silverThe electrode charging method of the battery capacity is characterized in that the discharging current density in the fourth step is 0.5mA/cm2。
9. The method of claim 1, wherein the sum of the time of the gradient charging and the alternating charging is less than or equal to 40 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115832480A (en) * | 2022-11-28 | 2023-03-21 | 贵州梅岭电源有限公司 | Charging control method for high-power zinc-silver storage battery |
| CN115849431A (en) * | 2022-10-11 | 2023-03-28 | 贵州梅岭电源有限公司 | Zinc-silver battery and high-specific-capacity AgO positive electrode material thereof |
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Cited By (2)
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| CN115849431A (en) * | 2022-10-11 | 2023-03-28 | 贵州梅岭电源有限公司 | Zinc-silver battery and high-specific-capacity AgO positive electrode material thereof |
| CN115832480A (en) * | 2022-11-28 | 2023-03-21 | 贵州梅岭电源有限公司 | Charging control method for high-power zinc-silver storage battery |
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