CN103050718A - Pole piece protecting method for prolonging dry storage life of zinc-silver battery - Google Patents
Pole piece protecting method for prolonging dry storage life of zinc-silver battery Download PDFInfo
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- CN103050718A CN103050718A CN2012105469863A CN201210546986A CN103050718A CN 103050718 A CN103050718 A CN 103050718A CN 2012105469863 A CN2012105469863 A CN 2012105469863A CN 201210546986 A CN201210546986 A CN 201210546986A CN 103050718 A CN103050718 A CN 103050718A
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Abstract
The invention discloses a pole piece protecting method (film forming agent soaking method) for prolonging a dry storage life of a zinc-silver battery. A formed and dried positive pole piece and a formed and dried negative pole piece are respectively soaked in film forming agents with different concentrations for a certain time and then thin protective films are generated on the surfaces of the pole pieces; through the adoption of the protective films, substance and energy exchanging between the pole pieces and outside environment is isolated, the positive pole decomposition is greatly reduced and the oxidation of the negative pole is further suppressed, so that the capacity loss of the battery is reduced. Through the adoption of the pole piece protecting method disclosed by the invention, the dry storage life of the zinc-silver battery can be prolonged from the current 5-8 years to 12 years or longer; and moreover, the protected pole piece has no influence on pole piece discharging. The pole piece protecting method for prolonging the dry storage life of the zinc-silver battery, disclosed by the invention, has the advantage that the dry storage life of the zinc-silver battery is prolonged and is used for weaponries with higher requirements on long storage life, such as missiles and rockets.
Description
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Technical field
The present invention relates to zinc-silver oxide cell dry state storage life prolongation technology, particularly the application of long storage life battery is relevant with this invention.The weaponrys such as the guided missile that this invention is had relatively high expectations for storage life, rocket.
Background technology
Apply for a patent in 1988 that (CN 87202960,1988) zinc-silver oxide cell life-prolonging technique has represented the level in this field, this life-prolonging technique mainly relies on the device for prolonging that is comprised of life-increasing switch and fuse, when activated batteries, the control life-increasing switch is closed, fuse is attempted by between the battery pack both positive and negative polarity, makes battery pack reach rapidly instructions for use, deposit the life-span thereby prolong desiccating of battery pack.Adopt this device zinc-silver oxide cell can be desiccated to deposit about life to 20 year, but this apparatus structure is complicated, the Emergency use flexibility is more loaded down with trivial details, all the time, does not obtain actual use.
Check warehouse-in dry state was stored after the zinc-silver oxide cell production was finished, and when treating to execute the task, took out and used, and required this moment still can satisfy instructions for use through battery after the long term storage.The phenomenons such as discharge voltage decline, capacity attenuation can occur through after certain storage period in battery, cause the Emergency use very flexible, even can not satisfy instructions for use.
The dry state storage life of zinc-silver oxide cell generally only has 5～8 years at present, can not satisfy the equipments such as following guided missile, carrier rocket to the dry state storage life demand (more than 12 years) of zinc-silver oxide cell.Therefore, prolong zinc-silver oxide cell dry state storage life pole piece resist technology and just seem particularly important.
Summary of the invention
The problem that the present invention solves is to prolong zinc-silver oxide cell dry state storage life, the invention provides a kind of pole piece guard method that prolongs zinc-silver oxide cell dry state storage life for solving described problem.
The pole piece guard method of prolongation zinc-silver oxide cell dry state storage life provided by the present invention comprises:
Step 1, will change into dry good positive and negative plate and be immersed in respectively in the film forming agent any one among described film forming agent sodium alginate, CMT-85, E-85ME, DCA-9A, sodium carboxymethylcellulose, PVA, gum arabic, starch, sodium metasilicate, the active thickener SAC;
Step 2, the positive and negative plate after soaking is cured processing, forms layer protecting film on the positive and negative plate surface.
Further, the mass concentration of described film forming agent is not more than 10%.
Further, described positive plate is immersed in the E-85ME aqueous solution that mass concentration is 0.5%-10%; Described negative plate is immersed in the etherification starch aqueous solution that mass concentration is 1%-8%.
Further, comprise that also positive and negative plate prewets before soaking, drain after soaking, striking, then be cured processing.
Further, immersion is as follows with cure parameter: soak time is 2s-30s; Curing temperature is 60 ℃-75 ℃; Be 16h-22h curing time curing time.
Advantage of the present invention comprises: will change into dry good positive/negative plate and be soaked in respectively certain hour in the variable concentrations film forming agent; just at the thin diaphragm of pole piece Surface Creation one deck; this layer diaphragm isolated material, the energy exchange of pole piece and external environment; greatly reduce anodal the decomposition; and then inhibition negative pole oxidation; thereby the decay of reduction battery capacity makes zinc-silver oxide cell dry state storage life be increased to 12 years even more of a specified duration, and after the protection pole piece discharge use is had no effect.
The present invention can satisfy the weaponrys such as following missile armament, carrier rocket to the user demand of zinc-silver oxide cell.Dry state storage life can reduce weaponry and change number of times with zinc-silver oxide cell after prolonging, and cuts the waste to a certain extent, saves cost.
Description of drawings
Fig. 1: certain guided missile model zinc-silver oxide cell load curve figure.
Fig. 2: discharge curve comparison diagram.
Among the figure: a. adopts pole piece resist technology cell discharge curve; B. do not adopt resist technology cell discharge curve.
Embodiment
By background technology as can be known, zinc-silver oxide cell dry state storage life is short in the prior art, and it is aging that inventor's research thinks that the reason that causes electrical property decline in the zinc-silver oxide cell dry state storage process mainly contains positive active material decomposition, negative electrode active material oxidation and barrier film.
In the storage process, following decomposition reaction easily occurs in the AgO in the positive plate:
This reaction expression AgO resolves into Ag
2O and oxygen, this reaction not only affects the capacity of battery, and affects the voltage of battery.This reaction has Ag equally
2O generates, and can cause the voltage drop of battery, has simultaneously oxygen to produce, and has not only reduced the content of positive active material AgO, and the oxygen that generates, can be gradually and the active zinc powder reaction of negative pole, and cause zinc powder oxidized, capacity attenuation.It is chain reaction that AgO decomposes oxidized with Zn, mutually promotes, larger on the impact of electrical property decay.
The source of negative terminal surface passivation comprises the O in the battery enclosure space
2, CO
2, steam and other active gases, and topmost source is that AgO decomposes the O that produces in the positive pole
2Following reaction occurs in the active material on oxygen and zinc electrode surface, forms one deck passivating film:
When this layer passivating film runs up to a certain degree, also can cause the activationary time prolongation of battery and the voltage drop under voltage drop, especially the high-multiplying power discharge condition.
For above-mentioned reason, the inventor thinks that adopting the film forming agent infusion method can effectively isolate pole piece directly contacts with active material between pole piece, reduce the generation of passivating film, thereby suppress the decline of electrical property, zinc-silver oxide cell dry state storage life is prolonged, battery product is accomplished available at any time, to improve the motor-driven adjustment capability of contingency tasks in wartime.
The zinc-silver oxide cell positive and negative plate need possess the three basic condition with film forming agent:
(1) easily form fine and close diaphragm on the pole piece surface: film forming agent is wanted effectively to intercept material between positive/negative plate, energy exchange in storage process, and thickness is enough thin.
(2) film forming agent with the electrode active surface material any reaction does not occur: the film forming agent component is simple, needs to stablize in the battery storage environment, not with pole piece surface reactive material and the outer substance reaction of film forming agent.
(3) easily be dissolved in fast or be scattered in electrolyte: when battery added the electrolyte discharge, the formed diaphragm in pole piece surface should not affect electrolyte permeability, infiltrates pole piece.If electrolyte still has diaphragm to cover electrode surface after adding, easily intercept the passage of electrolyte, when causing actual discharge, the electrode reaction area reduces, and current density increases, and perhaps causes the loss of battery capacity.
According to above-mentioned primary condition, by further research, in final definite sodium alginate, etherificate xylan (CMT-85), medium-viscosity depolymerised galactomannan (E-85ME), etherificate guar gum paste (DCA-9A), sodium carboxymethylcellulose, polyvinyl alcohol (PVA), gum arabic, starch, sodium metasilicate, active thickener (SAC) solution any one may be used to film forming agent, and the mass concentration of described film forming agent is not more than 10%.
In one embodiment of the invention, changing into dry good zinc-silver oxide cell positive plate, to adopt concentration be that the E-85ME aqueous solution of 0.5%-10% is as film forming agent, changing into dry good negative plate employing concentration is that the 1%-8% etherification starch is as film forming agent, change into drying and refer to well pole piece charging and finish, and after charging, carried out dry processing.Be implemented as follows: positive and negative plate is prewetted with pure water respectively, and namely pole piece takes out immediately and the surface water mark is removed totally after dipping in water fully, and it is to prevent that film forming agent from infiltrating in a large number pole piece inside and causing electrical property to descend that this step processes; Be soak at room temperature 2s～30s in the E-85ME aqueous solution of 0.5%-10% with the positive plate after prewetting in mass concentration, take out and drain surface solution, carry out striking smooth, the environment of then putting into temperature and be 60 ℃-75 ℃ solidifies 16h-22h; Be soak at room temperature 2s～30s in the etherification starch aqueous solution of 1%-8% with the negative plate after prewetting in mass concentration, take out and drain surface solution, carry out striking smooth, the environment of then putting into temperature and be 60 ℃-75 ℃ solidifies 16h-22h; Then carry out the battery assembling.
In another one embodiment of the present invention, compound concentration is 3% E-85ME film forming agent and 3% etherification starch film forming agent in beaker respectively, can heat and stir to promote it fully to dissolve in the process for preparation; Then get the zinc-silver oxide cell positive and negative plate some, in pure water, prewet respectively; Then, positive plate is soaked 3s in 3% E-85ME film forming agent, negative plate soaks 3s in 3% etherification starch film forming agent; Drain striking smooth after, 70 ℃ of dry 18h of constant temperature in vacuum drying chamber.
Pole piece after will processing through above-mentioned employing pole piece guard method is packaged into cell according to certain compound mode (5 of positive plates, 6 of negative plates), is numbered a; Get undressed pole piece and be packaged into cell according to same way as, be numbered b.A, two cells of b are placed 8 days (Approximate Equivalent 12 years) under 75 ℃ of environment; carry out accelerated aging test; cell a capacity attenuation about 10%; allow loss amount under the 20%(normal condition far below former capacity), as seen adopt the cell capacity after pole piece is protected can satisfy life requirements in 12 years.Simultaneously two cells finishing after the accelerated life test are discharged (according to the load request of accompanying drawing 1), observe the discharge voltage situation of change, test result sees Table 1, accompanying drawing 2.Discharge voltage a is the discharge voltage of cell a in the table 1, and discharge voltage b is the discharge voltage of cell b.
Table 1 discharge voltage relatively
Test result to above-mentioned ripe sample shows, adopt the cell behind the pole piece resist technology can satisfy storage life requirement in 12 years, and discharge voltage is also slightly high than the battery without conservation treatment, can satisfy guided missile, the user demand of rocket weapon equipment.
Although the present invention with preferred embodiment openly as above; but it is not to limit the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; can utilize method and the technology contents of above-mentioned announcement that technical solution of the present invention is made possible change and modification; therefore; every content that does not break away from technical solution of the present invention; to any simple modification, equivalent variations and modification that above embodiment does, all belong to the protection range of technical solution of the present invention according to technical spirit of the present invention.
Claims (5)
1. pole piece guard method that prolongs zinc-silver oxide cell dry state storage life is characterized in that:
Step 1, will change into dry good positive and negative plate and be immersed in respectively in the film forming agent any one among described film forming agent sodium alginate, CMT-85, E-85ME, DCA-9A, sodium carboxymethylcellulose, PVA, gum arabic, starch, sodium metasilicate, the active thickener SAC;
Step 2, the positive and negative plate after soaking is cured processing, forms layer protecting film on the positive and negative plate surface.
2. the pole piece guard method of prolongation zinc-silver oxide cell dry state storage life as claimed in claim 1, it is characterized in that: the mass concentration of described film forming agent is not more than 10%.
3. the pole piece guard method of prolongation zinc-silver oxide cell dry state storage life as claimed in claim 1 is characterized in that: described positive plate is immersed in the E-85ME aqueous solution that mass concentration is 0.5%-10%; Described negative plate is immersed in the etherification starch aqueous solution that mass concentration is 1%-8%.
4. the pole piece guard method of prolongation zinc-silver oxide cell dry state storage life as claimed in claim 1; it is characterized in that: the pole piece guard method of described prolongation zinc-silver oxide cell dry state storage life is prewetted before also comprising the positive and negative plate immersion; immersion drains afterwards, striking, then is cured processing.
5. the pole piece guard method of prolongation zinc-silver oxide cell dry state storage life as claimed in claim 1 is characterized in that: soak with cure parameter as follows: soak time is 2s-30s; Curing temperature is 60 ℃-75 ℃; Be 16h-22h curing time curing time.
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| CN201210546986.3A CN103050718B (en) | 2012-12-17 | 2012-12-17 | A kind of pole piece guard method for extending dry storage life of zinc-silver battery |
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| CN201210546986.3A CN103050718B (en) | 2012-12-17 | 2012-12-17 | A kind of pole piece guard method for extending dry storage life of zinc-silver battery |
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| CN103050718B CN103050718B (en) | 2016-08-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169563A (en) * | 2016-09-12 | 2016-11-30 | 贵州梅岭电源有限公司 | A kind of zinc-silver cell possessing stabilized electrodes voltage |
| CN106252612A (en) * | 2016-10-11 | 2016-12-21 | 河南新太行电源股份有限公司 | A kind of zinc-silver oxide cell negative plate drying process |
| CN110504460A (en) * | 2019-07-31 | 2019-11-26 | 中国电子科技集团公司第十八研究所 | Chemical heating system and method for zinc-silver reserve battery |
| CN112216880A (en) * | 2020-09-24 | 2021-01-12 | 中国电子科技集团公司第十八研究所 | Zinc-silver reserve battery manufacturing method based on humidity control and zinc-silver reserve battery |
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| JPS56138866A (en) * | 1980-03-31 | 1981-10-29 | Toshiba Battery Co Ltd | Silver ii oxide battery |
| JPS58126670A (en) * | 1982-01-22 | 1983-07-28 | Kawaguchiko Seimitsu Kk | Silver oxide battery |
| WO2009120352A1 (en) * | 2008-03-27 | 2009-10-01 | Zpower, Inc. | Improved electrodes and electrochemical cells employing the same |
| CN101325255B (en) * | 2007-06-15 | 2010-08-25 | 比亚迪股份有限公司 | Zinc cathode, preparation method thereof and zinc secondary battery using zinc cathode |
| CN102005568A (en) * | 2010-10-20 | 2011-04-06 | 深圳市豪鹏科技有限公司 | Battery positive plate and manufacturing method thereof |
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2012
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Patent Citations (5)
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| JPS56138866A (en) * | 1980-03-31 | 1981-10-29 | Toshiba Battery Co Ltd | Silver ii oxide battery |
| JPS58126670A (en) * | 1982-01-22 | 1983-07-28 | Kawaguchiko Seimitsu Kk | Silver oxide battery |
| CN101325255B (en) * | 2007-06-15 | 2010-08-25 | 比亚迪股份有限公司 | Zinc cathode, preparation method thereof and zinc secondary battery using zinc cathode |
| WO2009120352A1 (en) * | 2008-03-27 | 2009-10-01 | Zpower, Inc. | Improved electrodes and electrochemical cells employing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169563A (en) * | 2016-09-12 | 2016-11-30 | 贵州梅岭电源有限公司 | A kind of zinc-silver cell possessing stabilized electrodes voltage |
| CN106252612A (en) * | 2016-10-11 | 2016-12-21 | 河南新太行电源股份有限公司 | A kind of zinc-silver oxide cell negative plate drying process |
| CN106252612B (en) * | 2016-10-11 | 2018-08-03 | 河南新太行电源股份有限公司 | A kind of zinc-silver oxide cell negative plate drying process |
| CN110504460A (en) * | 2019-07-31 | 2019-11-26 | 中国电子科技集团公司第十八研究所 | Chemical heating system and method for zinc-silver reserve battery |
| CN112216880A (en) * | 2020-09-24 | 2021-01-12 | 中国电子科技集团公司第十八研究所 | Zinc-silver reserve battery manufacturing method based on humidity control and zinc-silver reserve battery |
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| CN103050718B (en) | 2016-08-03 |
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