CN102723471A - Gel zinc paste for alkaline battery and preparation method thereof - Google Patents
Gel zinc paste for alkaline battery and preparation method thereof Download PDFInfo
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- CN102723471A CN102723471A CN2012102294890A CN201210229489A CN102723471A CN 102723471 A CN102723471 A CN 102723471A CN 2012102294890 A CN2012102294890 A CN 2012102294890A CN 201210229489 A CN201210229489 A CN 201210229489A CN 102723471 A CN102723471 A CN 102723471A
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Abstract
The invention discloses gel zinc paste for an alkaline battery and a preparation method thereof. The gel zinc paste comprises zinc powder mixture and alkaline electrolyte which are mixed according to a mass ratio of 100 to 30-50; the zinc powder mixture comprises mercury-free zinc powder, gel, indium hydroxide or indium oxide and zinc oxide which are mixed according to a mass ratio of 100 to 0.5-5 to 0.01-0.1 to 1; the alkaline electrolyte comprises potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water which are mixed according to a mass ratio of 40 to 6-7 to 0.2-0.5 to 0.05-0.1 to 52.5-53.5. The gel comprises carboxymethyl cellulose, polyving akohol, polyacrylic acid, sodium polyacrylate, polyacrylic acid derivatives and the like. According to the gel zinc paste and the preparation method provided by the invention, the production process is simple, the product quality is easily controlled, the service life and storage period of the battery can be prolonged, and the application range of the battery can be enlarged.
Description
Technical field
The present invention relates to a kind of calamine cream that can be applicable to aspects such as alkaline Mn cell, zinc-air cell, relate in particular to a kind of alkaline battery with gel calamine cream and preparation method thereof.
Background technology
In recent years along with the exploitation with the zero discharge motor vehicle that increases of portable apparatus, people all at the battery system of seeking a kind of high-energy-density to satisfy its requirement.Zinc-air battery is as efficient, clean green energy resource new technology; Have advantages such as capacity is big, specific energy is high, cost is low, discharge performance is stable, safe, pollution-free; Having become the exploitation focus of world today's energy field, is a kind of chemical power source with great market prospect.
The operation principle of zinc-air cell is: zinc is anode active material, and airborne oxygen is cathode active material, and potassium hydroxide is electrolyte; The anode reaction that zinc is oxidized to zinc oxide takes place on the zinc electrode, oxygen reduction takes place on the air electrode become cathode reaction hydroxy.Because the cathode reaction material is airborne oxygen, need not be stored in the battery, so zinc-air cell can provide than other battery more energy.
Calamine cream less stable in the high concentration strong base solution of using at present; Be prone to dehydration and hydrolysis when particularly battery is stored under higher temperature, the electrolyte of separating can reduce anodal sex change to battery seal place and positive extreme direction migration; Increased interior resistance, discharge performance worsens.The sedimentation cohesion will take place in the dispersion zinc powder after the hydrolysis in the calamine cream, make particle become big, and surface area reduces, and the negative electrode active material utilance descends.The leakage of the easy generation of battery is simultaneously climbed the alkali phenomenon and is caused its performance to reduce.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, the alkaline battery of useful life that can prolong battery and storage period is with gel calamine cream and preparation method thereof.
The objective of the invention is to realize through following technical scheme:
Alkaline battery of the present invention is used the gel calamine cream, comprises that zinc powder mixture is that mix 100:30 ~ 50 with alkaline electrolyte by mass ratio;
Said zinc powder mixture comprises that mercury less zinc powder, gel, indium hydroxide or indium oxide, zinc oxide are that 100:0.5 ~ 5:0.01 ~ 0.1:1 mixes by mass ratio;
Said alkaline electrolyte comprises that potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water are that mix 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 by mass ratio.
Above-mentioned alkaline battery of the present invention comprises the steps with the preparation method of gel calamine cream;
Is that 100:0.5 ~ 5:0.01 ~ 0.1:1 mix with gel, indium hydroxide or indium oxide, zinc oxide by mass ratio with mercury less zinc powder, through batch mixer handle mixed in 10 ~ 30 minutes said zinc powder mixture;
In mass ratio is that the ratio of 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 takes by weighing potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water; Water is added in the electrolyte quota groove; At the state that stirs adding potassium hydroxide down, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively; Make its whole dissolvings, promptly get said alkaline electrolyte after cooling;
Is that 100:30 ~ 50 fully mix with alkaline electrolyte by mass ratio with said zinc powder mixture, and the mode stir process of employing vacuum stirring 5 ~ 20 minutes obtains the gel calamine cream.
Alkaline battery of the present invention is with gel calamine cream and preparation method thereof, because calamine cream adopts zinc powder mixture and electrolyte mixing vacuum stirring to form, has that production technology is simple, product quality is controlled easily and finished product rate advantages of higher; Owing to added effective gel, can make zinc powder and electrolyte in the calamine cream form the lotion that stable and uniform is disperseed, improve guarantor's fluidity ability of calamine cream, reduce its self discharge.The effect that simultaneously can promote between the zinc powder, contact between zinc powder and the collector body improves the shock resistance of battery; Owing to adopt the mode of vacuum stirring to prepare, the gas that calamine cream produces in the preparation process of having drained reduces the cell expansion distortion, helps the long term storage of battery.
Embodiment
To do to describe in detail further to the embodiment of the invention below.
Alkaline battery of the present invention is used the gel calamine cream, and its preferable embodiment is:
Comprise that zinc powder mixture is that mix 100:30 ~ 50 with alkaline electrolyte by mass ratio;
Said zinc powder mixture comprises that mercury less zinc powder, gel, indium hydroxide or indium oxide, zinc oxide are that 100:0.5 ~ 5:0.01 ~ 0.1:1 mixes by mass ratio;
Said alkaline electrolyte comprises that potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water are that mix 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 by mass ratio.
Said gel comprises one or more in carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate and the polyacrylic acid derivative.
Above-mentioned alkaline battery of the present invention is with the preparation method of gel calamine cream, and its preferable embodiment comprises the steps;
Is that 100:0.5 ~ 5:0.01 ~ 0.1:1 mix with gel, indium hydroxide or indium oxide, zinc oxide by mass ratio with mercury less zinc powder, through batch mixer handle mixed in 10 ~ 30 minutes said zinc powder mixture;
In mass ratio is that the ratio of 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 takes by weighing potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water; Water is added in the electrolyte quota groove; At the state that stirs adding potassium hydroxide down, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively; Make its whole dissolvings, promptly get said alkaline electrolyte after cooling;
Is that 100:30 ~ 50 fully mix with alkaline electrolyte by mass ratio with said zinc powder mixture, and the mode stir process of employing vacuum stirring 5 ~ 20 minutes obtains the gel calamine cream.
Alkaline battery of the present invention is used the gel calamine cream.This calamine cream adopts zinc powder mixture and alkaline electrolyte mixing final vacuum to stir and forms.Through in calamine cream, adding effective gel; Can make zinc powder and electrolyte in the calamine cream form the lotion that stable and uniform is disperseed; Can keep electrolyte equably around making zinc powder; Guarantee that each position when battery discharge, zinc particle surface has even, sufficient electrolyte to cover, prevent that calamine cream zinc powder and electrolyte in storage process from producing uneven sedimentation.The gel effect that promotes between the zinc powder in addition, contact between zinc powder and the collector body simultaneously improves battery and is receiving vibration and the generation that descends of electric voltage exception in use.Can prolong the useful life and the storage period of battery to a great extent, improve the range of application of battery.
Alkaline battery of the present invention is with the preparation method of gel calamine cream, and said calamine cream is stirred by zinc powder mixture and alkaline electrolyte mixing final vacuum and processes, and specifically comprises the steps;
(1) with zinc powder and gel, indium hydroxide (In (OH)
3) or indium oxide (In
2O
3), zinc oxide (ZnO) is 100 by mass ratio: (0.5 ~ 5): (0.01 ~ 0.1): 1 mixes, and handles mixing in 10 ~ 30 minutes through batch mixer.
(2) be 40 in mass ratio: (6 ~ 7): (0.2 ~ 0.5): (0.05 ~ 0.1): the ratio of (52.5 ~ 53.5) takes by weighing potassium hydroxide (KOH), zinc oxide (ZnO), calcium oxide (CaO), sodium stannate (Na
2SnO
33H
2O) and water.Water is added in the electrolyte quota groove,, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively, make its whole dissolvings, promptly get said alkaline electrolyte after cooling at the state that stirs adding potassium hydroxide down.
(3) zinc powder mixture with step (1) preparation is 100 with the alkaline electrolyte that step (2) prepares by mass ratio: mix fully (30 ~ 50), and the mode stir process of employing vacuum stirring 5 ~ 20 minutes obtains the gel calamine cream.
Gel comprises one or more mixtures in carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyacrylic acid (PAA), Sodium Polyacrylate (PAAS) and the polyacrylic acid derivative in the step (1).
The invention has the beneficial effects as follows:
1) calamine cream of the present invention adopts zinc powder mixture and electrolyte mixing vacuum stirring to form, and has that production technology is simple, product quality is controlled easily and finished product rate advantages of higher.
2) in the calamine cream of the present invention owing to added effective gel, can make the zinc powder in the calamine cream form the lotion that stable and uniform is disperseed with electrolyte, improve guarantor's fluidity ability of calamine cream, reduce its self discharge.The effect that simultaneously can promote between the zinc powder, contact between zinc powder and the collector body improves the shock resistance of battery.
3) calamine cream of the present invention adopts the mode of vacuum stirring to prepare, and the gas that calamine cream produces in the preparation process of having drained reduces the cell expansion distortion, helps the long term storage of battery.
Specific embodiment 1:
(1) gets 40g potassium hydroxide, 6g zinc oxide, 0.5g calcium oxide, 0.08g sodium stannate, 53.42g water.Earlier water is added in the electrolyte quota groove,, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively, make its whole dissolvings, promptly get alkaline electrolyte after cooling at the state that stirs adding potassium hydroxide down.
(2) get 100g zinc powder, 0.05g indium oxide, 1g zinc oxide, 2g Sodium Polyacrylate and 0.5g carboxymethyl cellulose and mix, stir process mixed it in 10 minutes.Get above-mentioned electrolyte 36g and mix, adopt de-airing mixer to handle and promptly got the gel calamine cream in 8 minutes with zinc powder mixture.
Adopt this calamine cream to assemble zinc-air cell as negative pole, can preserve under the normal temperature more than 2 years, battery does not have the bulging phenomenon of leakage.
Specific embodiment 2:
(1) gets 40g potassium hydroxide, 7g zinc oxide, 0.2g calcium oxide, 0.05g sodium stannate, 52.75g water.Earlier water is added in the electrolyte quota groove,, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively, make its whole dissolvings, promptly get alkaline electrolyte after cooling at the state that stirs adding potassium hydroxide down.
(2) get 100g zinc powder, 0.08g indium hydroxide, 1g zinc oxide, 0.8g polyacrylic acid and 1.2g Sodium Polyacrylate and mix, stir process mixed it in 10 minutes.Get above-mentioned electrolyte 40g and mix, adopt de-airing mixer to handle and promptly got the gel calamine cream in 10 minutes with zinc powder mixture.
Adopt this calamine cream to assemble zinc-air cell as negative pole, high temperature can be preserved more than 2 months for 50 ℃, and battery does not have the bulging phenomenon of leakage.
Specific embodiment 3:
(1) gets 40g potassium hydroxide, 6.5g zinc oxide, 0.4g calcium oxide, 0.06g sodium stannate, 53.04g water.Earlier water is added in the electrolyte quota groove,, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively, make its whole dissolvings, promptly get alkaline electrolyte after cooling at the state that stirs adding potassium hydroxide down.
(2) get 100g zinc powder, 0.08g indium hydroxide, 1g zinc oxide, 0.5g polyvinyl alcohol and 1.6g Sodium Polyacrylate and mix, stir process mixed it in 10 minutes.Get above-mentioned electrolyte 45g and mix, adopt de-airing mixer to handle and promptly got the gel calamine cream in 15 minutes with zinc powder mixture.
Adopt this calamine cream to assemble zinc-air cell as negative pole, can preserve under the normal temperature more than 2 years, battery does not have the bulging phenomenon of leakage.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (3)
1. an alkaline battery is used the gel calamine cream, it is characterized in that, comprises that zinc powder mixture is that mix 100:30 ~ 50 with alkaline electrolyte by mass ratio;
Said zinc powder mixture comprises that mercury less zinc powder, gel, indium hydroxide or indium oxide, zinc oxide are that 100:0.5 ~ 5:0.01 ~ 0.1:1 mixes by mass ratio;
Said alkaline electrolyte comprises that potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water are that mix 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 by mass ratio.
2. alkaline battery according to claim 1 is used the gel calamine cream, it is characterized in that, said gel comprises one or more in carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate and the polyacrylic acid derivative.
3. claim 1 or 2 described alkaline batteries is characterized in that with the preparation method of gel calamine cream, comprise the steps;
Is that 100:0.5 ~ 5:0.01 ~ 0.1:1 mix with gel, indium hydroxide or indium oxide, zinc oxide by mass ratio with mercury less zinc powder, through batch mixer handle mixed in 10 ~ 30 minutes said zinc powder mixture;
In mass ratio is that the ratio of 40:6 ~ 7:0.2 ~ 0.5:0.05 ~ 0.1:52.5 ~ 53.5 takes by weighing potassium hydroxide, zinc oxide, calcium oxide, sodium stannate and water; Water is added in the electrolyte quota groove; At the state that stirs adding potassium hydroxide down, let its dissolving, add zinc oxide, calcium oxide and sodium stannate then successively; Make its whole dissolvings, promptly get said alkaline electrolyte after cooling;
Is that 100:30 ~ 50 fully mix with alkaline electrolyte by mass ratio with said zinc powder mixture, and the mode stir process of employing vacuum stirring 5 ~ 20 minutes obtains the gel calamine cream.
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Cited By (8)
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CN104167528A (en) * | 2014-08-19 | 2014-11-26 | 合肥献芝新能源有限公司 | Zinc electrode for zinc-air batteries and preparation method of zinc electrode |
CN104868166A (en) * | 2014-02-25 | 2015-08-26 | 常州优特科新能源科技有限公司 | Electrolyte additive for zinc-series battery |
CN106159276A (en) * | 2016-07-19 | 2016-11-23 | 横店集团东磁股份有限公司 | A kind of alkaline Mn cell negative zinc cream additive and application thereof |
CN109390581A (en) * | 2018-10-10 | 2019-02-26 | 嘉兴华荣电池有限公司 | Alkaline battery negative paste |
US20190067737A1 (en) * | 2017-08-28 | 2019-02-28 | City University Of Hong Kong | Method for fabricating a polymeric material for use in an energy storage apparatus, a polymeric material and an energy storage apparatus comprising thereof |
CN113346082A (en) * | 2021-05-28 | 2021-09-03 | 浙江野马电池股份有限公司 | Alkaline manganese battery with sodium alginate and preparation method thereof |
CN113903914A (en) * | 2021-08-31 | 2022-01-07 | 浙江恒威电池股份有限公司 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
CN113937280A (en) * | 2021-08-31 | 2022-01-14 | 嘉兴学院 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
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CN1913199A (en) * | 2006-08-24 | 2007-02-14 | 广州市天球实业有限公司 | Non-mercury button cell negative zinc cream and its making method |
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Cited By (12)
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CN104868166A (en) * | 2014-02-25 | 2015-08-26 | 常州优特科新能源科技有限公司 | Electrolyte additive for zinc-series battery |
CN104167528A (en) * | 2014-08-19 | 2014-11-26 | 合肥献芝新能源有限公司 | Zinc electrode for zinc-air batteries and preparation method of zinc electrode |
CN104167528B (en) * | 2014-08-19 | 2017-02-15 | 合肥献芝新能源有限公司 | Zinc electrode for zinc-air batteries and preparation method of zinc electrode |
CN106159276A (en) * | 2016-07-19 | 2016-11-23 | 横店集团东磁股份有限公司 | A kind of alkaline Mn cell negative zinc cream additive and application thereof |
US20190067737A1 (en) * | 2017-08-28 | 2019-02-28 | City University Of Hong Kong | Method for fabricating a polymeric material for use in an energy storage apparatus, a polymeric material and an energy storage apparatus comprising thereof |
US11177504B2 (en) * | 2017-08-28 | 2021-11-16 | City University Of Hong Kong | Method for fabricating a polymeric material for use in an energy storage apparatus, a polymeric material and an energy storage apparatus comprising thereof |
CN109390581A (en) * | 2018-10-10 | 2019-02-26 | 嘉兴华荣电池有限公司 | Alkaline battery negative paste |
CN113346082A (en) * | 2021-05-28 | 2021-09-03 | 浙江野马电池股份有限公司 | Alkaline manganese battery with sodium alginate and preparation method thereof |
CN113903914A (en) * | 2021-08-31 | 2022-01-07 | 浙江恒威电池股份有限公司 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
CN113937280A (en) * | 2021-08-31 | 2022-01-14 | 嘉兴学院 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
CN113937280B (en) * | 2021-08-31 | 2024-01-30 | 浙江恒威电池股份有限公司 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
CN113903914B (en) * | 2021-08-31 | 2024-05-03 | 浙江恒威电池股份有限公司 | Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel |
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Application publication date: 20121010 |