CN101087020A - A method for making zinc electrode using scraping plasm - Google Patents

A method for making zinc electrode using scraping plasm Download PDF

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Publication number
CN101087020A
CN101087020A CNA2006100142417A CN200610014241A CN101087020A CN 101087020 A CN101087020 A CN 101087020A CN A2006100142417 A CNA2006100142417 A CN A2006100142417A CN 200610014241 A CN200610014241 A CN 200610014241A CN 101087020 A CN101087020 A CN 101087020A
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China
Prior art keywords
zinc
electrode
slurry
zinc electrode
making
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CNA2006100142417A
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CN100492724C (en
Inventor
孟宪玲
武彩霞
刘春�
张健
赵力群
李广森
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CETC 18 Research Institute
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CETC 18 Research Institute
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention relates to a method of producing zinc electrode by slush, the invention belongs to zinc electrode used in zinc battery producing field. Zinc active material, water solution of additive and agglomerant are mixed evenly, and then mixed to slurry, then conducting framework is adhibited with slurry by conducting groove, and produced to Zinc electrode band via drawknife with definite clearance, then the Zinc electrode band is dried, rolled, cut to zinc electrode piece with appropriate size, the producing zinc electrode by slush in the invention possesses advantages that active material is distributed evenly, discharging voltage is high, utilization of electrode is high; the craftwork possesses advantages that operation is easy, easy to be mechanical and automatization, coherence of quality and efficiency of battery is increased, pollution of environment is little.

Description

A kind of method of making zinc electrode using scraping plasm
Technical field
The invention belongs to zinc battery zinc electrode preparing technical field, particularly relate to a kind of method of making zinc electrode using scraping plasm.
Background technology
At present, the making zinc battery comprises with the main method of zinc electrode: powder is pressed into method, is coated with cream method and electrodeposition process.Powder is pressed into legal system and is equipped with the main process of zinc electrode and comprises: the zinc active material that will contain binding agent directly is pressed on the conducting matrix grain, compression molding, the thickness of electrode of this method preparation is thicker, and inhomogeneous, intensity difference, electrode polarizes in charge and discharge process greatly, distortion is serious, and then cause battery later stage decreased performance rapid, shorten battery life, and can not serialization production and deficiency such as contaminated environment easily; Being coated with the cream legal system is equipped with the main process of zinc electrode and comprises: will add an amount of binding agent in the active material, the furnishing paste is applied on the conducting matrix grain, compression molding, the zinc electrode of this method preparation, the active material cycle performance is better, but can not realize serialization production, the quality conformance level is lower; The electro-deposition formula prepares zinc electrode, needs to consume a large amount of electric energy, generally is only limited to a reserve cell of high rate discharge.
Summary of the invention
The present invention is for solving problems of the prior art, and a kind of simple to operate, the distribution of electrodes good uniformity, the thin thickness that can be continuously produced, make are provided, thereby improves the method for the making zinc electrode using scraping plasm of high current density discharge performance.
The present invention for the technical scheme that solves the technical problem employing that exists in the known technology is:
The method of making zinc electrode using scraping plasm comprises following process:
(1) prepare the zinc slurry in proportion:
Earlier be 0.1%~5% binding agent to be joined in the hot water by mass percentage, be stirred to dissolving and become the transparence adhesive solution, be cooled to room temperature; Be that zinc active material mass percent 0.2%~2% takes by weighing adhesive solution by solids content again, after adhesive solution and distilled water mixing and stirring, add the zinc active material that contains additive and be mixed into the zinc slurry;
Wherein: binding agent is one or more composite alkali resistance binding agents of methylcellulose MC, sodium carboxymethylcellulose CMC, hydroxypropyl methylcellulose HPMC, PVAC polyvinylalcohol, poly(ethylene oxide) PEO, polytetrafluoroethylene PTFE and styrene butadiene rubber sbr;
Zinc active material is to contain the zinc powder of mass percent 0.5%~3% additive or the mixture of oxide powder and zinc or zinc powder and oxide powder and zinc;
Wherein: additive is one or more mixtures in metals such as beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, thallium, tin, lead, bismuth, titanium, chromium, zirconium, cadmium, mercury, yttrium, lanthanide series and oxide or its hydroxide;
(2) place electrode to scrape the stock tank of slurry with device in composite zinc slurry, conducting matrix grain passes stock tank from bottom to top, makes the conducting matrix grain two sides be stained with slurry, passes the gap of two scrapings above the stock tank again, wipes redundant sizing agent off, prepares the continuous electrode band;
(3) be cut into the zinc electrode sheet of required size after continuous electrode is drying, the roll-in, then the guide lug place cleaned up, carry out spot welding or roller weldering guide lug again, obtain zinc electrode.
The present invention can also take following technical measures to realize:
The method of making zinc electrode using scraping plasm adds starch solution with adhesive solution in described (1), stir, and then the zinc active material that will contain additive is mixed into the zinc slurry;
Wherein: the compound method of starch solution is to take by weighing starch by 1%~2% mass percent, and it is slowly joined in 100 ℃ the hot water, stir 2min after, be cooled to room temperature.
The method of making zinc electrode using scraping plasm, described starch solution solid masses percentage composition is 0.1%~1% of a zinc active material.
The method of making zinc electrode using scraping plasm, described conducting matrix grain are a kind of of metal lath, metal knitted net, punch metal net or foam metal net.
Guide lug place cleaning equipment is the dry powder cleaning machine in the method for making zinc electrode using scraping plasm, described (3).
The method of making zinc electrode using scraping plasm, the metal on the described conducting matrix grain are the copper of silver or copper or nickel or band coating, and coating material is a kind of in zinc, lead, silver, the tin, or the nickel of band coating, and described coating material is a kind of in zinc, lead, silver, the tin.
Advantage and good effect that the present invention has are: owing to adopted the method for making zinc electrode using scraping plasm, realize that electrode is thin, good uniformity, intensity is good, has good high current density discharge performance, thereby has improved the specific power and the specific energy of battery.Scraping paste-making method simultaneously can carry out continuously, simple to operate, can save lot of manpower and material resources, improve the quality conformance level and the battery production efficient of electrode, little to the production environment pollution simultaneously, solved the problem that present conventional method can not realize the electrode automatic continuous production.
Description of drawings
Fig. 1 is the device schematic diagram of making zinc electrode using scraping plasm of the present invention,
Fig. 2 is the zinc electrode cutaway view of making zinc electrode using scraping plasm of the present invention,
Fig. 3 is the uniformity test distribution map of making zinc electrode using scraping plasm of the present invention;
Fig. 4 is for making zinc electrode using scraping plasm of the present invention and be pressed into formula zinc electrode uniformity consistency comparison diagram;
Fig. 5 is that making zinc electrode using scraping plasm of the present invention is at 166mA/cm 2Discharge curve under the current density.
Label among the figure is respectively: the 1-stock tank; The 2-scraper; The 3-conducting matrix grain; The 4-zinc active material.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, enumerate following examples now, and conjunction with figs. is described in detail as follows:
Please refer to accompanying drawing 1-5:
Embodiment 1:
The preparation of 2%HPMC solution:
Take by weighing the 2gHPMC powder, it is slowly joined in the distilled water about 98g80 ℃, constantly stir,, be cooled to room temperature until being dissolved into transparence.
Synthesizing of zinc slurry:
Adopting zinc powder or zinc oxide is the zinc electrode active material, takes by weighing 2%HPMC solution 50g and distilled water 60g respectively, after the mixing and stirring, the 100g zinc active material is slowly added, and constantly stirs until evenly.
Making zinc electrode using scraping plasm:
The zinc for preparing slurry is packed in the stock tank 1 of the zinc electrode of preparation shown in the accompanying drawing 1 Pulp scraping device, is provided with the scraper 2 of a pair of adjustable clearance above the stock tank 1, conducting matrix grain 3 is passed from stock tank from top to bottom.Adjust the scraper spacing according to thickness of electrode, the conducting matrix grain 3 that is stained with the zinc slurry is slowly passed through in the middle of two scrapers 2 that have the gap, unnecessary zinc slurry is wiped off, promptly prepare the zinc electrode band of uniformity.The zinc electrode of desired thickness and size is made in zinc electrode band drying, roll-in, the cutting of pulling out, adopted the dry powder cleaning machine that the guide lug place is cleaned up at last, carry out spot welding or roller weldering guide lug again, obtain scraping the zinc electrode of slurry preparation.
Embodiment 2
The preparation of 2%HPMC solution:
The preparation of 2%HPMC solution is with embodiment 1.
The preparation of 1% starch solution:
Mass percent by 1% takes by weighing 1g starch, and it is slowly joined in the hot water of 100 ℃ of 99g, behind the stirring 2min, naturally cools to room temperature.
Synthesizing of zinc slurry:
Adopting zinc powder or zinc oxide is the zinc electrode active material, takes by weighing the distilled water of 30g 2%HPMC solution, 30g 1% starch solution and 30g respectively, after the mixing and stirring, the 100g zinc active material is slowly added, and constantly stirs, until evenly.
Scrape the zinc electrode of slurry preparation:
With reference to accompanying drawing 1, Fig. 2.
The manufacturing process of making zinc electrode using scraping plasm is with embodiment 1, and conducting matrix grain is the silver-colored net that stretches, and electrode size is 69mm * 170mm.
Scrape the slurry result of the test:
As shown in Figure 2, adopt the synthetic zinc slurry of this prescription, can prepare and scrape slurry formula zinc electrode uniformly, zinc active material 4 is evenly distributed on conducting matrix grain 1 both sides.Simultaneously the result also shows the adhesiveness and mobile good than among the embodiment 1 of zinc slurry.
Comparative Examples
The preparation of 6%PVA solution:
Take by weighing 6g PVA powder, slowly join then in the hot water of about 80 ℃ of 94g, constantly stir, until dissolving.
Be pressed into the preparation of formula zinc electrode:
Take by weighing 10g 6%PVA solution, and it is joined in the 100g zinc active material 4 close powder, it is online in the silver that stretches directly to spread powder then, compression molding.
Embodiment 3
The preparation of zinc-silver oxide cell:
The zinc electrode that embodiment 2 is made is as negative pole, and the silver electrode of same size is as positive pole, and barrier film adopts the cellulose hydrate film, and it is 40% KOH solution that electrolyte adopts mass percent concentration, is made into zinc-silver oxide cell.
Scrape slurry formula zinc electrode uniformity test:
On the zinc electrode of embodiment 2 and Comparative Examples making, choose 5 points respectively, be cut into the small pieces of 10mm * 10mm, and weigh, obtain m by position shown in Figure 3 1, m 2... m 5By the mass deviation percentage of following formula (1) calculating each point, estimate the uniformity of electrode then according to the mass deviation percentage of each point.
w p = ( m n - m ‾ m ‾ ) × 100 % ( n = 1,2 · · · 5 ) - - - ( 1 )
In the formula: w pBe mass deviation percentage; It is the average quality of 5 sections; N is the code name of 5 sections shown in Figure 2.
The formula that is pressed into zinc electrode test result in test result and the Comparative Examples as shown in Figure 4.As can be seen from the figure, the maximum deviation that is pressed into formula zinc electrode 1 is 8.8%, and peak and minimum point differ and reach 17.4%; And the maximum deviation of scraping slurry formula zinc electrode 2 only is 1.2%, and peak and minimum point differ 2.2%.This shows, scrapes slurry formula zinc electrode 2 and compares with being pressed into formula zinc electrode 1, and its uniformity obviously improves.Improve the electrode uniformity, can reduce polarization of electrode, improve the utilance of active material and the discharge voltage of battery, therefore, employing is scraped paste-making method and is expected to prepare the more superior zinc electrode of performance, improves the combination property of zinc battery greatly.
Scrape slurry formula zinc electrode electric performance test:
With the making zinc electrode using scraping plasm and the zinc-silver oxide cell that is assembled into of auxiliary silver electrode of preparation among the embodiment 2, press 1.1mA/cm 2, change 4mA/cm 2, change 1.1mA/cm 2Charging system charge to 2.15V, then with 166mA/cm 2Current density discharge 6min.Discharge curve as shown in Figure 5.From accompanying drawing 5, as can be seen, scrape slurry formula zinc electrode and have good high current density discharge performance.
Though the present invention scrapes the method for slurry system zinc electrode and is illustrated with the above embodiments and accompanying drawing, the present invention is not limited to embodiment and accompanying drawing, and the method for scraping slurry system zinc electrode can be used for any zinc battery preparation such as zinc-manganese, zinc-silver, zinc-nickel, zinc-air.

Claims (6)

1, a kind of method of making zinc electrode using scraping plasm is characterized in that comprising following process:
(1) prepare the zinc slurry in proportion:
Earlier be 0.1%~5% binding agent to be joined in the hot water by mass percentage, be stirred to dissolving and become the transparence adhesive solution, be cooled to room temperature; Be that zinc active material mass percent 0.2%~2% takes by weighing adhesive solution by solids content again, after adhesive solution and distilled water mixing and stirring, add the zinc active material that contains additive and be mixed into the zinc slurry;
Wherein: binding agent is one or more composite alkali resistance binding agents of methylcellulose MC, sodium carboxymethylcellulose CMC, hydroxypropyl methylcellulose HPMC, PVAC polyvinylalcohol, poly(ethylene oxide) PEO, polytetrafluoroethylene PTFE and styrene butadiene rubber sbr;
Zinc active material is to contain the zinc powder of mass percent 0.5%~3% additive or the mixture of oxide powder and zinc or zinc powder and oxide powder and zinc;
Wherein: additive is one or more mixtures in metals such as beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, thallium, tin, lead, bismuth, titanium, chromium, zirconium, cadmium, mercury, yttrium, lanthanide series and oxide or its hydroxide;
(2) place electrode to scrape the stock tank of slurry with device in composite zinc slurry, conducting matrix grain passes stock tank from bottom to top, makes the conducting matrix grain two sides be stained with slurry, passes the gap of two scrapings above the stock tank again, wipes redundant sizing agent off, prepares the continuous electrode band;
(3) be cut into the zinc electrode sheet of required size after continuous electrode is drying, the roll-in, then the guide lug place cleaned up, carry out spot welding or roller weldering guide lug again, obtain zinc electrode.
2, the method for making zinc electrode using scraping plasm according to claim 1 is characterized in that: adhesive solution in described (1) is added starch solution, stir, and then the zinc active material that will contain additive is mixed into the zinc slurry;
Wherein: the compound method of starch solution is to take by weighing starch by 1%~2% mass percent, and it is slowly joined in 100 ℃ the hot water, stir 2min after, be cooled to room temperature.
3, the method for making zinc electrode using scraping plasm according to claim 2 is characterized in that: described starch solution solid masses percentage composition is 0.1%~1% of a zinc active material.
4, the method for making zinc electrode using scraping plasm according to claim 1 is characterized in that: described conducting matrix grain is a kind of of metal lath, metal knitted net, punch metal net or foam metal net.
5, the method for making zinc electrode using scraping plasm according to claim 1 is characterized in that: guide lug place cleaning equipment is the dry powder cleaning machine in described (3).
6, the method for making zinc electrode using scraping plasm according to claim 4, it is characterized in that: the metal on the described conducting matrix grain is the copper of silver or copper or nickel or band coating, coating material is a kind of in zinc, lead, silver, the tin, or the nickel of band coating, described coating material is a kind of in zinc, lead, silver, the tin.
CNB2006100142417A 2006-06-09 2006-06-09 A method for making zinc electrode using scraping plasm Expired - Fee Related CN100492724C (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747571B (en) * 2008-12-02 2012-04-25 北京有色金属研究总院 Composite binder for cathode of Ni-MH power battery
CN102496698A (en) * 2011-11-29 2012-06-13 中国电子科技集团公司第十八研究所 Active substance granulation method used for zinc electrode
CN102580893A (en) * 2012-03-20 2012-07-18 重庆德凯覆铜板有限公司 Gluing machine edge scraping device capable of saving glue
CN103035896A (en) * 2012-11-27 2013-04-10 常州大学 Environment-friendly zinc material battery
CN103531752A (en) * 2012-07-04 2014-01-22 北京精密机电控制设备研究所 Novel composite electrode and preparation method thereof
CN105633339A (en) * 2014-12-01 2016-06-01 中国电子科技集团公司第十八研究所 Preparation method for ultra-thin silver oxide positive plate for zinc-silver reserve cell
CN106601980A (en) * 2016-11-29 2017-04-26 中国电子科技集团公司第十八研究所 Preparation method for thin type zinc electrode used for zinc-silver battery
CN106823826A (en) * 2017-02-15 2017-06-13 北京新源国能科技集团股份有限公司 A kind of continuous preparation method of the compound forward osmosis membrane of high flux
CN107793073A (en) * 2017-09-23 2018-03-13 南京律智诚专利技术开发有限公司 A kind of production method of alkaline-resisting pressure transmitter
CN108807839A (en) * 2018-05-28 2018-11-13 河南新太行电源股份有限公司 A kind of direct press type zinc-silver oxide cell cathode board production technology
CN109962242A (en) * 2019-04-15 2019-07-02 北京航空航天大学 A kind of additive of zinc-base battery
CN110148704A (en) * 2019-04-24 2019-08-20 浙江浙能技术研究院有限公司 A kind of structure and preparation method of network-like pieces of light-gauge metal zinc electrode
CN110364732A (en) * 2018-04-10 2019-10-22 中国科学院上海硅酸盐研究所 With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747571B (en) * 2008-12-02 2012-04-25 北京有色金属研究总院 Composite binder for cathode of Ni-MH power battery
CN102496698A (en) * 2011-11-29 2012-06-13 中国电子科技集团公司第十八研究所 Active substance granulation method used for zinc electrode
CN102496698B (en) * 2011-11-29 2016-03-09 中国电子科技集团公司第十八研究所 A kind of active substance granulation method used for zinc electrode
CN102580893A (en) * 2012-03-20 2012-07-18 重庆德凯覆铜板有限公司 Gluing machine edge scraping device capable of saving glue
CN103531752A (en) * 2012-07-04 2014-01-22 北京精密机电控制设备研究所 Novel composite electrode and preparation method thereof
CN103035896A (en) * 2012-11-27 2013-04-10 常州大学 Environment-friendly zinc material battery
CN105633339A (en) * 2014-12-01 2016-06-01 中国电子科技集团公司第十八研究所 Preparation method for ultra-thin silver oxide positive plate for zinc-silver reserve cell
CN106601980A (en) * 2016-11-29 2017-04-26 中国电子科技集团公司第十八研究所 Preparation method for thin type zinc electrode used for zinc-silver battery
CN106823826A (en) * 2017-02-15 2017-06-13 北京新源国能科技集团股份有限公司 A kind of continuous preparation method of the compound forward osmosis membrane of high flux
CN107793073A (en) * 2017-09-23 2018-03-13 南京律智诚专利技术开发有限公司 A kind of production method of alkaline-resisting pressure transmitter
CN110364732A (en) * 2018-04-10 2019-10-22 中国科学院上海硅酸盐研究所 With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery
CN108807839A (en) * 2018-05-28 2018-11-13 河南新太行电源股份有限公司 A kind of direct press type zinc-silver oxide cell cathode board production technology
CN109962242A (en) * 2019-04-15 2019-07-02 北京航空航天大学 A kind of additive of zinc-base battery
CN110148704A (en) * 2019-04-24 2019-08-20 浙江浙能技术研究院有限公司 A kind of structure and preparation method of network-like pieces of light-gauge metal zinc electrode

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