CN102738468A - Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery - Google Patents
Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery Download PDFInfo
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- CN102738468A CN102738468A CN2012102294848A CN201210229484A CN102738468A CN 102738468 A CN102738468 A CN 102738468A CN 2012102294848 A CN2012102294848 A CN 2012102294848A CN 201210229484 A CN201210229484 A CN 201210229484A CN 102738468 A CN102738468 A CN 102738468A
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- zinc
- air cell
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- inhibitor
- negative pole
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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
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Abstract
The invention discloses an inorganic mercury-substituting inhibitor for prolonging a storage life of a zinc air battery. The inhibitor is compounded by a plurality of inorganic compounds, comprises two or a plurality of anion groups selected from SnO3<2->, CL<->, SO4<2->, OH<->, NO4<->, SiO3<2->, PO4<3-> and two kinds or several kinds in citrate, and further comprises one to five kinds of cations: Y<3+>, <Bi3+>, <In3+>, <Ca2+>, <Ce4+>, <Na+>, La<3+> and <Ag+>. The inhibitor provided in the invention can completely replace mercury in the zinc air battery without affecting work performance of the battery. After storing zinc electrode added with the inhibitor and the zinc electrode containing 6% of the mercury at a temperature of 50 plus or minus 1 DEG C for the same time, the two electrodes are put in the zinc air battery with the same model to test discharge performance of the battery, the result is that the two electrodes have a fairly equal discharge performance.
Description
Technical field
The present invention relates to a kind of corrosion inhibiter that is used for the alkaline zinc-air battery zinc electrode, relate in particular to a kind of zinc-air cell inorganic corrosion inhibitor as mercury substitute of storage life that prolongs.
Background technology
Advantages such as zinc-air cell has that capacity is big, specific energy is high, discharge performance is stable, raw material cheaply are easy to get, production and use non-environmental-pollution can be used as the power supply of railway signal, radio communication, navigation light, agricultural black light lamp and electric automobile.Zinc-air cell can also be used for national defence by the very high silver-zinc battery of displacement cost, like the battery of usefulness such as torpedo, guided missile.Button zinc-air battery for little electric current, long-life work can be used for occasions such as wrist-watch, hearing aids and calculator.Therefore, the zinc-air cell purposes very extensively has very big development prospect.Yet there is thermodynamic instability in the zinc negative pole in alkaline solution, easyly dissolves, liberation of hydrogen (Zn+2OH
--2e → ZnO+H
2O, 2H
2O+2e → 2OH
-+ H
2), this is the main cause of zinc-air cell self discharge, also is its performance main reasons for decrease in storage process.In order to prolong the storage life of zinc-air cell, traditional method is in zinc electrode, to add a spot of mercury as corrosion inhibiter.Because mercury belongs to the one-level poisonous substance, serious environment pollution, so its use amount has obtained strict control.
At present also there is not a kind of mercury that can replace fully in the zinc-air cell not influence the corrosion inhibiter of battery operated performance again.
Summary of the invention
The purpose of this invention is to provide a kind of mercury that can replace fully in the zinc-air cell does not influence the inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell storage life of battery operated performance again.
The objective of the invention is to realize through following technical scheme:
The inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell of the present invention storage life is composited by multiple inorganic compound, comprises following wantonly two kinds or multiple anionic group: SnO
3 2-, Cl
-, SO
4 2-, OH
-, NO
4 -, SiO
3 2-, PO
4 3-, in the citrate two kinds or several kinds, also comprise following any to five kinds of cation: Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+
Technical scheme by the invention described above provides can find out, the inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell provided by the invention storage life owing to be composited by multiple inorganic compound, comprises following wantonly two kinds or multiple anionic group: SnO
3 2-, Cl-, SO
4 2-, OH-, NO
4-, SiO
3 2-, PO
4 3-, in the citrate two kinds or several kinds, also comprise following any to five kinds of cation: Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+The mercury that can replace fully in the zinc-air cell does not influence battery operated performance again, the zinc electrode of adding this corrosion inhibiter with mercurous 6% zinc electrode stores the identical time in 50 ± 1 ℃ after in the zinc-air cell of same model the discharge performance of test battery suitable.
Embodiment
To do to describe in detail further to the embodiment of the invention below.
The inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell of the present invention storage life, its preferable embodiment is:
Be composited by multiple inorganic compound, comprise following wantonly two kinds or multiple anionic group: SnO
3 2-, Cl
-, SO
4 2-, OH
-, NO
4 -, SiO
3 2-, PO
4 3-, in the citrate two kinds or several kinds, also comprise following any to five kinds of cation: Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+
This corrosion inhibiter makes an addition in the negative pole of zinc-air cell, and its addition with respect to the negative pole of zinc-air cell is 0.002-1wt%.
Join in the said negative pole after said corrosion inhibiter and zinc powder mix through dry powder machinery or said corrosion inhibiter joined and be incorporated in the electrolyte in the said negative pole.
When the method for described corrosion inhibiter through dry powder blend joins in the said negative pole; Described corrosion inhibiter is with after zinc powder mixes; To the polyacrylic acid of Sodium Polyacrylate that wherein adds 0.1-1wt% and 0.2-2wt% as thickener or gel; After the continuation mechanical agitation is even, to wherein adding electrolyte, process the negative pole of zinc-air cell again.
The inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell of the present invention storage life is used for the corrosion inhibitor as mercury substitute of alkaline zinc-air battery, and it has good corrosion inhibition, has satisfied that battery is nontoxic, " green " environmental protection requirement and can overcome the deficiency of existing corrosion inhibiter.
The inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell of the present invention storage life mainly is made up of several kinds of inorganic compounds, and its total molecular formula can be write and be A
XB
Y, anionic group B is SnO
3 2-, Cl
-, SO
4 2-, OH
-, NO
4 -, SiO
3 2-, PO
4 3-, two or more in the citrate, corresponding cation A is Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+In the metal ion one is to five kinds.Can be mixed even or directly add in its electrolyte with zinc powder is dried, also can two kinds of methods have both at the same time, its content be 0.002-1wt% (with respect to zinc electrode).This corrosion inhibiter mainly improves the deposition quality of zinc through the synergy of several kinds of inorganic matters, reduce separating out of hydrogen thereby improve overpotential of hydrogen evolution, slow down zinc from corrosion reaction.
The present invention is with its advantage of compared with techniques in the past, this corrosion inhibiter stable performance, and easy to use, consumption is few, and corrosion mitigating effect is obvious, and pollution-free.
In concrete the application:
Zinc-air cell is made up of positive pole, negative pole and barrier film.
Anodal by after carbon, PTFE and the catalyst mix, compacting or roll-in are to collector.
Barrier film is the harmless cloth of micropore such as PP, PE, or its graft copolymer membrane and multilayer complex films.
Negative pole is a metal zinc, and granularity is 200 orders, and purity is 99.995%.
Zinc powder is made into the calamine cream shape usually, the consisting of of calamine cream: zinc powder, gel, inorganic inhibitor, electrolyte, and wherein zinc powder is irregular, consumption is 50-80% (accounting for the percentage of calamine cream weight).
Gel is PAA, PAAS etc., and consumption is 0.1-1% (accounting for the percentage of calamine cream weight).
Inorganic inhibitor is A
XB
Y, anionic group B is SnO
3 2-, Cl
-, SO
4 2-, OH
-, NO
4 -, SiO
3 2-, PO
4 3-, two or more in the citrate, cation A are Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+In the metal ion one is to five kinds.
Electrolyte solution is the KOH solution that contains the 36.5wt% of little zinc hydrochlorate (0.40M/L).
The quality of each zinc powder of surveying is 46.2g; Probe temperature is 50 ± 1 ℃.
Following specific embodiment all carries out under above-mentioned experiment condition.
Specific embodiment 1:
In zinc powder, add the CaCl of 0.3wt%
2Corrosion inhibiter with the composition of natrium citricum; After doing mixed stirring, again to Sodium Polyacrylate that wherein adds 0.52wt% and 0.48wt% polyacrylic acid, the back of continuing to stir adds an amount of electrolyte; Vacuum stirring evenly obtains calamine cream; Above-mentioned calamine cream is pretended to negative pole is prepared into zinc-air cell, and storage was carried out discharge test after 20 days in probe temperature, and capacity is 24.99Ah.The blank zinc powder that does not contain corrosion inhibiter during as the zinc-air cell negative pole after the same terms stores discharge capacity be 0.31Ah.And mercurous 6% zinc powder, as GND, with identical current discharge, capacity is 27.50Ah after the process storage of the same terms under the situation that does not add corrosion inhibiter.
Specific embodiment 2:
With the indium hydroxide of sodium stannate that adds 0.2wt% in the electrolyte and 0.05wt% as corrosion inhibiting solution; With accounting for the calamine cream percentage by weight is that 0.52% Sodium Polyacrylate, 0.48% polyacrylic acid and zinc powder vacuum mix and obtain calamine cream; Use above-mentioned calamine cream to pretend to be prepared into zinc-air cell as negative pole; Carry out discharge test after in probe temperature, storing 20 days, capacity is 26.91Ah.The blank zinc powder that does not contain corrosion inhibiter during as the zinc-air cell negative pole after the same terms stores discharge capacity be 0.31Ah.And mercurous 6% zinc powder, as GND, with identical current discharge, capacity is 27.50Ah after the process storage of the same terms under the situation that does not add corrosion inhibiter.
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 (4)
1. one kind prolongs the zinc-air cell inorganic corrosion inhibitor as mercury substitute of storage life, it is characterized in that, is composited by multiple inorganic compound, comprises following wantonly two kinds or multiple anionic group: SnO
3 2-, Cl
-, SO
4 2-, OH
-, NO
4 -, SiO
3 2-, PO
4 3-, in the citrate two kinds or several kinds, also comprise following any to five kinds of cation: Y
3+, Bi
3+, In
3+, Ca
2+, Ce
4+, Na
+, La
3+, Ag
+
2. the inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell according to claim 1 storage life is characterized in that this corrosion inhibiter makes an addition in the negative pole of zinc-air cell, and its addition with respect to the negative pole of zinc-air cell is 0.002-1wt%.
3. the inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell according to claim 2 storage life; It is characterized in that, join in the said negative pole after said corrosion inhibiter and zinc powder mix through dry powder machinery or said corrosion inhibiter joined and be incorporated in the electrolyte in the said negative pole.
4. the inorganic corrosion inhibitor as mercury substitute of prolongation zinc-air cell according to claim 3 storage life; It is characterized in that when the method for described corrosion inhibiter through dry powder blend joined in the said negative pole, described corrosion inhibiter was with after zinc powder mixes; To the polyacrylic acid of Sodium Polyacrylate that wherein adds 0.1-1wt% and 0.2-2wt% as thickener or gel; After the continuation mechanical agitation is even, to wherein adding electrolyte, process the negative pole of zinc-air cell again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102294848A CN102738468A (en) | 2012-07-03 | 2012-07-03 | Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102294848A CN102738468A (en) | 2012-07-03 | 2012-07-03 | Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery |
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| Publication Number | Publication Date |
|---|---|
| CN102738468A true CN102738468A (en) | 2012-10-17 |
Family
ID=46993558
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102294848A Pending CN102738468A (en) | 2012-07-03 | 2012-07-03 | Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993324A (en) * | 2014-06-03 | 2014-08-20 | 西北大学 | Alloy corrosion inhibitor and corrosion inhibition method of high-chloride ion medium |
| CN104051819A (en) * | 2013-03-13 | 2014-09-17 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354752A2 (en) * | 1988-08-09 | 1990-02-14 | Alcan International Limited | Aluminium batteries |
| CN1050010C (en) * | 1995-10-11 | 2000-03-01 | 中国科学院金属腐蚀与防护研究所 | Corrosion inhibitor as mercury substitute in alkaline zinc series cell |
| CN1571191A (en) * | 2004-04-26 | 2005-01-26 | 四会永利五金电池有限公司 | An alkaline non-mercury button battery calamine cream and method for making same |
| CN1941461A (en) * | 2006-08-24 | 2007-04-04 | 广州市天球实业有限公司 | Production of non-pump button battery and its battery |
| CN101353798A (en) * | 2008-07-24 | 2009-01-28 | 中南大学 | Alkaline aluminum electrokinetic cell anodic inhibitor and preparation of alkaline electrolysing solution |
-
2012
- 2012-07-03 CN CN2012102294848A patent/CN102738468A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354752A2 (en) * | 1988-08-09 | 1990-02-14 | Alcan International Limited | Aluminium batteries |
| CN1050010C (en) * | 1995-10-11 | 2000-03-01 | 中国科学院金属腐蚀与防护研究所 | Corrosion inhibitor as mercury substitute in alkaline zinc series cell |
| CN1571191A (en) * | 2004-04-26 | 2005-01-26 | 四会永利五金电池有限公司 | An alkaline non-mercury button battery calamine cream and method for making same |
| CN1941461A (en) * | 2006-08-24 | 2007-04-04 | 广州市天球实业有限公司 | Production of non-pump button battery and its battery |
| CN101353798A (en) * | 2008-07-24 | 2009-01-28 | 中南大学 | Alkaline aluminum electrokinetic cell anodic inhibitor and preparation of alkaline electrolysing solution |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051819A (en) * | 2013-03-13 | 2014-09-17 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104051819B (en) * | 2013-03-13 | 2017-02-08 | 沈阳鑫科能源技术有限公司 | Electrolyte additive of electrolyte circulating type zinc air battery |
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN103993324A (en) * | 2014-06-03 | 2014-08-20 | 西北大学 | Alloy corrosion inhibitor and corrosion inhibition method of high-chloride ion medium |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
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Application publication date: 20121017 |