CN1050010C - Corrosion inhibitor as mercury substitute in alkaline zinc series cell - Google Patents
Corrosion inhibitor as mercury substitute in alkaline zinc series cell Download PDFInfo
- Publication number
- CN1050010C CN1050010C CN95112048A CN95112048A CN1050010C CN 1050010 C CN1050010 C CN 1050010C CN 95112048 A CN95112048 A CN 95112048A CN 95112048 A CN95112048 A CN 95112048A CN 1050010 C CN1050010 C CN 1050010C
- Authority
- CN
- China
- Prior art keywords
- corrosion inhibitor
- mercury
- alkaline zinc
- corrosion
- series cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 28
- 230000007797 corrosion Effects 0.000 title claims abstract description 26
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003112 inhibitor Substances 0.000 title claims abstract description 10
- 150000003751 zinc Chemical class 0.000 title claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract 2
- 229910020489 SiO3 Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 229940095064 tartrate Drugs 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- -1 polyoxyethylene phosphate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a corrosion inhibitor instead of mercury in alkaline zinc series of cells. The present invention is characterized in that the corrosion inhibitor is mainly formed by compositing numbers of inorganic compounds and has a molecular formula of M<Y>X<Z>, wherein an anion base group X can be one or more kinds of SO4 <-2>, Cl<->, PO4<-3>, NO4<->, SiO3<2->, SCN<2->, OH<->, S<2->, tartrate radicals, citric acid radicals and metaphosphoric acid radicals. A corresponding anion M can be two to five kinds of metal ions, such as Ca<2+>, mg<2+>, Cs<+>Li<+>, Na<+>, Al<3+>, Sn<2+>, In<3+>, Sb<3+>, Bi<3+>, Ga<3+>, Ce<3+>, La<3+>, Ag<+>, etc., and the addition quantity of the present invention in respect to zinc powder is from 0.005 to 5 wt. %. The present invention has the advantages of no toxicity and favorable effect of corrosion inhibition, and can be used as a corrosion inhibitor instead of mercury.
Description
The present invention relates to alkaline zinc series cell, corrosion inhibitor as mercury substitute in the zinc series cell is provided especially.
Alkaline zinc series chemical power source, its anode are zinc, and negative electrode is manganese dioxide, silver oxide, mercury oxide, nickel oxide and air etc., and electrolyte then is alkaline solution.Alkaline zinc series cell is owing to advantage is subjected to people's such as capacity height, power be big favor, but exist more serious self-discharge phenomenon in the battery, usually add a certain amount of mercury (it is generally acknowledged and contain the basic demand that 3.6%Hg can satisfy the normal use of battery in the zinc powder).As everyone knows, mercury not only pollutes environment, and human body is also caused great harm.Along with the enhancing of environmental consciousness, replace mercury to become extremely urgent problem with low toxicity or nontoxic corrosion inhibiter.
People are usually by using anti-corrosion kirsite, adding the purpose that approach such as organic inhibition and inorganic inhibitor reach precipitate and remove mercury.In the patent No. is 4,735, and in 876 (1988) the United States Patent (USP), people such as Miura think that containing elements such as In, Al, Mg, Pb in the zinc powder can reduce mercury content in the zinc powder, and do not influence the normal use of battery.People's patent No.s such as Rossler are to point out in 4,195,120 (1980) the United States Patent (USP), and polyoxyethylene phosphate dissolves by generation and the zinc anode that absorption on zinc surface suppresses hydrogen, and its content is 0.001%-5% (with respect to zinc powder weight).People such as Katsuo are JP61 in the patent No., point out in 176,068 (1986) the Japan Patent, zinc powder is put into contained SnCL
2The aqueous solution in carry out one section of surface treatment to after, filtration, cleaning, drying, thus obtain the zinc powder that tin is contained on the surface, this zinc powder hydrogen-separating quantity in alkali lye obviously reduces.
The object of the present invention is to provide a kind of nontoxic and effective corrosion inhibitor as mercury substitute.
The invention provides corrosion inhibiter and mainly be composited by some inorganic compounds, its molecular formula is: M
YX
Z, its anionic group can be SO
4 2-, Cl
-, PO
4 3-, SiO
3 2-, NO
3 -, SCN
-, OH
-, S
2-,, Tartaric acid root, citrate, metaphosphoric acid radical one or more, corresponding cation M can be Ca
2+, Mg
2+, Cs
+, Li
+, Na
+, Al
3+, Sn
2+, In
3+, Sb
3+, Bi
3+, Ga
3+, Ce
3+, La
3+, Ag
+Deng two in the metal ion to five kinds.Can directly add in the electric liquid or zinc powder is put into its aqueous solution carry out surface treatment, also can two kinds of methods have both at the same time, its content is 0.005-5% (with respect to zinc powder weight, difference).This corrosion inhibiter mainly by chemical reaction or absorption, deposits or is adsorbed in zinc surface, corrosion reaction is played slowed down effect.
Can add a kind of quaternary ammonium salt cationic corrosion inhibiter for further improving its corrosion mitigating effect, its molecular formula is R
1R
2R
3R
4NBr, wherein R
1-R
4Be alkyl or aromatic radical, it contains carbon number is 1-18, and its content is 0.0001-0.5% as corrosion inhibiter 2 because its surface activity is adsorbed on electrode and the solution interface obstruction H
2O and OH
-To the electrode surface diffusion, thereby inhibitory action is played in zinc anode dissolving and cathode hydrogen evolution reaction.This quaternary ammonium salt cationic corrosion inhibiter also can add separately, certainly the effect relative mistake some.
Below by embodiment in detail the present invention is described in detail
Example 1
Electrolyte solution adopts the 40%KOH solution that contains a little zinc hydrochlorate; Sample zinc granule degree is the 150-200 order, and purity is 99.995%, and sampling amount is 1.0g; Experimental temperature is 50 ± 1 ℃, and following example all carries out under above-mentioned experiment condition.
In electric liquid, add by La
2(SO
4)
3Corrosion inhibiter 1 (content is 0.3%) with the sodium metaphosphate composition, after zinc powder stored 14 days therein, recording hydrogen-separating quantity is 0.95ml, zinc powder is (being blank solution) in the solution that does not contain corrosion inhibiter, hydrogen-separating quantity is 13.4ml in during identical, and the zinc powder that contains Hg4% in blank solution under the same conditions, hydrogen-separating quantity is 0.41ml.
Embodiment 2 is containing zinc powder by CeCl
30.3%, CsOH0.6%, GaCl
30.7%, AgNO
3Carry out surface treatment in the aqueous solution of the corrosion inhibiter 1 of composition such as 0.4%, store 14 days then in alkali lye, recording hydrogen-separating quantity is 0.45ml, near the liberation of hydrogen level that contains the zinc powder of Hg4%.
Embodiment 3 adds softex kw (content is 0.02%) in electric liquid, zinc powder between 14 day storage life in hydrogen-separating quantity be 2.55ml.
Embodiment 4 will handle the zinc powder obtain by example 2 methods put into the alkali lye that contains 0.03% corrosion inhibiter 2, between 14 days storage life in hydrogen-separating quantity be 0.35ml, be better than containing the corrosion mitigating effect of Hg4% zinc powder.
Embodiment 5 in alkali lye, add with example 1 in same composition and content corrosion inhibiter 1 and with example 3 in the corrosion inhibiter 2 of same amount, zinc powder hydrogen-separating quantity in 14 days storage life is 0.55ml, is better than the effect of adding two kinds of corrosion inhibiter separately.
Claims (2)
1. corrosion inhibitor as mercury substitute in the alkaline zinc series cell, it is characterized in that: this corrosion inhibiter is composited by inorganic compound, and its molecular formula is M
YX
Z, anionic group X is SO
4 2-, Cl
-, PO
4 3-, NO
4 -, SiO
3 2-, SCN
-, OH
-, S
2-, the Tartaric acid root, citrate, one or more in the metaphosphoric acid radical, corresponding cation M is Ca
2+, Mg
2+, Cs
+Li
+, Na
+, Al
3+, Sn
2+, In
3+, Sb
3+, Bi
3+, Ga
3+, Ce
3+, La
3+, Ag
+In the metal ion two is to five kinds, and its addition with respect to zinc powder is a 0.005-5% weight.
2. by corrosion inhibitor as mercury substitute in the described alkaline zinc series cell of claim 1, it is characterized in that add the 0.0001-0.5%wt quaternary ammonium salt and make auxiliary agent, its molecular formula is R
1R
2R
3R
4NBr, wherein R
1-R
4Be alkyl or aromatic radical, it contains carbon number is 1-18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112048A CN1050010C (en) | 1995-10-11 | 1995-10-11 | Corrosion inhibitor as mercury substitute in alkaline zinc series cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112048A CN1050010C (en) | 1995-10-11 | 1995-10-11 | Corrosion inhibitor as mercury substitute in alkaline zinc series cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1147158A CN1147158A (en) | 1997-04-09 |
| CN1050010C true CN1050010C (en) | 2000-03-01 |
Family
ID=5079271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112048A Expired - Fee Related CN1050010C (en) | 1995-10-11 | 1995-10-11 | Corrosion inhibitor as mercury substitute in alkaline zinc series cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050010C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102738468A (en) * | 2012-07-03 | 2012-10-17 | 北京中航长力能源科技有限公司 | Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424974A (en) * | 2011-12-21 | 2012-04-25 | 清华大学 | Inorganic-organic composite corrosion inhibitor of metal zinc electrode |
| CN103993324B (en) * | 2014-06-03 | 2016-07-13 | 西北大学 | A kind of alloy corrosion inhibitor and corrosion inhibition method of high chloride ion medium |
| CN113690436A (en) * | 2021-07-02 | 2021-11-23 | 浙江野马电池股份有限公司 | Corrosion inhibitor for zinc cathode of alkaline manganese battery |
| CN117525307B (en) * | 2024-01-05 | 2024-03-22 | 山东华太新能源电池有限公司 | Alkaline battery cathode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073808A (en) * | 1992-07-11 | 1993-06-30 | 吉林大学 | Be used for zinc-maganese dioxide dry cell for the mercury organic composite additive |
-
1995
- 1995-10-11 CN CN95112048A patent/CN1050010C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073808A (en) * | 1992-07-11 | 1993-06-30 | 吉林大学 | Be used for zinc-maganese dioxide dry cell for the mercury organic composite additive |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102738468A (en) * | 2012-07-03 | 2012-10-17 | 北京中航长力能源科技有限公司 | Inorganic mercury-substituting inhibitor for prolonging storage life of zinc air battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1147158A (en) | 1997-04-09 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |