ZA200405167B - Hydrogen evolution inhibiting additives for zinc electrowinning. - Google Patents
Hydrogen evolution inhibiting additives for zinc electrowinning. Download PDFInfo
- Publication number
- ZA200405167B ZA200405167B ZA200405167A ZA200405167A ZA200405167B ZA 200405167 B ZA200405167 B ZA 200405167B ZA 200405167 A ZA200405167 A ZA 200405167A ZA 200405167 A ZA200405167 A ZA 200405167A ZA 200405167 B ZA200405167 B ZA 200405167B
- Authority
- ZA
- South Africa
- Prior art keywords
- zinc
- electrowinning
- zinc electrowinning
- cpc
- current efficiency
- Prior art date
Links
- 239000011701 zinc Substances 0.000 title claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052725 zinc Inorganic materials 0.000 title claims description 32
- 238000005363 electrowinning Methods 0.000 title claims description 29
- 239000000654 additive Substances 0.000 title claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 title description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 9
- 239000001257 hydrogen Substances 0.000 title description 9
- 230000002401 inhibitory effect Effects 0.000 title description 2
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 24
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 4
- 229960004830 cetylpyridinium Drugs 0.000 claims description 3
- -1 cetylpyridinium halide Chemical class 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Primary Cells (AREA)
Description
PSN
HYDROGEN EVOLUTION INHIBITING ADDITIVES FOR ZINC ELECTROWINNIG
The invention is related to additives for zinc electrowinning that inhibit hydrogen evolution and/or improve current efficiency for zinc eletrodeposition, specifically cetylpyridinium-based additives.
Improving the energy efficiency of the zinc electrowinning process by inhibition of the parasitic hydrogen evolution reaction, which occurs in parallel with zinc deposition, is of major technological and commercial interest. One way of minimizing the cathodic hydrogen evolution is by the use of additives, generally organic compounds, which selectively increase the hydrogen evolution overpotential. Mackinnon et al. (Journal of Applied Electrochemistry, Volume 20, pages 728-736, 1990) and Scott et al. (Journal of Applied Electrochemistry,
Volume 18, pages 120-127, 1988) describe the use of animal glue in combination with antimony to improve the current efficiency for zinc electrowinning when compared to additive-free electrolytes.
There is a need for improved additives that minimize hydrogen evolution during zinc electrowinning while providing the same or improved performance over tradisional additives.
Therefore, a need exists to provide
AMENDED SHEET
(NN WO 03/016593 PCT/CA02/01250 hydrogen evolution during zinc electrowinning while providing the same or improved performance over traditional additives. J
Therefore, it is an object of this invention to provide improved additives for zinc electrowinning that minimize hydrogen evolution while providing similar or improved performance over traditional additives.
Cetylpyridinium chloride (CPC), a cetylpyridinium salt, was tested as an additive in a zinc electrowinning process in two separate zinc electrowinning electrolyte compositions: 1) with antimony and 2) with both antimony and glue.
The CPC additive had the most significant influence in the presence of antimony or antimony + glue combination, where it increased the current efficiency by 23.2% and 7.6%, respectively. Moreover, the presence of 0.05 mM CPC did not increase the overall cell voltage. :
Methods And Apparatus ‘
Commercial beaker test cells containing a commercial . electrowinning electrolyte (liquor) were connected to a power supply and placed in a 37 °C water bath. The anodes and cathodes were made of lead and aluminium, respectively. The laboratory ' supplied MSDS sheet indicated for the electrolyte the following composition: zinc sulfate 28 - 34% by weight, magnesium sulfate 9 - 15 g/1 (grams/litre) and manganese 1.5 - 2.5 g/l.
After allowing the temperature inside the test cells to reach the desired value of 37 °C, a constant current of 0.045 A, representing an electrowinning current density of 450 - amperes/meter’, was applied for either 4 or 20 hours to a non- agitated electrolyte. After completion of the experiment the electrode assembly was removed from the glass beaker, rinsed with distilled water and the cathode deposit carefully scraped off and weighed with four digits precision using a digital
Mettler AE 100 analytical balance. The test cells were rinsed between experiments with distilled water and acetone in order to remove traces of the organic additives. Replicates were also performed and the standard deviation was estimated.
The zinc electrodeposition current efficiency was calculated based on Faraday's law: :
CE) =2F"M1 109 (1) 1-1-4, where
CE - current efficiency for Zn electrodeposition (%)
Z - no. of electrons exchanged [=2]
F - Faraday’s number [=96485.3 C mol™] , mg - amount of zinc deposit (g) - applied current [=0.045 A] : t - time (s)
Az, - atomic weight of zinc [=65.39].
The cetylpyridinium chloride (CPC) (e.g. Sigma-Aldrich,
U.S.) had the following structure:
C,H, ,N'C1” cl
NN (CH.) = SRM
CH,
Example 1
Zinc Electrowinning Liquor with antimony present
Antimony (Sb) in 0.04 mg/l (milligrams/litre) concentration was added as antimony - potassium tartrate to the zinc electrowinning electrolyte. Both four and twenty hour runs were performed. The experimental results of the four-hour runs are summarized in Table 1. ’ without the CPC additive present in the electrolyte, Sb had a detrimental effect on the current efficiency, i.e. between
. © WO 03/016593 PCT/CA02/01250 65.1% (cell no. 15) and 74.7% (cell no. 14). On average, the : current efficiency without the CPC additive present was 69.9%. , Adding CPC improved the current efficiency on average by 23.2%, i.e. from 69.9% to 93.1%.
Table 1: Effect of CPC on the current efficiency of zinc electrowinning in the electrolyte containing 0.04 mg/l Sb (as Sb-tartrate).
Conditions: | Current efficiency (%) | Average
Temperature: 37 °C | per Cell No. CE (%)
No additive © 7 [65.1 [69.9 i +1.0 +6.8
CPC 0.05 mM (mM = EER 92.7 93.1 millimolar) | +2.9 +0.9 on
The effect of CPC in"longer-term (20 hours) experiment is shown in Table 2. Without the CPC additive, the current efficiency of cell no. 15 was only 36.6%, whilst with 0.05 mM .CPC present the zinc electrowinning current efficiency was 58.9%. Thus, with the CPC additive the current efficiency was higher by 22.3%.
Table 2: Effect of CPC on the zinc electrowinning : current efficiency in 20 hour experiment with 0.04 mg/l Sb in the electrolyte.
Conditions: | Current efficiency (%) :
Temperature: 37 °C | per Cell No. i
I
"5 .
Example 2 : }
Zinc Electrowinning Liquor with both antimony and glue
Similar experiments to those in Example 1 were performed with an electrolyte containing 0.04 mg/l of Sb and 10 mg/l of glue (e.g. “pearl glue” supplied by Hudson Industries,
Johnstown, New York). Both 4 and 20 hour runs were carried out.
The effect of the CPC additive on the zinc electrowinning current efficiency in the 4 hour runs is shown in Table 3.
The presence of glue minimizes to a certain extent the negative effect of antimony, yielding current efficiencies between 88.9% and 90%. However, adding 0.05 mM CPC brought : about additional increases of current efficiency, i.e. from 89.4% on average in the absence to 97% in the presence of CPC (Table 3).
= nD © WO 03/016393 PCT/CA02/01250
Table 3: Effect of CPC on the current efficiency of zinc electrowinning in the electrolyte containing . 0.04 mg/l Sb (as Sb-tartrate) + 10 mg/l glue.
Conditions: { Current efficiency Average
Temperature: 37 °C | (%) per Cell No. CE (%)
No additive — 88.9 |90.0 [89.4 +0.9 40.8
CPC 0.05 mM (96.3 95.8 97.0 $1.8 5 . . The 20 hour experiments (Table 4) showed that CPC in 0.05 mM concentration increased the current efficiency of cell no. 16 from 77.2% to 87.3%.
Table 4: Effect of CPC on the zinc electrowinning : current efficiency in 20 hour experiment with 0.04 mg/l Sb and 10 mg/l glue in the electrolyte.
Conditions: | Current efficiency (%) per
Temperature: 37 °C [Cell No.
Ee 7 So To -
The cell voltage is another important figure of merit of the electrowinning process. An increase in the cell voltage represents an increase in the amount of energy required and,
4 hour experiments with 0.04 mg/l Sb and 10 mg/l glue in the electrolyte.
Conditions: Average cell voltage (V)
Temperature: 37 °C
Time: 4 hours
Accordingly, while this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the scope of the invention. "Comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps or components or groups thereof. 8
AMENDED SHEET
Claims (1)
- © WO 03/016593 PCT/CA02/01250 WE CLAIM: . 1. A method of improved zinc electrowinning, comprising: , adding a cetylpyridinium salt additive to a zinc electrowinning electrolyte.2. A method according to claim 1, wherein said cetylpyridinium salt is a cetylpyridinium halide.3. A method according to claim 2, wherein said cetylpyridinium halide is cetylpyridinium chloride.4. A method according to claim 3, wherein said cetylpyridinium chloride is at 0.05 millimolar (mM) concentration in said zinc electrowinning liquor.5. A method according to claim 1, wherein said zinc electrowinning electrolyte contains zinc sulfate.6. A method according to claim 1, wherein said zinc electrowinning electrolyte contains antimony.7. A method according to claim 1, wherein said zinc 3 electrowinning electrolyte contains glue.48. A method according to claim 7, wherein said glue is animal glue.10. A method according to the invention for improved zinc electrowinning, substantially as hereinbefore described or exemplified.11. A method for improved zinc electrowinning including any new and inventive integer or combination of integers, substantially as herein described. AMENDED SHEET
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31182501P | 2001-08-14 | 2001-08-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200405167B true ZA200405167B (en) | 2005-06-27 |
Family
ID=23208657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200405167A ZA200405167B (en) | 2001-08-14 | 2004-06-29 | Hydrogen evolution inhibiting additives for zinc electrowinning. |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20050011769A1 (en) |
| EP (1) | EP1417357B1 (en) |
| JP (1) | JP2004537653A (en) |
| KR (1) | KR100599993B1 (en) |
| CN (1) | CN100342061C (en) |
| AU (1) | AU2002322888B2 (en) |
| BR (1) | BR0211933A (en) |
| CA (1) | CA2457071C (en) |
| DE (1) | DE60203301T2 (en) |
| ES (1) | ES2238586T3 (en) |
| HK (1) | HK1075920A1 (en) |
| MX (1) | MXPA04001459A (en) |
| NO (1) | NO20040651L (en) |
| RU (1) | RU2288299C2 (en) |
| WO (1) | WO2003016593A2 (en) |
| ZA (1) | ZA200405167B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100540748C (en) * | 2006-06-15 | 2009-09-16 | 云南冶金集团总公司 | Assembled gelatin additive |
| CN103993330A (en) * | 2014-05-07 | 2014-08-20 | 成都理工大学 | Zinc electrolysis technology of zinc ammonia complex aqueous solution |
| CN106676578B (en) * | 2015-11-11 | 2018-09-28 | 沈阳有色金属研究院 | A kind of new and effective joint additive of Zinc electrolysis |
| CN110512236B (en) * | 2019-09-27 | 2021-05-04 | 中国科学院长春应用化学研究所 | Combined additive and application thereof in zinc electrodeposition |
| CN115133159A (en) * | 2022-09-01 | 2022-09-30 | 河南师范大学 | Functional aqueous zinc ion battery electrolyte and preparation method and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028199A (en) * | 1974-08-05 | 1977-06-07 | National Development Research Corporation | Method of producing metal powder |
| CA1064852A (en) * | 1975-12-31 | 1979-10-23 | Cominco Ltd. | Method for evaluating a system for electrodeposition of metals |
| CA1111125A (en) * | 1978-07-05 | 1981-10-20 | Robert C. Kerby | Method and apparatus for control of electrowinning of zinc |
| US4699696A (en) * | 1986-04-15 | 1987-10-13 | Omi International Corporation | Zinc-nickel alloy electrolyte and process |
| US4717458A (en) * | 1986-10-20 | 1988-01-05 | Omi International Corporation | Zinc and zinc alloy electrolyte and process |
| CN1023818C (en) * | 1991-03-19 | 1994-02-16 | 昆明工学院 | Vacuum distillation zinc extraction method of hot galvanizing residue |
| US5635051A (en) * | 1995-08-30 | 1997-06-03 | The Regents Of The University Of California | Intense yet energy-efficient process for electrowinning of zinc in mobile particle beds |
| US6086691A (en) * | 1997-08-04 | 2000-07-11 | Lehockey; Edward M. | Metallurgical process for manufacturing electrowinning lead alloy electrodes |
| CN1065919C (en) * | 1998-04-24 | 2001-05-16 | 昆明理工大学 | Vacuum distillation of hard zinc to extract zinc and to concentrate germanium, indium and silver |
| US6238542B1 (en) * | 1998-09-15 | 2001-05-29 | Thomas Helden | Water soluble brighteners for zinc and zinc alloy electrolytes |
| EP1013799A1 (en) * | 1998-12-23 | 2000-06-28 | Half Tone Ltd. | Solution and process for the electrodeposition of gold and gold alloys |
-
2002
- 2002-08-13 RU RU2004107493/02A patent/RU2288299C2/en not_active IP Right Cessation
- 2002-08-13 ES ES02754027T patent/ES2238586T3/en not_active Expired - Lifetime
- 2002-08-13 AU AU2002322888A patent/AU2002322888B2/en not_active Ceased
- 2002-08-13 CA CA002457071A patent/CA2457071C/en not_active Expired - Fee Related
- 2002-08-13 US US10/486,711 patent/US20050011769A1/en not_active Abandoned
- 2002-08-13 WO PCT/CA2002/001250 patent/WO2003016593A2/en active IP Right Grant
- 2002-08-13 KR KR1020047002247A patent/KR100599993B1/en not_active IP Right Cessation
- 2002-08-13 JP JP2003520877A patent/JP2004537653A/en not_active Ceased
- 2002-08-13 MX MXPA04001459A patent/MXPA04001459A/en not_active Application Discontinuation
- 2002-08-13 DE DE60203301T patent/DE60203301T2/en not_active Expired - Fee Related
- 2002-08-13 CN CNB028160207A patent/CN100342061C/en not_active Expired - Fee Related
- 2002-08-13 EP EP02754027A patent/EP1417357B1/en not_active Expired - Lifetime
- 2002-08-13 BR BR0211933-1A patent/BR0211933A/en not_active IP Right Cessation
-
2004
- 2004-02-13 NO NO20040651A patent/NO20040651L/en not_active Application Discontinuation
- 2004-06-29 ZA ZA200405167A patent/ZA200405167B/en unknown
-
2005
- 2005-09-14 HK HK05108025A patent/HK1075920A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1417357B1 (en) | 2005-03-16 |
| WO2003016593A3 (en) | 2003-10-09 |
| RU2004107493A (en) | 2005-06-10 |
| CN1653209A (en) | 2005-08-10 |
| HK1075920A1 (en) | 2005-12-30 |
| BR0211933A (en) | 2004-10-26 |
| KR100599993B1 (en) | 2006-07-13 |
| DE60203301T2 (en) | 2006-04-13 |
| KR20040044443A (en) | 2004-05-28 |
| CA2457071C (en) | 2007-05-29 |
| ES2238586T3 (en) | 2005-09-01 |
| DE60203301D1 (en) | 2005-04-21 |
| WO2003016593A2 (en) | 2003-02-27 |
| RU2288299C2 (en) | 2006-11-27 |
| AU2002322888B2 (en) | 2007-06-21 |
| EP1417357A2 (en) | 2004-05-12 |
| MXPA04001459A (en) | 2005-02-17 |
| CA2457071A1 (en) | 2003-02-27 |
| US20050011769A1 (en) | 2005-01-20 |
| JP2004537653A (en) | 2004-12-16 |
| CN100342061C (en) | 2007-10-10 |
| NO20040651L (en) | 2004-04-16 |
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