CN101969121A - Method for improving charging and discharging cycle life of zinc electrode - Google Patents
Method for improving charging and discharging cycle life of zinc electrode Download PDFInfo
- Publication number
- CN101969121A CN101969121A CN2010102817911A CN201010281791A CN101969121A CN 101969121 A CN101969121 A CN 101969121A CN 2010102817911 A CN2010102817911 A CN 2010102817911A CN 201010281791 A CN201010281791 A CN 201010281791A CN 101969121 A CN101969121 A CN 101969121A
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- China
- Prior art keywords
- zinc electrode
- electrode
- charge
- zinc
- cycle life
- 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.)
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- 239000011701 zinc Substances 0.000 title claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000007599 discharging Methods 0.000 title abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006230 acetylene black Substances 0.000 claims abstract description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims abstract 4
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract 4
- 239000002253 acid Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 abstract description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- CMGJQFHWVMDJKK-UHFFFAOYSA-N lanthanum;trihydrate Chemical compound O.O.O.[La] CMGJQFHWVMDJKK-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for improving charging and discharging cycle life of a zinc electrode. In the method, the zinc electrode is prepared by adding one or more of four additives, namely acetylene black, bismuth oxide, lead oxide and lanthanum hydroxide-coated calcium zincate, into calcium zincate serving as a main raw material of the zinc electrode, wherein not more than 1.2g of acetylene black, not more than 10g of bismuth oxide, not more than 14g of lead oxide and not more than 8g of lanthanum hydroxide-coated calcium zincate are added into every 100g of calcium zincate. The method prolongs the charging and discharging cycle life of the zinc electrode by using a mercury-free additive.
Description
Technical field
The present invention relates to electrochemical field, specifically is that a kind of being applied to the zinc electrode is the method for improving the zinc electrode charge and discharge circulation life in the secondary cell of negative pole.
Background technology
Zinc electrode has specific energy height, aboundresources, cheap, excellent properties such as toxicity is little, non-environmental-pollution, equilibrium potential are low, good reversibility, is widely used as the anode material of battery.But, it with zinc never a large amount of appearance of alkaline secondary cell of anode because zinc electrode exists problems such as liberation of hydrogen, dendrite, deformation to cause the zinc electrode charge and discharge circulation life short.
The zinc electrode that use is made without any additive is at 20% KOH solution, selecting Hg/HgO for use is reference electrode, nickel foam is to electrode, constitute three-electrode system, carry out charge and discharge cycles test, find that the zinc electrode capacity attenuation is very fast, in five charge and discharge cycles, capacity attenuation finishes, and its capacity attenuation situation as shown in Figure 1.
Adding certain additive in the zinc electrode is an important method improving the zinc electrode electric property.In containing the battery of zinc electrode, the zinc granule amalgamation is slowed down the zinc corrosion at present by utilizing mercury; Usually add in the zinc granule or be mixed with indium, thallium, gallium, bismuth, cadmium, tin, plumbous one or more elements, to obtain low rate of corrosion and gassing rate.
Along with the enhancing of people's environmental consciousness, mercury-free battery becomes the main flow of research and development.The present invention is by adding some specific no mercury additive in electrode, improving the zinc electrode charge and discharge circulation life.
Summary of the invention
The objective of the invention is provides a kind of method of improving the zinc electrode charge and discharge circulation life at the short situation of zinc electrode charge and discharge circulation life, adds one or more no mercury additives in zinc electrode, to improve the charge and discharge circulation life of zinc electrode.
In the multiple additives of improving the zinc electrode performance, calcium hydroxide (Ca (OH)
2) be a kind of additive the most frequently used in the zinc electrode.Its main effect is that zinc battery when discharge and zincate form zincic acid calcium (Ca[Zn (OH) under alkali condition
3]
22H
2O) insoluble compound reduces the solubility of zinc electrode discharging product in alkaline solution; During the zinc battery charging, zincic acid calcium is by reversible reaction
The calcium hydroxide that decomposites (Ca (OH)
2) form the shape that tridimensional network helps keeping zinc electrode, reduce the deformation of zinc electrode.
The present invention is that the feedstock production zinc electrode (is equivalent to add calcium hydroxide (Ca (OH) in zinc electrode with zincic acid calcium
2) additive) add other additive simultaneously, improve the cycle life of zinc electrode by the acting in conjunction of multiple additives.
Concrete grammar of the present invention is as follows:
With zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) be the primary raw material of zinc electrode, interpolation comprises acetylene black, bismuth oxide (Bi
2O
3), lead oxide (PbO) coats lanthanum hydroxide (La (OH)
3) zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) etc. four kinds of additives neutralize one or more, make zinc electrode.Wherein every 100g zinc electrode is added acetylene black and is no more than 1.2g, adds bismuth oxide (Bi
2O
3) be no more than 10g, add lead oxide (PbO) and be no more than 14g, add coating lanthanum hydroxide (La (OH)
3) zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) be no more than 8g.
Selecting Hg/HgO for use is reference electrode, and nickel foam constitutes three-electrode system for electrode and employing having been added the zinc electrode of above-mentioned additive preparation, carries out the charge and discharge cycles test.
Use method of the present invention, zinc electrode participated in proper additive, adopt no mercury additive after, the specific capacity of zinc electrode and charge and discharge cycles number of times all improve significantly.
Description of drawings
Fig. 1 is the capacity attenuation situation map of no any additives charge and discharge cycles;
Fig. 2 is the capacity attenuation situation map of the embodiment of the invention 1 charge and discharge cycles;
Fig. 3 is the capacity attenuation situation map of the embodiment of the invention 2 charge and discharge cycles;
Fig. 4 is the capacity attenuation situation map of the embodiment of the invention 3 charge and discharge cycles.
Embodiment
Embodiment 1:
Take by weighing zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) 91.2g, acetylene black 0.8g, bismuth oxide (Bi
2O
3) 2g, after lead oxide (PbO) 6g mixes, under the pressure of 10Mpa, continue 1min, make zinc electrode.
Selecting Hg/HgO for use is reference electrode, and nickel foam is electrode and the zinc electrode that adopts method for preparing to be added 20% KOH solution in electrolytic cell, constitutes three-electrode system, carries out charge and discharge cycles and tests.The capacity attenuation of hundred charge and discharge cycles is seen accompanying drawing 2.Compare with the zinc electrode without any additive, specific capacity strengthens to some extent, and the charge and discharge cycles number of times also has remarkable enhancing, but specific capacity is lower after hundred charge and discharge cycles.
Embodiment 2:
Take by weighing zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) 83.6g, acetylene black 0.4g, bismuth oxide (Bi
2O
3) 6g, after lead oxide (PbO) 10g mixes, under the pressure of 10Mpa, continue 1min, make zinc electrode.
Selecting Hg/HgO for use is reference electrode, and nickel foam is electrode and the zinc electrode that adopts method for preparing to be added 20% KOH solution in electrolytic cell, constitutes three-electrode system, carries out charge and discharge cycles and tests.The capacity attenuation of hundred charge and discharge cycles is seen accompanying drawing 3.Compare with the zinc electrode without any additive, specific capacity strengthens to some extent, and the charge and discharge cycles number of times also has remarkable enhancing, but specific capacity is not high after hundred charge and discharge cycles.
Embodiment 3:
Take by weighing zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) 75.2g, acetylene black 0.8g, bismuth oxide (Bi
2O
3) 10g, lead oxide (PbO) 10g coats lanthanum hydroxide (La (OH)
3) zincic acid calcium (Ca[Zn (OH)
3]
22H
2O) after 4g mixes, under the pressure of 10Mpa, continue 1min, make zinc electrode.
Selecting Hg/HgO for use is reference electrode, and nickel foam is electrode and the zinc electrode that adopts method for preparing to be added 20% KOH solution in electrolytic cell, constitutes three-electrode system, carries out charge and discharge cycles and tests.The capacity attenuation of hundred charge and discharge cycles is seen accompanying drawing 4.Compare with the zinc electrode without any additive, specific capacity and charge and discharge cycles number of times all strengthen significantly, and specific capacity descends less after hundred charge and discharge cycles.
Claims (1)
1. a method of improving the zinc electrode charge and discharge circulation life is characterized in that with zincic acid calcium being the primary raw material of zinc electrode, adds acetylene black, bismuth oxide, and lead oxide, one or more in four kinds of additives of zincic acid calcium of coating lanthanum hydroxide are made zinc electrode; Wherein every 100g zinc electrode is added acetylene black and is no more than 1.2g, adds bismuth oxide and is no more than 10g, adds lead oxide and is no more than 14g, adds the zincic acid calcium that coats lanthanum hydroxide and is no more than 8g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102817911A CN101969121A (en) | 2010-09-15 | 2010-09-15 | Method for improving charging and discharging cycle life of zinc electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102817911A CN101969121A (en) | 2010-09-15 | 2010-09-15 | Method for improving charging and discharging cycle life of zinc electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101969121A true CN101969121A (en) | 2011-02-09 |
Family
ID=43548240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102817911A Pending CN101969121A (en) | 2010-09-15 | 2010-09-15 | Method for improving charging and discharging cycle life of zinc electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101969121A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038602A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN112038622A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Calcium zincate negative electrode material for zinc-based secondary battery, preparation method of calcium zincate negative electrode material and zinc-based secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220779A (en) * | 1997-03-27 | 1999-06-23 | 能量研究公司 | Calcium-zincate electrode for alkaline batteries and method for making same |
| CN1828983A (en) * | 2005-03-03 | 2006-09-06 | 河南环宇集团有限公司 | Method for preparing power type columnar sealed zinc-nickel alkaline accumulator zinc negative pole |
| CN101071850A (en) * | 2007-05-25 | 2007-11-14 | 新乡联达华中电源有限公司 | Zinc cathode of secondary zinc-nickel battery and preparation method thereof |
-
2010
- 2010-09-15 CN CN2010102817911A patent/CN101969121A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220779A (en) * | 1997-03-27 | 1999-06-23 | 能量研究公司 | Calcium-zincate electrode for alkaline batteries and method for making same |
| CN1828983A (en) * | 2005-03-03 | 2006-09-06 | 河南环宇集团有限公司 | Method for preparing power type columnar sealed zinc-nickel alkaline accumulator zinc negative pole |
| CN101071850A (en) * | 2007-05-25 | 2007-11-14 | 新乡联达华中电源有限公司 | Zinc cathode of secondary zinc-nickel battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《电化学》 20050310 孟宪玲等 稀土氧化物对二次锌电极性能的影响 第58页第1至4段 1 第11卷, 第01期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038602A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN112038622A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Calcium zincate negative electrode material for zinc-based secondary battery, preparation method of calcium zincate negative electrode material and zinc-based secondary battery |
| CN112038602B (en) * | 2020-09-02 | 2021-11-16 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN112038622B (en) * | 2020-09-02 | 2021-11-30 | 河南超力新能源有限公司 | Calcium zincate negative electrode material for zinc-based secondary battery, preparation method of calcium zincate negative electrode material and zinc-based secondary battery |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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Application publication date: 20110209 |