CN102044713A - Method for reducing solubility of discharging product of zinc electrode - Google Patents
Method for reducing solubility of discharging product of zinc electrode Download PDFInfo
- Publication number
- CN102044713A CN102044713A CN2010105503672A CN201010550367A CN102044713A CN 102044713 A CN102044713 A CN 102044713A CN 2010105503672 A CN2010105503672 A CN 2010105503672A CN 201010550367 A CN201010550367 A CN 201010550367A CN 102044713 A CN102044713 A CN 102044713A
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- CN
- China
- Prior art keywords
- zinc electrode
- zinc
- electrolyte
- solubility
- discharging product
- 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 58
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 48
- 238000007599 discharging Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 8
- 238000007600 charging Methods 0.000 claims abstract description 7
- 238000007796 conventional method Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 21
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical class [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- 229940072033 potash Drugs 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 2
- PJAIMBYNTXNOCN-UHFFFAOYSA-N 3,6-dibromo-1h-indole Chemical compound BrC1=CC=C2C(Br)=CNC2=C1 PJAIMBYNTXNOCN-UHFFFAOYSA-N 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 abstract 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 16
- 238000004448 titration Methods 0.000 description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
Abstract
The invention provides a method for reducing solubility of a discharging product of a zinc electrode. In the method, charging and discharging of a cell are carried out by preparing an alkaline electrolyte and combining the alkaline electrolyte and calcium zincate serving as a zinc electrode according to a conventional method, wherein the alkaline electrolyte comprises the following components: 0.2-0.5g/mL potassium hydroxide, 0.01-0.03g/mL lithium hydroxide, 0.08-0.12g/mL potassium fluoride dihydrate, 0.04-0.24g/mL potassium carbonate and 0.002-0.006g/mL sodium hexametaphosphate. By utilizing the electrolyt and application method of the electrolyt provided by the invention, the solubility of the discharging product of the zinc electrode in the electrolyt is reduced by more than 80%, and the problem of shorthand zinc battery service life caused by overlarge solubility of the discharging product of the zinc electrode in the alkaline electrolyt is solved.
Description
Technical field
The present invention relates to a kind of method that reduces zinc electrode discharging product solubility in alkaline electrolyte, belong to electrochemical field.
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 alkaline battery.But because zinc electrode cycle life is short, be never a large amount of appearance of alkaline secondary cell of anode with zinc, its reason is that zinc electrode discharging product ZnO solubility in alkaline electrolyte is excessive, is a short main cause of zinc electrode cycle life.
Zinc electrode discharging product ZnO solubility in electrolyte is excessive, causes in charge and discharge cycles zinc electrode to be easy to generate dendrite or causes the zinc electrode distortion serious.The generation of dendrite or the distortion of electrode reduce the cycle life of zinc battery rapidly.
Summary of the invention
Problems such as zinc electrode discharging product solubility in alkaline electrolyte is excessive in order to overcome, the cycle life of zinc battery is short the invention provides a kind of method that reduces zinc electrode discharging product solubility.
The present invention is to provide a kind of like this method that reduces zinc electrode discharging product solubility, it is characterized in that through the following step:
A. prepare the alkaline electrolyte of following component:
Potassium hydroxide 0.2～0.5g/mL
Lithium hydroxide 0.01～0.03g/mL
Two hydration potassium fluorides, 0.08～0.12g/mL
Potash 0.04～0.24g/mL
Calgon 0.002～0.006g/mL
Perhaps,
Potassium hydroxide 0.2～0.5g/mL
Lithium hydroxide 0.01～0.03g/mL
Two hydration potassium fluorides, 0.08～0.12g/mL
Potash 0.04～0.24g/mL
Calgon 0.002～0.006g/mL
Tetramethylammonium hydroxide 0.0005～0.003g/mL
Softex kw 0.0024～0.0075g/mL;
B. with zincic acid calcium as zinc electrode;
C. steps A gained alkaline electrolyte and the described zinc electrode of step B are made up according to a conventional method and carry out battery charging and discharging.
Because calcium hydroxide is a kind of additive commonly used in the zinc electrode, its main effect is when zinc battery discharges and zincate forms zincic acid calcium (Ca[Zn (OH) under alkali condition
3]
22H
2O) insoluble compound has reduced the solubility of zinc electrode discharging product in alkaline solution, when zinc battery charges, by the reversible reaction of zincic acid calcium
The zinc oxide that decomposites (ZnO) is finished charging process.Mix the inhomogeneous poor effect that causes when avoiding adding calcium hydroxide, the present invention is that raw material prepares zinc electrode with zincic acid calcium directly.
Use described alkaline electrolyte after the zinc battery discharge, detect the solubility of zinc ion in alkaline electrolyte, concrete detection method is as follows: get described electrolyte 100ml, add 10g zincic acid calcium, left standstill 2～3 days, zincic acid calcium is reached capacity in electrolyte; Take out supernatant liquor, and leave standstill clarification after 1～2 day, get the 10ml clarified solution, in this clarified solution, splash into excessive hydrochloric acid precipitation is disappeared, with in and potassium hydroxide in the electrolyte, make zincic acid calcium become calcium chloride and zinc chloride simultaneously; Add the black T of indicator network again after adding cushioning liquid in above-mentioned and in the electrolyte, show pink, use the EDTA titration, the terminal point of titration is blue, notes the volume of the EDTA that is consumed, repeats 3 titration; By following formula, calculate the concentration of zinc ion:
C
Zn＝C
EDTA·V/V
Zn
C in the formula
ZnThe concentration of zinc ion in the expression sample, mol/L; C
EDTAThe concentration of expression EDTA, mol/L; V represents the mean value of the volume of three used EDTA of titration, mL; V
ZnThe volume of representing solution to be measured, mL.
The concentration of gained zinc ion is low more, and the solubility of zinc electrode discharging product in alkaline electrolyte is just low more.
Advantage of the present invention and effect: The present invention be directed to the excessive present situation of zinc electrode discharging product solubility in alkaline electrolyte, add multiple no mercury additive in the alcaliotropism electrolyte, in zinc electrode, add the discharging product that certain additive changes zinc electrode simultaneously, reduce the solubility of zinc electrode discharging product in alkaline electrolyte.Usually the method that adopts zinc powder to mix with calcium hydroxide is added calcium hydroxide in zinc electrode, and there is the uneven shortcoming of mixing unavoidably in this method, the present invention directly with zincic acid calcium as zinc electrode, avoided this shortcoming.Adopt alkaline electrolyte of the present invention, the solubility that makes the zinc electrode discharging product in electrolyte is reduced more than 80%, solved the zinc electrode discharging product causes zinc battery to shorten useful life because of solubility is excessive problem in alkaline electrolyte.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
Get potassium hydroxide 27g, lithium hydroxide 1g, two hydration potassium fluoride 8g, potash 12g, Tetramethylammonium hydroxide 0.05g, calgon 0.6g is dissolved in the 100mL water, be made into alkaline electrolyte, and make up according to a conventional method as zinc electrode with zincic acid calcium and to carry out battery charging and discharging.
Detect the solubility of zinc electrode discharging product in the above-mentioned electrolyte by following method: get above-mentioned electrolyte 100mL, add 10g zincic acid calcium, left standstill 2 days, zincic acid calcium is reached capacity in electrolyte; Take out supernatant liquor, and leave standstill clarification after 1 day, get the 10ml clarified solution, and in clarified solution, splash into excessive hydrochloric acid precipitation is disappeared, with in and potassium hydroxide in the electrolyte, make zincic acid calcium become calcium chloride and zinc chloride simultaneously; Add the black T of indicator network again after adding cushioning liquid in described and in the electrolyte, show pink, use the EDTA titration, the terminal point of titration is blue, notes the volume of the EDTA that is consumed, repeats 3 titration, by following formula: C
Zn=C
EDTAV/V
Zn, the concentration that calculates zinc ion is 0.0308mol/L.
Contrast detects: take by weighing potassium hydroxide 27g, be made into the electrolyte 100ml without any additive.After detecting as stated above, the zinc ion concentration that records is 0.252mol/L.
As from the foregoing, in the described electrolyte of the embodiment of the invention zinc ion concentration just conventional without any 12% of zinc ion concentration in the electrolyte of additive.
Embodiment 2
Get potassium hydroxide 20g, lithium hydroxide 2g, two hydration potassium fluoride 8g, potash 4g, calgon 0.2g, softex kw 0.24g is dissolved in the 100mL water, be made into alkaline electrolyte, and make up according to a conventional method as zinc electrode with zincic acid calcium and to carry out battery charging and discharging.
Detect the solubility of zinc electrode discharging product in the above-mentioned electrolyte by following method: get above-mentioned electrolyte 100ml, add 10g zincic acid calcium, left standstill 3 days, zincic acid calcium is reached capacity in electrolyte; Take out supernatant liquor, and leave standstill clarification after 2 days, get the 10ml clarified solution, and in clarified solution, splash into excessive hydrochloric acid precipitation is disappeared, with in and potassium hydroxide in the electrolyte, make zincic acid calcium become calcium chloride and zinc chloride simultaneously; Add the black T of indicator network again after adding cushioning liquid in described and in the electrolyte, show pink, use the EDTA titration, the terminal point of titration is blue, notes the volume of the EDTA that is consumed, repeats 3 titration, by following public affairs: C
ZnC
EDTAV/V
Zn, the concentration that calculates zinc ion is 0.0386mol/L.
Contrast detects: take by weighing potassium hydroxide 20g, be made into the electrolyte 100ml without any additive.After detecting as stated above, the zinc ion concentration that records is 0.257mol/L.
Zinc ion concentration is just without any 15% of zinc ion concentration in the electrolyte of additive in the present embodiment 2 described electrolyte.
Embodiment 3
Get potassium hydroxide 50g, lithium hydroxide 3g, two hydration potassium fluoride 12g, potash 4g, Tetramethylammonium hydroxide 0.05g, calgon 0.4g, softex kw 0.75g are dissolved in the 100mL water, be made into alkaline electrolyte, and make up according to a conventional method as zinc electrode with zincic acid calcium and to carry out battery charging and discharging.
Detect the solubility of zinc electrode discharging product in the above-mentioned electrolyte by following method: get above-mentioned electrolyte 100ml, add 10g zincic acid calcium, left standstill 3 days, zincic acid calcium is reached capacity in electrolyte; Take out supernatant liquor, and leave standstill clarification after 1 day, get the 10ml clarified solution, and splash into excessive hydrochloric acid at clarified solution precipitation is disappeared, with in and potassium hydroxide in the electrolyte, make zincic acid calcium become calcium chloride and zinc chloride simultaneously; Add the black T of indicator network again after adding cushioning liquid in described and in the electrolyte, show pink, use the EDTA titration, the terminal point of titration is blue, notes the volume of the EDTA that is consumed, repeats 3 titration, by following formula: C
Zn=C
EDTAV/V
Zn, the concentration that calculates zinc ion is 0.0495mol/L.
Contrast detects: take by weighing potassium hydroxide 50g, be made into the electrolyte 100ml without any additive.After detecting as stated above, the zinc ion concentration that records is 0.2475mol/L.
Zinc ion concentration is without any 20% of zinc ion concentration in the electrolyte of additive in the present embodiment 3 described electrolyte.
Claims (1)
1. method that reduces zinc electrode discharging product solubility is characterized in that through the following step:
A. prepare the alkaline electrolyte of following component:
Potassium hydroxide 0.2～0.5g/mL
Lithium hydroxide 0.01～0.03g/mL
Two hydration potassium fluorides, 0.08～0.12g/mL
Potash 0.04～0.24g/mL
Calgon 0.002～0.006g/mL
Perhaps,
Potassium hydroxide 0.2～0.5g/mL
Lithium hydroxide 0.01～0.03g/mL
Two hydration potassium fluorides, 0.08～0.12g/mL
Potash 0.04～0.24g/mL
Calgon 0.002～0.006g/mL
Tetramethylammonium hydroxide 0.0005～0.003g/mL
Softex kw 0.0024～0.0075g/mL;
B. with zincic acid calcium as zinc electrode;
C. steps A gained alkaline electrolyte and the described zinc electrode of step B are made up according to a conventional method and carry out battery charging and discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105503672A CN102044713A (en) | 2010-11-19 | 2010-11-19 | Method for reducing solubility of discharging product of zinc electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105503672A CN102044713A (en) | 2010-11-19 | 2010-11-19 | Method for reducing solubility of discharging product of zinc electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102044713A true CN102044713A (en) | 2011-05-04 |
Family
ID=43910639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105503672A Pending CN102044713A (en) | 2010-11-19 | 2010-11-19 | Method for reducing solubility of discharging product of zinc electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102044713A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151527A (en) * | 2012-12-28 | 2013-06-12 | 中银（宁波）电池有限公司 | Alkaline battery additive |
| WO2020060985A1 (en) * | 2018-09-17 | 2020-03-26 | ZAF Energy Systems, Incorporated | Zinc alkaline secondary battery including anchored electrolyte additives |
| CN111048846A (en) * | 2019-12-18 | 2020-04-21 | 陈发生 | Nickel-zinc battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034829A (en) * | 1986-08-01 | 1989-08-16 | 北安普敦广场城市大学 | The storage battery of alkaline electrolyte |
-
2010
- 2010-11-19 CN CN2010105503672A patent/CN102044713A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034829A (en) * | 1986-08-01 | 1989-08-16 | 北安普敦广场城市大学 | The storage battery of alkaline electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库（电子期刊）》 20061231 赵逸群 添加剂对锌电池负极及电解液性能影响的研究 第22-25、46-47、51-52 1 , * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151527A (en) * | 2012-12-28 | 2013-06-12 | 中银（宁波）电池有限公司 | Alkaline battery additive |
| WO2020060985A1 (en) * | 2018-09-17 | 2020-03-26 | ZAF Energy Systems, Incorporated | Zinc alkaline secondary battery including anchored electrolyte additives |
| US11258103B2 (en) | 2018-09-17 | 2022-02-22 | ZAF Energy Systems, Incorporated | Zinc alkaline secondary battery including anchored electrolyte additives |
| CN111048846A (en) * | 2019-12-18 | 2020-04-21 | 陈发生 | Nickel-zinc battery |
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Application publication date: 20110504 |