CN1482698A - Method for preparing secondary basic zinc electrode material - Google Patents
Method for preparing secondary basic zinc electrode material Download PDFInfo
- Publication number
- CN1482698A CN1482698A CNA031283314A CN03128331A CN1482698A CN 1482698 A CN1482698 A CN 1482698A CN A031283314 A CNA031283314 A CN A031283314A CN 03128331 A CN03128331 A CN 03128331A CN 1482698 A CN1482698 A CN 1482698A
- Authority
- CN
- China
- Prior art keywords
- zinc
- calcium
- reaction
- electrode material
- ball milling
- 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.)
- Pending
Links
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
Abstract
The invention discloses a process for the manufacture of secondary alkaline zinc electrode material calcium zincate, composed of zinc oxide, zinc acetate, zinc nitrate, or zinc chloride and calcium oxide, calcium hydroxide, calcium acetate, calcium nitrate or calcium chloride, in potassium hydroxide or aqueous medium, reaction for 6-24 hours at room temperature through rolling ball grinding, filtering, washing and seasoning using deionized water for production, the calcium zincate is synthesized through ball milling, the equipment and process required by the invention are simple and reliable, thus easy for realizing mass production.
Description
Technical Field
The invention relates to a preparation method of a secondary alkaline zinc electrode material. It belongs to the technical field of electrochemistry, inorganic material synthesis and electronic products.
Background
The zinc has the characteristics of good reversibility, low equilibrium potential, small overpotential, high gravimetric energy and volumetric energy, and the like, and the zinc has rich resources, low cost, no toxicity and environmental friendliness, is an ideal battery cathode material, so the zinc is widely used in various chemical power supplies, and the chemical power supply taking the zinc as the cathode occupies more than 90 percent of the output in a primary battery. In order to fully utilize the resources of zinc, attempts have been made to prepare zinc as a secondary zinc electrode which can be repeatedly charged and discharged. Although some progress is made after long-term efforts, due to the thermodynamic instability of the zinc electrode and the greater solubility of the zinc electrode reaction product in an alkaline medium, dendrite and deformation are easily generated during repeated charge and discharge, so that the performance of the secondary battery is not ideal, and the commercialization process is seriously influenced.
In order to suppress the formation of zinc dendrites and to reduce deformation, the solubility of the zinc electrode reaction product in alkaline media must be reduced, and it has been found that at suitable KOH concentrations, the solubility of calcium zincate is significantly less than that of zinc oxide. Therefore, calcium oxide or hydroxide has attracted attention as an additive for zinc electrodes. Yui Sato, etc. Ca (OH)2And Bi2O3Meanwhile, the zinc electrode prepared by grinding the film after being added into the zinc cathode material and mixed is obviously improved in cycle life (J Power Sources, V9, 1983, p 147). Sanyo electric appliances Japan, Inc. added Ca (OH) to the zinc negative electrode material2Also, the cell performance is improved (JP63,245,859, 01,163,966). G. Gagnon, etc. adding Ca (OH) to zinc electrode2The cell was cycled for 400 more weeks, still maintaining 70% of theoretical capacity (J electrochem. soc., V134, 1987, p 2091). Japanese patent 02,103,857 discloses the use of Zn, ZnO and Ca (OH)2The prepared zinc paste is coated on a current collector to prepare a zinc electrode, so that the service life of the battery is prolonged. Energy research of America Inc. 64.5% ZnO, 25% Ca (OH)28% PbO and 2.5% PTFE are mixed to prepare a zinc electrode, and the zinc electrode has good performance (USP 5,460,899). Charkey in U.S. Pat. No. 5,863,676 in 1999 reported using ZnO and Ca (OH)2The calcium zincate can be synthesized by stirring in an alkaline medium at the temperature of between 40 and 80 ℃ for 48 to 72 hours, and the zinc electrode prepared by using the calcium zincate has good cycle performance. In summary, in the past, calcium compounds were added to zinc electrodes, and zinc was formed during the charging and discharging of the battery after the electrodes were made by a physical mixing methodCalcium, thereby reducing the solubility of the zinc electrode discharge product, but in this way calcium zincate is formed very slowly and incompletely. The method disclosed in Charkey' 5,863,676, however, requires not only maintaining the constant temperature condition of heating, but also stirring for 48-72 hours, and the process is complicated, the reaction time is too long, and it is not suitable for large-scale production.
Disclosure of Invention
The invention aims at the problems to provide a preparation method of a secondary alkaline zinc electrode material, which hassimple process and short reaction time and is suitable for large-scale production.
The technical scheme provided by the invention is as follows: a preparation method of secondary alkaline zinc electrode material, using zinc oxide, zinc acetate, zinc nitrate or zinc chloride and calcium oxide, calcium hydroxide, calcium acetate, calcium nitrate or calcium chloride as raw materials, in 0-40 deg.C alkaline medium or aqueous medium, through rolling ball milling reaction for 4-36 hours, preferable time is 6-24 hours, the best time is 8-12 hours; then filtering, washing with deionized water, and drying to obtain the required secondary alkaline zinc electrode material.
The molar ratio of zinc to calcium in the raw materials for the reaction is 4: 1 to 1: 1.
The reaction medium is potassium hydroxide or sodium hydroxide water solution with concentration of 0-30 wt%, preferably 10-22%.
The reaction temperature in the preparation process of the product is preferably 10-30 ℃.
The rolling ball milling speed in the rolling ball milling is 50-200 r/min, preferably 100 r/min and 120 r/min. The drying temperature is 50-100 ℃.
The ball milling reaction adopts two agate balls with the diameter of 20-30mm and the diameter of 8-15mm, and the number ratio of the big balls to the small balls is 1: 3-1: 8.
Compared with the prior art, the invention has the advantages that the achieved effect is as follows:
1. the material prepared by the invention has a monoclinic crystal structure, and the chemical formula of the main component is Ca (OH)2·2Zn(OH)2·2H2The particle size is 0.1-20 microns, the material performance is excellent, the specific discharge capacity of 0.2C can reach 250mAh/g calcium zincate, the reversibility and the stability are good, and the material is a cathode material with important application prospect in an alkaline secondary battery.
2. When the calcium zincate is prepared, the raw materials are proportioned according to the stoichiometric proportion, the reaction is complete, and no unreacted zinc-calcium raw material diffraction peak is found on an X-ray powder diffraction pattern.
3. The invention has simple process, short reaction time, easy mastering and stable, uniform and reliable product quality, and is suitable for industrial scale production.
4. Clean and pollution-free, and does not contain any harmful elements.
5. The material prepared by the invention can be used as the main active material of the negative electrode of various secondary alkaline batteries, such as the negative electrode material in the secondary batteries of alkaline zinc/manganese dioxide, alkaline zinc/air (oxygen), alkaline zinc/silver oxide, alkaline zinc/nickel oxide and the like.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a secondary alkaline zinc electrode material (calcium zincate) synthesized according to the present invention;
FIG. 2 is a scanning electron microscope image of the synthesized secondary alkaline zinc electrode material of the invention, with a magnification of 3000 times;
FIG. 3 is a charge-discharge curve of the secondary alkaline zinc electrode material synthesized by the present invention at the third formation;
FIG. 4 is a charge-discharge cycle curve of the secondary alkaline zinc electrode material synthesized by the present invention.
Detailed Description
The invention adopts the following raw material selection and material preparation principles:
the synthetic calcium zincate is zinc oxide (ZnO) and zinc acetate (Zn (CH)3COO)2·2H2O), zinc nitrate (Zn (NO)3)2·6H2O), zinc chloride (ZnCl)2) In (1)A calcium oxide (CaO) and calcium hydroxide (Ca (OH)2) Calcium acetate (Ca (CH)3COO)2·H2O), calcium nitrate (Ca (NO)3)2·4H2O), calcium chloride (CaCl)2) Any one of the above is used as a raw material, and the basic synthesis reaction is as follows:
1. synthetic material formulation
Accurately analyzing the components and contents of the raw materials to ensure that the molar ratio of Ca to Zn is between 1 and 0.25, and the optimal ratio is between 0.5 and 0.33.
3. Process for manufacturing secondary alkaline zinc electrode material
Accurately weighing any group of raw materials for reaction according to the proportion, putting the raw materials into a plastic or ceramic reaction tank, adding a reaction medium (deionized water or potassium hydroxide or sodium water solution, wherein the reaction medium is selected according to the raw materials in the synthetic reaction formula), putting two kinds of agate balls in the reaction tank, putting the reaction tank on a rolling ball mill, performing rolling ball milling reaction for 4-36 hours at room temperature, then filtering, washing with deionized water, and drying at 50-100 ℃ to obtain the required secondary alkaline zinc electrode material.
Example 1:
ZnO 81.4g, Ca (OH)237.0g，H2Adding 300ml of O into a plastic reaction tank, adding 5 agate balls with the diameter of 20m and 20 agate balls with the diameter of 13mm, placing the reaction tank on a rolling ball mill, performing rolling ball milling reaction for 20 hours at room temperature, filtering, washing with deionized water, and drying for 24 hours at 60 ℃ to obtain the required secondary alkaline zinc electrode material. From the X-ray powder diffraction pattern (fig. 1), and the scanning electron micrograph (fig. 2), it can be seen that the obtained secondary basic zinc electrode material has a monoclinic crystal structure. The charge-discharge curves of the obtained secondary alkaline zinc electrode material are shown in fig. 3 and 4, which show that the secondary alkaline zinc electrode material is charged to 2.0V at 0.2C, then is charged at constant voltage for 30 minutes, and is discharged to 1.5V at 0.2C; 0.4C discharged to after 3 hours of 0.3C charging1.5V。
Example 2:
ZnCl is accurately weighed268.2g，CaCl227.7g of 20 wt% aqueous solution of potassium hydroxide (420 ml) are added into a plastic reaction tank, 6 agate balls with the diameter of 25mm and 36 agate balls with the diameter of 9mm are placed into the reaction tank, the reaction tank is placed on a rolling ball mill, the rolling ball milling reaction is carried out for 10 hours at the temperature of 30 ℃, then the filtration and the washing are carried out, and the drying is carried out for 20 hours at the temperature of 80 ℃, so that the required secondary alkaline zinc electrode can be obtained.
Claims (10)
1. A preparation method of a secondary alkaline zinc electrode material is characterized by comprising the following steps: zinc oxide, zinc acetate, zinc nitrate or zinc chloride and calcium oxide, calcium hydroxide, calcium acetate, calcium nitrate or calcium chloride are used as raw materials, and the raw materials are subjected to rolling ball milling reaction for 4 to 36 hours in an alkaline medium or a water medium at the temperature of between 0 and 40 ℃, then are filtered, washed by deionized water and dried to obtain the required secondary alkaline zinc electrode material.
2. The method of claim 1, wherein: the molar ratio of zinc to calcium in the reaction raw materials is 4: 1 to 1: 1.
3. The method according to claim 1 or 2, characterized in that: the reaction medium is potassium hydroxide or sodium hydroxide water solution with the concentration of 0-30 wt%.
4. The method of claim 3, wherein: the concentration of the potassium hydroxide or sodium hydroxide aqueous solution is 10-22 wt%.
5. The method according to claim 1 or 2, characterized in that: the reaction time of the rolling ball milling is 6 to 24 hours.
6. The method according to claim 5, wherein: the reaction time of the rolling ball milling is 8 to 12 hours.
7. The method according to claim 1 or 2, characterized in that: the reaction temperature is 10-30 ℃.
8. The method according to claim 1 or 2, characterized in that: the rollingball milling speed is 50-200 r/min.
9. The method according to claim 1 or 2, characterized in that: the drying temperature is 50-100 ℃.
10. The method according to claim 1 or 2, characterized in that: the ball milling reaction adopts two agate balls with the diameter of 20-30mm and the diameter of 8-15mm, and the number ratio of the big balls to the small balls is 1: 3-1: 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031283314A CN1482698A (en) | 2003-07-17 | 2003-07-17 | Method for preparing secondary basic zinc electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031283314A CN1482698A (en) | 2003-07-17 | 2003-07-17 | Method for preparing secondary basic zinc electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1482698A true CN1482698A (en) | 2004-03-17 |
Family
ID=34153346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031283314A Pending CN1482698A (en) | 2003-07-17 | 2003-07-17 | Method for preparing secondary basic zinc electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1482698A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006032208A1 (en) | 2004-09-24 | 2006-03-30 | Byd Company Limited | Methods for fabricating calcium zincate for negative electrodes |
| CN102044669A (en) * | 2010-12-01 | 2011-05-04 | 中南大学 | Zinc cathode active substance of zinc-nickel secondary battery and preparation method and application method thereof |
| KR20170134499A (en) * | 2015-04-03 | 2017-12-06 | 에질 | Process for preparing calcium zincate crystals and uses thereof |
| CN111354921A (en) * | 2018-12-21 | 2020-06-30 | 法国电力公司 | Method for producing zinc electrodes via the water route |
-
2003
- 2003-07-17 CN CNA031283314A patent/CN1482698A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006032208A1 (en) | 2004-09-24 | 2006-03-30 | Byd Company Limited | Methods for fabricating calcium zincate for negative electrodes |
| CN102044669A (en) * | 2010-12-01 | 2011-05-04 | 中南大学 | Zinc cathode active substance of zinc-nickel secondary battery and preparation method and application method thereof |
| CN102044669B (en) * | 2010-12-01 | 2012-10-03 | 中南大学 | Zinc cathode active substance of zinc-nickel secondary battery and preparation method and application method thereof |
| KR20170134499A (en) * | 2015-04-03 | 2017-12-06 | 에질 | Process for preparing calcium zincate crystals and uses thereof |
| CN107743475A (en) * | 2015-04-03 | 2018-02-27 | 依瑟尔有限公司 | Method for preparing calcium zincates crystal and application thereof |
| US10472248B2 (en) * | 2015-04-03 | 2019-11-12 | Easyl | Method for manufacturing calcium zincate crystals, and the uses thereof |
| CN114084899A (en) * | 2015-04-03 | 2022-02-25 | 依瑟尔有限公司 | Method for producing calcium zincate crystals and use thereof |
| KR102492012B1 (en) | 2015-04-03 | 2023-01-26 | 에질 | Method for producing calcium zincate crystals and uses thereof |
| CN111354921A (en) * | 2018-12-21 | 2020-06-30 | 法国电力公司 | Method for producing zinc electrodes via the water route |
| CN111354921B (en) * | 2018-12-21 | 2023-12-22 | 法国电力公司 | Method for producing zinc electrode by water path |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108832103B (en) | Modified high-nickel ternary cathode material and preparation method and application thereof | |
| CN101335348B (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 | |
| CN108878859A (en) | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof, lithium ion battery | |
| CN112909242B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN114005978B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| WO2010069209A1 (en) | Iron electrode material with low self discharge | |
| CN112645390B (en) | Lithium cobaltate precursor with coating structure, preparation method and application thereof | |
| CN111689528A (en) | Ternary material precursor and preparation method and application thereof | |
| JP4405547B2 (en) | Method for producing calcium zincate for cathode | |
| CN114566632B (en) | Positive electrode material for sodium ion battery and preparation method thereof | |
| CN107697897B (en) | Polynary layered oxide of zinc-nickel secondary batteries negative electrode material zinc titanium and preparation method thereof and the battery for using the negative electrode material | |
| CN115520910A (en) | Preparation method of oxide positive electrode material of sodium-ion battery | |
| CN112960703A (en) | Preparation method of lithium ion battery anode core-shell material with concentration gradient | |
| CN116053444A (en) | Doped layered anode material and application thereof in sodium ion battery | |
| CN112694131B (en) | Zinc manganate negative electrode material, method for preparing same by adopting coprecipitation method and application thereof | |
| CN112919554B (en) | Fluorine-doped lithium cathode material and preparation method and application thereof | |
| CN1482698A (en) | Method for preparing secondary basic zinc electrode material | |
| CN116053445A (en) | High-voltage P2 type layered positive electrode material and application thereof in sodium ion battery | |
| CN1274038C (en) | Method for preparing low-temperature semi-solid phase of lithium ion battery positive material | |
| CN1279641C (en) | Alkaline primary battery positive electrode material and preparation method of positive electrode thereof | |
| CN113461064B (en) | High-capacity cathode material nano Li 1.3 Mn 0.4 Ti 0.3 O 2 Preparation method of (1) | |
| CN113241432B (en) | ZnO/Bi 2 O 3 Preparation method of composite material and application of composite material in nickel-zinc battery | |
| CN1765732A (en) | Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction | |
| CN1397498A (en) | Process for preparing calcium zincate as negative electrode material of secondary ZnNi battery | |
| CN113772747A (en) | Cobalt-free lithium-rich material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |