CN111261953A - Electrolyte of high-specific-energy zinc-nickel battery and preparation method thereof - Google Patents
Electrolyte of high-specific-energy zinc-nickel battery and preparation method thereof Download PDFInfo
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- CN111261953A CN111261953A CN201911227957.9A CN201911227957A CN111261953A CN 111261953 A CN111261953 A CN 111261953A CN 201911227957 A CN201911227957 A CN 201911227957A CN 111261953 A CN111261953 A CN 111261953A
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- electrolyte
- zinc
- nickel battery
- nickel
- battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011701 zinc Substances 0.000 abstract description 10
- 229910052725 zinc Inorganic materials 0.000 abstract description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- 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 relates to the technical field of zinc-nickel batteries, and provides an electrolyte of a high-specific-energy zinc-nickel battery and a preparation method thereof, aiming at solving the problems that the active substance of the positive electrode of the existing high-specific-energy zinc-nickel battery is softened and falls off and the zinc electrode is self-dissolved in the circulating process to cause deformation, passivation and dendrite of the zinc electrode, wherein the electrolyte of the high-specific-energy zinc-nickel battery comprises the following components in percentage by mass: 15-35% of alkali, 1.5-3.5% of additive, 1-4% of silica sol and the balance of water. The electrolyte has high utilization rate, and the added silica sol colloid electrolyte can effectively prevent the zincate from layering, so that the battery is stable in charging and discharging: the starting performance and the deep discharge resistance are well improved; the growth of crystals is also inhibited, and the cycle life of the battery is prolonged; the preparation method has simple steps, has no special requirements on equipment and is easy for industrialization.
Description
Technical Field
The invention relates to the technical field of zinc-nickel batteries, in particular to an electrolyte of a zinc-nickel battery with high specific energy and a preparation method thereof.
Background
At present, the market in the field of domestic lead-acid storage batteries is applied to power supplies for automobile starting, communication and the like, the lead-acid storage batteries have obvious competitiveness, but with the research and development and application of new secondary power supplies (such as lithium batteries) in recent years, the lead-acid storage batteries have the defects of low specific energy density, low utilization rate of active substances, poor high-rate discharge performance, short cycle life and the like, and particularly, the fully hybrid plug-in hybrid vehicles provide more strict standards for the energy of the batteries and become the largest restriction factor entering the electric automobile market.
Compared with lithium batteries and lead-acid batteries, the zinc-nickel batteries have obvious advantages in the aspects of specific energy, environmental protection and the like, and compared with lithium batteries, the zinc-nickel batteries have outstanding use safety, low-temperature performance, recyclability and cost performance, so that the research and development of the series of batteries have great attraction, and particularly, the battery capacity attenuation is less during heavy current discharge, and the zinc-nickel batteries are secondary batteries capable of being recycled. But the limited cycle times are the biggest obstacles to the development of high specific energy iron batteries.
Chinese patent literature discloses 'electrolyte for rechargeable zinc-nickel battery, zinc-nickel battery and preparation method thereof', the application publication number of which is CN105304946A, the electrolyte for zinc-nickel battery of the invention can greatly reduce the dissolution of zinc electrode, greatly improve the cycle performance of zinc-nickel battery, and the cycle performance of zinc-nickel battery using the electrolyte for zinc-nickel battery of the invention exceeds 1000 times. However, in the zinc-nickel battery of the invention, the problems of deformation, passivation, dendrite and the like of the zinc electrode caused by self-dissolution of the zinc electrode in the circulation process of the zinc electrode further cause the consistency problem of the battery.
Disclosure of Invention
The invention provides the electrolyte of the high-specific-energy zinc-nickel battery, aiming at overcoming the problems of deformation, passivation and dendrite of a zinc electrode caused by softening and dropping of an active substance of the positive electrode of the conventional high-specific-energy zinc-nickel battery and self-dissolution of the zinc electrode in the circulating process, and realizing the improvement of the cycle life of the high-specific-energy zinc-nickel battery.
The invention also provides a preparation method of the electrolyte of the high-specific-energy zinc-nickel battery, which has simple steps, has no special requirements on equipment and is easy to industrialize.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrolyte of the high-specific-energy zinc-nickel battery comprises the following components in percentage by mass: 15-35% of alkali, 1.5-3.5% of additive, 1-4% of silica sol and the balance of water.
Because the electrolyte in the zinc-nickel battery is dissolved with more zinc oxide, the electrolyte is easily inconsistent in concentration after being saturated by zincate, namely, the concentration of the zincate in the electrolyte at the bottom layer is higher, and the top is lower. Therefore, in the discharging process, the active substance on the top of the pole piece is easier to react, and after repeated charging and discharging, the active substance is easy to deposit on the middle lower part of the pole piece, so that the zinc negative pole is deformed.
The invention creatively adds silica sol into the electrolyte, and the adopted colloid forms a three-dimensional network structure by utilizing surface hydroxyl under the bridging action of zincate, thereby fixing the electrolyte and converting the electrolyte from a liquid state to a gel state. The silicasol colloid electrolyte can effectively prevent zincate layering, so that the battery is stable in charging and discharging: the starting performance and the deep discharge resistance are well improved; but also inhibits the growth of crystals and prolongs the cycle life of the battery. Alkali liquor is added to replace simple substances and the like which are adsorbed on the surfaces of the particles, so that the particles are prevented from growing and coalescing, the utilization rate of electrode active substances is improved, the simple substances can also prevent electrode expansion, the reversibility of electrode reaction is improved, oxygen evolution polarization in the electrode charging process is enhanced, the cycle life of the electrode is prolonged, and the like.
Preferably, the base is selected from KOH, NaOH, LiOH, Mg (OH)2、Al(OH)2、Ca(OH)2One or more of them.
The electrolyte concentration is too high, the conductivity is good, the utilization rate of the positive electrode and the negative electrode is easily improved, the self-corrosion behavior of the zinc electrode can be increased, if the electrolyte concentration is too low, the dissolution process of zinc oxide can be reduced, but the conductivity of the electrolyte is poor, so that the positive electrode and the negative electrode cannot fully react, the electrolyte concentration is reduced, in order to ensure that the positive electrode and the negative electrode fully react, the ion electrolysis degree of the electrolyte is increased by adding other alkali liquor, and the utilization rate of the electrolyte is improved.
Preferably, the additive is zinc oxide or lead oxide.
Preferably, the colloidal particles of the silica sol have a particle diameter of 10 to 20 nm. The surface hydroxyl of the silica sol colloid in the particle size range rapidly forms a three-dimensional network structure under the bridging action of zincate, and the electrolyte is fixed and rapidly converted into a gel state from a liquid state.
A preparation method of electrolyte of a high specific energy zinc-nickel battery comprises the following steps:
(1) weighing the raw materials according to the proportion, adding alkali into water, heating, stirring and dissolving to obtain alkali liquor;
(2) and adding an additive and silica sol into the alkali liquor, uniformly stirring, and performing water bath ultrasonic treatment to obtain the electrolyte of the zinc-nickel battery with high specific energy.
Preferably, in the step (1), the temperature for heating and dissolving is 50 to 75 ℃.
Preferably, in the step (1), the stirring rate is controlled to be 120 to 200 rmp.
Preferably, in the step (2), the temperature of the water bath is 45-65 ℃.
Preferably, in the step (2), the ultrasonic frequency is 40-60 KHZ; the ultrasonic time is 0.5-6 h. In the ultrasonic frequency range, the dissolved electrolyte can be ensured to fully enter the gaps of the condensed silica sol particles, and the high-speed and effective electron conduction rate in the reaction is ensured.
Preferably, in the steps (1) and (2), feeding is carried out in a batch feeding mode, and the batch feeding ensures sufficient dissolution of the raw materials and stability of the electrolyte.
Therefore, the invention has the following beneficial effects:
(1) the high-specific-energy zinc-nickel battery has high utilization rate of the electrolyte, and the addition of the silica sol colloid electrolyte can effectively prevent the zincate from layering, so that the battery is stable in charging and discharging: the starting performance and the deep discharge resistance are well improved; the growth of crystals is also inhibited, and the cycle life of the battery is prolonged;
(2) the preparation method has simple steps, has no special requirements on equipment and is easy for industrialization.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Weighing raw materials according to the following mixture ratio, 35 percent of KOH, 1.5 percent of zinc oxide, 1 percent of silica sol with the particle size of 10nm of colloidal particles and the balance of water, wherein the sum of the components is 100 percent; adding alkali into water, heating at 50 ℃, and stirring at 200rmp for dissolving to obtain a KOH solution;
(2) adding zinc oxide and silica sol into KOH solution, stirring uniformly, and performing ultrasonic treatment for 0.5h at the frequency of 60KHZ in a water bath at the temperature of 45 ℃ to obtain the electrolyte of the zinc-nickel battery with high specific energy.
Example 2
(1) Weighing raw materials according to the following mixture ratio, 10% of KOH, 5% of NaOH, 3.5% of lead oxide, 4% of silica sol with the particle size of 20nm of colloidal particles and the balance of water, wherein the sum of the components is 100%; adding alkali into water, heating at 75 deg.C, stirring at 120rmp for dissolving to obtain alkali solution;
(2) adding lead oxide and silica sol into alkali liquor in batches, stirring uniformly, and performing ultrasonic treatment for 6 hours at the frequency of 40KHZ in a water bath at the temperature of 65 ℃ to obtain the electrolyte of the zinc-nickel battery with high specific energy.
Example 3
(1) Weighing the raw materials in the following proportion, Mg (OH)220％、Al(OH)25％、Ca(OH)25 percent of zinc oxide, 2 percent of silica sol with the grain diameter of 15nm, and the balance of water, wherein the sum of all the components is 100 percent; adding alkali into water for 3 times, heating at 60 deg.C, stirring at 150rmp for dissolving to obtain alkali solution;
(2) adding zinc oxide and silica sol into alkali liquor, stirring uniformly, and performing ultrasonic treatment for 2h at the frequency of 30KHZ in a water bath at 50 ℃ to obtain the electrolyte of the high-specific-energy zinc-nickel battery.
Comparative example
The electrolyte for the zinc-nickel battery of the comparative example comprises the following components in percentage by weight: 30% of potassium hydroxide, 2% of sodium phosphate and 15% of potassium borate; the balance being water.
The electrolytes of examples 1 to 3 and comparative example were used to prepare zinc-nickel batteries, and the cycle life of the zinc-nickel batteries was measured, and the results are shown in table 1:
TABLE 1 test results
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The electrolyte of the high-specific-energy zinc-nickel battery is characterized by comprising the following components in percentage by mass: 15-35% of alkali, 1.5-3.5% of additive, 1-4% of silica sol and the balance of water.
2. The electrolyte for a high specific energy zinc-nickel battery of claim 1, wherein the base is selected from KOH, NaOH, LiOH, Mg (OH)2、Al(OH)2、Ca(OH)2One or more of them.
3. The electrolyte for a high specific energy zinc-nickel battery of claim 1, wherein the additive is zinc oxide or lead oxide.
4. The electrolyte of a high specific energy zinc-nickel battery according to claim 1, wherein the colloidal particles of the silica sol have a particle size of 10 to 20 nm.
5. A method for preparing the electrolyte of a high specific energy zinc-nickel battery according to any one of claims 1 to 4, comprising the steps of:
(1) weighing the raw materials according to the proportion, adding alkali into water, heating, stirring and dissolving to obtain alkali liquor;
(2) and adding an additive and silica sol into the alkali liquor, uniformly stirring, and performing water bath ultrasonic treatment to obtain the electrolyte of the zinc-nickel battery with high specific energy.
6. The method for preparing the electrolyte of the high specific energy zinc-nickel battery according to claim 5, wherein the temperature for heating and dissolving in the step (1) is 50-75 ℃.
7. The method for preparing the electrolyte of the high specific energy zinc-nickel battery according to claim 5, wherein in the step (1), the stirring rate is controlled to be 120-200 rmp.
8. The method for preparing the electrolyte of the high-specific-energy zinc-nickel battery according to claim 5, wherein the water bath temperature in the step (2) is 45-65 ℃.
9. The method for preparing the electrolyte of the high-specific-energy zinc-nickel battery according to claim 5, wherein in the step (2), the ultrasonic frequency is 40-60 KHZ; the ultrasonic time is 0.5-6 h.
10. The method for preparing the electrolyte of the high specific energy zinc-nickel battery according to claim 5, wherein the feeding in steps (1) and (2) is performed in a batch feeding manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911227957.9A CN111261953A (en) | 2019-12-04 | 2019-12-04 | Electrolyte of high-specific-energy zinc-nickel battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911227957.9A CN111261953A (en) | 2019-12-04 | 2019-12-04 | Electrolyte of high-specific-energy zinc-nickel battery and preparation method thereof |
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| CN111261953A true CN111261953A (en) | 2020-06-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201911227957.9A Pending CN111261953A (en) | 2019-12-04 | 2019-12-04 | Electrolyte of high-specific-energy zinc-nickel battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113054262A (en) * | 2021-03-12 | 2021-06-29 | 湖南源达新材料有限公司 | Hydrogel electrolyte for zinc-nickel battery, zinc-nickel battery and preparation method |
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Application publication date: 20200609 |