CN114551913A - Electrolyte for aluminum alloy anode material and slow release agent thereof - Google Patents
Electrolyte for aluminum alloy anode material and slow release agent thereof Download PDFInfo
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- CN114551913A CN114551913A CN202011343353.3A CN202011343353A CN114551913A CN 114551913 A CN114551913 A CN 114551913A CN 202011343353 A CN202011343353 A CN 202011343353A CN 114551913 A CN114551913 A CN 114551913A
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- electrolyte
- release agent
- aluminum alloy
- alloy anode
- slow release
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 239000011780 sodium chloride Substances 0.000 claims abstract description 21
- 229910020212 Na2SnO3 Inorganic materials 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 description 16
- 239000012730 sustained-release form Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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
-
- 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
- H01M2300/0088—Composites
-
- 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 an electrolyte for an aluminum alloy anode material and a slow release agent thereof, belonging to the field of metal-air batteries. The electrolyte system consists of a matrix component and a slow release agent. The matrix component is one or two of NaCl and KCl, and the concentration is 1-10%. The slow release agent is KOH, NaOH or Na2SnO3Or ZnO, and the total concentration range of the added ZnO is 0.05mol/L-2 mol/L. The electrolyte and the slow release agent thereof can effectively improve the product state of the aluminum alloy anode material in neutral electrolyte, and convert flocculent precipitates which are difficult to fall off into fine particles; the hydrogen evolution corrosion rate of the aluminum alloy anode is reduced, the service life of the aluminum alloy anode is prolonged, and the utilization rate of the anode is improved. On the other hand, the discharge voltage of the aluminum alloy anode in the electrolyte system is increased, and the electrochemical activity is enhanced. The electrolyte system has the advantages of low cost, high safety and simple operationGreen and environment-friendly, and has important significance for prolonging the service life of the battery and improving the discharge performance.
Description
Technical Field
The invention belongs to the field of metal air batteries, and particularly relates to an electrolyte for an aluminum alloy anode material and a sustained-release agent thereof.
Background
Aluminum as a battery anode material has the following unique advantages: (1) the electrochemical equivalent is high (2980Ah/kg), and high-power discharge can be provided; (2) the electrode potential is relatively negative, and the standard electrode potential is-1.66V vs. For the anode material, the electrode potential is about negative, which can provide a higher discharge voltage for the battery; (3) the resources are rich and the price is low; (4) aluminum is an amphoteric metal, can be applied to neutral and alkaline batteries, and has a wide application range. In conclusion, the aluminum alloy anode is a battery anode material with better application prospect.
In a neutral electrolyte system, the compact oxide film on the surface of the aluminum alloy anode causes the actual electrode potential to move forward compared with the theoretical electrode potential, and the polarization phenomenon of the battery is serious. In addition, the corrosion product of the aluminum alloy anode is flocculent Al (OH)3It is very difficult to peel off from the anode surface, and product accumulation is easily formed, which seriously reduces the service life of the battery.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide an electrolyte and a sustained release agent thereof, which can not only change the shape of an aluminum alloy anode product, but also improve the electrochemical activity thereof.
The technical scheme of the invention is as follows:
an electrolyte for an aluminum alloy anode material comprises a neutral matrix component and a slow release agent; the slow release agent is KOH, NaOH or Na2SnO3Or ZnO, and the total concentration range of the slow release agent is 0.05mol/L-2 mol/L.
Preferably, the slow release agent is at least one of KOH and NaOH and Na2SnO3And ZnO.
Preferably, the neutral matrix component is one or two of NaCl and KCl, and the specific concentration is as follows: the concentration range of NaCl in the matrix components is as follows: 1% -10%; the concentration range of KCl in the matrix composition is as follows: 0% -10%;
preferably, the addition range of KOH in the sustained-release agent is as follows: 0.05mol/L-1 mol/L; sustained release agentThe addition range of the medium NaOH is as follows: 0mol/L-0.5 mol/L; na in sustained release agent2SnO3The addition range of (A) is as follows: 0mol/L-0.3 mol/L; the adding range of ZnO in the sustained-release agent is as follows: 0mol/L-0.9 mol/L.
The change effect on the state of the aluminum alloy anode corrosion product is not obvious due to the excessively low content of the slow-release agent, and the anode polarization phenomenon is not obviously improved; the hydrogen evolution corrosion rate of the aluminum alloy anode can be greatly increased due to the excessively high content of the slow release agent, and the utilization rate of the anode is seriously reduced.
The preferable concentration of KOH in the sustained-release agent is as follows: 0.3mol/L-0.8 mol/L;
the preferable concentration of NaOH in the sustained-release agent is as follows: 0.1mol/L-0.3 mol/L;
na in the sustained-release agent2SnO3The preferred concentrations are: 0.05mo1/L-0.1 mol/L;
the preferable concentration of ZnO in the sustained-release agent is as follows: 0.01mol/L-0.2 mol/L.
The invention also provides a metal-air battery which comprises the electrolyte.
The specific reaction principle that the electrolyte slow-release agent can change the form of the aluminum alloy anode product is as follows:
Al(OH)3+OH-→AlO2 -+2H2O
adding KOH or NaOH, and further adding Na2SnO3Or ZnO can reduce the hydrogen evolution corrosion rate and improve the discharge voltage of the battery by depositing a tin layer or a zinc layer on the surface of the anode.
The invention changes the product form through the interaction of the electrolyte slow-release agent and the reaction product, and simultaneously improves the discharge performance of the aluminum alloy anode.
In conclusion, the electrolyte and the sustained-release agent thereof have the advantages of low cost, high safety, simple operation, environmental protection and the like, and have important significance for prolonging the service life of the battery and improving the discharge performance.
Drawings
FIG. 1 is a graph comparing the forms of corrosion products of aluminum alloy anode materials in the presence of electrolyte release agents (left) and in the absence of electrolyte release agents (right).
Detailed Description
Comparative example 1
The electrolyte was 3.5% NaCl.
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Comparative example 2
The electrolyte is 2% NaCl and 1% KCl.
The utilization rate and specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Comparative example 3
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.01mol/L NaOH.
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 1
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.5mol/L KOH.
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 2
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.6mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 3
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.8 mol/LZnO.
The utilization rate and specific energy of the aluminum alloy anode in the electrolyte and the current density are tested by utilizing electronic loadThe degree is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 4
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the sustained release agent is 0.1mol/LKOH, 0.1mol/LNaOH and 0.05mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 5
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the sustained release agent is 0.3mol/LKOH, 0.1mol/LNaOH and 0.05mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 6
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the sustained release agent is 0.3mol/LKOH, 0.2mol/LNaOH and 0.05mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 7
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.3mol/L KOH, 0.2mol/L NaOH and 0.1mol/L Na2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 8
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.7mol/L KOH, 0.2mol/L NaOH and 0.1mol/L Na2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 9
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the sustained release agent is 0.7mol/LKOH, 0.3mol/LNaOH and 0.05mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 10
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the sustained release agent is 0.7mol/LKOH, 0.5mol/LNaOH and 0.05mol/LNa2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 11
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.7mol/L KOH, 0.5mol/L NaOH and 0.2mol/L Na2SnO3。
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 12
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.9mol/L KOH, 0.2mol/L NaOH and 0.1mol/L Na2SnO3And 0.1mol/L ZnO.
The utilization rate and the specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and the current density is 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
Example 13
The electrolyte comprises the following components: the matrix component is 3.5% NaCl; the slow release agent is 0.9mol/L KOH, 0.2mol/L NaOH and 0.1mol/L Na2SnO3And 0.4mol/L ZnO.
The utilization rate and specific energy of the aluminum alloy anode in the electrolyte are tested by utilizing electronic load, and electricity is usedThe flow density was 1mA/cm2The cut-off voltage was 0.3V, and the results are shown in Table 1.
TABLE 1 test results of aluminum alloy anode material properties
Claims (7)
1. The electrolyte for the aluminum alloy anode material is characterized by comprising a neutral matrix component and a slow release agent; the slow release agent is KOH, NaOH or Na2SnO3Or one or more of ZnO; the total concentration range of the slow release agent is 0.05mol/L-2 mol/L.
2. The electrolyte of claim 1, wherein the slow release agent is at least one of KOH and NaOH, and Na2SnO3And ZnO.
3. The electrolyte of claim 1, wherein the KOH is added in a range of 0.05mol/L to 1 mol/L; the addition range of the NaOH is 0mol/L-0.5 mol/L; the Na is2SnO3The addition range of (A) is 0mol/L-0.3 mol/L; the addition range of the ZnO is 0mol/L-0.9 mol/L.
4. The electrolyte of claim 3, wherein the KOH is added in a range of 0.3mol/L to 0.8 mol/L; the addition range of the NaOH is 0.1-0.3 mol/L; the Na is2SnO3The adding range is 0.05mol/L-0.1 mol/L; the addition range of the ZnO is 0.01mol/L-0.2 mol/L.
5. The electrolyte of claim 1, wherein the neutral matrix component is one or both of NaCl and KCl.
6. The electrolyte of claim 5, wherein the mass concentration of NaCl ranges from 1% to 10%; the mass concentration range of the KCl is 0-10%.
7. A metal-air battery, characterized in that it comprises the electrolyte of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011343353.3A CN114551913A (en) | 2020-11-25 | 2020-11-25 | Electrolyte for aluminum alloy anode material and slow release agent thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011343353.3A CN114551913A (en) | 2020-11-25 | 2020-11-25 | Electrolyte for aluminum alloy anode material and slow release agent thereof |
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| CN114551913A true CN114551913A (en) | 2022-05-27 |
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Citations (6)
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|---|---|---|---|---|
| CN1040287A (en) * | 1988-08-09 | 1990-03-07 | 艾尔坎国际有限公司 | Aluminum cell |
| CN103633396A (en) * | 2013-07-31 | 2014-03-12 | 河南科技大学 | Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method |
| CN105140594A (en) * | 2015-08-17 | 2015-12-09 | 上海电力学院 | Composite additive of aluminum-air battery electrolyte and preparation method of composite additive |
| JP2017054738A (en) * | 2015-09-10 | 2017-03-16 | トヨタ自動車株式会社 | Electrolytic solution for metal air battery, and metal air battery |
| CN106887650A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of aluminium-air cell electrolyte and its preparation |
| CN107460518A (en) * | 2017-06-22 | 2017-12-12 | 浙江工业职业技术学院 | A kind of metal nano ceramic coating preparation method |
-
2020
- 2020-11-25 CN CN202011343353.3A patent/CN114551913A/en active Pending
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|---|---|---|---|---|
| CN1040287A (en) * | 1988-08-09 | 1990-03-07 | 艾尔坎国际有限公司 | Aluminum cell |
| CN103633396A (en) * | 2013-07-31 | 2014-03-12 | 河南科技大学 | Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method |
| CN105140594A (en) * | 2015-08-17 | 2015-12-09 | 上海电力学院 | Composite additive of aluminum-air battery electrolyte and preparation method of composite additive |
| JP2017054738A (en) * | 2015-09-10 | 2017-03-16 | トヨタ自動車株式会社 | Electrolytic solution for metal air battery, and metal air battery |
| CN106887650A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of aluminium-air cell electrolyte and its preparation |
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