CN116581437A - Quasi-solid electrolyte for air battery and preparation method and application thereof - Google Patents

Quasi-solid electrolyte for air battery and preparation method and application thereof Download PDF

Info

Publication number
CN116581437A
CN116581437A CN202310317490.7A CN202310317490A CN116581437A CN 116581437 A CN116581437 A CN 116581437A CN 202310317490 A CN202310317490 A CN 202310317490A CN 116581437 A CN116581437 A CN 116581437A
Authority
CN
China
Prior art keywords
quasi
electrolyte
solid electrolyte
air battery
aluminum
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
Application number
CN202310317490.7A
Other languages
Chinese (zh)
Inventor
唐有根
吕超南
王海燕
李熠鑫
朱元鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202310317490.7A priority Critical patent/CN116581437A/en
Publication of CN116581437A publication Critical patent/CN116581437A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M2300/0091—Composites in the form of mixtures
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention discloses an air battery quasi-solid electrolyte, a preparation method and application thereof. The quasi-solid electrolyte of the air battery comprises an alkali solution and clay, so that the self-corrosion of the anode is greatly inhibited, and meanwhile, the ionic conductivity is kept high, and the stability is high. The aluminum-air battery adopting the electrolyte has the advantages of obviously reduced corrosion inhibition rate, high specific capacity, high energy density, long service life and the like. The preparation method is simple, low in cost and suitable for industrial production.

Description

Quasi-solid electrolyte for air battery and preparation method and application thereof
Technical Field
The invention relates to a battery electrolyte, in particular to an air battery quasi-solid electrolyte, a preparation method and application thereof, and belongs to the technical field of batteries.
Background
Metal-air batteries have received increasing attention to their higher theoretical energy density using oxygen in the air as the cathode active material. Among various metal-air (metals such as aluminum, zinc, magnesium, etc.), the theoretical specific capacity of an aluminum-air battery (2.98 Ahg -1 ) Is far greater than the theoretical specific capacity (0.82 Ah -1 ) And theoretical specific capacity of magnesium air cell (2.20 Ahg -1 ) And is combined withAnd aluminum resources are abundant, the price is low, and more researches are carried out. Aluminum air cells typically utilize a strong alkaline solution (KOH or NaOH) as the electrolyte to remove passivation layers from the aluminum surface and improve the electrochemical performance of the cell. However, aluminum anodes are severely self-corroding in alkaline electrolytes, producing large amounts of hydrogen and shortening battery life. In addition, the liquid electrolyte has a series of problems such as leakage, difficult storage, and the like.
The aluminum alloy anode material for the air battery provided by the Chinese patent application publication No. CN109461942A is added with magnesium, zinc, indium, gallium and antimony on the basis of aluminum, so that the self-corrosion rate of the aluminum anode material is reduced and the electrochemical performance of the aluminum anode material is improved in terms of alloying. However, the corrosion inhibition effect of the aluminum alloy anode in the pure alkali solution is still not ideal. An alkaline aqueous electrolyte for an aluminum-air battery and application thereof are disclosed in Chinese patent application publication No. CN111463524A, wherein the electrolyte is a high-concentration potassium acetate potassium hydroxide solution, the composite electrolyte obviously inhibits corrosion of an aluminum anode, and simultaneously, the polarization of the battery is greatly increased, so that the voltage of the battery is reduced. Therefore, the development of a novel electrolyte which is low in cost, environment-friendly and low in polarization is the focus of the next research.
Disclosure of Invention
Aiming at the defects of high corrosiveness, unstable performance, short service life and the like of the electrode in the prior art, the first aim of the invention is to provide an air battery quasi-solid electrolyte. The electrolyte has excellent corrosion inhibition effect on the electrode, can effectively reduce anode corrosion, and has high ionic conductivity and strong stability.
The second object of the invention is to provide a method for preparing the quasi-solid electrolyte of the air battery. The method is simple, has easily available raw materials and low cost, and is suitable for industrial mass production.
A third object of the present invention is to provide an application of a quasi-solid electrolyte for an air battery. When the electrolyte is applied to the aluminum air battery, the corrosion inhibition rate of the aluminum electrode can be obviously reduced, the aluminum air battery has higher specific capacity, and the comprehensive performance of the aluminum air battery is improved.
In order to achieve the technical purpose, the invention provides an air battery quasi-solid electrolyte which comprises an alkali solution and clay.
The clay added in the invention contains oxygen and hydrogen groups, can form hydrogen bonds with water molecules, effectively inhibit the activity of the water molecules, increase the activation energy of hydrogen evolution reaction, greatly reduce the self-corrosion of the battery anode, and under the action of an electric field, cations in the electrolyte migrate in a jump-type movement mode between adsorption sites, thereby forming a rapid ion channel between clay layers, so that the quasi-solid electrolyte can still maintain higher ion conductivity while inhibiting the anode corrosion. In addition, the rich hydrophilic groups in the clay enable the clay to have excellent compatibility with the aqueous solution, so that the quasi-solid electrolyte is formed, and the problem of electrolyte leakage is solved.
As a preferred embodiment, the clay includes at least one of kaolin, hydrotalcite, and montmorillonite. More preferably, the clay is kaolin. The kaolin has the characteristics of rich content, low price, environmental friendliness and stable structure.
As a preferable embodiment, the clay is contained in the electrolyte in an amount of 5 to 70wt%, more preferably 10 to 60wt%. The control of the clay content in a proper range is beneficial to obtaining electrolyte with excellent performance, when the clay content is too low, quasi-solid state cannot be effectively formed, flowing solution still exists in the electrolyte, and the corrosion inhibition effect is limited; when the clay content is too high, it cannot completely interact with the solution and is in powder form.
As a preferable scheme, the content of the clay in the electrolyte is 30-50 wt%.
As a preferred embodiment, the alkali in the alkaline solution is an alkali metal hydroxide.
As a preferred embodiment, the alkali metal hydroxide comprises at least one of KOH, naOH, liOH.
As a preferable embodiment, the concentration of the alkali solution is 1 to 7mol/L. Controlling the concentration of the alkaline solution in a reasonable range is beneficial to improving the electrochemical performance of the electrolyte, the requirement of high capacity and high energy density cannot be met if the concentration of the alkaline solution is too low, and anode corrosion is accelerated to a certain extent if the concentration of the alkaline solution is too high, so that the service life of the battery is relatively reduced.
As a preferable embodiment, the concentration of the alkali solution is 4 to 6mol/L. The quasi-solid electrolyte with excellent performance can be obtained by adopting the concentration of the alkali solution.
The invention also provides a preparation method of the quasi-solid electrolyte of the air battery, which is obtained by mixing and stirring the alkali solution and clay.
As a preferable scheme, the mixing and stirring process is as follows: stirring for 5-20 min at room temperature.
The invention also provides application of the quasi-solid electrolyte of the air battery, which is applied to the aluminum air battery. The corrosion inhibition rate of the aluminum anode of the aluminum air battery adopting the electrolyte is obviously reduced and can be as low as 0.036 mg.min -1 cm -2 Has higher specific capacity and energy density and good stability, wherein the specific capacity can reach 2763 mAh.g -1 The energy density can reach 4.56 KWh.kg -1 。
The action mechanism of the quasi-solid electrolyte in the aluminum-air battery is as follows: taking kaolin as an example, the kaolin with the required concentration has remarkable effect of inhibiting hydrogen evolution under alkaline conditions, and can homogenize the stripping of aluminum ions and stabilize discharge voltage. This is because the presence of kaolin reduces the reactivity of water molecules, making it difficult for equation (1) to proceed, while allowing equation (2) to occur uniformly on the surface of the aluminum anode.
2Al + 6H 2 O + 2OH - → 2Al(OH) 4 - + 3H 2 ↑ (1)
Al + 4OH - → Al(OH) 4ads + 4e - (2)
In the process, firstly, the kaolin contains rich silica, alumina and hydroxyl bonds, can absorb a large amount of water molecules, and forms hydrogen bonds with the water molecules to weaken the activity of the water molecules, so that the self-corrosion reaction of the aluminum anode is inhibited; secondly, the special electrolyte state is favorable for uniform stripping of aluminum ions so as to stabilize discharge voltage; again, the layered structure of kaolin provides a fast path for migration of metal cations, ensuring high ionic conductivity of the quasi-solid electrolyte and reducing battery polarization.
Compared with the prior art, the invention has the following beneficial effects:
(1) The clay is creatively added into the alkaline solution for the first time, so that the quasi-solid electrolyte has excellent corrosion inhibition effect, can effectively reduce the self-corrosion of the anode, and keeps high ion conductivity;
(2) The electrolyte has the advantages of simple preparation method, easily obtained raw materials, low cost, safety and environmental protection, and is suitable for industrial scale production;
(3) When the quasi-solid electrolyte is applied to an aluminum air battery, the problem of too fast hydrogen evolution corrosion of the aluminum air battery can be effectively controlled, the stability of the activity of the electrolyte is ensured, the energy density of the aluminum air battery is greatly improved, and the large-scale popularization and application are facilitated.
Drawings
FIG. 1 is a graph comparing corrosion rates of quasi-solid electrolytes of different concentrations.
Fig. 2 is a graph of discharge curves of aluminum air cells assembled with different concentrations of quasi-solid state electrolytes.
Detailed Description
Example 1
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 33wt%, and the concentration of the KOH aqueous solution is 4mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 4mol/L is prepared, 50g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 2
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 41 weight percent, and the concentration of the KOH aqueous solution is 4mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 4mol/L is prepared, 70g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 3
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 50wt%, and the concentration of the KOH aqueous solution is 4mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 4mol/L is prepared, and then 100g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 4
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 33wt%, and the concentration of the KOH aqueous solution is 6mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 6mol/L is prepared, 50g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 5
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 41 weight percent, and the concentration of the KOH aqueous solution is 6mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 6mol/L is prepared, 70g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 6
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and kaolin, wherein the content of the kaolin in the electrolyte is 50wt%, and the concentration of the KOH aqueous solution is 6mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 6mol/L is prepared, and then 100g of kaolin is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 7
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and hydrotalcite, wherein the content of the hydrotalcite in the electrolyte is 23wt%, and the concentration of the KOH aqueous solution is 4mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 4mol/L is prepared, 30g of hydrotalcite is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min to be uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 8
The quasi-solid electrolyte of the air battery comprises a KOH aqueous solution and hydrotalcite, wherein the content of the hydrotalcite in the electrolyte is 33 weight percent, and the concentration of the KOH aqueous solution is 4mol/L.
The preparation process of the battery electrolyte comprises the following steps: 100g of KOH aqueous solution with the concentration of 4mol/L is prepared, 50g of hydrotalcite is added into the KOH aqueous solution at normal temperature, and the mixture is magnetically stirred for 20min until the mixture is uniform.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 9
A quasi-solid electrolyte was prepared by the method of example 1, except that: the addition amount of kaolin was 2.1g, wherein the content of kaolin in the electrolyte was 2wt%.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Example 10
A quasi-solid electrolyte was prepared by the method of example 1, except that: the amount of kaolin added was 4.2g, wherein the content of kaolin in the electrolyte was 4wt%.
The quasi-solid electrolyte prepared in this example was used as an electrolyte for an aluminum air cell, and the electrochemical properties of the aluminum air cell were tested and are shown in table 1.
Comparative example 1
KOH solution with a concentration of 4mol/L was prepared as an electrolyte for an aluminum air cell and the electrochemical properties of the cell were tested and are shown in Table 1.
Comparative example 2
KOH solution with a concentration of 6mol/L was prepared as an electrolyte for an aluminum air cell and the electrochemical properties of the cell were tested and are shown in Table 1.
Testing corrosion rates of aluminum anodes in the electrolytes prepared in examples 1 to 6 and comparative examples 1 to 2 using hydrogen evolution, and testing open circuit voltages of aluminum anodes in the above electrolytes at room temperature at 20mAcm using an electrochemical workstation three electrode system -2 The full cell specific capacity at current density and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the self-corrosion rates of the anodes in the electrolytes of preferred examples 1 to 8 were 0.036 to 0.082, and the open circuit potentials were-1.49 to-1.76The specific discharge capacity is 1375-2763 mAh g -1 Compared with the comparative example data, the self-corrosion rate is greatly reduced, the open circuit potential is shifted negatively, and the specific discharge capacity is greatly increased. According to the test data, the mass content of clay is preferably 33% -50%, and the concentration range of alkali liquor is preferably 4-6 mol/L.

Claims (10)

1. An air battery quasi-solid electrolyte is characterized in that: comprises an alkaline solution and clay.
2. The quasi-solid electrolyte for an air cell of claim 1, wherein: the clay comprises at least one of kaolin, hydrotalcite and montmorillonite.
3. An air battery quasi-solid state electrolyte as claimed in claim 1 or 2, wherein: the clay content in the electrolyte is 5-70 wt%.
4. An air cell quasi-solid electrolyte as claimed in claim 3 wherein: the clay accounts for 30-50wt% of the electrolyte.
5. The quasi-solid electrolyte for an air cell of claim 1, wherein: the alkali in the alkali solution is alkali metal hydroxide.
6. The quasi-solid electrolyte for an air cell of claim 5, wherein: the alkali metal hydroxide includes at least one of KOH, naOH, liOH.
7. An air cell quasi-solid state electrolyte as defined in claim 1, 5 or 6, wherein: the concentration of the alkali solution is 1-7 mol/L.
8. The quasi-solid electrolyte for an air cell of claim 7, wherein: the concentration of the alkali solution is 4-6 mol/L.
9. The method for preparing the quasi-solid electrolyte of the air battery as claimed in claims 1 to 8, which is characterized in that: mixing and stirring the alkali solution and clay to obtain the product.
10. Use of an air battery quasi-solid electrolyte as claimed in claims 1 to 8, characterized in that: the method is applied to the aluminum air battery.
CN202310317490.7A 2023-03-29 2023-03-29 Quasi-solid electrolyte for air battery and preparation method and application thereof Pending CN116581437A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310317490.7A CN116581437A (en) 2023-03-29 2023-03-29 Quasi-solid electrolyte for air battery and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310317490.7A CN116581437A (en) 2023-03-29 2023-03-29 Quasi-solid electrolyte for air battery and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116581437A true CN116581437A (en) 2023-08-11

Family

ID=87536621

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310317490.7A Pending CN116581437A (en) 2023-03-29 2023-03-29 Quasi-solid electrolyte for air battery and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116581437A (en)

Similar Documents

Publication Publication Date Title
CN111463524B (en) Alkaline water-based electrolyte for aluminum-air battery and application thereof
US5108856A (en) Electrolyte compositions and methods
Wen et al. Preliminary study on zinc–air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction
CN110165340A (en) A kind of aluminium-air cell alkaline electrolyte and aluminium-air cell
JPH11500258A (en) Additives for primary electrochemical cells with manganese dioxide cathode
CZ294824B6 (en) Alkaline galvanic cell and process for producing thereof
CN113078331B (en) Electrolyte of hydrogen battery and application thereof
CN117855442A (en) Lithium battery anode lithium supplementing agent and preparation method and application thereof
Deutscher et al. Investigations on an aqueous lithium secondary cell
CN111509307A (en) Preparation method and application of inorganic colloidal electrolyte of water-based zinc ion battery
CN116581437A (en) Quasi-solid electrolyte for air battery and preparation method and application thereof
CN112234219B (en) Composite additive for alkaline zinc-air battery electrolyte, electrolyte and metal-air battery
CN115395144A (en) Alkaline electrolyte for aluminum-air battery and preparation method and application thereof
CN115133159A (en) Functional aqueous zinc ion battery electrolyte and preparation method and application thereof
CN110137631B (en) Composite corrosion inhibitor, alkaline electrolyte added with same and aluminum-air battery
CN111416139A (en) Electrolyte corrosion inhibitor, aluminum-air battery, alkaline electrolyte and preparation method thereof
CN113991218A (en) High-specific-capacity and high-power alkaline aluminum air battery electrolyte and preparation method thereof
Abrashev et al. Optimization of the bi-functional oxygen electrode (BOE) structure for application in a Zn-air accumulator
CN113249737A (en) Battery for producing hydrogen by metal
CN110233314A (en) Double electrolyte aluminium-air cells
KR102535066B1 (en) Electrolyte for aluminum air battery and method of fabricating the same
US2863789A (en) Electrolyte for an air-depolarized cell
CN116247312A (en) Water system sodium ion battery
CN103426635A (en) Method for manufacturing cathode current collector
CN117276759A (en) Electrolyte for inhibiting anode corrosion of aluminum air battery and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination