CN113594559A - Electrolyte, preparation method thereof and aluminum ion battery - Google Patents

Electrolyte, preparation method thereof and aluminum ion battery Download PDF

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CN113594559A
CN113594559A CN202110872165.8A CN202110872165A CN113594559A CN 113594559 A CN113594559 A CN 113594559A CN 202110872165 A CN202110872165 A CN 202110872165A CN 113594559 A CN113594559 A CN 113594559A
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electrolyte
aluminum
hydrogen bond
ion battery
bond acceptor
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CN113594559B (en
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付超鹏
蒙鹏宇
张佼
孙宝德
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2300/0005—Acid 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
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Abstract

An electrolyte, a preparation method thereof and an aluminum ion battery belong to the technical field of electrochemistry. The electrolyte comprises a eutectic system formed by mixing hydrated aluminum salt and a hydrogen bond acceptor, wherein the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 4-20, and the hydrogen bond acceptor contains C-O, N-O.OCH and OCH3C ═ S, and — CN. The electrolyte can solve the problems that the existing electrolyte has serious corrosivity and humidity sensitivity, and is used for an aluminum ion battery to enable the aluminum ion battery to have better capacity and cycle performance.

Description

Electrolyte, preparation method thereof and aluminum ion battery
Technical Field
The application relates to the technical field of electrochemistry, in particular to an electrolyte, a preparation method thereof and an aluminum ion battery.
Background
Aluminum metal is a low-cost, high-energy-density carrier, so that an electrochemical energy storage device based on aluminum metal has great potential in the field of large-scale energy storage, and can meet the ever-increasing energy storage and conversion requirements. At present, the aluminum-based electrochemical energy storage devices mainly comprise two types, one type is a chargeable aluminum ion battery, the other type is an aluminum air battery, and most of the chargeable aluminum ion batteries use acidic room-temperature non-aqueous ionic liquid (AlCl)3/[EMIm]Cl) as an electrolyte, which is highly corrosive and moisture sensitive.
Disclosure of Invention
The application provides an electrolyte, a preparation method thereof and an aluminum ion battery, wherein the electrolyte can solve the problems that the existing electrolyte has serious corrosivity and humidity sensitivity, and is used for the aluminum ion battery so that the aluminum ion battery has higher discharge capacity and better cycle performance.
The embodiment of the application is realized as follows:
in a first aspect, an embodiment of the present application provides an electrolyte, which includes a eutectic system formed by mixing a hydrated aluminum salt and a hydrogen bond acceptor, wherein a molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 4-20, and the hydrogen bond acceptor contains C-O, N-O, OCH3C ═ S, and — CN.
In a second aspect, an embodiment of the present application provides a method for preparing an electrolyte, including:
and mixing the hydrated aluminum salt and the hydrogen bond acceptor to obtain the electrolyte.
In a third aspect, embodiments of the present application provide an aluminum ion battery, which includes a positive electrode tab, a negative electrode tab, and the electrolyte solution of the first aspect.
The electrolyte, the preparation method thereof and the aluminum ion battery have the beneficial effects that:
the hydrated aluminum salt contains crystal water, and under the action of the crystal water, aluminum ions and C (O, N-O), OCH3Functional groups such as C, S and CN are easy to form hydrogen bonds, so that Gibbs free energy of the whole system is reduced, and the melting point of the whole system is reduced; at the same time, C is O, N-O, OCH3Functional groups such as C ═ S and — CN are also liable to undergo self-correlation intermolecular interaction by hydrogen bond and ionic bond, lowering the melting point of the whole system, and forming a eutectic system which is liquid at ordinary temperature. In addition, the hydration caused by the crystal water in the hydrated aluminum salt can reduce the viscosity of the eutectic system and improve the ionic conductivity of the whole system, and the eutectic system formed when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 4-20 is suitable for useUsed as an electrolyte. The electrolyte has less risk of corroding the shell of the aluminum ion battery and has no humidity sensitivity. In addition, the electrolyte aluminum is used for the ion battery, so that the aluminum ion battery has higher discharge capacity and better cycle performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a graph showing a cycle performance test of an aluminum ion battery according to example 1 of the present application;
fig. 2 is a graph showing a cycle performance test of the aluminum ion battery according to example 2 of the present application;
fig. 3 is a cycle performance test chart of the aluminum ion battery of example 6 of the present application;
FIG. 4 shows the aluminum ion battery of example 3 of the present application in 0.1Ag-1The first-turn charge-discharge curve diagram under the current density;
FIG. 5 shows the aluminum ion battery of example 4 of the present application in 0.1Ag-1The first-turn charge-discharge curve diagram under the current density;
FIG. 6 shows the aluminum ion battery of example 7 of the present application in 0.1Ag-1The first-turn charge-discharge curve diagram under the current density;
FIG. 7 shows the aluminum ion battery of example 8 of the present application in 0.1Ag-1The first-turn charge-discharge curve diagram under the current density;
fig. 8 is a graph showing a rate capability test of the aluminum ion battery of example 5 of the present application;
FIG. 9 is a thermogravimetric analysis plot of the electrolyte of example 1 of the present application;
FIG. 10 is a thermogravimetric analysis plot of the electrolyte of example 9 of the present application;
FIG. 11 is a thermogravimetric analysis plot of the electrolyte of example 10 of the present application;
FIG. 12 is a thermogravimetric analysis plot of the electrolyte of example 11 of the present application;
FIG. 13 is a graph showing a comparison between the total amount of water and the amount of free water in the electrolytes of examples 1, 9 to 11 of the present application;
FIG. 14 is a graph showing the results of tests on ionic conductivity and density of the electrolyte solutions of examples 1 and 9 to 12 of the present application;
fig. 15 shows the results of melting point tests of the eutectic electrolyte solutions of examples 1 and 9 to 12;
fig. 16 is a graph showing the results of a capacity test of the aluminum-ion battery of comparative example 1 of the present application at different numbers of cycles;
fig. 17 is a graph showing the results of a capacity test of the aluminum-ion battery of comparative example 2 of the present application at different numbers of cycles.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
At present, the aluminum-based electrochemical energy storage devices mainly comprise two types, one type is a chargeable aluminum ion battery, the other type is an aluminum air battery, and most of the chargeable aluminum ion batteries use acidic room-temperature non-aqueous ionic liquid (AlCl)3/[EMIm]Cl) as an electrolyte, and the electrolyte has serious corrosivity and humidity sensitivity and has strong corrosion effect on metal utensils such as stainless steel battery shells and the like.
Recently, eutectic fluxes having electrochemical properties similar to those of ionic liquids have attracted increasing attention in metal-based batteries, but not all of them are suitable for use as electrolytes for aluminum-ion batteries, and some of them do not contribute to good electrical properties of aluminum-ion batteries when used as electrolytes for aluminum-ion batteries.
The embodiment of the application provides an electrolyte, a preparation method thereof and an aluminum ion battery, wherein the electrolyte can solve the problems that the existing electrolyte has serious corrosivity and humidity sensitivity, and is used for the aluminum ion battery so that the aluminum ion battery has higher discharge capacity and better cycle performance.
The electrolyte, the preparation method thereof and the aluminum ion battery of the embodiment of the application are specifically described as follows:
in a first aspect, an embodiment of the present application provides an electrolyte, which includes a eutectic system formed by mixing a hydrated aluminum salt and a hydrogen bond acceptor, wherein a molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 4-20, and the hydrogen bond acceptor contains C-O, N-O, OCH3C ═ S, and — CN.
The hydrated aluminum salt contains crystal water, and under the action of the crystal water, aluminum ions and C (O, N-O), OCH3Functional groups such as C ═ S and — CN are likely to form hydrogen bonds, and decrease gibbs free energy of the entire system, thereby decreasing the melting point of the entire system. Among them, the inventors of the present application found in their studies that if a hydrated aluminum salt is replaced with a general aluminum salt, the aluminum salt and the above hydrogen bond acceptor cannot form a eutectic system.
At the same time, C is O, N-O, OCH3Functional groups such as C ═ S and — CN are also liable to undergo self-correlation intermolecular interaction by hydrogen bond and ionic bond, lowering the melting point of the whole system, and forming a eutectic system which is liquid at ordinary temperature. In addition, the hydration caused by the crystal water in the hydrated aluminum salt can reduce the viscosity of the eutectic system and improve the ionic conductivity of the whole system, and the eutectic system formed when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 4-20 is suitable for being used as an electrolyte.
The electrolyte disclosed by the embodiment of the application has less risk of corroding the shell of the aluminum ion battery and does not have humidity sensitivity. In addition, the electrolyte aluminum is used for the ion battery, so that the aluminum ion battery has higher discharge capacity and better cycle performance.
In some embodiments, the hydrogen bond acceptor comprises at least one of urea, N-methylurea, ethylurea, tetramethylpiperidine oxide, 4-methoxy-tetramethylpiperidine oxyl, succinonitrile, and thiourea.
Wherein urea, N-methylurea and ethylurea each contain a C ═ O functional group, tetramethylpiperidine oxide contains an N-O functional group, and 4-methoxy-tetramethylpiperidine oxyl contains N-O and OCH3The functional group, succinonitrile contains a-CN functional group, and thiourea contains a C ═ S functional group.
In some embodiments, the hydrated aluminum salt comprises at least one of aluminum chloride hexahydrate, aluminum perchlorate nonahydrate, aluminum nitrate nonahydrate, and aluminum sulfate octadecahydrate.
In some embodiments, the hydrated aluminum salt and the hydrogen bond acceptor are present in a molar ratio of 1:8 to 20.
The ratio of the hydrated aluminum salt to the hydrogen bond acceptor influences the conductivity and viscosity of the electrolyte, the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 8-20, the electrolyte can be guaranteed to have high conductivity, and the electrolyte has low density so that the transmission speed of aluminum ions in the electrolyte is high. Illustratively, the molar ratio of hydrated aluminum salt to hydrogen bond acceptor is in a range between any or any of 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, and 1: 20.
Further, the inventor of the present application found in research that the main existence form of water molecules in the eutectic system of the electrolyte can be controlled by controlling the ratio of the hydrated aluminum salt and the hydrogen bond acceptor, and in some possible embodiments, the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 8-12. Within this molar ratio range, the hydrated aluminum salt and the hydrogen bond acceptor enable water molecules in the eutectic system of the electrolyte to be dominated by crystal water rather than by free water, which means that aluminum can achieve a deposition behavior in the electrolyte while reducing side reactions of hydrogen evolution.
In a second aspect, an embodiment of the present application provides a method for preparing an electrolyte solution according to an embodiment of the first aspect, including: and mixing the hydrated aluminum salt and the hydrogen bond acceptor to obtain the electrolyte.
Hydrated aluminum salt is solid at normal temperature, a hydrogen bond acceptor is solid at normal temperature, after the hydrated aluminum salt and the hydrogen bond acceptor are mixed, under the bipolar action of crystal water of the hydrated aluminum salt, aluminum ions and functional groups of C-O, N-O, OCH3, C-S and-CN are easy to form hydrogen bonds, and Gibbs free energy of the whole system is reduced, so that the melting point of the whole system is reduced; meanwhile, functional groups of C-O, N-O, OCH3, C-S and-CN are easy to generate self-correlation intermolecular action through hydrogen bonds and ionic bonds, and the melting point of the whole system is reduced, so that a eutectic system is formed, and the eutectic system is liquid at normal temperature.
In some embodiments, the hydrated aluminum salt and the hydrogen bond acceptor are mixed and heated at a temperature of 60 ℃ to a predetermined temperature that is less than the boiling point of the hydrogen bond acceptor.
The formation of a eutectic system can be accelerated by mixing hydrated aluminum salt and a hydrogen bond acceptor and then heating the mixture.
Optionally, the heating time is 30-60 min, such as 30min, 40min, 45min, 50min or 60 min.
Further, when the hydrated aluminum salt and the hydrogen bond acceptor are mixed and stirred, the stirring process is beneficial to fully and uniformly mixing the hydrated aluminum salt and the hydrogen bond acceptor, so that the aluminum ions of the hydrated aluminum salt and the hydrogen bond acceptor are bonded together through hydrogen bonds.
Optionally, the stirring time is 1-6 h, for example, any one of 1h, 2h, 3h, 4h, 5h and 6h or a range between any two.
In a third aspect, embodiments of the present application provide an aluminum ion battery, which includes a positive electrode tab, a negative electrode tab, and the electrolyte solution of the first aspect.
The electrolyte disclosed by the embodiment of the application has less risk of corroding the shell of the aluminum ion battery and does not have humidity sensitivity. In addition, the electrolyte aluminum is used for the ion battery, so that the aluminum ion battery has higher discharge capacity and better cycle performance.
The negative electrode material of the negative electrode plate comprises aluminum, and the negative electrode plate can be an aluminum foil or an aluminum alloy foil containing aluminum, for example, the aluminum alloy foil is an Al-Mg-Sn aluminum alloy foil.
Illustratively, the thickness of the negative electrode sheet is 1 to 300 μm, for example, 1 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, and 300 μm, or a range between any two.
In some embodiments, the positive electrode sheet includes a positive electrode material including at least one of vanadium pentoxide, manganese dioxide, molybdenum disulfide, polypyrrole, polythiophene, polyaniline, and graphite.
Vanadium pentoxide, manganese dioxide, molybdenum disulfide, polypyrrole, polythiophene, polyaniline and graphite can realize aluminum ion intercalation. The positive electrode material can be formed on the positive electrode current collector by a slurry coating method, a magnetron sputtering method, an electrodeposition method and the like, so as to obtain the positive electrode plate.
The electrolyte, the preparation method thereof and the aluminum ion battery of the present application are further described in detail with reference to the following examples.
Example 1
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum perchlorate nonahydrate and succinonitrile according to a molar ratio of 1:12, heating at 80 ℃ for 40min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 100 microns, and the positive material of the positive plate is V2O5The positive current collector is molybdenum foil, and the diaphragm uses a glass fiber filter membrane.
Example 2
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum nitrate nonahydrate and methylurea in a molar ratio of 1:4, heating at 60 ℃ for 30min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum alloy foil with the thickness of 10 microns, the positive material of the positive plate is polyaniline, the positive current collector is carbon paper, and the diaphragm is a glass fiber filter membrane.
Example 3
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum chloride hexahydrate and tetramethylpiperidine oxide in a molar ratio of 1:8, heating at 70 ℃ for 60min, naturally cooling to room temperature, and stirring for 6h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 300 microns, and the positive material of the positive plate is MnO2The positive current collector is titanium foil, and the diaphragm uses a glass fiber filter membrane.
Example 4
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum sulfate octadecahydrate and 4-methoxy-tetramethylpiperidine oxygen radical at a molar ratio of 1:12, heating at 85 ℃ for 45min, naturally cooling to room temperature, and stirring for 2h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 50 microns, the positive material of the positive plate is sulfur, the positive current collector is carbon cloth, and the diaphragm is a glass fiber filter membrane.
Example 5
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum perchlorate nonahydrate, aluminum sulfate octadecahydrate and 4-methoxy-tetramethylpiperidine oxygen radical according to the molar ratio of 1:1:12, heating at the temperature of 75 ℃ for 35min, then naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 50 microns, the positive material of the positive plate is polypyrrole, the positive current collector is carbon cloth, and the diaphragm is a glass fiber filter membrane.
Example 6
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum perchlorate nonahydrate, aluminum chloride hexahydrate and 4-methoxy-tetramethylpiperidine oxygen radical at a molar ratio of 0.5:1:12, heating at 75 ℃ for 35min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 50 microns, the positive material of the positive plate is polythiophene, the positive current collector is carbon paper, and the diaphragm is a glass fiber filter membrane.
Example 7
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum nitrate nonahydrate, aluminum sulfate octadecahydrate, aluminum chloride hexahydrate and dimethyl urea in a molar ratio of 0.3:0.1:0.6:20, heating at 60 ℃ for 40min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 50 microns, the positive material of the positive plate is polyaniline, the positive current collector is carbon cloth, and the diaphragm is a glass fiber filter membrane.
Example 8
The embodiment provides an electrolyte, which comprises the following preparation steps:
mixing aluminum nitrate nonahydrate, aluminum sulfate octadecahydrate, aluminum chloride hexahydrate, aluminum perchlorate nonahydrate and thiourea in a molar ratio of 0.3:0.1:0.3:0.3:18, heating at 80 ℃ for 30min, naturally cooling to room temperature, and stirring for 2h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 50 microns, the positive material of the positive plate is molybdenum disulfide, the positive current collector is a molybdenum foil, and the diaphragm uses a glass fiber filter membrane.
Examples 9 to 12
Examples 9 to 12 each provide an electrolyte solution, which was prepared in a different manner from example 1 only in the molar ratio of aluminum perchlorate nonahydrate to succinonitrile, and in examples 9 to 12, the molar ratios of aluminum perchlorate nonahydrate to succinonitrile were 1:20, 1:16, 1:8 and 1:4, respectively.
Comparative example 1
Mixing aluminum perchlorate nonahydrate and succinonitrile according to a molar ratio of 1:30, heating at 80 ℃ for 40min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 100 microns, and the positive material of the positive plate is V2O5The current collector is molybdenum foil, and the diaphragm uses a glass fiber filter membrane.
Comparative example 2
Mixing aluminum nitrate nonahydrate and dimethyl sulfone according to a molar ratio of 1:16, heating at 80 ℃ for 40min, naturally cooling to room temperature, and stirring for 3h to obtain the eutectic system electrolyte.
The embodiment also provides an aluminum ion battery, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte, wherein the negative plate is an aluminum foil with the thickness of 100 microns, and the positive material of the positive plate is V2O5The current collector is molybdenum foil, and the diaphragm uses a glass fiber filter membrane.
Test example 1
The cycle performance of the aluminum ion batteries of examples 1, 2 and 6 was measured, and the cycle test charts are shown in fig. 1 to 3.
As can be seen from FIG. 1, the first-turn reversible discharge capacity of the aluminum-ion battery of example 1 was 179mAh g-1(ii) a As can be seen from fig. 2, the first-turn reversible discharge capacity of the aluminum-ion battery of example 2 is 201mAh g-1(ii) a As can be seen from FIG. 3, the first-turn reversible discharge capacity of the aluminum-ion battery of example 6 is 183mAh g-1As can be seen from the cycle performance diagrams of fig. 1 to 3,the electrolyte used in the aluminum ion battery in the embodiments 1, 2 and 6 can make the aluminum ion battery have good cycle performance.
Test example 2
The aluminum ion batteries of example 3, example 4, example 7, and example 8 were tested at 0.1Ag-1The first-turn charge-discharge curves of the current density of (1) are shown in fig. 4 to 7, respectively.
As can be seen from fig. 4, the first-turn discharge capacity of the aluminum-ion battery of example 3 was 351mAh g-1As can be seen from fig. 5, the first-turn discharge capacity of the aluminum-ion battery of example 4 is 2442mAh g-1As can be seen from fig. 6, the first-cycle discharge capacity of the aluminum-ion battery of example 7 was 179mAh g-1As can be seen from fig. 7, the first-turn discharge capacity of the aluminum-ion battery of example 8 is 124mAh g-1The application of the electrolyte of the embodiment 3, the embodiment 4, the embodiment 7 and the embodiment 8 in the aluminum ion battery can enable the aluminum ion battery to have higher first-turn discharge capacity.
Test example 3
The rate capability of the aluminum ion battery of example 5 was tested, and the rate capability test chart is shown in fig. 8.
Test example 4
Thermogravimetric analyses were performed on the electrolytes of example 1, example 9 to example 11, and the obtained thermogravimetric analysis graphs are shown in fig. 9 to fig. 12. Then, the thermogravimetric analysis graphs were analyzed, and the total amount of water and the amount of free water in the electrolytes of examples 1, 9 to 11 were recorded and plotted as a bar graph, and the results thereof are shown in fig. 13.
As can be seen from fig. 13, in the embodiment of the present application, when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 8-12, water molecules in the eutectic system of the electrolyte can be mainly crystallized water, but not mainly free water.
Test example 5
The ionic conductivities and densities of the electrolytes of examples 1, 9 to 12 were measured, and the results are shown in fig. 14.
As can be seen from FIG. 14, in the embodiment of the present invention, when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1: 8-20, the electrolyte has a high conductivity, and at the same time, has a low density, so that the transport speed of aluminum ions in the electrolyte is high.
Test example 6
The melting points of the eutectic electrolyte solutions of examples 1 and 9 to 12 of the present application were measured, and the results are shown in fig. 15.
As can be seen from fig. 15, the eutectic system electrolytes of examples 9, 11 and 12 of the present application have a melting point of less than 0 ℃, which indicates that the eutectic system electrolyte of the examples of the present application is in a liquid state at normal temperature.
Test example 7
The aluminum ion batteries of comparative example 1 and comparative example 2 were tested for capacity at different cycles, and the results are shown in fig. 16 and 17.
The aluminum ion battery of comparative example 1 is different from the aluminum ion battery of example 1 only in the electrolyte, and it can be known from the results of fig. 16 that when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is out of the range of 1:4 to 20, the aluminum ion battery has a low capacity as the electrolyte of the aluminum ion battery, indicating that the eutectic system of comparative example 1 is not suitable for the electrolyte of the aluminum ion battery.
The aluminum ion battery of comparative example 2 is different from the aluminum ion battery of example 10 only in the electrolyte, and it can be known from the results of fig. 17 that the capacity of the aluminum ion battery is low when the eutectic system of comparative example 2 is used as the electrolyte, indicating that the eutectic system of comparative example 2 is not suitable for use as the electrolyte of the aluminum ion battery.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. An electrolyte comprising hydrated aluminum salt andthe eutectic system is formed by mixing hydrogen bond acceptors, the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptors is 1: 4-20, and the hydrogen bond acceptors contain C-O, N-O, OCH3C ═ S, and — CN.
2. The electrolyte of claim 1, wherein the hydrogen bond acceptor comprises at least one of urea, N-methyl urea, ethyl urea, tetramethyl piperidine oxide, 4-methoxy-tetramethyl piperidine oxy-radical, succinonitrile, and thiourea.
3. The electrolyte of claim 1, wherein the hydrated aluminum salt comprises at least one of aluminum chloride hexahydrate, aluminum perchlorate nonahydrate, aluminum nitrate nonahydrate, and aluminum sulfate octadecahydrate.
4. The electrolyte according to any one of claims 1 to 3, wherein the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1:8 to 20.
5. A method for preparing the electrolyte according to any one of claims 1 to 4, comprising:
mixing the hydrated aluminum salt and the hydrogen bond acceptor to obtain the electrolyte.
6. The method of preparing the electrolyte according to claim 5, wherein the hydrated aluminum salt and the hydrogen bond acceptor are mixed and heated at a temperature of 60 ℃ to a preset temperature, the preset temperature being less than a boiling point of the hydrogen bond acceptor; optionally, the heating time is 30-60 min.
7. The method of producing the electrolyte solution according to claim 5 or 6, characterized in that the hydrated aluminum salt and the hydrogen bond acceptor are mixed and stirred; optionally, the stirring time is 1-6 h.
8. An aluminum ion battery comprising a positive electrode sheet, a negative electrode sheet and the electrolyte according to any one of claims 1 to 4.
9. The aluminum-ion battery of claim 8, wherein the positive plate comprises a positive electrode material comprising at least one of vanadium pentoxide, manganese dioxide, molybdenum disulfide, polypyrrole, polythiophene, polyaniline, graphite, and sulfur.
10. The aluminum-ion battery according to claim 8, wherein the thickness of the negative electrode sheet is 1 to 300 μm.
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