CN113594559B - Electrolyte, preparation method thereof and aluminum ion battery - Google Patents

Electrolyte, preparation method thereof and aluminum ion battery Download PDF

Info

Publication number
CN113594559B
CN113594559B CN202110872165.8A CN202110872165A CN113594559B CN 113594559 B CN113594559 B CN 113594559B CN 202110872165 A CN202110872165 A CN 202110872165A CN 113594559 B CN113594559 B CN 113594559B
Authority
CN
China
Prior art keywords
aluminum
electrolyte
ion battery
hydrogen bond
bond acceptor
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.)
Active
Application number
CN202110872165.8A
Other languages
Chinese (zh)
Other versions
CN113594559A (en
Inventor
付超鹏
蒙鹏宇
张佼
孙宝德
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.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong 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 Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN202110872165.8A priority Critical patent/CN113594559B/en
Publication of CN113594559A publication Critical patent/CN113594559A/en
Application granted granted Critical
Publication of CN113594559B publication Critical patent/CN113594559B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • H01M10/36—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

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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, and the hydrated aluminumThe molar ratio of the salt to the hydrogen bond acceptor is 1:4-20, wherein the hydrogen bond acceptor comprises C = O, N-O.OCH 3 C = 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, the 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 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 3 C = 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, an embodiment of the present application provides 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, OCH 3 Functional groups of 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; meanwhile, C = O, N-O, OCH 3 Functional groups such as C = S and — CN are also susceptible to self-correlation intermolecular interaction by hydrogen bonds and ionic bonds, and lower the melting point of the entire system, thereby forming a eutectic system which is liquid at normal 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 the 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 is a drawing of an embodiment of the present applicationThe aluminum ion battery of example 3 was charged at 0.1Ag -1 The 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 -1 The 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 -1 The 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 -1 The 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, the 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 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 3 C = 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, OCH 3 Functional groups, C = S, -CN, tend to form hydrogen bonds, lowering the gibbs free energy of the overall system, and thus lowering the melting point of the overall system. Among them, the inventors of the present application found in their studies that if the hydrated aluminum salt is replaced with a general aluminum saltAluminum salts and the above-mentioned hydrogen bond acceptors do not form a eutectic system.
Meanwhile, C = O, N-O, OCH 3 Functional groups such as C = S and — CN are also susceptible to self-correlation intermolecular interaction through hydrogen bonds and ionic bonds, and the melting point of the entire system is lowered, thereby forming a eutectic system which is liquid at normal 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 the 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 OCH 3 The 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 molar ratio of hydrated aluminum salt to hydrogen bond acceptor is 1:8 to 20.
The ratio of the hydrated aluminum salt to the hydrogen bond acceptor can influence the conductivity and viscosity of the electrolyte, the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1:8-20, and the electrolyte not only has high conductivity, but also 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 any one of 1:8, 1, 10, 1, 12, 1, 14, 1.
Further, the inventors of the present application have found in their studies that the predominant form of water molecules present in the eutectic system of the electrolyte can be controlled by controlling the ratio of hydrated aluminum salt to hydrogen bond acceptor, which in some possible embodiments is a molar ratio of 1:8 to 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.cndot, OCH3, C = S and CN easily 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.
Optionally, the heating time is 30 to 60min, such as 30min, 40min, 45min, 50min or 60min.
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.
Alternatively, the stirring time is 1 to 6 hours, for example, any one of 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, 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, in the range of any one or between any two of 1 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, and 300 μm.
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.
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 V 2 O 5 The 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 according to the 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 according to the 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 MnO 2 The positive current collector is titanium foil, and the diaphragm uses a glass fiber filter membrane.
Example 4
This embodiment provides an electrolyte, which includes:
mixing aluminum sulfate octadecahydrate and 4-methoxy-tetramethylpiperidine oxygen radical according to the molar ratio of 1.
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
This embodiment provides an electrolyte, which includes:
mixing aluminum perchlorate nonahydrate, aluminum sulfate octadecahydrate and 4-methoxy-tetramethylpiperidine oxygen radical according to a molar ratio of 1.
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-tetramethylpiperidinyloxy free radical at a molar ratio of 0.5.
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
This embodiment provides an electrolyte, which includes:
mixing aluminum nitrate nonahydrate, aluminum sulfate octadecahydrate, aluminum chloride hexahydrate and dimethyl urea in a molar ratio of 0.3.
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 at a molar ratio of 0.3.
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, and compared with example 1, the preparation method thereof is different only in the molar ratio of aluminum perchlorate nonahydrate to succinonitrile, and in examples 9 to 12, the molar ratio of aluminum perchlorate nonahydrate to succinonitrile is 1.
Comparative example 1
Mixing aluminum perchlorate nonahydrate and succinonitrile according to a molar ratio of 1.
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 V 2 O 5 The 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.
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 V 2 O 5 The 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 -1 As can be seen from the cycle performance diagrams of fig. 1 to 3, the application of the electrolyte in the embodiments 1, 2, and 6 to the aluminum ion battery 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 -1 The 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 -1 As can be seen from fig. 5, the first-turn discharge capacity of the aluminum-ion battery of example 4 is 2442mAh g -1 As can be seen from fig. 6, the first-cycle discharge capacity of the aluminum-ion battery of example 7 is 179mAh g -1 As can be seen from fig. 7, the first-turn discharge capacity of the aluminum-ion battery of example 8 is 124mAh g -1 The 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 examples 1, 9 to 11, and the obtained thermogravimetric analysis graphs are shown in fig. 9 to 12. Then, the thermogravimetric analysis graph was 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 result is 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 to 12, water molecules in the eutectic system of the electrolyte can be mainly crystallized water, rather than mainly free water.
Test example 5
The ionic conductivities and densities of the electrolytes of examples 1 and 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 application, when the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1:8 to 20, the electrolyte can have both high conductivity and low density, so that the transport speed of aluminum ions in the electrolyte is fast.
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 cycle numbers, 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 outside 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 (11)

1. The electrolyte is characterized by comprising 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 OCH 3 At least one functional group of C = S and-CN;
the hydrated aluminum salt comprises at least one of aluminum chloride hexahydrate, aluminum perchlorate nonahydrate, aluminum nitrate nonahydrate and aluminum sulfate octadecahydrate.
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 oxyl, succinonitrile, and thiourea.
3. The electrolyte of any one of claims 1-2, wherein the molar ratio of the hydrated aluminum salt to the hydrogen bond acceptor is 1:8-20.
4. A method of preparing the electrolyte of any of claims 1 to 3, comprising:
mixing the hydrated aluminum salt and the hydrogen bond acceptor to obtain the electrolyte.
5. The method of claim 4, 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.
6. The method for preparing the electrolyte according to claim 5, wherein the heating time is 30 to 60min.
7. The method of manufacturing the electrolyte according to claim 4, 5 or 6, wherein the hydrated aluminum salt and the hydrogen bond acceptor are mixed and stirred.
8. The method for preparing the electrolyte according to claim 7, wherein the stirring time is 1 to 6 hours.
9. An aluminum ion battery comprising a positive electrode sheet, a negative electrode sheet and the electrolyte according to any one of claims 1 to 3.
10. The aluminum-ion battery of claim 9, 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.
11. The aluminum-ion battery of claim 9, wherein the negative electrode sheet has a thickness of 1 to 300 μm.
CN202110872165.8A 2021-07-30 2021-07-30 Electrolyte, preparation method thereof and aluminum ion battery Active CN113594559B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110872165.8A CN113594559B (en) 2021-07-30 2021-07-30 Electrolyte, preparation method thereof and aluminum ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110872165.8A CN113594559B (en) 2021-07-30 2021-07-30 Electrolyte, preparation method thereof and aluminum ion battery

Publications (2)

Publication Number Publication Date
CN113594559A CN113594559A (en) 2021-11-02
CN113594559B true CN113594559B (en) 2023-03-21

Family

ID=78252716

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110872165.8A Active CN113594559B (en) 2021-07-30 2021-07-30 Electrolyte, preparation method thereof and aluminum ion battery

Country Status (1)

Country Link
CN (1) CN113594559B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115458811B (en) * 2022-09-02 2023-03-21 哈尔滨工业大学（深圳） Electrolyte based on sulfone-based eutectic solvent, preparation method thereof and lithium ion battery

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106694007B (en) * 2016-12-19 2019-09-10 中国科学院山西煤炭化学研究所 A kind of single dispersion metal atom/graphene composite catalyst and its preparation method and application
CN106654300B (en) * 2016-12-19 2019-06-25 中国科学院山西煤炭化学研究所 A kind of electrochemistry swelling graphite prepares single dispersion metal atom/graphene composite material method
CN110201670B (en) * 2019-05-21 2020-05-29 山东大学 Ferronickel double-metal hydroxide/foamed nickel catalyst based on ferric trichloride/urea eutectic solvent, and preparation method and application thereof
CN113097565A (en) * 2021-03-29 2021-07-09 北京理工大学 Ionic liquid-like electrolyte for aluminum secondary battery and preparation method thereof

Also Published As

Publication number Publication date
CN113594559A (en) 2021-11-02

Similar Documents

Publication Publication Date Title
Fukunaga et al. Intermediate-temperature ionic liquid NaFSA-KFSA and its application to sodium secondary batteries
Miyashiro et al. Improvement of degradation at elevated temperature and at high state-of-charge storage by ZrO2 coating on LiCoO2
CN109786820B (en) Boron-containing plastic crystal polymer and preparation method and application thereof
EP3944390A1 (en) Composite material and preparation method therefor, and lithium ion battery
JP2019033075A (en) Hybrid aqueous secondary battery
Seki et al. Physicochemical and electrochemical properties of glyme-LiN (SO2F) 2 complex for safe lithium-ion secondary battery electrolyte
Yang et al. Preparation of alkaline PVA-based polymer electrolytes for Ni–MH and Zn–air batteries
CN105322219B (en) Lithium-sulfur battery positive electrode, electrolyte and lithium-sulfur battery
AU2007259117A1 (en) Process for modifying the interfacial resistance of a metallic lithium electrode
CN111326779A (en) Method for improving transmission performance of eutectic solvent electrolyte flow battery and flow battery
WO2021004259A1 (en) Symmetrical aqueous sodium-ion battery
CN113594559B (en) Electrolyte, preparation method thereof and aluminum ion battery
Croce et al. The lithium polymer electrolyte battery IV. Use of composite electrolytes
Sano et al. Effect of temperature on Li electrodeposition behavior in room-temperature ionic liquids comprising quaternary ammonium cation
Ikeda et al. Multivalent cation conductive solid polymer electrolytes using photo-cross-linked polymers: II. Magnesium and zinc trifluoromethanesulfonate systems
Mahesh et al. Electrochemical behavior of Li [Li 0.2 Co 0.3 Mn 0.5] O 2 as cathode material in Li 2 SO 4 aqueous electrolyte
CN109980187A (en) A kind of nickel-cobalt lithium manganate cathode material of coated aluminum oxide and preparation method thereof
CN111320753B (en) Polymer, polymer electrolyte membrane, nonaqueous electrolyte solution, and lithium ion battery
Rangaswamy et al. A new tavorite LiTiPO 4 F electrode material for aqueous rechargeable lithium ion battery
CN116364898A (en) Sodium ion positive electrode material, preparation method thereof and sodium ion battery
CN113078310B (en) Intercalation MnO 2 And method for preparing the same
Wang et al. Electrochemical characteristics of Li 4 Ti 5 O 12/Ag composite nanobelts prepared via electrospinning
CN111326797B (en) Liquid polymer electrolyte, polymer electrolyte membrane and lithium ion battery
CN112751014A (en) Aqueous energy storage battery based on layered vanadium oxide negative electrode
Zerroual et al. Correlation between the electrochemical activity and the crystallite size of PbO2: a comparative study between the chemical and the electrochemical routes

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
GR01 Patent grant
GR01 Patent grant