CN104393290B - A kind of aluminum ion battery adopting MoS2 as cathode material and preparation method thereof - Google Patents

Abstract

A kind of employing MoS₂Aluminium ion battery for positive electrode and preparation method thereof, belongs to cell art, can be widely applied to the field such as electronic industry, communication industry, it is possible to be applied to the electrokinetic cell of electric automobile.The aluminium ion battery of the present invention comprises positive active material, negative pole, diaphragm material, liquid aluminium ion electrolyte and electrolytic cell device, and wherein positive active material is MoS₂, negative pole is high-purity aluminium flake, and liquid ion electrolyte is containing Al³⁺The nonaqueous solution electrolysis liquid of ion.Aluminium ion secondary cell provided by the present invention can be repeatedly charged and discharged, have high power capacity, efficiency for charge-discharge is high, good cycling stability and charge-discharge characteristic excellent, and electrode material wide material sources, preparation easily, low cost, environmental protection and cheap.

Description

A kind of aluminum ion battery adopting MoS2 as cathode material and preparation method thereof

technical field

_The invention belongs to an aluminum ion battery using MoS2 as a positive electrode material and a preparation method thereof, which can be used as a new type of green energy battery in the fields of electronics industry, communication industry, electric vehicle power battery and the like.

Background technique

At present, non-renewable fossil fuels such as coal, oil and natural gas are increasingly depleted, environmental pollution and greenhouse effect are increasing, and energy crisis and environmental protection have become two major problems facing the world. Therefore, the development of new green energy sources and energy storage devices has attracted more and more attention. Since Japan's SONY company successfully launched lithium-ion batteries, lithium-ion batteries have been widely used in electronic products, power energy, military fields, etc., and are currently developing into the power battery industry for electric vehicles. However, due to the limitation of lithium resources, the high cost and large safety hazards limit the further development of lithium-ion batteries. Therefore, in recent years, research on rechargeable batteries employing multiple cations has become increasingly active as an ion conductor that can replace lithium ions with the aim of increasing the capacity.

The content of aluminum in the earth's crust is second only to oxygen and silicon, ranking third. It is the most abundant metal element in the earth's crust, and the mining cost is low and the price is cheap. If it is used as a battery material, aluminum ion rechargeable batteries can be exchanged for trivalent Al ³⁺ is expected to greatly increase the capacity, so multivalent ion batteries based on aluminum ion intercalation and deintercalation are expected to be used in large-scale energy storage devices. Therefore, the development of new multivalent ion batteries with high specific capacity, good safety performance and good cycle stability has very important commercial application value.

Contents of the invention

The invention provides a novel secondary battery which can replace the lithium ion battery, a multivalent ion rechargeable battery and a preparation method thereof, which realizes high-capacity charge and discharge of the rechargeable aluminum ion battery, and has good cycle performance and high safety performance.

To achieve the above object, the present invention provides the following technical solutions:

The working principle of the rechargeable aluminum ion battery proposed by the invention is similar to that of the existing lithium ion battery and sodium ion battery.

An aluminum ion battery adopting _MoS2 as a positive electrode material is characterized in that it comprises a composite material composed of a positive electrode active material, a conductive material and a binder thereof, a negative electrode, an aluminum ion non-aqueous solution electrolyte, and an electrolytic cell device, wherein the positive electrode active material is MoS ₂ , the negative pole is high-purity aluminum; the aluminum ion non-aqueous solution is composed of 3-methylimidazole compounds and anhydrous aluminum chloride mixed in proportion.

The MoS ₂ material is commercially available, or prepared by chemical and physical methods of micron or nanoscale MoS ₂ , wherein the chemical methods include chemical vapor deposition, high temperature sulfidation, precursor decomposition, hydrothermal method and solution method etc.; physical methods include mechanical grinding, plasma spraying and high voltage arc method.

The conductive materials used in the composite material are platinum paste, silver paste, amorphous carbon and Super-P, wherein 10% (mass fraction) of binder is added when using amorphous carbon and Super-P.

The binder is one of polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE).

The 3-methylimidazole compounds include 1-butyl-3-methylimidazolium chloride, 1-propyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1 -One or more of butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate.

The mass ratio of anhydrous aluminum chloride and 3-methylimidazole compounds in the electrolyte of the aluminum ion battery is 1.1:1-1.6:1, preferably 1.3:1.

The electrolytic cell device is a glass electrolytic cell or a plastic electrolytic cell.

As mentioned above adopting _MoS2 as the preparation method of the aluminum ion battery of cathode material, comprises the following preparation steps:

1) Evenly fix the composite material composed of positive electrode material MoS ₂ and conductive material and its binder on the polished and clean inert metal foil current collector, and wrap it with a diaphragm material, wherein the inert metal foil current collector is molybdenum sheet, titanium sheet, nickel foam or precious metals such as gold and platinum group;

2) High-purity aluminum with a thickness of 0.2-2 mm is used as the negative electrode material after cleaning;

3) preparing a non-aqueous electrolyte solution containing freely movable Al ³⁺ ions;

4) After preparing the positive electrode material, negative electrode material and aluminum ion non-aqueous electrolyte, assemble the battery in an oxygen-free environment (such as in a glove box);

5) After the battery is assembled, all its electrodes are inserted into the electrolyte, and the charge and discharge test is performed after the electrolyte completely wets the electrodes.

The electrolytic cell device used in the aluminum ion battery is a glass electrolytic cell or a plastic electrolytic cell.

In step (1) of the above-mentioned aluminum ion battery preparation method, the separator material is ion-permeable and does not react with the positive and negative electrodes, and has stable chemical properties, good mechanical properties and electrochemical stability, such as polyolefin Microporous membrane separator material and glass fiber material.

In the step ( ₁ ) of the above-mentioned aluminum ion battery preparation method, the MoS2 material and the conductive material are mixed uniformly in proportion, and then fixed on the inert metal current collector as the positive electrode, wherein the fixing method can be smearing, pressing and bonding .

In step (1) of the above-mentioned aluminum ion battery preparation method, if amorphous carbon or Super _- P is used as the conductive material, the MoS2 material consumption is 50-85% (mass fraction), and the conductive material is 10-40% (mass fraction ), the binding agent is 5-10% (mass fraction). If platinum paste or silver paste is used as the conductive material, the amount of MoS ₂ material is 60-90% (mass fraction), and the amount of conductive material is 10-40% (mass fraction).

In the step (2) of the above-mentioned aluminum ion battery preparation method, the high-purity aluminum is first cut into sheets, then it is smoothed with sandpaper, and then it is cleaned. The cleaning method is to use an organic liquid, such as absolute ethanol Or soak in acetone and ultrasonically vibrate, and then dry in an oven at 60-120 degrees Celsius.

In step (3) of the above-mentioned aluminum ion battery preparation method, the liquid non-aqueous electrolyte containing Al ³⁺ ions must be prepared in a glove box, and then it can be used after being placed for more than 12 hours.

_The present invention uses MoS2 as the positive electrode and high-purity aluminum as the negative electrode to form a rechargeable aluminum ion battery. Due to the careful selection of positive and negative electrode materials, separators and electrolytes, etc. through experimental research in the present invention, combined with rigorous preparation methods, the present invention has the following characteristics: a new type of multivalent ion is proposed, that is, aluminum ion Battery system, which also promotes the development of energy storage equipment; due to the abundant reserves of aluminum in the earth's crust, the price is cheap, which greatly reduces the cost of battery preparation, and also improves the safety performance of ion batteries; the chemical stability of MoS ₂ and It has good thermal stability, large specific surface area and high surface activity, so it has unique physical and chemical characteristics, so it has a wide application prospect in electrochemical energy storage; the separator has good insulation performance and has good resistance to electrolyte ions. Permeability, good chemical stability and electrochemical stability; aluminum ion electrolyte, high conductivity, good thermal stability, and no chemical reaction with positive and negative electrode materials, separators and binders in the battery; the present invention Aluminum-ion batteries can be widely used in the electronics industry, communication industry and other fields, and can also be used in power batteries for electric vehicles.

Description of drawings

Fig. 1 is the charging and discharging performance test curve of the first 2 circles of the aluminum ion battery prepared in embodiment 1;

Fig. 2 is the cycle performance test curve of the aluminum ion battery prepared in Example 2.

detailed description

The present invention will be described in more detail through specific examples below, but the protection scope of the present invention is not limited to these examples.

Example 1

Using MoS ₂ as the positive electrode active material, the positive electrode plate is assembled according to the ratio of MoS ₂ : platinum slurry mass ratio of 70:30 and mixed evenly, and then the gel is evenly spread on the molybdenum sheet of 10mm×20mm, and finally in the 60- After standing in an oven at 120 degrees Celsius for more than 12 hours, wrap it with GF/D separator material as the positive electrode of the battery. The negative electrode is high-purity aluminum, which is soaked in absolute ethanol for 1-2 hours, dried by ultrasonic vibration, and then cut into a sheet of 10mm×20mm as the negative electrode. Anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride are formulated into an ionic liquid in a glove box in an argon atmosphere at a mass ratio of 1.3:1, as an electrolyte for an aluminum ion battery of the present invention. Finally, the prepared positive electrode, negative electrode and electrolyte were assembled into a battery in the glove box. After the battery is installed for 12 hours, the charge and discharge test is carried out between 0.5-2.15V.

Example 2

Use MoS ₂ as the positive electrode active material, mix it with the conductive material Super-P and the binder polytetrafluoroethylene (PTFE) at a mass ratio of 75:15:10, add it to absolute ethanol for dispersion, And after ultrasonic vibration for 20-30 minutes to mix evenly, put it in an oven at 60 degrees Celsius to bake until it becomes gel, and then spread the gel evenly on a molybdenum sheet of 10mm×20mm, and finally put it in an oven at 60-120 degrees Celsius for 12 After drying for more than an hour, wrap it with GF/D separator material as the positive electrode of the battery. The negative electrode is high-purity aluminum, which is soaked in absolute ethanol for 1-2 hours, dried by ultrasonic vibration, and then cut into a sheet of 10mm×20mm as the negative electrode. Anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride are formulated into an ionic liquid in a glove box in an argon atmosphere at a mass ratio of 1.3:1, as the electrolyte for an aluminum ion battery of the present invention. Finally, the prepared positive electrode, negative electrode and electrolyte were assembled into a battery in the glove box. After the battery is installed for 12 hours, the charge and discharge test is carried out between 0.5-2.15V.

Claims (11)

_1. An aluminum ion battery adopting MoS2 as positive electrode material is characterized in that it comprises a composite material composed of positive electrode active material, conductive material and binding agent thereof, negative pole and aluminum ion non-aqueous electrolyte and electrolytic cell device, wherein the positive electrode The active material is MoS ₂ , the negative electrode is high-purity aluminum; the aluminum ion non-aqueous solution is composed of 3-methylimidazole compound and anhydrous aluminum chloride mixed in proportion. _2. as claimed in claim ₁ , adopting MoS2 as the aluminum ion battery of positive electrode material, it is characterized in that said MoS2 material is commercially available, or micron or nanoscale _MoS2 prepared by chemical and physical methods, wherein chemical The methods include chemical vapor deposition, high temperature vulcanization, precursor decomposition, hydrothermal method and solution method; the physical methods include mechanical grinding method, plasma spraying method and high voltage arc method. 3. The aluminum ion battery adopting MoS2 as the positive electrode material as claimed in claim ₁ , wherein the binder is one of polyvinylidene fluoride or polytetrafluoroethylene. 4. adopt MoS as claimed in claim ₁ Be the aluminum ion battery of cathode material, it is characterized in that described 3-methylimidazole compound comprises 1-butyl-3-methylimidazolium chloride, 1-propyl- 3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate One or more types of salt. 5. adopt MoS as claimed in claim ₁ Be the aluminum ion battery of cathode material, it is characterized in that the quality of anhydrous aluminum chloride and 3-methylimidazoles compound in the aluminum ion non-aqueous electrolyte of described aluminum ion battery The ratio is 1.1:1 to 1.6:1. 6. adopt MoS according to claim ₁ as the preparation method of the aluminum ion battery of cathode material, it is characterized in that, comprise following preparation steps: 1) Evenly fix the positive electrode material MoS ₂ on the polished inert metal foil current collector, and wrap it with a separator material, wherein the inert metal foil current collector is molybdenum sheet, titanium sheet, nickel foam or gold and platinum group metal; 2) High-purity aluminum with a thickness of 0.2-2 mm is used as the negative electrode material after cleaning; 3) preparing a non-aqueous electrolyte solution containing freely movable Al ³⁺ ions; 4) After preparing the positive electrode material, negative electrode material and aluminum ion non-aqueous electrolyte, assemble the battery in an oxygen-free environment; 5) After the battery is assembled, all its electrodes are inserted into the aluminum ion non-aqueous electrolyte, and the charge and discharge test is performed after the aluminum ion non-aqueous electrolyte completely wets the electrodes. 7. adopting MoS according to claim ₆ is the preparation method of the aluminum ion battery of cathode material, it is characterized in that, in step (1), described membrane material has ion permeability and does not react with positive and negative electrodes, And it has stable chemical properties, good mechanical properties and electrochemical stability, including polyolefin microporous membrane separator materials and glass fiber materials. 8. adopt MoS according to claim ₆ as the preparation method of the aluminum ion battery of cathode material, it is characterized in that, in step ( ₁ ), MoS material and conductive material are uniformly mixed in proportion, then it is fixed on an inert The metal current collector is used as the positive electrode, and the fixing methods are smearing, pressing and bonding. 9. adopt MoS according to claim ₆ as the preparation method of the aluminum ion battery of cathode material, it is characterized in that, in step (1), when using amorphous carbon or Super-P as conductive material, MoS ₂ material The dosage is 50-85%, the conductive material is 10-40%, the binder is 5-10%; when using platinum paste or silver paste as the conductive material, the MoS ₂ material dosage is 60-90%, the conductive material is 10% -40%. 10. adopt MoS according to claim ₆ as the preparation method of the aluminum ion battery of cathode material, it is characterized in that, in step (2), at first high-purity aluminum is cut into flake, then it is smoothed with sandpaper , and then clean it, wherein the cleaning method is to soak it with absolute ethanol or acetone and ultrasonically vibrate, and then dry it in an oven at 60-120 degrees Celsius. 11. adopt MoS according to claim ₆ as the preparation method of the aluminum ion battery of cathode material, it is characterized in that, in step (3), the liquid non-aqueous electrolyte that contains ^Al ion must carry out in glove box Prepare it, then let it sit for more than 12 hours before using it.