CN104393290A - Aluminum-ion battery using MoS2 as positive electrode material and preparation method of battery - Google Patents
Aluminum-ion battery using MoS2 as positive electrode material and preparation method of battery Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The invention provides an aluminum-ion battery using MoS2 as a positive electrode material and a preparation method of the battery, belongs to the technical field of batteries, can be widely applied to the fields of electronic industry and communications industry, and also can be taken as a power battery for an electric automobile. The aluminum-ion battery comprises a positive electrode active material, a negative electrode, a diaphragm material, a molten aluminum ion electrolyte solution and an electrolytic tank, wherein the positive electrode active material is MoS2, the negative electrode is a high-purity aluminum sheet, and the molten aluminum ion electrolyte solution is non-aqueous electrolyte solution containing Al3<+> ions. According to the aluminum-ion battery using the MoS2 as the positive electrode material and the preparation method of the battery, a provided aluminum-ion storage battery can be repeatedly charged and discharged, and has high capacity, high charging and discharging efficiency, good circulation stability and excellent charging and discharging features; in addition, the electrode material source is wide, the preparation method is easy, the cost is low, and the battery is green and environment-friendly and is low in price.
Description
Technical field
The invention belongs to a kind of employing MoS
2for the aluminium ion battery and preparation method thereof of positive electrode, can be used as new green power battery applications in fields such as electronic industry, communications industry and power battery of electric vehicle.
Background technology
Current, the non-renewable fossil fuel such as coal, oil and natural gas is day by day exhausted, and environmental pollution and greenhouse effect increasingly sharpen, and energy crisis and environmental protection become two hang-ups that the world faces.Therefore, development of new green energy resource and energy storage device more and more attract much attention.Since Japanese Sony Corporation successfully releases lithium ion battery, lithium ion battery is just rapid to be widely used in many-sides such as electronic product, power source, military fields, develops to the electrokinetic cell industrial aspect of electric automobile at present.But the limitation due to lithium resource causes cost intensive and larger potential safety hazard to limit further developing of lithium ion battery.Thus, in recent years, as aiming at high capacity, the ionic conductor of lithium ion can being replaced, adopt the research of the class rechargeable battery of polycation to become increasingly active.
The content of aluminium element in the earth's crust is only second to oxygen and silicon, and occupying the 3rd, be the metallic element that in the earth's crust, content is the abundantest, and cost of winning is low, and low price, if as battery material, aluminium ion rechargeable battery exchanges the Al of 3 valencys
3+, be expected to significantly improve capacity, so be expected to for extensive energy storage device based on the multivalent ion battery of aluminium ion embedding and deintercalation.Therefore, develop that specific capacity is high, security performance good, the novel multivalent ion battery of good cycling stability, there is very important commercial exploitation.
Summary of the invention
The invention provides a kind of novel secondary battery replacing lithium ion battery, and multivalent ion rechargeable battery and preparation method thereof, achieve the high power capacity discharge and recharge of rechargeable aluminium ion battery, and good cycle and security performance high.
For achieving the above object, the invention provides following technical scheme:
The rechargeable aluminium ion battery that the present invention proposes, its operation principle and existing lithium ion battery, sodium-ion battery operation principle are similar.
A kind of employing MoS
2for the aluminium ion battery of positive electrode, its feature comprises the composite material of positive active material and electric conducting material and binding agent composition thereof, negative pole and aluminium ion nonaqueous solution electrolysis liquid and electrolytic cell device, and wherein positive active material is MoS
2, negative pole is rafifinal; Aluminium ion nonaqueous solution electrolysis liquid is mixed in proportion by 3-methylimidazole compounds and anhydrous Aluminum chloride.
Described MoS
2material is commercially available or the micron order prepared by chemical method and physical method or nanoscale MoS
2, wherein chemical method comprises chemical vapour deposition technique, high temperature vulcanized method, presoma decomposition method, hydro thermal method and solwution method etc.; Physical method comprises mechanical milling method, plasma spraying method and high-voltage arc method etc.
The electric conducting material adopted in described composite material is platinum slurry, silver slurry, amorphous carbon and Super-P, wherein will add the binding agent of 10% (mass fraction) when using amorphous carbon and Super-P.
Described binding agent is the one in Kynoar (PVDF) or polytetrafluoroethylene (PTFE).
Described 3-methylimidazole compounds comprises one or more in 1-butyl-3-methylimidazolium chloride, 1-propyl group-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole chloride, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate.
In the electrolyte of described aluminium ion battery, the mass ratio of anhydrous Aluminum chloride and 3-methylimidazole compounds is 1.1:1-1.6:1, and preferred proportion is 1.3:1.
Described electrolytic cell device is glass electrolytic cell or plastics electrolytic cell.
Employing MoS described above
2for the preparation method of the aluminium ion battery of positive electrode, comprise following preparation process:
1) by positive electrode MoS
2evenly be fixed on the clean inert metal paillon foil collector of polishing with the composite material of electric conducting material and binding agent composition thereof, and wrap up with diaphragm material, wherein inert metal paillon foil collector is molybdenum sheet, titanium sheet, nickel foam or the noble metal such as gold and platinum family;
2) be the rafifinal of 0.2-2mm by thickness, as negative material after cleaning;
3) preparation is containing the Al that can move freely
3+the nonaqueous solution electrolysis liquid of ion;
4) after getting out positive electrode, negative material and aluminium ion nonaqueous solution electrolysis liquid, assembled battery in oxygen-free environment (as in glove box);
5) after battery pack installs, its electrode is all inserted in electrolyte, after the whole wetting electrode of liquid to be electrolysed, carry out charge-discharge test again.
The electrolytic cell device of aluminium ion used in battery is glass electrolytic cell or plastics electrolytic cell.
In above-mentioned aluminium ion battery preparation method step (1), described diaphragm material is for having ion permeability and not reacting with both positive and negative polarity, and there is stable chemical property, good mechanical performance and electrochemical stability, as microporous polyolefin film diaphragm material and glass fiber material.
In above-mentioned aluminium ion battery preparation method step (1), described MoS
2material and electric conducting material mix in proportion, and are then fixed on inert metal collector, and as positive pole, wherein fixed form can for smearing, suppressing and bonding.
In above-mentioned aluminium ion battery preparation method step (1), if when using amorphous carbon or Super-P as electric conducting material, MoS
2material usage is 50-85% (mass fraction), electric conducting material is 10-40% (mass fraction), binding agent is 5-10% (mass fraction).If when using platinum slurry or silver slurry as electric conducting material, MoS
2material usage is 60-90% (mass fraction), electric conducting material is 10-40% (mass fraction).
In above-mentioned aluminium ion battery preparation method step (2), first rafifinal is cut into sheet, then it is level and smooth with sand papering, clean again, the method of wherein cleaning is, with organic liquid, as absolute ethyl alcohol or acetone soak and ultrasonic vibration, then in 60-120 degree Celsius of baking oven, carry out drying.
In above-mentioned aluminium ion battery preparation method step (3), containing Al
3+the liquid nonaqueous solution electrolysis liquid of ion must be prepared in glove box, then its essence is put after more than 12 hours and can use.
The present invention uses MoS
2as positive pole, rafifinal, as negative pole, constitutes a kind of chargeable aluminium ion battery.Meticulous selection has been carried out because the present invention studies by experiment to positive and negative pole material, barrier film and electrolyte thereof etc., and in conjunction with tight preparation method, so the present invention has following characteristics: propose a kind of novel multivalent ion, i.e. aluminium ion battery system, which also promotes the development of energy storage device; Because aluminium element is at the rich reserves of the earth's crust, low price, greatly reduces the preparation cost of battery, also improves the security performance of ion battery simultaneously; MoS
2chemical stability and Heat stability is good, specific area is large, surface activity is high, therefore has unique physics and chemistry characteristic, so have a wide range of applications in electrochemical energy storage; Barrier film has good insulation property, has good transparent performance to electrolyte ion, has good chemical stability and electrochemical stability; Aluminium ion electrolyte, conductance is high, Heat stability is good, with positive and negative pole material, barrier film and binding agent etc. in battery, chemical reaction does not occur; Aluminium ion battery of the present invention can be widely used in the field such as electronic industry, communication industry, also can be applicable to the electrokinetic cell of electric automobile.
Accompanying drawing explanation
Fig. 1 is 2 circle charge-discharge performance test curves before the aluminium ion battery of embodiment 1 preparation;
Fig. 2 is the cycle performance test curve of aluminium ion battery prepared by embodiment 2.
Embodiment
The present invention will be described in more detail by specific embodiment below, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1
Use MoS
2as positive active material, MoS is pressed in positive plate assembling
2: platinum slurry mass ratio is that the ratio mixing of 70:30 is even, is then spread upon uniformly on the molybdenum sheet of 10mm × 20mm by gelling material, finally wraps up as anode with GF/D diaphragm material after 60-120 degree Celsius of baking oven leaves standstill oven dry in more than 12 hours.Negative pole is rafifinal, and it is soaked 1-2 hour in absolute ethyl alcohol, and after ultrasonic vibration drying, is cut into the sheet of 10mm × 20mm as negative pole.Anhydrous Aluminum chloride and 1-ethyl-3-methylimidazole chloride are mixed with ionic liquid for 1.3:1, in mass ratio as aluminium ion battery electrolyte of the present invention in the glove box of ar gas environment.Finally ready positive pole, negative pole and electrolyte are assembled into battery in glove box.After battery installs 12 hours, between 0.5-2.15V, carry out charge-discharge test.
Embodiment 2
Use MoS
2as positive active material, by itself and electric conducting material Super-P and polyfluortetraethylene of binding element (PTFE) in mass ratio for the ratio of 75:15:10 mixes, join in absolute ethyl alcohol and disperse, and be shelved on after ultrasonic vibration 20-30min mixes in the baking oven of 60 degrees Celsius and be dried to gel, then gelling material is spread upon on the molybdenum sheet of 10mm × 20mm uniformly, finally leave standstill at 60-120 degree Celsius of baking oven and within more than 12 hours, dry rear GF/D diaphragm material parcel as anode.Negative pole is rafifinal, and it is soaked 1-2 hour in absolute ethyl alcohol, and after ultrasonic vibration drying, is cut into the sheet of 10mm × 20mm as negative pole.Anhydrous Aluminum chloride and 1-ethyl-3-methylimidazole chloride are mixed with ionic liquid for 1.3:1, in mass ratio as aluminium ion battery electrolyte of the present invention in the glove box of ar gas environment.Finally ready positive pole, negative pole and electrolyte are assembled into battery in glove box.After battery installs 12 hours, between 0.5-2.15V, carry out charge-discharge test.
Claims (12)
1. one kind adopts MoS
2for the aluminium ion battery of positive electrode, it is characterized in that comprising the composite material of positive active material and electric conducting material and binding agent composition thereof, negative pole and aluminium ion nonaqueous solution electrolysis liquid and electrolytic cell device, wherein positive active material is MoS
2, negative pole is rafifinal; Aluminium ion nonaqueous solution electrolysis liquid is mixed in proportion by 3-methylimidazole compounds and anhydrous Aluminum chloride.
2. adopt MoS as claimed in claim 1
2for the aluminium ion battery of positive electrode, it is characterized in that described MoS
2material is commercially available or the micron order prepared by chemical method and physical method or nanoscale MoS
2, wherein chemical method comprises chemical vapour deposition technique, high temperature vulcanized method, presoma decomposition method, hydro thermal method and solwution method; Physical method comprises mechanical milling method, plasma spraying method and high-voltage arc method.
3. employing MoS according to claim 1
2for the aluminium ion battery of positive electrode, it is characterized in that, the electric conducting material adopted in described composite material is platinum slurry, silver slurry, amorphous carbon and Super-P, wherein will add the binding agent of 10% when using amorphous carbon and Super-P.
4. as claim 1 or as described in adopt MoS
2for the aluminium ion battery of positive electrode, it is characterized in that described binding agent is the one in Kynoar or polytetrafluoroethylene.
5. adopt MoS as claimed in claim 1
2for the aluminium ion battery of positive electrode, it is characterized in that one or more that described 3-methylimidazole compounds comprises in 1-butyl-3-methylimidazolium chloride, 1-propyl group-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole chloride, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate.
6. adopt MoS as claimed in claim 1
2for the aluminium ion battery of positive electrode, it is characterized in that the mass ratio of anhydrous Aluminum chloride and 3-methylimidazole compounds in the aluminium ion nonaqueous solution electrolysis liquid of described aluminium ion battery is 1.1:1-1.6:1.
7. employing MoS according to claim 1
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, comprise following preparation process:
1) by positive electrode MoS
2evenly be fixed on the clean inert metal paillon foil collector of polishing, and wrap up with diaphragm material, wherein inert metal paillon foil collector is molybdenum sheet, titanium sheet, nickel foam or gold and platinum group metal;
2) be the rafifinal of 0.2-2mm by thickness, as negative material after cleaning;
3) preparation is containing the Al that can move freely
3+the nonaqueous solution electrolysis liquid of ion;
4) after getting out positive electrode, negative material and aluminium ion nonaqueous solution electrolysis liquid, assembled battery in oxygen-free environment;
5) after battery pack installs, its electrode is all inserted in aluminium ion nonaqueous solution electrolysis liquid, after the whole wetting electrode of aluminium ion nonaqueous solution electrolysis liquid, carry out charge-discharge test again.
8. employing MoS according to claim 7
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, in step (1), described diaphragm material is for having ion permeability and not reacting with both positive and negative polarity, and there is stable chemical property, good mechanical performance and electrochemical stability, comprise microporous polyolefin film diaphragm material and glass fiber material.
9. employing MoS according to claim 7
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, in step (1), MoS
2material and electric conducting material Homogeneous phase mixing in proportion, is then fixed on inert metal collector, and as positive pole, wherein fixed form is for smearing, suppressing and bonding.
10. employing MoS according to claim 7
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, in step (1), when using amorphous carbon or Super-P as electric conducting material, MoS
2material usage is 50-85%, electric conducting material is 10-40%, binding agent is 5-10%; When using platinum slurry or silver slurry as electric conducting material, MoS
2material usage is 60-90%, electric conducting material is 10-40%.
11. employing MoS according to claim 7
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, in step (2), first rafifinal is cut into sheet, then it is level and smooth with sand papering, then clean, the method for wherein cleaning is, soak and ultrasonic vibration with absolute ethyl alcohol or acetone, then in 60-120 degree Celsius of baking oven, carry out drying.
12. employing MoS according to claim 7
2for the preparation method of the aluminium ion battery of positive electrode, it is characterized in that, in step (3), containing Al
3+the liquid nonaqueous solution electrolysis liquid of ion must be prepared in glove box, then its essence is put after more than 12 hours and could use.
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Cited By (17)
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| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
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| CN105449271A (en) * | 2016-01-05 | 2016-03-30 | 北京金吕能源科技有限公司 | Aluminium ion secondary battery taking CuS as cathode and preparation technology thereof |
| CN105632780A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Low temperature inorganic fused salt aluminium ion supercapacitor battery and preparation method therefor |
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| CN105633327A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Aluminum-ion secondary battery employing TiS<2> as positive electrode and preparation technology of aluminum-ion secondary battery |
| CN106450269A (en) * | 2016-11-11 | 2017-02-22 | 中国科学院金属研究所 | Positive material for aluminium-ion secondary battery, preparation method and application thereof |
| CN107275615A (en) * | 2017-06-29 | 2017-10-20 | 厦门大学 | A kind of sulphur copper compound C-base composte material is the aluminium ion battery of positive pole |
| CN107293693A (en) * | 2017-08-18 | 2017-10-24 | 北京理工大学 | Positive electrode for aluminium-sulfur battery and preparation method thereof |
| CN108565530A (en) * | 2018-04-14 | 2018-09-21 | 佛山市领卓科技有限公司 | A kind of lithium-air battery and preparation method thereof |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
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