CN104701541A - Lithium-ion battery with WS2 serving as positive electrode and preparation method of lithium-ion battery - Google Patents
Lithium-ion battery with WS2 serving as positive electrode and preparation method of lithium-ion battery Download PDFInfo
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- CN104701541A CN104701541A CN201510002870.7A CN201510002870A CN104701541A CN 104701541 A CN104701541 A CN 104701541A CN 201510002870 A CN201510002870 A CN 201510002870A CN 104701541 A CN104701541 A CN 104701541A
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- ion battery
- aluminium ion
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- 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
Abstract
The invention discloses a lithium-ion battery with WS2 serving as a positive electrode and a preparation method of the lithium-ion battery and belongs to the field of lithium-ion batteries and the preparation method of the lithium-ion batteries. The lithium-ion battery comprises a positive electrode, a negative electrode, a diaphragm material and an aluminum ion electrolyte, wherein the positive active material is WS2; a negative electrode is a high-purity aluminum sheet; the electrolyte is aluminum ion electrolyte which is formed by mixing aluminum halide with a plurality of inorganic acid salts according to a ratio. The lithium-ion battery prepared by the method is stable in cycle performance, relatively wide in electrochemical window, continuous and high in coulombic efficiency and relatively wide in battery using temperature range; the lithium-ion battery can be widely applied to a plurality of fields such as portable electronic devices, electric vehicles, communication industry and aerospace.
Description
Technical field
The invention belongs to ion battery and preparation field thereof, relate to the technology of preparing of novel aluminum ion battery, particularly WS
2the preparation method of the positive electrode mixed with conductive agent, binding agent and whole battery.
Technical background
In recent years, huge ambient pressure, greenhouse effect etc. that continuous minimizing and use thereof along with non-regeneration energies such as oil, coal, natural gases bring, develop and utilize clean reproducible energy to become the focus of current research.Wherein electric energy becomes the key factor of whole renewable and clean energy resource forest ecosystem because it is in the core stage of various energy resources conversion.Such as, the tidal power, hydroelectric power generation, wind power generation, solar power generation etc. of current existence all form the form with electric energy.But the unsteadiness that the electric energy ubiquity that these regenerative resources produce is certain, makes it cannot enter electrical network in large quantities.Therefore, the efficiency utilization of these electric energy be realized, then relate to the storage problem of electric energy.The charge and discharge of secondary cell is current solution electrical power storage is the most also most promising mode.Present secondary cell is still based on lithium ion battery, and lithium ion battery is widely used on the electronic product such as mobile phone, computer and other portable type electronic products because of its higher energy density and high voltage platform.But by the impact of global lithium reserves, the production cost of lithium ion battery is difficult to reduce always.Meanwhile, the widely used carbon negative pole material of current business makes it in use there is potential safety hazard.By the impact of above various factors, the scientific research personnel of countries in the world takes up to research and develop novel rechargeable battery, and wherein aluminium ion battery is because the low cost of aluminium element abundant in the earth's crust and exploitation has made it slowly the enter into sight line of people.Relative to traditional lithium ion, aluminium ion can shift three electronics, and therefore its specific capacity has very large potentiality to be exploited.In addition aluminium ion radius is also less than lithium ion radius, is conducive to the deintercalation of ion on electrode material, thus is conducive to the structure of holding electrode material in theory, improves circulating battery stability, extends battery.At present, about the report of aluminium ion battery is also fewer, this is not mainly because correlative study is also very general, and the parameters such as battery specific capacity mentioned in the report simultaneously rarely had are not also very desirable, therefore fails to cause the extensive attention of business.And this just makes exploitation specific capacity high, it is urgent and important that the aluminium ion battery of stable cycle performance becomes very.
Summary of the invention
The present invention is directed to the lithium ion battery generally used now and have that resource scarcity, production cost are high, exist in use procedure the feature of certain potential safety hazard, develop a kind of novel aluminium ion battery, and realize that this cell safety is reliable, the circulation of Large Copacity, long-time stable.This aluminium ion battery electrode material is cheap and easy to get, production process is simply effective, is beneficial to commercialization and promotes.
For achieving the above object, the present invention comprises following technical scheme:
The present invention relates to a kind of WS
2make the aluminium ion battery of positive pole, wherein comprise positive pole, negative pole and aluminium ion electrolyte.
The optimal technical scheme of described aluminium ion battery is, battery positive electrode active material WS
2for nanoscale or micron order, purity is more than or equal to the dusty raw materials of 99%.
The optimal technical scheme of described aluminium ion battery is, when aluminium ion electrolyte is liquid, should comprise diaphragm material in battery.
The optimal technical scheme of described aluminium ion battery is, described diaphragm material should have ion by the one in the glass fiber material of property, polypropylene micropore diaphragm material, polyethylene micropore diaphragm material.
The optimal technical scheme of described aluminium ion battery is, in described aluminium ion electrolyte, the mol ratio of aluminum halide and inorganic acid salt is 0.5-2.Inorganic acid salt is the mixture of one or more arbitrary proportions in 1-butyl-3-methylimidazolium chloride, 1-propyl group-3-methylimidazolium chloride, 1-ethyl-3-methylimidazole chloride, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate.
The optimal technical scheme of described aluminium ion battery is, described in described aluminium ion electrolyte, the optimal technical scheme of aluminium ion battery is, the plus plate current-collecting body of described ion battery is the one in molybdenum sheet, nickel foam, platinized platinum, carbon paper.
Concrete preparation process is as follows:
1). as the WS of aluminium ion cell positive material
2powdered, its particle diameter is at 10nm-10 μm;
2). by above-mentioned Powdered WS
2be coated with on a current collector after conductive agent, binding agent Homogeneous phase mixing, as positive pole, the material of collector has molybdenum sheet, titanium sheet and platinum group metal;
3). using after the cleaning of the high-purity aluminium flake of thickness 0.1-1mm as negative pole;
4). by aluminum halide and inorganic acid salt Homogeneous phase mixing, as electrolyte;
5). with WS
2as positive pole, high-purity aluminium flake as negative pole, the ionic liquid that mixes as electrolyte, assembled battery in the glove box being full of argon gas; Oxygen content in glove box and water content are all less than 0.1ppm.
The optimal technical scheme of described aluminium ion battery is, step (2) described conductive agent is carbon nano-tube, acetylene black, super carbon, graphite, carbon dust, platinum slurry, the one in silver slurry; Binding agent is the one in polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), platinum slurry, silver slurry.
The optimal technical scheme of described aluminium ion battery is, WS in step (2)
2consumption is 30-90wt%, conductive agent is 1-40wt%, binding agent is 1-30wt%.
In step (3) high-purity aluminium flake first cutting into about the sheet of 10 × 15mm, then use sand papering, remove the oxide-film on its surface, recycling absolute ethyl alcohol or acetone soak carry out ultrasonic cleaning, finally in 60 DEG C of baking ovens, carry out drying.
The electrolyte that in step (4), aluminum halide mixes with inorganic acid salt must carry out in the glove box under argon shield, can use after the battery assembled need leave standstill at least 24 hours.
The invention belongs to a kind of new normal temperature ion battery, i.e. normal temperature aluminium ion battery, and propose a kind of new positive electrode-WS
2.Because the electrode material to battery, electrolyte, barrier film etc. have carried out meticulous selecting, and carried out accurate enforcement with regard to its whole preparation process, therefore the present invention possesses following characteristics: the electrode material adopted due to battery is simple and easy to get, and low production cost makes whole battery cost greatly reduce; Simultaneously relative to traditional lithium ion battery, aluminium ion battery is more safe and reliable, and possesses the potentiality developing higher capacity.The WS that this battery adopts
2layered Structural Positive Electrode Materials shows the cycle performance of stability and high efficiency in the charge-discharge test continued; WS simultaneously
2stable chemical nature, specific surface knot is large, possesses excellent energy-storage property, high rate performance etc. as secondary aluminium ion battery electrode material.Therefore, aluminium ion battery involved in the present invention and the WS used thereof
2positive electrode can be applicable to the multiple fields such as electronics industry, electric automobile in the development in future.
Accompanying drawing explanation
Fig. 1 is aluminium ion battery charging/discharging performance testing curve prepared by embodiment 1;
Fig. 2 is the cycle performance test curve of aluminium ion battery prepared by embodiment 1.
Specific embodiments
Aluminium ion battery involved in the present invention mainly comprises anode, negative pole, electrolyte, barrier film, plus plate current-collecting body and battery container.Just very WS
2starch with platinum, carbon nano-tube, acetylene black, super carbon, graphite, carbon dust, the conductive agent such as polytetrafluoroethylene and polyvinylidene fluoride, binding agent one or more homogeneous mixture.Plus plate current-collecting body is molybdenum sheet; Negative pole is high-purity aluminium flake; Barrier film is the one in glass fibre, polypropylene micropore diaphragm, polyethylene micropore barrier film.Electrolyte is the mixture of one or more arbitrary proportions in aluminum halide and 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.
The present invention will be described in more detail by the following specific embodiments, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1:
Positive active material is WS
2, WS
2the consumption starched with conduction platinum mixes by 1:2wt%.Now, the platinum slurry that conducts electricity takes into account conductive agent and binding agent two kinds of functions simultaneously.Make both Homogeneous phase mixing by spraying alcohol and coordinating to stir for a long time, finally obtain colloid substance.Above-mentioned colloid substance is evenly coated on plus plate current-collecting body molybdenum sheet, and is placed in lasting dry 24 hours of 120 DEG C of baking ovens, obtain the present invention's anode.Get high-purity aluminium flake that 0.25mm is thick, dry after ultrasonic cleaning a few hours in absolute ethyl alcohol, obtain battery cathode.By AlCl
3ionic liquid is mixedly configured into, as the present invention's electrolyte with the ratio of 1-butyl-3-methylimidazolium chloride salt 1.3:1 in molar ratio.Being assembled in the glove box being full of argon gas of whole battery is carried out, and in glove box, the content of oxygen and water is less than 0.1ppm.The battery assembled will leave standstill 24 hours, to ensure that active material infiltrates well at electrolyte.Discharge and recharge is carried out at the potential region of 0.4-2.1V subsequently with gained battery.Fig. 1 and Fig. 2 is respectively charge-discharge performance test curve and the cycle performance test curve of this battery.This WS is shown in figure
2the aluminium ion battery doing positive pole has good chemical property.
Embodiment 2:
Positive active material is WS
2, it is mixed by 75:15:10wt% with conductive agent carbon nano-tube (CNT), polyfluortetraethylene of binding element (PTFE), and is placed in a certain amount of alcohol and disperses, within ultrasonic 60 minutes, make three's Homogeneous phase mixing.Mixture is placed in 60 DEG C of baking ovens and is dried to glue, be evenly coated in by gluey active material on plus plate current-collecting body molybdenum sheet, gained positive pole dry 24 hours in 120 DEG C of baking ovens obtain the present invention's positive pole.Negative pole is high-purity aluminium flake of ultrasonic cleaning a few hours in alcohol, and electrolyte is AlCl
3the ionic liquid be made into is mixed with the ratio of 1-propyl group-3-methylimidazolium chloride salt 1:1 in molar ratio.The housing of battery is 50ml glass reactor, and be furnished with can the teflon seal lid in electrode insertion hole.Whole battery be assembled in oxygen, water content is less than in the glove box of 0.1ppm.The battery assembled will leave standstill more than 24 hours, to ensure the good contact of positive active material and electrolyte.
Embodiment 3:
Positive active material is WS
2it is mixed by 70:15:15wt% with conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF), add absolute ethyl alcohol to disperse, within ultrasonic 60 minutes, be placed in the baking oven of 60 DEG C and be dried to glue, gluey active material is evenly coated in the nickel foam of anode collection pole, and continues dry 24 hours in 120 DEG C of baking ovens.Adopt two roller roller compacting positive plate, make positive active material and plus plate current-collecting body close contact, so far obtain the present invention's anode.Negative pole is high-purity aluminium flake of ultrasonic cleaning a few hours in alcohol, and electrolyte is AlCl
3mix with the ratio of 1-butyl-3-methylimidazole hexafluorophosphate 1:1 in molar ratio the ionic liquid be made into, barrier film is glass fibre (GF/D).Whole battery be assembled in oxygen, water content is less than in 0.1ppm and carries out.Battery obtains WS described in the invention after sealing, clean, leaving standstill 24 hours
2for the aluminium ion battery of positive pole.
Claims (10)
1. a WS
2make the aluminium ion battery of positive pole, it is characterized in that, wherein comprise positive pole, negative pole and aluminium ion electrolyte, wherein positive active material is WS
2, negative pole is high-purity aluminium flake, and electrolyte is the aluminium ion electrolyte that aluminum halide and multiple inorganic acid salt mix in proportion.
2. WS according to claim 1
2make the aluminium ion battery of positive pole, it is characterized in that, described aluminium ion battery positive electrode active material WS
2for nanoscale or micron order, purity is more than or equal to the dusty raw materials of 99%.
3. WS according to claim 1
2make the aluminium ion battery of positive pole, it is characterized in that, when described aluminium ion electrolyte is liquid, in battery, should diaphragm material be comprised; Described diaphragm material should have ion by the one in the glass fiber material of property, polypropylene micropore diaphragm material, polyethylene micropore diaphragm material.
4. WS according to claim 1
2make the aluminium ion battery of positive pole, it is characterized in that, in described aluminium ion electrolyte, the mol ratio of aluminum halide and inorganic acid salt is 0.5-2; Inorganic acid salt is the mixture of one or more arbitrary proportions in 1-butyl-3-methylimidazolium chloride, 1-propyl group-3-methylimidazolium chloride, 1-ethyl-3-methylimidazole chloride, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate.
5. WS according to claim 1
2make the aluminium ion battery of positive pole, it is characterized in that, the plus plate current-collecting body of described ion battery is the one in molybdenum sheet, nickel foam, platinized platinum, carbon paper.
6. WS according to claim 1
2be the preparation method of the aluminium ion battery of positive pole, it is characterized in that, comprise following preparation process:
1). as the WS of aluminium ion cell positive material
2powdered, its particle diameter is at 10nm-10 μm;
2). by above-mentioned Powdered WS
2be coated with on a current collector after conductive agent, binding agent Homogeneous phase mixing, as positive pole, the material of collector has molybdenum sheet, titanium sheet and platinum group metal;
3). using after the cleaning of the high-purity aluminium flake of thickness 0.1-1mm as negative pole;
4). by aluminum halide and inorganic acid salt Homogeneous phase mixing, as electrolyte;
5). with WS
2as positive pole, high-purity aluminium flake as negative pole, the ionic liquid that mixes as electrolyte, assembled battery in the glove box being full of argon gas; Oxygen content in glove box and water content are all less than 0.1ppm.
7. WS according to claim 6
2be the preparation method of the aluminium ion battery of positive pole, it is characterized in that, step (2) described conductive agent is carbon nano-tube, acetylene black, super carbon, graphite, carbon dust, platinum slurry, the one in silver slurry; Binding agent is the one in polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), platinum slurry, silver slurry.
8. WS according to claim 6
2be the preparation method of the aluminium ion battery of positive pole, it is characterized in that, WS in step (2)
2consumption is 30-90wt%, conductive agent is 1-40wt%, binding agent is 1-30wt%.
9. WS according to claim 6
2be the preparation method of the aluminium ion battery of positive pole, it is characterized in that, in step (3) high-purity aluminium flake first cutting into about the sheet of 10 × 15mm, then sand papering is used, remove the oxide-film on its surface, recycling absolute ethyl alcohol or acetone soak and carry out ultrasonic cleaning, finally in 60 DEG C of baking ovens, carry out drying.
10. WS according to claim 6
2be the preparation method of the aluminium ion battery of positive pole, it is characterized in that, the electrolyte that in step (4), aluminum halide mixes with inorganic acid salt must carry out in the glove box under argon shield, can use after the battery assembled need leave standstill at least 24 hours.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106602129A (en) * | 2016-12-12 | 2017-04-26 | 北京科技大学 | Multi-ion battery and preparation method thereof |
| CN106784867A (en) * | 2016-12-23 | 2017-05-31 | 盐城工学院 | A kind of fuel cell and preparation method thereof and fuel cell anode materials |
| WO2017117838A1 (en) * | 2016-01-05 | 2017-07-13 | 北京金吕能源科技有限公司 | Low-temperature inorganic-molten-salt aluminum-ion supercapacitor cell, and method for preparing same |
| CN108428934A (en) * | 2018-04-11 | 2018-08-21 | 北京科技大学 | A kind of microballoon AlV3O9Method as aluminium ion anode |
| CN109037789A (en) * | 2018-07-27 | 2018-12-18 | 江西迪比科股份有限公司 | A kind of lithium aluminium double ion rechargeable battery |
| US10418663B2 (en) | 2016-05-17 | 2019-09-17 | Industrial Technology Research Institute | Metal-ion battery |
| CN110600706A (en) * | 2019-09-23 | 2019-12-20 | 易航时代(北京)科技有限公司 | Tungsten disulfide nanosheet/nitrogen-doped carbon nanofiber composite material, preparation method and application thereof, and aluminum ion battery |
| CN110707320A (en) * | 2019-07-31 | 2020-01-17 | 青岛大学 | Two-dimensional transition metal sulfide micron sheet, positive electrode, battery and method |
| US11296329B2 (en) | 2016-12-16 | 2022-04-05 | Industrial Technology Research Institute | Metal-ion battery |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105449271B (en) * | 2016-01-05 | 2019-07-09 | 北京金吕能源科技有限公司 | A kind of CuS is the aluminium ion secondary cell and its preparation process of anode |
| WO2017117838A1 (en) * | 2016-01-05 | 2017-07-13 | 北京金吕能源科技有限公司 | Low-temperature inorganic-molten-salt aluminum-ion supercapacitor cell, and method for preparing same |
| 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 |
| US10418663B2 (en) | 2016-05-17 | 2019-09-17 | Industrial Technology Research Institute | Metal-ion battery |
| CN106602129A (en) * | 2016-12-12 | 2017-04-26 | 北京科技大学 | Multi-ion battery and preparation method thereof |
| CN106602129B (en) * | 2016-12-12 | 2019-09-06 | 北京科技大学 | A kind of polyion battery and preparation method thereof |
| US11296329B2 (en) | 2016-12-16 | 2022-04-05 | Industrial Technology Research Institute | Metal-ion battery |
| CN106784867A (en) * | 2016-12-23 | 2017-05-31 | 盐城工学院 | A kind of fuel cell and preparation method thereof and fuel cell anode materials |
| CN106784867B (en) * | 2016-12-23 | 2019-07-09 | 盐城工学院 | A kind of fuel cell and preparation method thereof and fuel cell anode materials |
| CN108428934A (en) * | 2018-04-11 | 2018-08-21 | 北京科技大学 | A kind of microballoon AlV3O9Method as aluminium ion anode |
| CN109037789B (en) * | 2018-07-27 | 2021-04-13 | 江西迪比科股份有限公司 | Lithium-aluminum double-ion rechargeable battery |
| CN109037789A (en) * | 2018-07-27 | 2018-12-18 | 江西迪比科股份有限公司 | A kind of lithium aluminium double ion rechargeable battery |
| CN110707320A (en) * | 2019-07-31 | 2020-01-17 | 青岛大学 | Two-dimensional transition metal sulfide micron sheet, positive electrode, battery and method |
| CN110707320B (en) * | 2019-07-31 | 2022-07-22 | 青岛大学 | Two-dimensional transition metal sulfide micron sheet, anode, battery and method |
| CN110600706A (en) * | 2019-09-23 | 2019-12-20 | 易航时代(北京)科技有限公司 | Tungsten disulfide nanosheet/nitrogen-doped carbon nanofiber composite material, preparation method and application thereof, and aluminum ion battery |
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Application publication date: 20150610 |