CN104952629A - Aluminum capacitor battery and preparation method thereof - Google Patents
Aluminum capacitor battery and preparation method thereof Download PDFInfo
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- CN104952629A CN104952629A CN201510338875.7A CN201510338875A CN104952629A CN 104952629 A CN104952629 A CN 104952629A CN 201510338875 A CN201510338875 A CN 201510338875A CN 104952629 A CN104952629 A CN 104952629A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 79
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 65
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 89
- 239000000463 material Substances 0.000 claims description 66
- 239000005030 aluminium foil Substances 0.000 claims description 43
- 239000006258 conductive agent Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 239000007921 spray Substances 0.000 claims description 24
- -1 Delanium Chemical compound 0.000 claims description 20
- 239000011258 core-shell material Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000005660 chlorination reaction Methods 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 5
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical group CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011257 shell material Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005098 hot rolling Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011888 foil Substances 0.000 abstract 4
- 229910021383 artificial graphite Inorganic materials 0.000 abstract 1
- 229910021382 natural graphite Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- 230000004888 barrier function Effects 0.000 description 22
- 230000008569 process Effects 0.000 description 22
- 239000007772 electrode material Substances 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000003273 ketjen black Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 229940098458 powder spray Drugs 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 4
- 229910016467 AlCl 4 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000002847 impedance measurement Methods 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to an aluminum capacitor battery and a preparation method thereof, and belongs to the technical field of energy storage devices. The aluminum capacitor battery comprises a positive electrode, a negative electrode and electrolyte; the positive electrode comprises aluminum foil and a positive electrode material adhered to the aluminum foil; the positive electrode material comprises a positive electrode active material and a positive electrode binder; the positive electrode material is one of natural graphite, synthetic graphite and graphene; the negative electrode comprises aluminum foil and a negative electrode material adhered to the aluminum foil; the negative electrode material comprises a negative electrode active material and a negative electrode binder; the negative electrode material is one of active carbon and the graphene; the electrolyte is aluminum ion-contained electrolyte. The energy density of the aluminum capacitor battery disclosed by the invention can reach more than 40Wh/kg, and the power density of the aluminum capacitor battery can reach more than 6300W/kg.
Description
Technical field
The present invention relates to a kind of aluminum capacitor battery and preparation method thereof, belong to energy storage device technical field.
Background technology
Electrochemical capacitor is filling electrolyte between porous electrode, when applying voltage at capacitor batteries two ends, porous electrode assembles positron-electron respectively, and form electric field between two electrodes, the charged particle in electrolyte is attracted to gather on the interface of porous electrode, between electrode and electrolyte interface, form electric charge current collection layer, can electric energy be released in use.Namely said process constitutes the charge and discharge process of electrochemical capacitor.Electrochemical capacitor operation principle determine its have charging rate fast, have extended cycle life, the feature such as large current discharging capability is strong, power density high and low temperature performance is good, thus in electric automobile, fuel combination automobile, exceptional load vehicle, wind power generation, photovoltaic generation, electric power, railway, communication, consumption electronic products etc., have huge using value and market potential.
The energy density of general electrochemical capacitor is lower, and range of application receives larger restriction.Along with the appearance of the capacitor batteries of Large Copacity, high-energy-density, change this present situation.The kind of the electrode material that capacitor batteries uses and the patterns affect that reacts the energy density of capacitor batteries, the electrode material of existing capacitor batteries mainly contain active carbon series and transition metal oxide serial.Simple employing active carbon material is not high as the capacity of the capacitor batteries of electrode material, specific energy, and the cost of transition metal oxide is too high, is unfavorable for promoting the use of.In order to improve the specific energy of capacitor batteries, the energy density improving capacitor batteries by means of novel electrochemical energy storage mechanism receives extensive concern.
Notification number is that the Chinese invention patent (authorized announcement date on June 18th, 2003) of CN1111885C discloses a kind of high performance double layer capacitors comprising aluminium carbon composite electrodes, and specifically disclose the aluminium impregnated carbon combination electrode that its double layer capacitor comprises a pair porous, comprise the activated carbon fiber prefabrication of the aluminium dipping of fusing, also comprise a pair current collector plate, ionic conduction dividing plate, water-free electrolyte solution.This double electric layer capacitor employs the activated carbon of aluminium dipping as electrode, employs a large amount of aluminium, can reduce its energy density.
Summary of the invention
Aluminum capacitor battery that the object of the present invention is to provide a kind of energy density high and preparation method thereof.
In order to realize above object, the technical scheme of aluminum capacitor battery of the present invention is as follows:
A kind of aluminum capacitor battery, comprises positive electrode, negative electrode and electrolyte; Described positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, described positive electrode comprises positive electrode active materials and positive electrode binder, described negative electrode comprises aluminium foil and sticks to the negative material on aluminium foil, described negative material comprises negative active core-shell material and negative electrode binder, described electrolyte is for comprising aluminum ions electrolyte, described positive electrode active materials is selected from the one in native graphite, Delanium, Graphene, and negative active core-shell material is selected from the one in active carbon, Graphene.
The positive electrode of aluminum capacitor battery of the present invention and negative electrode all adopt the mode be attached to by electrode material on aluminium foil, decrease the consumption of aluminium, improve the ratio that electrode active material is shared in the electrodes, in the adsorption process that more electrode active material is participated in electric charge, improve the energy density of capacitor batteries.Binding agent wherein can make the combination close and firm more of electrode active material and aluminium foil, avoids electrode active material and comes off in charge and discharge process, cause the loss of capacitor batteries capacity.
In the present invention, the weight ratio of positive electrode active materials and positive electrode binder is 100:8-10; The weight ratio of described negative active core-shell material and negative electrode binder is 100:7-18.The excessive electrode active material that affects of the ratio of binding agent of preferably can avoiding of the weight ratio of this electrode active material and binding agent gives full play to charge-discharge performance, can avoid again the firmness that the too small reduction electrode active material of ratio is combined with aluminium foil.
The thickness of positive/negative electrode plates is excessive, the desorption of the ion be adsorbed in positive/negative active material can be caused to become difficulty, affect the discharge performance of capacitor batteries, and the thickness of positive/negative electrode plates is too small, after being then alternately arranged with barrier film, in limited space can the amount of hold electrodes material will relatively reduce, reduce the energy density of capacitor batteries, therefore, the positive electrode pole piece thickness of capacitor batteries of the present invention is preferably between 30 μm-500 μm, and the thickness of negative electrode pole piece is preferably between 100 μm-500 μm.
In order to improve the adsorption capacity of negative active core-shell material to charged ion, the specific area of the carbon material used as anode of capacitor batteries of the present invention is preferably as 259m
2/ g ~ 1700m
2/ g.The specific area of positive electrode active materials is at 0.4m
2/ g ~ 754m
2/ g.
In order to improve the conductance of positive electrode or negative material, the positive pole of capacitor batteries of the present invention or negative pole all can comprise conductive agent, and the weight ratio of described positive electrode active materials, positive electrode binder and positive conductive agent is 100:8-10:5-10; Same, the weight ratio of described negative active core-shell material, negative electrode binder and cathode conductive agent is 100:7-18:5-10.
Positive electrode binder and negative electrode binder can independently be selected from Kynoar, polytetrafluoroethylene any one.
Positive conductive agent and cathode conductive agent can independently be selected from SP, Ketjen black, KS-6 any one.
In order to improve the conduction efficiency of electrolyte intermediate ion, the electrolyte of capacitor batteries of the present invention comprises electrolytic salt and solvent, and described electrolytic salt is AlCl
3.AlCl in described electrolyte
3concentration be 0.6 ~ 1.8mol/L.
In order to improve the efficiency of transmission of electrolyte intermediate ion further, the electrolyte of capacitor batteries of the present invention uses ionic liquid as solvent, described solvent is preferably chlorinated butyl pyridine, chlorination 1-ethyl-3-methylimidazole, one or more in chlorination 1-butyl-3-methylimidazole.
The preparation method of positive electrode of the present invention, comprises the steps:
1) batch mixing: by positive electrode active materials, positive electrode binder mixing, obtain positive pole premixed powder body material;
2) spheroidising: by step 1) in the positive pole premixed powder body material that obtains carry out spheroidising, obtain positive pole nodularization powder body material;
3) spray: by step 2) in the positive pole nodularization powder body material that obtains spray on aluminium foil, obtain positive pole powder electrode;
4) sinter: by step 3) in the positive pole powder electrode that obtains sinter at 120-200 DEG C, obtain positive pole sintered electrode, described positive pole sintered electrode is described positive electrode.
The preparation method of negative electrode of the present invention, comprises the steps:
1) batch mixing: by negative active core-shell material, negative electrode binder mixing, obtain negative pole premixed powder body material;
2) spheroidising: by step 1) in the negative pole premixed powder body material that obtains carry out spheroidising, obtain negative pole nodularization powder body material;
3) spray: by step 2) in the negative pole nodularization powder body material that obtains spray on aluminium foil, obtain negative pole Powder electrode;
4) sinter: by step 3) in the negative pole Powder electrode that obtains sinter at 120-200 DEG C, obtain negative pole sintered electrode, described negative pole sintered electrode is described negative electrode.
The preparation method of above-mentioned positive electrode and negative electrode can eliminate the use of organic solvent in traditional electrode preparation method, simplifies technique, improves production efficiency, and it also avoid the reduction of the organic solvent residual conductance caused in the electrodes.Spheroidising can improve the surface area of powder body material, is conducive to the movement of electric charge.Sintering can make the binding agent in electrode material better electrode active material is bonded in aluminium foil surface.
In order to improve the combination degree of electrode material on electrode and aluminium foil, described step 4) in sintered electrode after 150-160 DEG C of hot-rolling pressure, obtain described electrode.
Step 1) in batch mixing time, speed of agitator is preferably 10 ~ 500r/min, and mixing time is preferably 10 ~ 300min.
Step 2) in the spheroidising time be preferably 10-300min.
Step 4) in sintering time be preferably 30 ~ 300min.
The technical scheme of the preparation method of aluminum capacitor battery of the present invention is as follows:
The preparation method of aluminum capacitor battery of the present invention, comprises the steps:
The battery core prepared carried out immersion treatment before entering shell, and described immersion treatment is: battery core is placed in electrolyte vacuum and soaks 10 ~ 120min.Vacuum degree is preferably-0.01 ~-0.05MPa.The battery core of soaking enters shell, and sealing, namely obtains described aluminum capacitor battery.
In order to the moisture be mixed into when preventing battery core to make is introduced in the electrolyte of capacitor batteries, above-mentioned battery core is soaked after carrying out drying process again, and the temperature of described drying process is 50 ~ 200 DEG C, and drying time is 12 ~ 36h.Described drying is dry under the vacuum degree of-0.01 ~-0.03MPa.
In order to make electrolyte and battery core fully infiltrate, carry out into shell again after leaving standstill 1-24h after steeping.
Electrode active material is bonded in electrode aluminium foil constituting aluminum capacitor battery by the electrode of aluminum capacitor battery of the present invention by binding agent, simplify the manufacturing process of aluminum capacitor battery, reduce production cost, and improves the energy density of capacitor batteries.
Further, aluminum capacitor battery of the present invention adopts AlCl
3as electrolytic salt, adopt chlorinated butyl pyridine, chlorination 1-ethyl-3-methylimidazole, chlorination 1-butyl-3-methylimidazole plasma liquid as solvent.
In the electrolytic solution, AlCl
3to dissociate the Cl with solvent
-in conjunction with formation [AlCl
4 -], solvent molecule dissociates Cl
-after define cation (use BP
+represent).When charging, positive electrode surface have accumulated positive charge, attracts [AlCl
4 -] gather at positive electrode surface, accordingly, negative terminal surface attracts BP
+gather in negative terminal surface.When discharging, there occurs the process contrary with said process.Positive pole and negative pole there occurs following reaction respectively:
Positive pole: C
n[AlCl
4 -]+e
-→ C
n+ AlCl
4 -
Negative pole: C
n[BP
+] → C
n+ BP
+
Quickly, therefore the power of aluminum capacitor battery of the present invention is higher for above-mentioned reaction rate.And by means of the effect of above-mentioned reaction, the energy density of aluminum capacitor battery of the present invention can reach more than 40Wh/kg, and energy density is much larger than existing ultracapacitor and lithium-ion capacitor battery.
Accompanying drawing explanation
Fig. 1 is the reaction principle schematic diagram of aluminum capacitor battery of the present invention;
Fig. 2 is the aluminum capacitor battery charging and discharging curve under constant current conditions in enforcement 1;
Fig. 3 is the ac impedance measurement curve of the aluminum capacitor battery of embodiment 1-4.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
The aluminum capacitor battery of the present embodiment, comprises positive electrode, negative electrode, barrier film and electrolyte.
Positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, positive electrode pole piece thickness is 200 μm, positive electrode comprises positive electrode active materials native graphite, positive electrode binder Kynoar and positive conductive agent Super-P (hereinafter referred to as SP), the weight ratio of graphite, Kynoar, SP is 100:9:5, and the specific area of native graphite is 1.3m
2/ g.
Negative electrode comprises aluminium foil and is attached to the negative material on aluminium foil, negative electrode thickness is 300 μm, negative material comprises negative active core-shell material active carbon, negative electrode binder Kynoar, conductive agent SP, the weight ratio of active carbon, Kynoar, conductive agent is 100:9:5, and the specific area of active carbon is 1700m
2/ g.
Electrolyte is by electrolytic salt and solvent composition, and in the present embodiment, electrolytic salt is AlCl
3, solvent is chlorinated butyl pyridine ([BP] Cl), AlCl in electrolyte
3concentration be 1.3mol/L.Described barrier film is microporous polypropylene membrane.
The preparation method of the positive electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get positive electrode active materials graphite, positive electrode binder Kynoar, positive conductive agent SP, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 50r/min, and mixing time is 20min, obtains positive pole premixed powder body material;
2) spheroidising: by step 1) obtained positive pole premixed powder body material is transported in balling machine (the RQM-30 balling machine of Luoyang Qi Xing technological development Co., Ltd), carry out spheroidising, the power of balling machine is 50kW, the nodularization time is 30min, obtains positive pole nodularization powder body material;
3) spraying: by step 2) obtained positive pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain positive pole powder electrode;
4) sintering: by step 3) the positive pole powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 120 DEG C of conditions, and sintering time is 30min, obtains positive pole sintered electrode;
5) roll-in: by step 4) the positive pole sintered electrode that obtains uses hot calender roller process at 150 DEG C, and controlling pole piece thickness is 200 μm, i.e. obtained described positive electrode.
The preparation method of the negative electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get negative active core-shell material active carbon, negative electrode binder Kynoar, cathode conductive agent SP, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 50r/min, and mixing time is 20min, obtains negative pole premixed powder body material;
2) spheroidising: by step 1) obtained negative pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 50kW, and the nodularization time is 30min, obtains negative pole nodularization powder body material;
3) spraying: by step 2) obtained negative pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain negative pole Powder electrode;
4) sintering: by step 3) the negative pole Powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 120 DEG C of conditions, and sintering time is 30min, obtains negative pole sintered electrode;
5) roll-in: by step 4) the negative pole sintered electrode that obtains uses hot calender roller process at 150 DEG C, and controlling pole piece thickness is 300 μm, i.e. obtained described negative electrode.
The preparation method of above-mentioned aluminum capacitor battery comprises the steps:
1), after above-mentioned positive electrode, negative electrode, barrier film being stacked successively according to the order of positive electrode, barrier film, negative electrode, barrier film, winding makes the cylindrical takeup type battery core that diameter is 58mm on the winder;
2) by step 1) in the battery core that obtains carry out vacuumize, baking temperature is 80 DEG C, and vacuum degree is-0.03MPa, and drying time is 12h;
3) AlCl of above-mentioned 1.3mol/L is got
3the electrolyte of/chlorinated butyl pyridine ([BP] Cl), by step 2 under the vacuum degree of-0.05MPa) in dried battery core be immersed in this electrolyte, soak time is 30min;
4) by step 3) in soak after battery core load in aluminum hull, sealing, leaves standstill 10h, namely makes aluminum capacitor battery.
Embodiment 2
The aluminum capacitor battery of the present embodiment, comprises positive electrode, negative electrode, barrier film and electrolyte.
Positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, positive electrode pole piece thickness is 30 μm, positive electrode is positive electrode active materials Graphene, positive electrode binder polytetrafluoroethylene and positive conductive agent SP, the weight ratio of Graphene, polytetrafluoroethylene, SP is 100:10:7, and the specific area of Graphene is 754m
2/ g.
Negative electrode comprises aluminium foil and is attached to the negative material on aluminium foil, negative electrode thickness is 100 μm, negative material comprises negative active core-shell material Graphene, negative electrode binder polytetrafluoroethylene, conductive agent KS-6, the weight ratio of Graphene, polytetrafluoroethylene, KS-6 is 100:7:7, and the specific area of Graphene is 259m
2/ g.
Electrolyte is by electrolytic salt and solvent composition, and in the present embodiment, electrolytic salt is AlCl
3, solvent is chlorination 1-ethyl-3-methylimidazole ([EMIm] Cl), AlCl in electrolyte
3concentration be 0.6mol/L.Described barrier film is polyethene microporous membrane.
The preparation method of the positive electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get positive electrode active materials Graphene, positive electrode binder polytetrafluoroethylene, positive conductive agent SP, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 10r/min, and mixing time is 300min, obtains positive pole premixed powder body material;
2) spheroidising: by step 1) obtained positive pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 100kW, and the nodularization time is 10min, obtains positive pole nodularization powder body material;
3) spraying: by step 2) obtained positive pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain positive pole powder electrode;
4) sintering: by step 3) the positive pole powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 150 DEG C of conditions, and sintering time is 300min, obtains positive pole sintered electrode;
5) roll-in: by step 4) the positive pole sintered electrode that obtains uses hot calender roller process at 150 DEG C, and controlling pole piece thickness is 30 μm, i.e. obtained described positive electrode.
The preparation method of the negative electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get negative active core-shell material Graphene, negative electrode binder polytetrafluoroethylene, cathode conductive agent KS-6, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 10r/min, and mixing time is 300min, obtains negative pole premixed powder body material;
2) spheroidising: by step 1) obtained negative pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 100kW, and the nodularization time is 10min, obtains negative pole nodularization powder body material;
3) spraying: by step 2) obtained negative pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain negative pole Powder electrode;
4) sintering: by step 3) the negative pole Powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 150 DEG C of conditions, and sintering time is 300min, obtains negative pole sintered electrode;
5) roll-in: by step 4) the negative pole sintered electrode that obtains uses hot calender roller process at 150 DEG C, and controlling pole piece thickness is 100 μm, i.e. obtained described negative electrode.
The preparation method of above-mentioned aluminum capacitor battery comprises the steps:
1), after above-mentioned positive electrode, negative electrode, barrier film being stacked successively according to the order of positive electrode, barrier film, negative electrode, barrier film, winding makes the cylindrical takeup type battery core that diameter is 58mm on the winder;
2) by step 1) in the battery core that obtains carry out vacuumize, baking temperature is 50 DEG C, and vacuum degree is-0.01MPa, and drying time is 20h;
3) AlCl of above-mentioned 0.6mol/L is got
3the electrolyte of/chlorination 1-ethyl-3-methylimidazole ([EMIm] Cl), by step 2 under the vacuum degree of-0.01MPa) in dried battery core be immersed in this electrolyte, soak time is 120min;
4) by step 3) in soak after battery core load in aluminum hull, sealing, leaves standstill 1h, namely makes aluminum capacitor battery.
Embodiment 3
The aluminum capacitor battery of the present embodiment, comprises positive electrode, negative electrode, barrier film and electrolyte.
Positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, positive electrode pole piece thickness is 500 μm, positive electrode is positive electrode active materials native graphite, positive electrode binder Kynoar and positive conductive agent Ketjen black, the weight ratio of native graphite, Kynoar, Ketjen black is 100:8:7, and the specific area of native graphite is 0.4m
2/ g.
Negative electrode comprises aluminium foil and is attached to the negative material on aluminium foil, negative electrode thickness is 500 μm, negative material comprises negative active core-shell material active carbon YP50 (Kuraray), negative electrode binder polytetrafluoroethylene, conductive agent Ketjen black, the weight ratio of active carbon, polytetrafluoroethylene, Ketjen black is 100:10:7, and the specific area of active carbon is 800m
2/ g.
Electrolyte is by electrolytic salt and solvent composition, and in the present embodiment, electrolytic salt is AlCl
3, solvent is chlorination 1-butyl-3-methylimidazole ([BMIm] Cl), AlCl in electrolyte
3concentration be 1.8mol/L.Described barrier film is cellulosic separator.
The preparation method of the positive electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get positive electrode active materials native graphite, positive electrode binder Kynoar, positive conductive agent Ketjen black, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 500r/min, and mixing time is 10min, obtains positive pole premixed powder body material;
2) spheroidising: by step 1) obtained positive pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 10kW, and the nodularization time is 300min, obtains positive pole nodularization powder body material;
3) spraying: by step 2) obtained positive pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain positive pole powder electrode;
4) sintering: by step 3) the positive pole powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 200 DEG C of conditions, and sintering time is 60min, obtains positive pole sintered electrode;
5) roll-in: by step 4) the positive pole sintered electrode that obtains uses hot calender roller process at 160 DEG C, and controlling pole piece thickness is 500 μm, i.e. obtained described positive electrode.
The preparation method of the negative electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get negative active core-shell material active carbon, negative electrode binder polytetrafluoroethylene, cathode conductive agent Ketjen black, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 500r/min, and mixing time is 10min, obtains negative pole premixed powder body material;
2) spheroidising: by step 1) obtained negative pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 100kW, and the nodularization time is 300min, obtains negative pole nodularization powder body material;
3) spraying: by step 2) obtained negative pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain negative pole Powder electrode;
4) sintering: by step 3) the negative pole Powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 200 DEG C of conditions, and sintering time is 60min, obtains negative pole sintered electrode;
5) roll-in: by step 4) the negative pole sintered electrode that obtains uses hot calender roller process at 160 DEG C, and controlling pole piece thickness is 500 μm, i.e. obtained described negative electrode.
The preparation method of above-mentioned aluminum capacitor battery comprises the steps:
1), after above-mentioned positive electrode, negative electrode, barrier film being stacked successively according to the order of positive electrode, barrier film, negative electrode, barrier film, winding makes the cylindrical takeup type battery core that diameter is 58mm on the winder;
2) by step 1) in the battery core that obtains carry out vacuumize, baking temperature is 200 DEG C, and vacuum degree is-0.03MPa, and drying time is 36h;
3) AlCl of above-mentioned 1.8mol/L is got
3the electrolyte of/chlorination 1-butyl-3-methylimidazole ([BMIm] Cl), by step 2 under the vacuum degree of-0.02MPa) in dried battery core be immersed in this electrolyte, soak time is 10min;
4) by step 3) in soak after battery core load in aluminum hull, sealing, leaves standstill 24h, namely makes aluminum capacitor battery.
Embodiment 4
The aluminum capacitor battery of the present embodiment, comprises positive electrode, negative electrode, barrier film and electrolyte.
Positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, positive electrode pole piece thickness is 450 μm, positive electrode is positive electrode active materials Delanium, positive electrode binder Kynoar and positive conductive agent Ketjen black, the weight ratio of Delanium, Kynoar, Ketjen black is 100:10:10, and the specific area of Delanium is 1m
2/ g.
Negative electrode comprises aluminium foil and is attached to the negative material on aluminium foil, negative electrode thickness is 350 μm, negative material comprises negative active core-shell material Graphene, negative electrode binder polytetrafluoroethylene, conductive agent SP, the weight ratio of Graphene, polytetrafluoroethylene, SP is 100:18:10, and the specific area of Graphene is 1500m
2/ g.
Electrolyte is by electrolytic salt and solvent composition, and in the present embodiment, electrolytic salt is AlCl
3, solvent is chlorination 1-butyl-3-methylimidazole ([BMIm] Cl), AlCl in electrolyte
3concentration be 1.2mol/L.Described barrier film is polypropylene diaphragm.
The preparation method of the positive electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get positive electrode active materials Delanium, positive electrode binder Kynoar, positive conductive agent Ketjen black, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 25r/min, and mixing time is 20min, obtains positive pole premixed powder body material;
2) spheroidising: by step 1) obtained positive pole premixed powder body material is transported in ultrasonic balling machine, and carry out spheroidising, the power of balling machine is 15kW, and the nodularization time is 30min, obtains positive pole nodularization powder body material;
3) spraying: by step 2) obtained positive pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain positive pole powder electrode;
4) sintering: by step 3) the positive pole powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 180 DEG C of conditions, and sintering time is 100min, obtains positive pole sintered electrode;
5) roll-in: by step 4) the positive pole sintered electrode that obtains uses hot calender roller process at 155 DEG C, and controlling pole piece thickness is 450 μm, i.e. obtained described positive electrode.
The preparation method of the negative electrode of the present embodiment comprises the steps:
1) batch mixing: proportionally get negative active core-shell material Graphene, negative electrode binder polytetrafluoroethylene, cathode conductive agent SP, put into V-type to mix powder machine and mix, the rotating speed that V-type mixes powder machine is 25r/min, and mixing time is 30min, obtains negative pole premixed powder body material;
2) spheroidising: by step 1) obtained negative pole premixed powder body material is transported in balling machine, and carry out spheroidising, the power of balling machine is 10kW, and the nodularization time is 30min, obtains negative pole nodularization powder body material;
3) spraying: by step 2) obtained negative pole nodularization powder body material sprays to two surfaces of aluminium foil by electrostatic powder spray gun, and quantity for spray controls as 50mg/cm
2, obtain negative pole Powder electrode;
4) sintering: by step 3) the negative pole Powder electrode that obtains puts into the IR bake of 100kW, sintering processes under 180 DEG C of conditions, and sintering time is 100min, obtains negative pole sintered electrode;
5) roll-in: by step 4) the negative pole sintered electrode that obtains uses hot calender roller process at 155 DEG C, and controlling pole piece thickness is 350 μm, i.e. obtained described negative electrode.
The preparation method of above-mentioned aluminum capacitor battery comprises the steps:
1), after above-mentioned positive electrode, negative electrode, barrier film being stacked successively according to the order of positive electrode, barrier film, negative electrode, barrier film, winding makes the cylindrical takeup type battery core that diameter is 58mm on the winder;
2) by step 1) in the battery core that obtains carry out vacuumize, baking temperature is 180 DEG C, and vacuum degree is-0.03MPa, and drying time is 36h;
3) AlCl of above-mentioned 1.2mol/L is got
3the electrolyte of/chlorination 1-butyl-3-methylimidazole ([BMIm] Cl), by step 2 under the vacuum degree of-0.03MPa) in dried battery core be immersed in this electrolyte, soak time is 10min;
4) by step 3) in soak after battery core load in aluminum hull, sealing, leaves standstill 24h, namely makes aluminum capacitor battery.
Embodiment 5
The difference of the present embodiment and embodiment 1 is, positive electrode does not comprise positive conductive agent, and negative material does not comprise cathode conductive agent.
Embodiment 6
The difference of the present embodiment and embodiment 1 is, time prepared by aluminum capacitor battery, positive pole, negative pole, barrier film are made lamination type electric core, other steps are identical with embodiment 1.
Experimental example
The capacitor batteries that above-described embodiment 1-6 is obtained is tested in the following manner:
The electro-chemical test of aluminum capacitor battery: all electro-chemical tests are all test at ambient temperature.Constant current test is all tested on LAND CT2001A battery test system, and ac impedance measurement is then test on Autolab electrochemical workstation.The current density of constant current test is 1-10A/g, and the frequency of ac impedance measurement is 100kHz to 10mHz.
Test result is as shown in table 1 and Fig. 2-3:
Table 1
| Embodiment | Energy density | Power density |
| Embodiment 1 | 40 | 6530 |
| Embodiment 2 | 39 | 6380 |
| Embodiment 3 | 35 | 6217 |
| Embodiment 4 | 39 | 6230 |
| Embodiment 5 | 40 | 6120 |
| Embodiment 6 | 39 | 6320 |
From the results shown in Table 1, the energy density of aluminum capacitor battery of the present invention reaches 40Wh/kg, and power density reaches 6300W/kg.
The electrode of capacitor batteries of the present invention uses binding agent to be bonded on aluminium foil by electrode active material, has both improve the energy density of capacitor batteries, in turn simplify the manufacture craft of electrode, reduce production cost.
Claims (10)
1. an aluminum capacitor battery, is characterized in that, comprises positive electrode, negative electrode and electrolyte; Described positive electrode comprises aluminium foil and sticks to the positive electrode on aluminium foil, and described positive electrode comprises positive electrode active materials and positive electrode binder, and described positive electrode is the one in native graphite, Delanium, Graphene; Described negative electrode comprises aluminium foil and sticks to the negative material on aluminium foil, and described negative material comprises negative active core-shell material and negative electrode binder, and described negative material is the one in active carbon, Graphene; Described electrolyte is for comprising aluminum ions electrolyte.
2. aluminum capacitor battery as claimed in claim 1, it is characterized in that, the weight ratio of described positive electrode active materials and positive electrode binder is 100:8-10; The weight ratio of described negative active core-shell material and negative electrode binder is 100:7-18.
3. aluminum capacitor battery as claimed in claim 1, it is characterized in that, described positive electrode comprises positive conductive agent, and the weight ratio of described positive electrode active materials, positive electrode binder and positive conductive agent is 100:8-10:5-10.
4. aluminum capacitor battery as claimed in claim 1, it is characterized in that, described negative material comprises cathode conductive agent, and the weight ratio of described negative active core-shell material, negative electrode binder and cathode conductive agent is 100:7-18:5-10.
5. aluminum capacitor battery as claimed in claim 1, it is characterized in that, described electrolyte comprises electrolytic salt and ion liquid solvent, and described electrolytic salt is AlCl
3, AlCl in described electrolyte
3concentration be 0.6 ~ 1.8mol/L.
6. aluminum capacitor battery as claimed in claim 5, it is characterized in that, described ion liquid solvent is chlorinated butyl pyridine, chlorination 1-ethyl-3-methylimidazole, one or more in chlorination 1-butyl-3-methylimidazole.
7. aluminum capacitor battery as claimed in claim 1, it is characterized in that, the preparation method of described positive electrode, comprises the steps:
1) batch mixing: by positive electrode active materials, positive electrode binder mixing, obtain positive pole premixed powder body material;
2) spheroidising: by step 1) in the positive pole premixed powder body material that obtains carry out spheroidising, obtain positive pole nodularization powder body material;
3) spray: by step 2) in the positive pole nodularization powder body material that obtains spray on aluminium foil, obtain positive pole powder electrode;
4) sinter: by step 3) in the positive pole powder electrode that obtains sinter at 120-200 DEG C, obtain positive pole sintered electrode, described positive pole sintered electrode is described positive electrode.
8. aluminum capacitor battery as claimed in claim 1, it is characterized in that, the preparation method of described negative electrode, comprises the steps:
1) batch mixing: by negative active core-shell material, negative electrode binder mixing, obtain negative pole premixed powder body material;
2) spheroidising: by step 1) in the negative pole premixed powder body material that obtains carry out spheroidising, obtain negative pole nodularization powder body material;
3) spray: by step 2) in the negative pole nodularization powder body material that obtains spray on aluminium foil, obtain negative pole Powder electrode;
4) sinter: by step 3) in the negative pole Powder electrode that obtains sinter at 120-200 DEG C, obtain negative pole sintered electrode, described negative pole sintered electrode is described negative electrode.
9. as claimed in claim 7 or 8 aluminum capacitor battery, is characterized in that, described step 4) after sintering through 150-160 DEG C of hot-rolling pressure.
10. a preparation method for aluminum capacitor battery as claimed in claim 1, is characterized in that, comprise the steps:
The battery core prepared is placed in described electrolyte vacuum and soaks 10 ~ 120min, take out into shell, sealing, obtains described aluminum capacitor battery.
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