CN104952629B - A kind of aluminum capacitor battery and preparation method thereof - Google Patents
A kind of aluminum capacitor battery and preparation method thereof Download PDFInfo
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- CN104952629B CN104952629B CN201510338875.7A CN201510338875A CN104952629B CN 104952629 B CN104952629 B CN 104952629B CN 201510338875 A CN201510338875 A CN 201510338875A CN 104952629 B CN104952629 B CN 104952629B
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Abstract
The present invention relates to a kind of aluminum capacitor batteries and preparation method thereof, belong to energy storage device technical field.The aluminum capacitor battery includes positive electrode, negative electrode and electrolyte；The positive electrode includes aluminium foil and the positive electrode that is adhered on aluminium foil, and the positive electrode includes positive electrode active materials and positive electrode binder, and the positive electrode is one of natural graphite, artificial graphite, graphene；The negative electrode includes aluminium foil and the negative electrode material that is adhered on aluminium foil, and the negative electrode material includes negative electrode active material and negative electrode binder, and the negative electrode material is one of active carbon, graphene；The electrolyte is to include aluminum ions electrolyte.Aluminum capacitor battery energy density of the invention is up to 40Wh/kg or more, and power density is up to 6300W/kg.
Description
Technical field
The present invention relates to a kind of aluminum capacitor batteries and preparation method thereof, belong to energy storage device technical field.
Background technique
Electrochemical capacitor is the filling electrolyte between porous electrode, more when applying voltage at capacitor batteries both ends
Assemble positron-electron on pore electrod respectively, and form electric field between two electrodes, attracts the charged particle aggregation in electrolyte
Onto the interface of porous electrode, charge current collection layer is formed between electrode and electrolyte interface, can release electric energy when in use.
The above process constitutes the charge and discharge process of electrochemical capacitor.Electrochemical capacitor working principle determines that it has charging
Speed is fast, has extended cycle life, the features such as large current discharging capability is strong, power density high and low temperature performance is good, thus in electronic vapour
Vehicle, fuel combination automobile, exceptional load vehicle, wind power generation, photovoltaic power generation, electric power, railway, communication, consumer electrical product
Etc. have huge application value and market potential.
The energy density of general electrochemical capacitor is lower, and application range has been more limited.With large capacity,
The appearance of the capacitor batteries of high-energy density changes this status.The type and hair for the electrode material that capacitor batteries use
The patterns affect of raw reaction the energy density of capacitor batteries, the main active charcoal series of the electrode material of existing capacitor batteries
With transition metal oxide series.Simply use capacity of the active carbon material as the capacitor batteries of electrode material, specific energy
It is not high, 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, by
It is had received widespread attention in novel electrochemical energy storage mechanism to improve the energy density of capacitor batteries.
Notification number is that the Chinese invention patent (authorized announcement date on June 18th, 2003) of CN1111885C discloses a kind of packet
High performance double layer capacitors containing aluminium carbon composite electrodes, and specifically disclosing its double layer capacitor includes a pair of porous aluminium dipping
Carbon composite electrode, including fusing aluminium dipping activated carbon fiber prefabrication, further include a pair of of current collector plate, ionic conduction every
Plate, water-free electrolyte solution.The activated carbon that the double layer capacitor has used aluminium to impregnate has used a large amount of as electrode
Aluminium can reduce its energy density.
Summary of the invention
The purpose of the present invention is to provide a kind of aluminum capacitor batteries and preparation method thereof that energy density is high.
In order to achieve the goal above, the technical solution of aluminum capacitor battery of the invention is as follows:
A kind of aluminum capacitor battery, including positive electrode, negative electrode and electrolyte；The positive electrode includes aluminium foil and is adhered to aluminium
Positive electrode on foil, the positive electrode include positive electrode active materials and positive electrode binder, the negative electrode include aluminium foil and
The negative electrode material being adhered on aluminium foil, the negative electrode material include negative electrode active material and negative electrode binder, and the electrolyte is
Comprising aluminum ions electrolyte, the positive electrode active materials are selected from one of natural graphite, artificial graphite, graphene, cathode
Active material is selected from one of active carbon, graphene.
The positive electrode and negative electrode of aluminum capacitor battery of the invention are all made of the mode being attached to electrode material on aluminium foil,
The dosage for reducing aluminium improves electrode active material shared ratio in the electrodes, so that there is more electrode active materials
It participates in the adsorption process to charge, improves the energy density of capacitor batteries.Binder therein can make electrode activity
The combination of material and aluminium foil is even closer securely to be avoided electrode active material and falls off in charge and discharge process, causes capacitor electric
The loss of tankage.
The weight ratio of positive electrode active materials and positive electrode binder is 100:8-10 in the present invention；The negative electrode active material with
The weight ratio of negative electrode binder is 100:7-18.The weight ratio of the electrode active material and binder preferably can be to avoid bonding
The excessive influence electrode active material of the ratio of agent gives full play to charge-discharge performance, and is avoided that the too small reduction electrode activity material of ratio
Expect the firmness in conjunction with aluminium foil.
The thickness of positive/negative electrode plates is excessive, and the desorption that will lead to the ion being adsorbed in positive/negative active material becomes
Difficulty influences the discharge performance of capacitor batteries, and the thickness of positive/negative electrode plates is too small, then limited after being alternately arranged with diaphragm
Space in can the amount of accommodate electrod material opposite will reduce, reduce the energy density of capacitor batteries, therefore, the present invention
The positive electrode pole piece thickness of capacitor batteries be preferably between 30 μm -500 μm that the thickness of negative electrode pole piece is preferably 100 μm -
Between 500 μm.
In order to improve negative electrode active material to the adsorption capacity of charged ion, the negative carbon material of capacitor batteries of the invention
The specific surface area of material is 259m2/ g~1700m2/g.The specific surface area of positive electrode active materials is in 0.4m2/ g~754m2/
g。
The anode or cathode of conductivity in order to improve positive electrode perhaps negative electrode material capacitor batteries of the invention are equal
It may include conductive agent, the weight ratio of the positive electrode active materials, positive electrode binder and positive conductive agent is 100:8-10:5-
10；Likewise, the weight ratio of the negative electrode active material, negative electrode binder and cathode conductive agent is 100:7-18:5-10.
Positive electrode binder and negative electrode binder can be respectively and independently selected from Kynoar, any one in polytetrafluoroethylene (PTFE)
Kind.
Positive conductive agent and cathode conductive agent can be respectively and independently selected from SP, Ketjen black, any one in KS-6.
In order to improve the conduction efficiency of electrolyte intermediate ion, the electrolyte of capacitor batteries of the invention include electrolytic salt and
Solvent, the electrolytic salt are AlCl3.AlCl in the electrolyte3Concentration be 0.6~1.8mol/L.
In order to further increase the efficiency of transmission of electrolyte intermediate ion, the electrolyte of capacitor batteries of the invention uses ion
For liquid as solvent, the solvent is preferably chlorinated butyl pyridine, chlorination 1- ethyl-3-methylimidazole, chlorination 1- butyl -3- first
One or more of base imidazoles.
The preparation method of positive electrode of the invention, includes the following steps:
1) mixing: positive electrode active materials, positive electrode binder are mixed, positive premixing powder body material is obtained；
2) spheroidising: the premixing powder body material of anode obtained in step 1) is subjected to spheroidising, obtains positive nodularization
Powder body material；
3) it sprays: anode nodularization powder body material obtained in step 2) being sprayed on aluminium foil, positive pole powder electrode is obtained；
4) it is sintered: positive pole powder electrode obtained in step 3) is sintered at 120-200 DEG C, obtain anode sintering electricity
Pole, the anode sintered electrode is the positive electrode.
The preparation method of negative electrode of the invention, includes the following steps:
1) mixing: negative electrode active material, negative electrode binder are mixed, and obtain cathode premixing powder body material；
2) spheroidising: the premixing powder body material of cathode obtained in step 1) is subjected to spheroidising, obtains cathode nodularization
Powder body material；
3) it sprays: cathode nodularization powder body material obtained in step 2) being sprayed on aluminium foil, cathode Powder electrode is obtained；
4) it is sintered: cathode Powder electrode obtained in step 3) is sintered at 120-200 DEG C, obtain cathode sintering electricity
Pole, the cathode sintered electrode are the negative electrode.
The preparation method of above-mentioned positive electrode and negative electrode can eliminate making for organic solvent in traditional electrode preparation method
With simplifying technique, improve production efficiency, and also avoid conductivity caused by the residual of organic solvent in the electrodes
It reduces.Spheroidising can be improved the surface area of powder body material, be conducive to the movement of charge.Sintering can make in electrode material
Electrode active material is preferably bonded in aluminium foil surface by binder.
In order to improve the combination degree of electrode material and aluminium foil on electrode, the sintered electrode in the step 4) passes through
The electrode is obtained after 150-160 DEG C of hot-rolling pressure.
In step 1) when mixing, speed of agitator is preferably 10~500r/min, and mixing time is preferably 10~300min.
The spheroidising time is preferably 10-300min in step 2).
Sintering time is preferably 30~300min in step 4).
The technical solution of the preparation method of aluminum capacitor battery of the invention is as follows:
The preparation method of aluminum capacitor battery of the invention, includes the following steps:
The battery core that preparation is completed carries out immersion treatment, the immersion treatment before entering shell are as follows: battery core is placed in electrolyte
In be soaked in vacuum 10~120min.Vacuum degree is preferably -0.01~-0.05MPa.The battery core impregnated enters shell, seals to get arriving
The aluminum capacitor battery.
Mixed moisture is introduced into the electrolyte of capacitor batteries when battery core being made in order to prevent, and above-mentioned battery core is dried
It is impregnated again after processing, the temperature of the drying process is 50~200 DEG C, and drying time is 12~36h.The drying-
It is dry under the vacuum degree of 0.01~-0.03MPa.
In order to infiltrate electrolyte sufficiently with battery core, carried out again into shell after standing 1-24h after steeping.
Electrode active material is bonded on aluminium foil by the electrode of aluminum capacitor battery of the invention by binder constitutes aluminium
The electrode of capacitor batteries simplifies the manufacturing process of aluminum capacitor battery, reduces production cost, and improves the energy of capacitor batteries
Metric density.
Further, aluminum capacitor battery of the invention uses AlCl3As electrolytic salt, using chlorinated butyl pyridine, chlorine
Change 1- ethyl-3-methylimidazole, chlorination 1- butyl -3- methylimidazole plasma liquid as solvent.
In the electrolytic solution, AlCl3With the free Cl out of solvent-In conjunction with formation [AlCl4 -], the free Cl out of solvent molecule-Shape afterwards
(BP is used at cation+It indicates).In charging, positive electrode surface has accumulated positive charge, attracts [AlCl4 -] in positive electrode surface collection
It is poly-, correspondingly, negative terminal surface attracts BP+Gather in negative terminal surface.In electric discharge, the process opposite with the above process has occurred.
Following reaction has occurred in anode and cathode respectively:
Anode: Cn[AlCl4 ?]+e?→Cn+AlCl4 ?
Cathode: Cn[BP+]→Cn+BP+
Above-mentioned reaction rate is very fast, therefore the power of aluminum capacitor battery of the invention is higher.Moreover, by means of above-mentioned anti-
The effect answered, the energy density of aluminum capacitor battery of the invention is up to 40Wh/kg or more, and energy density is much larger than existing super
Capacitor and lithium-ion capacitor battery.
Detailed description of the invention
Fig. 1 is the reaction principle schematic diagram of aluminum capacitor battery of the invention；
Fig. 2 be implement 1 in aluminum capacitor battery under constant current conditions charging and discharging curve；
Fig. 3 is the ac impedance measurement curve of the aluminum capacitor battery of embodiment 1-4.
Specific embodiment
Technical solution of the present invention is described in detail combined with specific embodiments below.
Embodiment 1
The aluminum capacitor battery of the present embodiment, including positive electrode, negative electrode, diaphragm and electrolyte.
Positive electrode includes aluminium foil and the positive electrode that is adhered on aluminium foil, and positive electrode pole piece is with a thickness of 200 μm, positive material
Material includes positive electrode active materials natural graphite, positive electrode binder Kynoar and positive conductive agent Super-P (hereinafter referred to as SP),
Graphite, Kynoar, SP weight ratio be 100:9:5, the specific surface area of natural graphite is 1.3m2/g。
Negative electrode includes aluminium foil and the negative electrode material that is attached on aluminium foil, and negative electrode is with a thickness of 300 μm, negative electrode material packet
Include negative electrode active material active carbon, negative electrode binder Kynoar, conductive agent SP, active carbon, Kynoar, conductive agent
Weight ratio is 100:9:5, and the specific surface area of active carbon is 1700m2/g。
Electrolyte is made of electrolytic salt and solvent, in the present embodiment, electrolytic salt AlCl3, solvent is chlorinated butyl
Pyridine ([BP] Cl), AlCl in electrolyte3Concentration be 1.3mol/L.The diaphragm is microporous polypropylene membrane.
The preparation method of the positive electrode of the present embodiment includes the following steps:
1) mixing: proportionally taking positive electrode active materials graphite, positive electrode binder Kynoar, positive conductive agent SP,
It is put into the mixed powder machine of V-type and is mixed, the revolving speed that V-type mixes powder machine is 50r/min, and mixing time 20min obtains positive premixing
Powder body material；
2) spheroidising: the premixing powder body material of anode made from step 1) is transported to balling machine and (opens star technology in Luoyang
The RQM-30 balling machine of development corporation, Ltd.) in, spheroidising is carried out, the power of balling machine is 50kW, and the nodularization time is
30min obtains positive nodularization powder body material；
3) it sprays: anode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain positive pole powder electrode；
4) it is sintered: the positive pole powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 120 DEG C
Sintering processes, sintering time 30min obtain positive sintered electrode；
5) roll-in: the positive sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 150 DEG C
Piece obtains the positive electrode with a thickness of 200 μm.
The preparation method of the negative electrode of the present embodiment includes the following steps:
1) negative electrode active material active carbon, negative electrode binder Kynoar, cathode conductive agent proportionally mixing: are taken
SP is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 50r/min, and it is pre- to obtain cathode by mixing time 20min
Mixed powder material；
2) spheroidising: the premixing powder body material of cathode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 50kW, and the nodularization time is 30min, obtain cathode nodularization powder body material；
3) it sprays: cathode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain cathode Powder electrode；
4) it is sintered: the cathode Powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 120 DEG C
Sintering processes, sintering time 30min obtain cathode sintered electrode；
5) roll-in: the cathode sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 150 DEG C
Piece obtains the negative electrode with a thickness of 300 μm.
The preparation method of above-mentioned aluminum capacitor battery includes the following steps:
1) above-mentioned positive electrode, negative electrode, diaphragm are successively stacked according to the sequence of positive electrode, diaphragm, negative electrode, diaphragm
Afterwards, the wound battery core of cylindrical roll that diameter is 58mm is made in winding on the winder；
2) battery core obtained in step 1) is dried in vacuo, drying temperature is 80 DEG C, and vacuum degree is -0.03MPa, is done
The dry time is 12h；
3) AlCl of above-mentioned 1.3mol/L is taken3The electrolyte of/chlorinated butyl pyridine ([BP] Cl), in the vacuum of -0.05MPa
Battery core after will be dry in step 2) under degree is immersed in the electrolyte, soaking time 30min；
4) battery core after impregnating in step 3) is fitted into aluminum hull, is sealed, stood 10h, that is, aluminum capacitor battery is made.
Embodiment 2
The aluminum capacitor battery of the present embodiment, including positive electrode, negative electrode, diaphragm and electrolyte.
Positive electrode includes aluminium foil and the positive electrode that is adhered on aluminium foil, and positive electrode pole piece is with a thickness of 30 μm, positive material
Material be positive electrode active materials graphene, positive electrode binder polytetrafluoroethylene (PTFE) and positive conductive agent SP, graphene, polytetrafluoroethylene (PTFE),
The weight ratio of SP is 100:10:7, and the specific surface area of graphene is 754m2/g。
Negative electrode includes aluminium foil and the negative electrode material that is attached on aluminium foil, and negative electrode is with a thickness of 100 μm, negative electrode material packet
Include negative electrode active material graphene, negative electrode binder polytetrafluoroethylene (PTFE), conductive agent KS-6, graphene, polytetrafluoroethylene (PTFE), KS-6
Weight ratio is 100:7:7, and the specific surface area of graphene is 259m2/g。
Electrolyte is made of electrolytic salt and solvent, in the present embodiment, electrolytic salt AlCl3, solvent is chlorination 1- second
Base -3- methylimidazole ([EMIm] Cl), AlCl in electrolyte3Concentration be 0.6mol/L.The diaphragm is polyethene microporous membrane.
The preparation method of the positive electrode of the present embodiment includes the following steps:
1) positive electrode active materials graphene, positive electrode binder polytetrafluoroethylene (PTFE), positive conductive agent proportionally mixing: are taken
SP is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 10r/min, mixing time 300min, is obtained positive pre-
Mixed powder material；
2) spheroidising: the premixing powder body material of anode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 100kW, and the nodularization time is 10min, obtain positive nodularization powder body material；
3) it sprays: anode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain positive pole powder electrode；
4) it is sintered: the positive pole powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 150 DEG C
Sintering processes, sintering time 300min obtain positive sintered electrode；
5) roll-in: the positive sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 150 DEG C
Piece obtains the positive electrode with a thickness of 30 μm.
The preparation method of the negative electrode of the present embodiment includes the following steps:
1) negative electrode active material graphene, negative electrode binder polytetrafluoroethylene (PTFE), cathode conductive agent proportionally mixing: are taken
KS-6 is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 10r/min, and mixing time 300min obtains cathode
It is pre-mixed powder body material；
2) spheroidising: the premixing powder body material of cathode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 100kW, and the nodularization time is 10min, obtain cathode nodularization powder body material；
3) it sprays: cathode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain cathode Powder electrode；
4) it is sintered: the cathode Powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 150 DEG C
Sintering processes, sintering time 300min obtain cathode sintered electrode；
5) roll-in: the cathode sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 150 DEG C
Piece obtains the negative electrode with a thickness of 100 μm.
The preparation method of above-mentioned aluminum capacitor battery includes the following steps:
1) above-mentioned positive electrode, negative electrode, diaphragm are successively stacked according to the sequence of positive electrode, diaphragm, negative electrode, diaphragm
Afterwards, the wound battery core of cylindrical roll that diameter is 58mm is made in winding on the winder；
2) battery core obtained in step 1) is dried in vacuo, drying temperature is 50 DEG C, and vacuum degree is -0.01MPa, is done
The dry time is 20h；
3) AlCl of above-mentioned 0.6mol/L is taken3The electrolyte of/chlorination 1- ethyl-3-methylimidazole ([EMIm] Cl) ,-
Battery core after will be dry in step 2) under the vacuum degree of 0.01MPa is immersed in the electrolyte, soaking time 120min；
4) battery core after impregnating in step 3) is fitted into aluminum hull, is sealed, stood 1h, that is, aluminum capacitor battery is made.
Embodiment 3
The aluminum capacitor battery of the present embodiment, including positive electrode, negative electrode, diaphragm and electrolyte.
Positive electrode includes aluminium foil and the positive electrode that is adhered on aluminium foil, and positive electrode pole piece is with a thickness of 500 μm, positive material
Material is positive electrode active materials natural graphite, positive electrode binder Kynoar and positive conductive agent Ketjen black, and natural graphite gathers partially
Vinyl fluoride, the weight ratio of Ketjen black are 100:8:7, and the specific surface area of natural graphite is 0.4m2/g。
Negative electrode includes aluminium foil and the negative electrode material that is attached on aluminium foil, and negative electrode is with a thickness of 500 μm, negative electrode material packet
Negative electrode active material active carbon YP50 (Kuraray), negative electrode binder polytetrafluoroethylene (PTFE), conductive agent Ketjen black are included, activity
Charcoal, polytetrafluoroethylene (PTFE), Ketjen black weight ratio be 100:10:7, the specific surface area of active carbon is 800m2/g。
Electrolyte is made of electrolytic salt and solvent, in the present embodiment, electrolytic salt AlCl3, solvent is chlorination 1- fourth
Base -3- methylimidazole ([BMIm] Cl), AlCl in electrolyte3Concentration be 1.8mol/L.The diaphragm is cellulosic separator.
The preparation method of the positive electrode of the present embodiment includes the following steps:
1) positive electrode active materials natural graphite, positive electrode binder Kynoar, positive conductive agent proportionally mixing: are taken
Ketjen black is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 500r/min, and mixing time 10min is obtained just
Pole is pre-mixed powder body material；
2) spheroidising: the premixing powder body material of anode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 10kW, and the nodularization time is 300min, obtain positive nodularization powder body material；
3) it sprays: anode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain positive pole powder electrode；
4) it is sintered: the positive pole powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 200 DEG C
Sintering processes, sintering time 60min obtain positive sintered electrode；
5) roll-in: the positive sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 160 DEG C
Piece obtains the positive electrode with a thickness of 500 μm.
The preparation method of the negative electrode of the present embodiment includes the following steps:
1) negative electrode active material active carbon, negative electrode binder polytetrafluoroethylene (PTFE), cathode conductive agent section proportionally mixing: are taken
Qin is black, is put into the mixed powder machine of V-type and is mixed, the revolving speed that V-type mixes powder machine is 500r/min, and mixing time 10min obtains cathode
It is pre-mixed powder body material；
2) spheroidising: the premixing powder body material of cathode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 100kW, and the nodularization time is 300min, obtain cathode nodularization powder body material；
3) it sprays: cathode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain cathode Powder electrode；
4) it is sintered: the cathode Powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 200 DEG C
Sintering processes, sintering time 60min obtain cathode sintered electrode；
5) roll-in: the cathode sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 160 DEG C
Piece obtains the negative electrode with a thickness of 500 μm.
The preparation method of above-mentioned aluminum capacitor battery includes the following steps:
1) above-mentioned positive electrode, negative electrode, diaphragm are successively stacked according to the sequence of positive electrode, diaphragm, negative electrode, diaphragm
Afterwards, the wound battery core of cylindrical roll that diameter is 58mm is made in winding on the winder；
2) battery core obtained in step 1) being dried in vacuo, drying temperature is 200 DEG C, and vacuum degree is -0.03MPa,
Drying time is 36h；
3) AlCl of above-mentioned 1.8mol/L is taken3The electrolyte of/chlorination 1- butyl -3- methylimidazole ([BMIm] Cl), -
Battery core after will be dry in step 2) under the vacuum degree of 0.02MPa is immersed in the electrolyte, soaking time 10min；
4) battery core after impregnating in step 3) is fitted into aluminum hull, is sealed, stood for 24 hours, that is, aluminum capacitor battery is made.
Embodiment 4
The aluminum capacitor battery of the present embodiment, including positive electrode, negative electrode, diaphragm and electrolyte.
Positive electrode includes aluminium foil and the positive electrode that is adhered on aluminium foil, and positive electrode pole piece is with a thickness of 450 μm, positive material
Material is positive electrode active materials artificial graphite, positive electrode binder Kynoar and positive conductive agent Ketjen black, and artificial graphite gathers partially
Vinyl fluoride, the weight ratio of Ketjen black are 100:10:10, and the specific surface area of artificial graphite is 1m2/g。
Negative electrode includes aluminium foil and the negative electrode material that is attached on aluminium foil, and negative electrode is with a thickness of 350 μm, negative electrode material packet
Include negative electrode active material graphene, negative electrode binder polytetrafluoroethylene (PTFE), conductive agent SP, the weight of graphene, polytetrafluoroethylene (PTFE), SP
Than being 1500m for the specific surface area of 100:18:10, graphene2/g。
Electrolyte is made of electrolytic salt and solvent, in the present embodiment, electrolytic salt AlCl3, solvent is chlorination 1- fourth
Base -3- methylimidazole ([BMIm] Cl), AlCl in electrolyte3Concentration be 1.2mol/L.The diaphragm is polypropylene diaphragm.
The preparation method of the positive electrode of the present embodiment includes the following steps:
1) positive electrode active materials artificial graphite, positive electrode binder Kynoar, positive conductive agent proportionally mixing: are taken
Ketjen black is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 25r/min, and mixing time 20min is obtained just
Pole is pre-mixed powder body material；
2) spheroidising: the premixing powder body material of anode made from step 1) is transported in ultrasonic balling machine, ball is carried out
Change processing, the power of balling machine are 15kW, and the nodularization time is 30min, obtain positive nodularization powder body material；
3) it sprays: anode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain positive pole powder electrode；
4) it is sintered: the positive pole powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 180 DEG C
Sintering processes, sintering time 100min obtain positive sintered electrode；
5) roll-in: the positive sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 155 DEG C
Piece obtains the positive electrode with a thickness of 450 μm.
The preparation method of the negative electrode of the present embodiment includes the following steps:
1) negative electrode active material graphene, negative electrode binder polytetrafluoroethylene (PTFE), cathode conductive agent proportionally mixing: are taken
SP is put into the mixed powder machine of V-type and is mixed, and the revolving speed that V-type mixes powder machine is 25r/min, and it is pre- to obtain cathode by mixing time 30min
Mixed powder material；
2) spheroidising: the premixing powder body material of cathode made from step 1) is transported in balling machine, is carried out at nodularization
Reason, the power of balling machine are 10kW, and the nodularization time is 30min, obtain cathode nodularization powder body material；
3) it sprays: cathode nodularization powder body material made from step 2) is sprayed to by electrostatic powder spray gun to two of aluminium foil
Surface, quantity for spray control are 50mg/cm2, obtain cathode Powder electrode；
4) it is sintered: the cathode Powder electrode that step 3) obtains being put into the infrared baking oven of 100kW, under the conditions of 180 DEG C
Sintering processes, sintering time 100min obtain cathode sintered electrode；
5) roll-in: the cathode sintered electrode that step 4) is obtained uses hot calender roller process, control electrode at 155 DEG C
Piece obtains the negative electrode with a thickness of 350 μm.
The preparation method of above-mentioned aluminum capacitor battery includes the following steps:
1) above-mentioned positive electrode, negative electrode, diaphragm are successively stacked according to the sequence of positive electrode, diaphragm, negative electrode, diaphragm
Afterwards, the wound battery core of cylindrical roll that diameter is 58mm is made in winding on the winder；
2) battery core obtained in step 1) being dried in vacuo, drying temperature is 180 DEG C, and vacuum degree is -0.03MPa,
Drying time is 36h；
3) AlCl of above-mentioned 1.2mol/L is taken3The electrolyte of/chlorination 1- butyl -3- methylimidazole ([BMIm] Cl), -
Battery core after will be dry in step 2) under the vacuum degree of 0.03MPa is immersed in the electrolyte, soaking time 10min；
4) battery core after impregnating in step 3) is fitted into aluminum hull, is sealed, stood for 24 hours, that is, aluminum capacitor battery is made.
Embodiment 5
The present embodiment difference from example 1 is that, positive electrode does not include positive conductive agent, and negative electrode material is not wrapped
Include cathode conductive agent.
Embodiment 6
The present embodiment difference from example 1 is that, aluminum capacitor battery prepare when, anode, cathode, diaphragm are made
Lamination type electric core, other steps are same as Example 1.
Experimental example
Capacitor batteries made from above-described embodiment 1-6 are carried out as follows test:
The electro-chemical test of aluminum capacitor battery: all electro-chemical tests are all to be tested at room temperature.Permanent electricity
Current test is tested on LAND CT2001A battery test system, and ac impedance measurement is then in Autolab electrochemical operation
It is tested on standing.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 invention reaches 40Wh/kg, power density
6300W/kg is reached.
Electrode active material is bonded on aluminium foil by the electrode of capacitor batteries of the invention using binder, both improves electricity
The energy density for holding battery, in turn simplifies the manufacture craft of electrode, reduces production cost.
Claims (5)
1. a kind of aluminum capacitor battery, which is characterized in that including positive electrode, negative electrode and electrolyte；The positive electrode includes aluminium foil
And it is adhered to the positive electrode on aluminium foil, the positive electrode includes positive electrode active materials and positive electrode binder, the anode material
Material is one of natural graphite, artificial graphite；The negative electrode includes aluminium foil and the negative electrode material that is adhered on aluminium foil, described
Negative electrode material includes negative electrode active material and negative electrode binder, and the negative electrode material is active carbon；The electrolyte includes electrolysis
Matter salt and ion liquid solvent, the electrolytic salt are AlCl3, AlCl in the electrolyte3Concentration be 0.6 ~ 1.8mol/L；
The ion liquid solvent is chlorinated butyl pyridine, chlorination 1- ethyl-3-methylimidazole, in chlorination 1- butyl -3- methylimidazole
One or more；
The preparation method of the positive electrode, includes the following steps:
1) mixing: positive electrode active materials, positive electrode binder are mixed, positive premixing powder body material is obtained；
2) spheroidising: the premixing powder body material of anode obtained in step 1) is subjected to spheroidising, obtains positive nodularization powder
Material；
3) it sprays: anode nodularization powder body material obtained in step 2 being sprayed on aluminium foil, positive pole powder electrode is obtained；
4) it is sintered: positive pole powder electrode obtained in step 3) being sintered at 120-200 DEG C, obtains positive sintered electrode,
The anode sintered electrode is the positive electrode；Pass through 150-160 DEG C of hot-rolling pressure after the step 4) sintering；
The preparation method of the negative electrode, includes the following steps:
1) mixing: negative electrode active material, negative electrode binder are mixed, and obtain cathode premixing powder body material；
2) spheroidising: the premixing powder body material of cathode obtained in step 1) is subjected to spheroidising, obtains cathode nodularization powder
Material；
3) it sprays: cathode nodularization powder body material obtained in step 2 being sprayed on aluminium foil, cathode Powder electrode is obtained；
4) it is sintered: cathode Powder electrode obtained in step 3) being sintered at 120-200 DEG C, obtains cathode sintered electrode,
The cathode sintered electrode is the negative electrode；Pass through 150-160 DEG C of hot-rolling pressure after the step 4) sintering.
2. the aluminum capacitor battery as described in claim 1, which is characterized in that the positive electrode active materials and positive electrode binder
Weight ratio is 100:8-10；The weight ratio of the negative electrode active material and negative electrode binder is 100:7-18.
3. the aluminum capacitor battery as described in claim 1, which is characterized in that the positive electrode includes positive conductive agent, described
The weight ratio of positive electrode active materials, positive electrode binder and positive conductive agent is 100:8-10:5-10.
4. the aluminum capacitor battery as described in claim 1, which is characterized in that the negative electrode material includes cathode conductive agent, described
The weight ratio of negative electrode active material, negative electrode binder and cathode conductive agent is 100:7-18:5-10.
5. a kind of preparation method of the aluminum capacitor battery as described in claim 1, which comprises the steps of:
The battery core that preparation is completed is placed in the electrolyte and is soaked in vacuum 10 ~ 120min, takes out into shell, seals to get described
Aluminum capacitor battery.
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| CN105977039A (en) * | 2016-06-29 | 2016-09-28 | 陈小刚 | Graphene activity composite electrode super-capacitor cell |
| CN107665990B (en) * | 2016-07-29 | 2021-02-26 | 横店集团东磁股份有限公司 | Chloride battery positive plate and preparation method thereof |
| TWI611618B (en) | 2016-12-16 | 2018-01-11 | 財團法人工業技術研究院 | Metal-ion battery |
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