CN103474250A - Super capacitor and manufacturing method thereof - Google Patents
Super capacitor and manufacturing method thereof Download PDFInfo
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- CN103474250A CN103474250A CN2012101877346A CN201210187734A CN103474250A CN 103474250 A CN103474250 A CN 103474250A CN 2012101877346 A CN2012101877346 A CN 2012101877346A CN 201210187734 A CN201210187734 A CN 201210187734A CN 103474250 A CN103474250 A CN 103474250A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 146
- 239000003792 electrolyte Substances 0.000 claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- 239000011258 core-shell material Substances 0.000 claims description 39
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- -1 pyrroles's salt cation Chemical class 0.000 claims description 34
- 239000011268 mixed slurry Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 239000005030 aluminium foil Substances 0.000 claims description 28
- 230000004888 barrier function Effects 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000009966 trimming Methods 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 14
- 239000006230 acetylene black Substances 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000003273 ketjen black Substances 0.000 claims description 8
- 238000003475 lamination Methods 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011883 electrode binding agent Substances 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 abstract description 27
- 230000007246 mechanism Effects 0.000 abstract description 24
- 150000001450 anions Chemical class 0.000 abstract description 12
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 7
- 230000004087 circulation Effects 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention provides a super capacitor. The super capacitor comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and an electrolyte. A positive-electrode active material is graphite whose specific surface area is 1 to 20m<2>/g. A negative-electrode active material is a carbon material whose specific surface area is 200-3000 m<2>/g. A mass ratio of the negative-electrode active material and the positive-electrode active material is 10-20. In addition, the invention also provides a manufacturing method of the super capacitor. An energy storage mechanism of the positive-electrode active material of the super capacitor of the invention is an anion embedding and embedding out mechanism. An electrode storage charge capability is increased so that a capacity of a whole system is increased too. Operation of the manufacturing method of the super capacitor provided in the invention is simple.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of ultracapacitor and preparation method thereof.
Background technology
The nineties in 20th century, along with human society, to the exploitation of electric automobile and to the demand of pulse power supply, stimulated the research of people to electrochemical capacitor, but the specific energy of electrochemical capacitor is still lower at present.For the lower problem of specific power that solves battery, people attempt battery and ultracapacitor are combined to use, when normal operation, by battery, provide required power; When starting or needing heavy-current discharge, by capacitor, provide required drive, can solve some practical problems like this, but increase the annex of battery simultaneously, with the developing direction such as short and small frivolous of current energy device, disagree; In addition, people are just attempting to utilize the principle of electrochemical capacitor and battery, and the exploitation mixed capacitor is as new energy storage unit.
Nineteen ninety Giner company has released the so-called fake capacitance device that metal oxide containing precious metals is electrode material or has claimed pseudo-capacitance device (Pseudo-capacitor).For further improving the specific energy of electrochemical capacitor, nineteen ninety-five, D.A.Evans etc. have proposed ideal polarized electrode and faraday's reaction electrode are combined to the concept that forms mixed capacitor (Electrochemical Hybrid Capacitor, EHC or be called Hybrid capacitor).1997, ESMA company disclosed the concept of NiOOH/AC mixed capacitor, had disclosed the new technology of accumulator material and electrochemical capacitor combination of materials.Calendar year 2001, G.G.Amatucci has reported the Li of organic system lithium ion battery material and active carbon combination
4ti
5o
12/ AC electrochemical mixed capacitor is another milestone of electrochemical mixed capacitor development.
The activated carbon that at present hybrid super capacitor of research mainly adopts high-specific surface area is as positive electrode, graphite or Li
4ti
5o
12as negative pole, form electric double layer on the anodal surface with electrolyte, the capacity of positive electrode has determined the capacity of whole system, because the capacity of anodal electric double layer is less, the capacity that has limited the whole system of ultracapacitor improves.
Summary of the invention
Given this, the present invention aims to provide a kind of ultracapacitor and preparation method thereof.Ultracapacitor provided by the invention, positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g, its energy storage mechanism is that anion embeds the mechanism that embedding goes out, and has improved electrode and has stored the ability of electric charge, thereby improved the capacity of whole system.Preparation method provided by the invention is simple to operate.
First aspect, the invention provides a kind of ultracapacitor, comprise positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte, positive pole comprises aluminium foil and is coated in the positive electrode on aluminium foil, negative pole comprises aluminium foil and is coated in the negative material on aluminium foil, positive electrode comprises positive electrode active materials, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, and positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g, negative material comprises negative active core-shell material, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of negative active core-shell material and positive electrode active materials is 10 ~ 20.
Conventional ultracapacitor positive electrode active materials mainly adopts the high-specific surface area (200 ~ 3000m such as active carbon, carbon nano-tube, Graphene
2/ g) material with carbon element, its energy storage mechanism is electric double layer mechanism, the positive electrode active materials in the present invention adopts low specific surface area (1 ~ 20m
2/ g) graphite, its energy storage mechanism is embedding and the embedding out energy storage of anion in graphite flake layer utilized in electrolyte, can effectively improve the ability that electrode stores electric charge, finally improves the capacity of ultracapacitor.Negative active core-shell material of the present invention, with the same with conventional super capacitor anode active material, mainly adopts high-specific surface area (200 ~ 3000m
2/ g) material with carbon element is as negative active core-shell material, and its energy storage mechanism is electric double layer mechanism, and the electric double layer that utilizes the cation in electrolyte to form on the negative active core-shell material surface carrys out energy storage.
Preferably, the derivative that material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
More preferably, material with carbon element is that specific area is 200～1500m
2the Graphene of/g or the derivative of Graphene.
Preferably, the derivative of Graphene is nitrogen-doped graphene or boron doped graphene.
Preferably, binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol.
Preferably, conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre.
Preferably, barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
Preferably, the solute of electrolyte is that general formula is M
+y
-salt, Y wherein
-for PF
6 -or BF
4 -, M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
Preferably, the solvent of electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.
Electrolyte is ionic liquid, and in electrolyte, anion is adapted at embedding with embedding and going out to carry out energy storage in the graphite flake layer structure under high voltage, and the cation in electrolyte forms electric double layer on the negative active core-shell material surface, thereby improves the capacity of whole ultracapacitor.
Preferably, the concentration of electrolyte is 0.5 ~ 1.2mol/L.
In addition, the present invention also provides a kind of preparation method of ultracapacitor, comprises the following steps:
Step (1) prepares positive plate and negative plate:
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by positive electrode active materials, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the ultracapacitor positive plate; Wherein, positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g;
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by negative active core-shell material, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the super capacitor anode sheet; Wherein, negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of negative active core-shell material and positive electrode active materials is 10 ~ 20;
Step (2) assembling ultracapacitor:
Dress up battery core according to positive plate, barrier film and negative plate order stack of laminations, by battery housing seal battery core, then inject il electrolyte by the liquid injection port be arranged on battery container in battery container, the sealing liquid injection port, obtain ultracapacitor.
Positive electrode active materials in the present invention adopts low specific surface area (1 ~ 20m
2/ g) graphite, its energy storage mechanism is embedding and the embedding out energy storage of anion in graphite flake layer utilized in electrolyte.Negative active core-shell material of the present invention, with the same with conventional super capacitor anode active material, mainly adopts high-specific surface area (200 ~ 3000m
2/ g) material with carbon element is as negative active core-shell material, and its energy storage mechanism is electric double layer mechanism, and the electric double layer that utilizes the cation in electrolyte to form on the negative active core-shell material surface carrys out energy storage.
Preferably, binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol.
Preferably, conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre.
Preferably, the derivative that material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
More preferably, material with carbon element is that specific area is 200 ~ 1500m
2the Graphene of/g or the derivative of Graphene.
Preferably, the derivative of Graphene is nitrogen-doped graphene or boron doped graphene.
Preferably, barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
Preferably, the solute of electrolyte is that general formula is M
+y
-salt, Y wherein
-for PF
6 -or BF
4 -, M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
Preferably, the solvent of electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.
Electrolyte is ionic liquid, and in electrolyte, anion is adapted at embedding with embedding and going out to carry out energy storage in the graphite flake layer structure under high voltage, and the cation in electrolyte forms electric double layer on the negative active core-shell material surface, thereby improves the capacity of whole ultracapacitor.
Preferably, the concentration of electrolyte is 0.5 ~ 1.2mol/L.
The invention provides a kind of ultracapacitor and preparation method thereof, there is following beneficial effect:
(1) ultracapacitor provided by the invention, the employing specific area is 1 ~ 20m
2the graphite of/g is as positive electrode active materials, and its energy storage mechanism is that anion embeds the mechanism that embedding goes out, and has improved electrode and has stored the ability of electric charge, thereby improved the capacity of whole system;
(2) preparation method of ultracapacitor provided by the invention, simple to operate, is easy to accomplish scale production.
The accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the cycle life test curve of the ultracapacitor of the embodiment of the present invention 1 preparation.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
First aspect, the invention provides a kind of ultracapacitor, comprise positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte, positive pole comprises aluminium foil and is coated in the positive electrode on aluminium foil, negative pole comprises aluminium foil and is coated in the negative material on aluminium foil, positive electrode comprises positive electrode active materials, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, and positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g, negative material comprises negative active core-shell material, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of negative active core-shell material and positive electrode active materials is 10 ~ 20.
Conventional ultracapacitor positive electrode active materials mainly adopts the high-specific surface area (200 ~ 3000m such as active carbon, carbon nano-tube, Graphene
2/ g) material with carbon element, its energy storage mechanism is electric double layer mechanism, the positive electrode active materials in the present invention adopts low specific surface area (1 ~ 20m
2/ g) graphite, its energy storage mechanism is embedding and the embedding out energy storage of anion in graphite flake layer utilized in electrolyte, can effectively improve the ability that electrode stores electric charge, finally improves the capacity of ultracapacitor.Negative active core-shell material of the present invention, with the same with conventional super capacitor anode active material, mainly adopts high-specific surface area (200 ~ 3000m
2/ g) material with carbon element is as negative active core-shell material, and its energy storage mechanism is electric double layer mechanism, and the electric double layer that utilizes the cation in electrolyte to form on the negative active core-shell material surface carrys out energy storage.
Preferably, the derivative that material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
More preferably, material with carbon element is that specific area is 200 ~ 1500m
2the Graphene of/g or the derivative of Graphene.
Preferably, the derivative of Graphene is nitrogen-doped graphene or boron doped graphene.
Preferably, binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol.
Preferably, conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre.
Preferably, barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
Preferably, the solute of electrolyte is that general formula is M
+y
-salt, Y wherein
-for PF
6 -or BF
4 -, M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
Preferably, the solvent of electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.
Electrolyte is ionic liquid, and in electrolyte, anion is adapted at embedding with embedding and going out to carry out energy storage in the graphite flake layer structure under high voltage, and the cation in electrolyte forms electric double layer on the negative active core-shell material surface, thereby improves the capacity of whole ultracapacitor.
Preferably, the concentration of electrolyte is 0.5 ~ 1.2mol/L.
In addition, the present invention also provides a kind of preparation method of ultracapacitor, comprises the following steps:
Step (1) prepares positive plate and negative plate:
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by positive electrode active materials, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the ultracapacitor positive plate; Wherein, positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g;
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by negative active core-shell material, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the super capacitor anode sheet; Wherein, negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of negative active core-shell material and positive electrode active materials is 10 ~ 20;
Step (2) assembling ultracapacitor:
Dress up battery core according to positive plate, barrier film and negative plate order stack of laminations, by battery housing seal battery core, then inject il electrolyte by the liquid injection port be arranged on battery container in battery container, the sealing liquid injection port, obtain ultracapacitor.
Positive electrode active materials in the present invention adopts low specific surface area (1 ~ 20m
2/ g) graphite, its energy storage mechanism is embedding and the embedding out energy storage of anion in graphite flake layer utilized in electrolyte.Negative active core-shell material of the present invention, with the same with conventional super capacitor anode active material, mainly adopts high-specific surface area (200 ~ 3000m
2/ g) material with carbon element is as negative active core-shell material, and its energy storage mechanism is electric double layer mechanism, and the electric double layer that utilizes the cation in electrolyte to form on the negative active core-shell material surface carrys out energy storage.
Preferably, binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol.
Preferably, conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre.
Preferably, the derivative that material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
More preferably, material with carbon element is that specific area is 200～1500m
2the Graphene of/g or the derivative of Graphene.
Preferably, the derivative of Graphene is nitrogen-doped graphene or boron doped graphene.
Preferably, barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
Preferably, the solute of electrolyte is that general formula is M
+y
-salt, Y wherein
-for PF
6 -or BF
4 -, M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
Preferably, the solvent of electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.
Electrolyte is ionic liquid, and in electrolyte, anion is adapted at embedding with embedding and going out to carry out energy storage in the graphite flake layer structure under high voltage, and the cation in electrolyte forms electric double layer on the negative active core-shell material surface, thereby improves the capacity of whole ultracapacitor.
Preferably, the concentration of electrolyte is 0.5 ~ 1.2mol/L.
The invention provides a kind of ultracapacitor and preparation method thereof, there is following beneficial effect:
(1) ultracapacitor provided by the invention, the employing specific area is 1 ~ 20m
2the graphite of/g is as positive electrode active materials, and its energy storage mechanism is that anion embeds the mechanism that embedding goes out, and has improved electrode and has stored the ability of electric charge, thereby improved the capacity of whole system;
(2) preparation method of ultracapacitor provided by the invention, simple to operate, is easy to accomplish scale production.
Embodiment mono-
A kind of preparation method of ultracapacitor comprises the following steps:
(1) by the 8.5g specific area, be 1m
2the graphite of/g, 0.5g Kynoar binding agent and 1g acetylene black conductor mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the ultracapacitor positive plate;
(2) by the 170g specific area, be 1500m
2the Graphene of/g, 10g Kynoar binding agent and 20g acetylene black conductor mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the super capacitor anode sheet;
In the present embodiment, the mass ratio of negative active core-shell material and positive electrode active materials is 20;
(3) get polypropylene diaphragm, dress up battery core with positive plate and negative plate stack of laminations, by battery housing seal battery core, again by being arranged on liquid injection port on battery container toward the il electrolyte tetraethyl ammonium hexafluorophosphate/dimethyl carbonate that injects 1.0mol/L in battery container, the sealing liquid injection port, obtain ultracapacitor.
The ultracapacitor of above-mentioned preparation is carried out under the current density of 0.1C to the charge discharge test, the energy density that records the present embodiment ultracapacitor is 60whkg.With existing commercial ultracapacitor, compare, existing maxwell is commercial, and super capacitor energy density is generally less than 10wh/kg.
Ultracapacitor prepared by the present embodiment carries out the cycle life test, and test result as shown in Figure 1.As can be seen from Figure 1, after 100 circulations, the energy density of ultracapacitor can also keep more than 90%.
Embodiment bis-
A kind of preparation method of ultracapacitor comprises the following steps:
(1) by the 8.5g specific area, be 20m
2the graphite of/g, 1g polytetrafluoroethylene binding agent and 0.5g Ketjen black conductive agent mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the ultracapacitor positive plate;
(2) by the 85g specific area, be 1500m
2the nitrogen-doped graphene of/g, 10g polytetrafluoroethylene binding agent and 5g Ketjen black conductive agent mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the super capacitor anode sheet;
In the present embodiment, the mass ratio of negative active core-shell material and positive electrode active materials is 10;
(3) get the polyethylene barrier film, dress up battery core with positive plate and negative plate stack of laminations, by battery housing seal battery core, again by being arranged on liquid injection port on battery container toward the il electrolyte N-methyl that injects 1.0mol/L in battery container-N-normal-butyl pyrroles hexafluorophosphate/diethyl carbonate, the sealing liquid injection port, obtain ultracapacitor.
The ultracapacitor of above-mentioned preparation is carried out under the current density of 0.1C to the charge discharge test, the energy density that records the present embodiment ultracapacitor is 63wh/kg.
Ultracapacitor prepared by the present embodiment carries out the cycle life test, and after 100 circulations, the energy density of ultracapacitor can also keep more than 90%.
Embodiment tri-
A kind of preparation method of ultracapacitor comprises the following steps:
(1) by the 9g specific area, be 10m
2the graphite of/g, 0.5g polyvinyl alcohol adhesive and the agent of 0.5g carbon nanotube conducting mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the ultracapacitor positive plate;
(2) by the 108g specific area, be 500m
2the boron doped graphene of/g, 6g polyvinyl alcohol adhesive and the agent of 6g carbon nanotube conducting mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the super capacitor anode sheet;
In the present embodiment, the mass ratio of negative active core-shell material and positive electrode active materials is 12;
(3) get polypropylene diaphragm, dress up battery core with positive plate and negative plate stack of laminations, by battery housing seal battery core, again by being arranged on liquid injection port on battery container toward the il electrolyte N-normal-butyl pyrroles tetrafluoroborate/propene carbonate that injects 0.8mol/L in battery container, the sealing liquid injection port, obtain ultracapacitor.
The ultracapacitor of above-mentioned preparation is carried out under the current density of 0.1C to the charge discharge test, the energy density that records the present embodiment ultracapacitor is 51wh/kg.
Ultracapacitor prepared by the present embodiment carries out the cycle life test, and after 100 circulations, the energy density of ultracapacitor can also keep more than 90%.
Embodiment tetra-
A kind of preparation method of ultracapacitor comprises the following steps:
(1) by the 8.7g specific area, be 15m
2the graphite of/g, 0.6g Kynoar binding agent and 0.7g conductive carbon fibre mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the ultracapacitor positive plate;
(2) by the 130.5g specific area, be 800m
2the boron doped graphene of/g, 9g Kynoar binding agent and 10.5g conductive carbon fibre mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the super capacitor anode sheet;
In the present embodiment, the mass ratio of negative active core-shell material and positive electrode active materials is 15;
(3) get the nonwoven fabrics barrier film, dress up battery core with positive plate and negative plate stack of laminations, by battery housing seal battery core, again by being arranged on liquid injection port on battery container toward the il electrolyte N-methyl that injects 0.5mol/L in battery container-N-N-ethyl pyrrole N-hexafluorophosphate/ethylene carbonate, the sealing liquid injection port, obtain ultracapacitor.
The ultracapacitor of above-mentioned preparation is carried out under the current density of 0.1C to the charge discharge test, the energy density that records the present embodiment ultracapacitor is 53wh/kg.
Ultracapacitor prepared by the present embodiment carries out the cycle life test, and after 100 circulations, the energy density of ultracapacitor can also keep more than 90%.
Embodiment five
A kind of preparation method of ultracapacitor comprises the following steps:
(1) by the 8.6g specific area, be 5m
2the graphite of/g, 0.7g Kynoar binding agent and 0.7g acetylene black conductor mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the ultracapacitor positive plate;
(2) by the 154.8g specific area, be 300m
2the boron doped graphene of/g, 12.6g Kynoar binding agent and 12.6g acetylene black conductor mix, and obtain mixed slurry, and mixed slurry is coated on aluminium foil, drying, roll film, trimming and process, and make the super capacitor anode sheet;
In the present embodiment, the mass ratio of negative active core-shell material and positive electrode active materials is 18;
(3) get the polyethylene barrier film, dress up battery core with positive plate and negative plate stack of laminations, by battery housing seal battery core, again by being arranged on liquid injection port on battery container toward the il electrolyte N-methyl triethyl ammonium hexafluorophosphate/acetonitrile that injects 1.2mol/L in battery container, the sealing liquid injection port, obtain ultracapacitor.
The ultracapacitor of above-mentioned preparation is carried out under the current density of 0.1C to the charge discharge test, the energy density that records the present embodiment ultracapacitor is 50wh/kg.
Ultracapacitor prepared by the present embodiment carries out the cycle life test, and after 100 circulations, the energy density of ultracapacitor can also keep more than 90%.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. a ultracapacitor, described ultracapacitor comprises positive pole, negative pole, barrier film and electrolyte between described positive pole and described negative pole, described positive pole comprises aluminium foil and is coated in the positive electrode on described aluminium foil, described negative pole comprises aluminium foil and is coated in the negative material on described aluminium foil, it is characterized in that, described positive electrode comprises positive electrode active materials, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, and described positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g, described negative material comprises negative active core-shell material, binding agent and the conductive agent that mass ratio is 85 ~ 90:5 ~ 10:5 ~ 10, described negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of described negative active core-shell material and described positive electrode active materials is 10 ~ 20.
2. ultracapacitor as claimed in claim 1, is characterized in that, the derivative that described material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
3. ultracapacitor as claimed in claim 2, is characterized in that, described Graphene derivative is nitrogen-doped graphene or boron doped graphene.
4. ultracapacitor as claimed in claim 1, is characterized in that, the solvent of described electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile, and it is M that the solute of described electrolyte is selected general formula
+y
-salt, described Y
-for PF
6 -or BF
4 -, described M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
5. ultracapacitor as claimed in claim 1, it is characterized in that, described binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol, described conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre, and described barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
6. the preparation method of a ultracapacitor, is characterized in that, comprises the following steps:
Step (1) prepares positive plate and negative plate:
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by positive electrode active materials, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the ultracapacitor positive plate; Wherein, described positive electrode active materials is that specific area is 1 ~ 20m
2the graphite of/g;
The ratio that is 85 ~ 90:5 ~ 10:5 ~ 10 in mass ratio by negative active core-shell material, binding agent and conductive agent mixes, and obtains mixed slurry, and described mixed slurry is coated on aluminium foil, drying, rolls film, trimming and processes, and makes the super capacitor anode sheet; Wherein, described negative active core-shell material is that specific area is 200 ~ 3000m
2the material with carbon element of/g, the mass ratio of described negative active core-shell material and described positive electrode active materials is 10 ~ 20;
Step (2) assembling ultracapacitor:
Dress up battery core according to positive plate, barrier film and negative plate order stack of laminations, by the described battery core of battery housing seal, inject il electrolyte by the liquid injection port be arranged on described battery container in described battery container again, seal described liquid injection port, obtain ultracapacitor.
7. the preparation method of ultracapacitor as claimed in claim 6, is characterized in that, the derivative that described material with carbon element is active carbon, carbon nano-tube, Graphene or Graphene.
8. the preparation method of ultracapacitor as claimed in claim 7, is characterized in that, described Graphene derivative is nitrogen-doped graphene or boron doped graphene.
9. the preparation method of ultracapacitor as claimed in claim 6, it is characterized in that, the solvent of described electrolyte is one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile, and it is M that the solute of described electrolyte is selected general formula
+y
-salt, described Y
-for PF
6 -or BF
4 -, described M
+for the Quaternary ammonium cation as shown in structural formula A, B, C, pyridiniujm cation or pyrroles's salt cation respectively:
In formula, R is the alkyl that carbon number is 1 ~ 6.
10. the preparation method of ultracapacitor as claimed in claim 6, it is characterized in that, described binding agent is Kynoar, polytetrafluoroethylene or polyvinyl alcohol, described conductive agent is acetylene black, Ketjen black, carbon nano-tube or conductive carbon fibre, and described barrier film is polyethylene barrier film, polypropylene diaphragm or nonwoven fabrics barrier film.
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| CN110931265A (en) * | 2019-11-11 | 2020-03-27 | 江苏大学 | A kind of synthesis method of (Co0.55Mn0.45)2P2O7/NG composite electrode material and its application |
| CN112542329A (en) * | 2020-11-17 | 2021-03-23 | 伊诺福科光学技术有限公司 | High energy density super capacitor |
| CN112951617A (en) * | 2021-02-05 | 2021-06-11 | 广州金立电子有限公司 | Electrochemical capacitor and preparation method thereof |
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