CN102945754A - Super electrochemical capacitor and preparation method thereof - Google Patents
Super electrochemical capacitor and preparation method thereof Download PDFInfo
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- CN102945754A CN102945754A CN201110233239XA CN201110233239A CN102945754A CN 102945754 A CN102945754 A CN 102945754A CN 201110233239X A CN201110233239X A CN 201110233239XA CN 201110233239 A CN201110233239 A CN 201110233239A CN 102945754 A CN102945754 A CN 102945754A
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the field of capacitors, and discloses a super electrochemical capacitor electrode and a super electrochemical capacitor. The super electrochemical capacitor electrode comprises a positive electrode and a negative electrode; the material of the positive electrode comprises aluminum foil, and positive electrode active material comprising grapheme, first conductive agent and first binding agent with the mass ratio being 85:10:5, which is coated on the aluminum foil; and the material of the negative electrode comprises aluminum foil, and negative electrode active material comprising titanium dioxide nanowire, second conductive agent and second binding agent with the mass ratio being 85:10:5, which is coated on the aluminum foil. As the negative electrode material of the super electrochemical capacitor electrode has a low potential plateau, and the positive electrode adopts the grapheme with large specific surface and good electric conductivity, the super electrochemical capacitor electrode can effectively reduce the internal resistance of the super electrochemical capacitor, and can also ensure that the super electrochemical capacitor forms high specific capacitance.
Description
Technical field
The invention belongs to capacitor area, it relates to a kind of super electrochemical capacitor.The invention still further relates to a kind of preparation method of this super electrochemical capacitor.
Background technology
The nineties in 20th century, to the exploitation of electric automobile and to the demand of pulse power supply, more stimulated the research of people to electrochemical capacitor.The specific energy of electrochemical capacitor is still lower at present, and the specific power of battery is lower, and people are just attempting to address this problem from two aspects: (1) unites use with battery and ultracapacitor, during normal operation, provides required power by battery; Start or when needing heavy-current discharge, then provided by capacitor, can improve on the one hand the bad shortcoming of cryogenic property of battery; Can solve the application scenario for the higher pulse current of power requirement, such as GSM, GPRS etc.Capacitor and battery are united use and can be extended the life of a cell, but this will increase the annex of battery, disagree with the developing direction such as short and small frivolous of present energy device.(2) utilize the principle of electrochemical capacitor and battery, the exploitation mixed capacitor is as new energy storage unit.
It is so-called fake capacitance device or the title pseudo-capacitance device (Pseudo-capacitor) of electrode material that nineteen ninety Giner company has released metal oxide containing precious metals.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 the concept that consists of 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 Li4Ti5O12/AC electrochemical mixed capacitor of organic system lithium ion battery material and active carbon combination, is another milestone of electrochemical mixed capacitor development.
At present take TiO2 (B) nano wire as negative pole, carbon nano-tube (CNT) is anodal, in 1mol/LLiPF6/EC-DMC-DEC electrolyte, be assembled into mixed capacitor, this system can be carried out preferably charge and discharge cycles in the 0-2.8V voltage range, under the 10C multiplying power, energy density reaches 12.8wh/kg, is the twice of symmetric form CNT//CNT capacitor.Although this system has been utilized the advantage of monodimension nanometer material, because the capacity of carbon nano-tube is lower, the total energy density that causes this system is not very high, so that capacitor energy density is low, causes the ratio electric capacity of capacitor low.
Summary of the invention
The object of the present invention is to provide a kind of energy density high, than the high super electrochemical capacitor of electric capacity.
A kind of super electrochemical capacitor comprises positive pole, negative pole, the barrier film between described positive pole and negative pole and electrolyte; Described positive pole, negative pole and barrier film are immersed in the described electrolyte; Wherein, the material of described positive pole comprises aluminium foil and the mass ratio that is coated on the described aluminium foil is respectively 80～93: the positive electrode active materials that 2～10: 5～10 Graphene, the first conductive agent and the first binding agent form; The material of described negative pole comprises aluminium foil and the mass ratio that is coated on the described Copper Foil is respectively 80～93: the negative active core-shell material that 2～10: 5～10 titanium dioxide nano thread, the second conductive agent and the second binding agent form.
In the above-mentioned super electrochemical capacitor, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
In the above-mentioned super electrochemical capacitor, electrode material or electrolyte material are as follows:
Described Graphene is that specific area is 400～1000m
2The Graphene of/g;
Described the first conductive agent and the second conductive agent are acetylene black, conductive black or carbon nano-tube, and these conductive agents all can be bought by the market and obtain;
Described the first binding agent and the second binding agent are Kynoar (PVDF) or polytetrafluoroethylene (PTFE);
Described electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated;
Described barrier film adopts the pp barrier film.
Another object of the present invention is to provide the preparation method of above-mentioned super electrochemical capacitor, its step is as follows:
S1, mass ratio is respectively 80～93: 2～10: 5～10 Graphene, the first conductive agent and the first binding agent are configured to positive electrode active materials, and mass ratio is respectively 80～93: 2～10: 5～10 titanium dioxide nano thread, the second conductive agent and the second binding agent are configured to negative active core-shell material;
S2, described positive electrode active materials is coated on the aluminium foil, drying makes positive pole after processing; Described negative active core-shell material is coated on the Copper Foil, and drying makes negative pole after processing;
S3, described positive pole, negative pole and barrier film are cut into after the required specification to enter to be equipped with in the container of electrolyte according to the order assembling of positive pole/barrier film/negative pole is rearmounted, obtain described super electrochemical capacitor.
Among the above-mentioned preparation method, among the step S2, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
The invention provides super electrochemical capacitor, its negative material has low current potential platform, so that the average working voltage of super electrochemical capacitor is higher than traditional double electric layer capacitor, the chemical energy that produces owing to embedding-Tuo embedding mechanism again, thus the energy density of system is risen; And positive pole has adopted the Graphene that specific area is higher, conductivity is good, and it can effectively reduce the internal resistance of whole super electrochemical capacitor, can make again the higher ratio electric capacity of formation of super electrochemical capacitor; The anodal grapheme material that adopts has good conductivity, can effectively reduce the internal resistance of whole super electrochemical capacitor, make the power density of hybrid super electrochemical capacitor reduce not to be too much than electric double layer capacitance, can keep good cycle life simultaneously.
Description of drawings
Fig. 1 is super electrochemical capacitor structural representation of the present invention;
Fig. 2 is preparation technology's flow chart of super electrochemical capacitor of the present invention.
Embodiment
A kind of super electrochemical capacitor, as shown in Figure 1, comprise anodal 6, negative pole 7, between described anodal 6 and negative pole 7 between barrier film 3 and electrolyte 8, the order assembling is rearmounted enters to fill in the container 9 of electrolyte 8 according to anodal 6/ barrier film, 3/ negative pole 7 for described anodal 6, negative pole 7, barrier film 3; Anodal 6 material comprises aluminium foil 1 and the mass ratio that is coated on the described aluminium foil 1 is respectively 80～93: the positive electrode active materials 2 that 2～10: 5～10 Graphene, the first conductive agent and the first binding agent form; The material of negative pole 7 comprises Copper Foil 5 and the mass ratio that is coated on the described Copper Foil 5 is respectively 80～93: the negative active core-shell material 4 that 2～10: 5～10 titanium dioxide nano thread, the second conductive agent and the second binding agent form.
In the above-mentioned super electrochemical capacitor, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
In the above-mentioned super electrochemical capacitor, electrode material or electrolyte material are as follows:
Graphene is that specific area is 400～1000m
2The Graphene of/g also can be selected the Graphene that carries out surface modification, as, the surface modified graphite alkene of the elements such as the B that mixes, N, O, F;
The first conductive agent and the second conductive agent are acetylene black, conductive black (such as, conductive black super P) or carbon nano-tube, and these conductive agents all can be bought by the market and obtain;
The first binding agent and the second binding agent are Kynoar (PVDF) or polytetrafluoroethylene (PTFE);
Titanium dioxide nano thread is titanium dioxide (B) nano wire, i.e. TiO
2(B) nano wire;
Described electrolyte is the formulated electrolyte of lithium-ion electrolyte salt and non-aqueous organic solvent; Lithium-ion electrolyte salt in the electrolyte is LiPF
6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3) or LiAsF
6In one or more, the non-aqueous organic solvent in the electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, butylene, r-butyrolactone, methyl ethyl carbonate alkene ester, methyl propyl carbonate, ethyl acetate or the acetonitrile;
Described barrier film can adopt the pp barrier film.
Another object of the present invention is to provide the preparation method of above-mentioned super electrochemical capacitor, as shown in Figure 2, comprise that step is as follows:
S1, mass ratio is respectively 80～93: 2～10: 5～10 Graphene, the first conductive agent and the first binding agent are configured to positive electrode active materials, and mass ratio is respectively 80～93: 2～10: 5～10 titanium dioxide nano thread, the second conductive agent and the second binding agent are configured to negative active core-shell material;
S2, described positive electrode active materials is coated on the aluminium foil, drying makes positive pole after processing; Described negative active core-shell material is coated on the Copper Foil, and drying makes negative pole after processing;
S3, described positive pole, negative pole and barrier film cut into cut into required specification after the required specification and enter to be equipped with in the container of electrolyte according to the order assembling of positive pole/barrier film/negative pole is rearmounted, obtain described super electrochemical capacitor.
Among the above-mentioned preparation method, among the step S2, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
Among the preparation method of above-mentioned super electrochemical capacitor, electrode material, electrolyte material are as follows:
Graphene is that specific area is 400～1000m
2The Graphene of/g also can be selected the Graphene that carries out surface modification, as, the surface modified graphite alkene of the elements such as the B that mixes, N, O, F;
The first conductive agent and the second conductive agent are acetylene black, conductive black (such as, conductive black super P) or carbon nano-tube, and these conductive agents all can be bought by the market and obtain;
The first binding agent and the second binding agent are Kynoar (PVDF) or polytetrafluoroethylene (PTFE);
Described electrolyte is the formulated electrolyte of lithium-ion electrolyte salt and non-aqueous organic solvent; Lithium-ion electrolyte salt in the electrolyte is LiPF
6, LiBF
4, LiBOB, LiCF
3SO
3, LiN (SO
2CF
3) or LiAsF
6In one or more, the non-aqueous organic solvent in the electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, ethylene sulfite, propylene sulfite, butylene, r-butyrolactone, methyl ethyl carbonate alkene ester, methyl propyl carbonate, ethyl acetate or the acetonitrile;
Barrier film can adopt the pp barrier film.
The invention provides super electrochemical capacitor, adopt ion to embed an electric double layer mechanism coordination that takes off embedding mechanism and ultra-capacitor and be combined in an energy storage capacitor, its negative material has low current potential platform, so that the average working voltage of super electrochemical capacitor is higher than traditional double electric layer capacitor, thereby the energy density of system is risen; And positive pole has adopted the Graphene that specific area is higher, conductivity is good, and it can effectively reduce the internal resistance of whole super electrochemical capacitor, can make again the higher ratio electric capacity of formation of super electrochemical capacitor; The anodal grapheme material that adopts has good conductivity, can effectively reduce the internal resistance of whole super electrochemical capacitor, make the power density of hybrid super electrochemical capacitor reduce not to be too much than electric double layer capacitance, can keep good cycle life simultaneously.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
1, super electrochemical capacitor electrode preparation:
Anodal.Be that (specific area is 400m for 85: 10: 5 Graphene with mass ratio
2/ g), acetylene black conductor, PVDF binding agent make positive electrode active materials after mixing, and positive electrode active materials is coated on the aluminium foil, 80 ℃ of baking 12h obtain anodal in vacuum;
Negative pole.Be 85: 10: 5 TiO with mass ratio
2(B) nano wire, acetylene black conductor, PVDF binding agent are made negative active core-shell material after mixing, and negative active core-shell material is coated on the Copper Foil, and 80 ℃ of baking 12h obtain negative pole in vacuum.
Wherein, the mass ratio of the positive electrode active materials on the positive pole and the negative active core-shell material on the negative pole is 1: 1.
2, assemble super electrochemical capacitor:
The above-mentioned positive pole that makes and annex are cut into required specification, and in glove box, according to the order assembling of positive pole/pp barrier film/negative pole, inject LiPF
6, propene carbonate and diethyl carbonate electrolyte, obtain super electrochemical capacitor.
Embodiment 2
1, super electrochemical capacitor electrode preparation:
Anodal.Be that (specific area is 700m for 80: 10: 10 Graphene with mass ratio
2/ g), carbon nanotube conducting agent, PVDF binding agent make positive electrode active materials after mixing, and positive electrode active materials is coated on the aluminium foil, 80 ℃ of baking 12h obtain anodal in vacuum;
Negative pole.Be 80: 10: 10 TiO with mass ratio
2(B) nano wire, carbon nanotube conducting agent, PVDF binding agent are made negative active core-shell material after mixing, and negative active core-shell material is coated on the Copper Foil, and 80 ℃ of baking 12h obtain negative pole in vacuum.
Wherein, the mass ratio of the positive electrode active materials on the positive pole and the negative active core-shell material on the negative pole is 1: 2.
2, assemble super electrochemical capacitor:
The above-mentioned positive pole that makes and annex are cut into required specification, and in glove box, according to the order assembling of positive pole/pp barrier film/negative pole, inject LiBOB and acetonitrile electrolyte, obtain super electrochemical capacitor.
Embodiment 3
1, super electrochemical capacitor electrode preparation:
Anodal.Be that (specific area is 1000m for 93: 2: 5 Graphene with mass ratio
2/ g), conductive black conductive agent, PTFE binding agent make positive electrode active materials after mixing, and positive electrode active materials is coated on the aluminium foil, 80 ℃ of baking 12h obtain anodal in vacuum;
Negative pole.Be 93: 2: 5 TiO with mass ratio
2(B) nano wire, conductive black super P conductive agent, PTFE binding agent are made negative active core-shell material after mixing, and negative active core-shell material is coated on the Copper Foil, and 80 ℃ of baking 12h obtain negative pole in vacuum.
Wherein, the mass ratio of the positive electrode active materials on the positive pole and the negative active core-shell material on the negative pole is 1: 5.
2, assemble super electrochemical capacitor:
Positive pole and annex are cut into required specification, and in glove box, according to the order assembling of positive pole/pp barrier film/negative pole, inject LiBF
4, dimethyl carbonate and ethylene carbonate electrolyte, obtain super electrochemical capacitor.
The super electrochemical capacitor that above embodiment 1～3 is assembled into carries out the constant current charge-discharge test, and the different energy densities and the cycle life that obtain are such as table 1; The more existing commercial capacitor of energy content of battery density improves a lot.The energy density of present commercial maxwell ultracapacitor BCAP0350E270T09 is 5.62Wh/kg, and the energy density of other model is 1.38～5.62Wh/kg.
Table 1
| Embodiment | The anode and cathode active materials mass ratio | Energy density (Wh/kg) | Capacity retention after 1000 circulations |
| 1 | 1∶1 | 30 | 99％ |
| 2 | 1∶2 | 33 | 99％ |
| 3 | 1∶5 | 38 | 99％ |
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a super electrochemical capacitor comprises positive pole, negative pole, the barrier film between described positive pole and negative pole and electrolyte; Described positive pole, negative pole and barrier film are immersed in the described electrolyte; It is characterized in that the material of described positive pole comprises aluminium foil and the mass ratio that is coated on the described aluminium foil is respectively 80～93: the positive electrode active materials that 2～10: 5～10 Graphene, the first conductive agent and the first binding agent form; The material of described negative pole comprises aluminium foil and the mass ratio that is coated on the described Copper Foil is respectively 80～93: the negative active core-shell material that 2～10: 5～10 titanium dioxide nano thread, the second conductive agent and the second binding agent form.
2. super electrochemical capacitor according to claim 1 is characterized in that, described Graphene is that specific area is 400～1000m
2The Graphene of/g.
3. super electrochemical capacitor according to claim 1 is characterized in that, described the first conductive agent and the second conductive agent are acetylene black, conductive black or carbon nano-tube; Described the first binding agent and the second binding agent are Kynoar or polytetrafluoroethylene.
4. according to claim 1 to 3 arbitrary described super electrochemical capacitors, it is characterized in that described electrolyte is the formulated electrolyte of lithium-ion electrolyte salt and non-aqueous organic solvent.
5. super electrochemical capacitor according to claim 1 is characterized in that, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
6. the preparation method of a super electrochemical capacitor is characterized in that, comprises the steps:
S1, Graphene, the first conductive agent and the first binding agent that mass ratio was respectively 85: 10: 5 are configured to positive electrode active materials, and titanium dioxide nano thread, the second conductive agent and the second binding agent that mass ratio was respectively 85: 10: 5 are configured to negative active core-shell material;
S2, described positive electrode active materials is coated on the aluminium foil, drying makes positive pole after processing; Described negative active core-shell material is coated on the Copper Foil, and drying makes negative pole after processing;
S3, described positive pole, negative pole and barrier film cut into after the required specification insert in the container that electrolyte is housed after der group according to positive pole/barrier film/negative pole turns, obtain described super electrochemical capacitor.
7. the preparation method of super electrochemical capacitor according to claim 6 is characterized in that, described Graphene is that specific area is 400～1000m
2The Graphene of/g.
8. the preparation method of super electrochemical capacitor according to claim 6 is characterized in that, among the described step S1, described the first conductive agent and the second conductive agent are acetylene black, conductive black or carbon nano-tube; Described the first binding agent and the second binding agent are Kynoar or polytetrafluoroethylene.
9. super electrochemical capacitor according to claim 6 is characterized in that, among the step S2, the mass ratio of described positive electrode active materials and described negative active core-shell material is 1: 1～1: 5.
10. super electrochemical capacitor according to claim 6 is characterized in that, among the step S3, described electrolyte is the formulated electrolyte of lithium-ion electrolyte salt and non-aqueous organic solvent.
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Cited By (4)
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| CN103413692A (en) * | 2013-08-25 | 2013-11-27 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor positive plate and lithium ion capacitor using same |
| CN105336507A (en) * | 2014-08-06 | 2016-02-17 | 上海华东电信研究院 | Positive material for super capacitor, preparation method of positive material and super capacitor employing positive material |
| CN105448529A (en) * | 2014-08-06 | 2016-03-30 | 上海华东电信研究院 | Super capacitor positive electrode material and preparation method thereof, and super capacitor by adoption of positive material |
| CN110246699A (en) * | 2019-05-17 | 2019-09-17 | 中国科学院电工研究所 | A kind of anode electrode piece of lithium-ion capacitor, lithium-ion capacitor and its cathode pre-embedding lithium method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413692A (en) * | 2013-08-25 | 2013-11-27 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor positive plate and lithium ion capacitor using same |
| CN103413692B (en) * | 2013-08-25 | 2017-03-15 | 中国科学院青岛生物能源与过程研究所 | A kind of lithium ion capacitor anode plate and the lithium-ion capacitor using the positive plate |
| CN105336507A (en) * | 2014-08-06 | 2016-02-17 | 上海华东电信研究院 | Positive material for super capacitor, preparation method of positive material and super capacitor employing positive material |
| CN105448529A (en) * | 2014-08-06 | 2016-03-30 | 上海华东电信研究院 | Super capacitor positive electrode material and preparation method thereof, and super capacitor by adoption of positive material |
| CN110246699A (en) * | 2019-05-17 | 2019-09-17 | 中国科学院电工研究所 | A kind of anode electrode piece of lithium-ion capacitor, lithium-ion capacitor and its cathode pre-embedding lithium method |
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