CN106653392A - Carbon composite material with high specific capacitance and preparation method and application of carbon composite material - Google Patents
Carbon composite material with high specific capacitance and preparation method and application of carbon composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 203
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims description 184
- 238000001354 calcination Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 235000002949 phytic acid Nutrition 0.000 claims description 5
- 229960003351 prussian blue Drugs 0.000 claims description 5
- 239000013225 prussian blue Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000002269 spontaneous effect Effects 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 229940015849 thiophene Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000003575 carbonaceous material Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 49
- 230000005540 biological transmission Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 235000001727 glucose Nutrition 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ferric ferrocyanide Chemical compound 0.000 description 1
- 150000002304 glucoses Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a carbon composite material with high specific capacitance and a preparation method and application of the carbon composite material. The carbon composite material with the high specific capacitance is prepared by mixing a first component carbon material with the atom doping content of 10%-25% and a second component carbon material with the atom doping content of 0-10%. According to the carbon composite material, the first component carbon material is relatively high in atom doping content and has the characteristic of high pseudocapacitance, the second component carbon material is relatively low in atom doping content and has relatively good conductivity, and the first component carbon material and the second component carbon material are optimized and complemented, so that the carbon composite material is manufactured into a pole piece; and in the lithium intercalation and deintercalation processes, the second component carbon material provides a conductive network and can provide one part of pseudocapacitance, the second component carbon material is more conducive to development of atom-doped pseudocapacitance in the conductive network and the two carbon materials interact with one another, thereby improving the overall performance of the electrode material.
Description
Technical field
The application is related to carbon electrode material field, the carbon combined material of more particularly to a kind of high specific capacitance and its preparation side
Method and application.
Background technology
Ultracapacitor has obtained extensive research by its quick lithium ion transport performance.And lithium rechargeable battery
Compare, super capacitor has the power density and cyclical stability of superelevation, is even more favored by academia and industrial quarters.According to
Storage lithium mechanism ultracapacitor can be divided into two classes, electric double layer capacitance and fake capacitance.
Material with carbon element is because electric conductivity is high, specific surface area is big, and the advantage such as precursor material is abundant of carbon, is widely used in
Ultracapacitor.In order to obtain high capacitance, carbon electrode material must possess three features, the first high-specific surface area, and second
Suitable pore-size distribution, the 3rd Heteroatom doping.Wherein, high-specific surface area and pore-size distribution, have there is considerable research, example
The material with carbon element of high-specific surface area, even aperture distribution is such as prepared by microwave method, calcination method, acid and alkali corrosion method.For atom
Doping aspect, existing research display, the atom doped fake capacitance that can increase material with carbon element, but its electric conductivity can be reduced, because
This, it is necessary to the seeking balance between electric conductivity and fake capacitance, the carbon electrode material good to obtain combination property.
The content of the invention
The purpose of the application is to provide a kind of carbon combined material of new high specific capacitance and its preparation method and application.
The application employs technical scheme below：
The one side of the application discloses a kind of carbon combined material of high specific capacitance, and the carbon combined material is by atom doped amount
For the first component material with carbon element of 10%-25%, mix with second component material with carbon element of the atom doped amount for 0%-10%.
It should be noted that in the application, the first component material with carbon element is more atom doped than high level due to having, and its is counterfeit
Electric capacity is of a relatively high, but its poorly conductive；The atom doped amount of the second component material with carbon element is low, and electric conductivity is preferable.The carbon of the application
Combined material, its key is that the first component material with carbon element of high fake capacitance, mixes with the second component material with carbon element of high conductivity
Close, the material with carbon element that two kinds have different advantages is mixed so as to have complementary advantages, and then improve the overall ratio electricity of carbon combined material
Capacitance.Wherein, amount atom doped in the second component material with carbon element is 0%-10%, when atom doped amount is 0, represents and adopts
Be not carry out atom doped material with carbon element.Also, it should be noted that the atom doped amount of the second component material with carbon element is
When 10%, the atom doped amount of the first component material with carbon element is greater than 10%, that is to say, that the first component material with carbon element and second
The atom doped amount of both component material with carbon elements is different.
Preferably, the atom doped repeatable at least one selected from N doping, oxygen doping, sulfur doping and phosphorus doping.
Preferably, the weight ratio of the first component material with carbon element and the second component material with carbon element is 2:8-8:2.
It should be noted that according to present invention thinking, if by high the first atom doped component material with carbon element and
Low atom doped the second component material with carbon element mixing, you can obtain the carbon combined material that specific capacitance improves；But, it is contemplated that than electricity
Hold improvement, the first component material with carbon element is particularly limited in the preferred scheme of the application is with the weight ratio of the second component material with carbon element
2:8-8:2。
The another side of the application discloses application of the carbon combined material of the application in ultracapacitor.
The another side of the application discloses pole piece prepared by a kind of carbon combined material by the application.
The another side of the application discloses a kind of ultracapacitor of the pole piece of employing the application.
It is appreciated that the carbon combined material of the high specific capacitance of the application offer, inherently grinds for ultracapacitor
Study carefully, therefore, pole piece is made into for ultracapacitor, can effectively improve the capacitive property of ultracapacitor.
A kind of preparation method of the carbon combined material for simultaneously disclosing the application again of the application, comprises the following steps,
(a) using carbon source with Prussian blue as raw material, or the carbon source containing foreign atom and iron acetate are used as raw material,
In being distributed to the mixed solution of water and ethanol, it is ground, grinding product is dried, as mixed material；Mixed material is existed
Calcine under blanket of nitrogen, calcination condition is that the speed of 2-5 DEG C/min is warming up to 450 DEG C -650 DEG C, is incubated 4-10h；After the completion of calcining
Natural cooling, then, makes calcined product be exposed in air so as to spontaneous combustion；The product of spontaneous combustion is entered using concentrated acid solution
Row washing, heats while stirring in washing process, and heating-up temperature is 60 DEG C -90 DEG C；Rear centrifugal drying is washed, atom has been obtained and is mixed
Miscellaneous amount is the first component material with carbon element of 10%-25%；
B the first component material with carbon element that () prepares step (a), in argon, and more than 650 DEG C at a temperature of calcine 6h,
Obtain the second component material with carbon element that atom doped amount is 0%-10%；
C the first component material with carbon element that () prepares step (a), the second component material with carbon element prepared with step (b) mixes, i.e.,
Obtain the carbon combined material.
It should be noted that in step (a), in the mixed solution of second alcohol and water, ethanol primarily serves peptizaiton, generally
According to water:Ethanol volume ratio 1:5 or so.
Also, it should be noted that in step (a), 450 DEG C -650 DEG C of calcining heat in calcination condition, different calcining temperature
Degree, the material with carbon element of acquisition has different electric conductivity and atom doped content, and generally speaking temperature is higher, foreign atom content phase
To relatively low, electric conductivity is stronger；As for the time of calcining, that is, 4-10h is incubated, primarily to ensureing that calcining is abundant, ensures material
Concordance.
Preferably, carbon source is glucose, the carbon source containing foreign atom be polyaniline, tripolycyanamide, sodium alginate, thiophene and
At least one in phytic acid.
It should be noted that in the Fe-base compound of the application employing, it is Prussian blue to also have a special effect, that is, carry
For nitrogen source, therefore, in a kind of implementation of the application, directly contained without other as carbon source using glucose
The carbon source of foreign atom, with it is Prussian blue mix, grind, calcine by obtain N doping material with carbon element.And adopt former containing doping
During the carbon source of son, in order to not introduce other hetero atoms, Fe-base compound adopts iron acetate, so can obtain containing foreign atom
Material with carbon element；Wherein, polyaniline and tripolycyanamide are the material with carbon element containing foreign atom nitrogen, and sodium alginate is the carbon containing foreign atom oxygen
Material, thiophene is the material with carbon element containing foreign atom sulfur, and phytic acid is the material with carbon element containing foreign atom phosphorus.
Preferably, in step (a), concentrated acid solution is concentrated sulphuric acid.Wherein dense acid solution wash be in order to remove material with carbon element in
Iron atom, the carbon shell material big so as to obtain specific surface area.
Preferably, in step (b), the temperature calcined in argon is 850 DEG C -1050 DEG C.
It should be noted that in step (b), calcining heat is higher, the content of foreign atom is lower, the realization side of the application
Using regulation and control calcining heat control foreign atom content in formula, this is a kind of regulatory pathway of foreign atom content, however not excluded that
The method of other the regulation and control foreign atom contents that can be used using laboratory.
The beneficial effect of the application is：
In the carbon combined material of the application, the atom doped amount of the first component material with carbon element is of a relatively high, with high fake capacitance
The characteristics of, and the atom doped amount of the second component material with carbon element is relatively low, with preferable electric conductivity, both optimize complementation；Cause
This, by the carbon combined material of the application pole piece is made, and during removal lithium embedded, the second component material with carbon element provide not only conduction
Network and a part of fake capacitance can be provided, the first component material with carbon element is more conducive to the counterfeit electricity of foreign atom inside conductive network
The performance of appearance, two kinds of material with carbon elements interact, so as to improve the overall performance of electrode material.
Description of the drawings
Fig. 1 is the process flow diagram that material with carbon element is prepared in the embodiment of the present application；
Fig. 2 is the structural representation that the first component material with carbon element and the second component material with carbon element interact in the embodiment of the present application
Figure；
Fig. 3 is the transmission electron microscope picture of the material with carbon element CS-650 prepared in the embodiment of the present application；
Fig. 4 is the transmission electron microscope picture of the material with carbon element CS-850 prepared in the embodiment of the present application；
Fig. 5 is the high rate performance comparison diagram that three kinds of material with carbon elements are prepared into pole piece in the embodiment of the present application, wherein " ■ " curve
For the high rate performance curve of material with carbon element CS-650, "●" curve is the high rate performance curve of material with carbon element CS-850, and " ▲ " curve is
The high rate performance curve of the carbon combined material of material with carbon element CS-650 and CS-850 composition；
Fig. 6 is the transmission electron microscope picture of the material with carbon element CS-1050 prepared in the embodiment of the present application；
Fig. 7 is the high rate performance comparison diagram that three kinds of material with carbon elements are prepared into pole piece in the application another embodiment, wherein
" ■ " curve is the high rate performance curve of material with carbon element CS-650, and "●" curve is the high rate performance curve of material with carbon element CS-1050,
" ▲ " curve is the high rate performance curve of the carbon combined material of material with carbon element CS-650 and CS-1050 composition.
Specific embodiment
Present inventor has found in substantial amounts of test and research process, atom doped to increase the counterfeit of material with carbon element
Electric capacity, and then improve the overall performance of electrode material；But, the increase of atom doped amount can reduce accordingly its electric conductivity.Cause
How simultaneously this, obtain the material with carbon element of high fake capacitance and high conductivity, this be for researcher in this field one cannot
The contradiction gone beyond.The application confirms through research, and the high material with carbon element of the atom doped amount with high fake capacitance and is led with height
The low material with carbon element mixing of electrical atom doped amount, as carbon combined material, can produce specific capacitances of the 1+1 more than 2 and multiplying power
Performance.
The preparation method of the carbon combined material of the application, as shown in figure 1, first mixing raw material, calcining forms composite wood
Material, then through pickling, removes the oxide of ferrum, that is, obtain the first high component material with carbon element of atom doped amount, further,
The high-temperature calcination of different temperatures is carried out to the first component material with carbon element, that is, obtains the second low component material with carbon element of atom doped amount, Fig. 1
Shown be the application two kinds of implementations in, 850 DEG C and 1050 DEG C of calcining heat is respectively adopted high to atom doped amount
The first component material with carbon element calcined, obtain the second low component material with carbon element of atom doped amount.
In the carbon combined material of the application, the atom doped amount of the first component material with carbon element is of a relatively high, with high fake capacitance
The characteristics of, and the atom doped amount of the second component material with carbon element is relatively low, with preferable electric conductivity, both optimize complementation, such as
Shown in Fig. 2, A represents the second low component material with carbon element of atom doped amount in Fig. 2, and B represents the first high component carbon of atom doped amount
Material, electronics is mainly transmitted by the second component material with carbon element, and the first component material with carbon element mainly plays high fake capacitance effect.
The application is described in further detail below by specific embodiment.Following examples only are entered to advance to the application
The explanation of one step, should not be construed as the restriction to the application.
Embodiment one
This example prepares carbon combined material by carbon source of glucose, and concrete preparation method is as follows：
A () weighs 0.06g glucoses and is placed in mortar, Deca 1mL water and 5mL ethanol, makes glucose slurry；Weigh
0.3g is Prussian blue, i.e. ferric ferrocyanide, is added into being ground in prepared glucose slurry, is subsequently placed in 80 DEG C of air blast and does
4 hours in dry case；Dried mixed material is taken out, is calcined in a nitrogen environment, calcination condition is：With the speed of 2 DEG C/min
Heat up, at 650 DEG C 6h is incubated；After the completion of calcining, room temperature is naturally cooled to, the sample after calcining is then taken out from quartz ampoule
Product, shake in atmosphere so as to fully carry out spontaneous combustion；After shaking about 30min in atmosphere, the sample for obtaining is poured into dense sulfur
In acid, 80 DEG C are heated in the environment of stirring, kept for 12 hours, finally, sample is carried out into centrifuge washing drying, baking temperature is
80 DEG C, that is, the first high component material with carbon element of the N doping amount of this example is obtained, be named as CS-650.
B () is calcined material with carbon element CS-650 at 850 DEG C, calcining whole process is carried out in argon, and insulation 6 is little
When, the second low component material with carbon element of the N doping amount of this example is obtained, it is named as CS-850.
C the first component material with carbon element that () this example prepares step (a), the second component material with carbon element prepared with step (b), presses
According to 5:5 weight obtain the carbon combined material of this example than mixing, is named as CS-650+850.
The material with carbon element CS-650 and CS-850 prepared to this example using transmission electron microscope is observed, as a result respectively such as Fig. 3 and
Visible in Fig. 4 shown in Fig. 4, improving the material with carbon element CS-850 obtained after calcining heat has carbon layers to occur, graphitization
Degree is higher, and electric conductivity is more preferable；And the material with carbon element CS-650 of Fig. 3 then occurs without carbon layers.
Meanwhile, the nitrogen that the material with carbon element CS-650 and CS-850 of this example preparation are determined using X-ray photoelectron spectroscopic analysis is mixed
Miscellaneous content, as a result shows, the N doping content of CS-650 is 9.1% for the N doping content of 12.8%, CS-850.
Carbon combined material CS-650+850 prepared by this example is prepared into into pole piece, concrete preparation method is as follows：
The CS-850 of the CS-650 and 0.04g of 0.04g is weighed, mixing is ground, 0.01g white carbon blacks is subsequently adding and is entered again
Row ground and mixed, adds afterwards PTFE the and 2mL isopropanols of 0.025g concentration 40% to be sufficiently mixed, and manufactures film forming, then
Electrode is made by rolling cut-parts.
CV is tested with electrochemical workstation, the capacitance tested under different electric current densities with Maccor test cabinets.CV is tested
Voltage range be -1.0V-0V, sweep speed 10-100mVs-1.The voltage range of charging and discharging curve be -1.0V-0V, electric current density
For 0.2-50A g-1.Test result is as shown in Figure 5.At the same time, as a comparison, this example is respectively adopted material with carbon element CS-650 and carbon
Material C S-850, replaces carbon combined material CS-650+850 and prepares pole piece, and carries out high rate performance test to it.Test result is such as
Shown in Fig. 5.
As the result of Fig. 5 shows, the high rate performance of three kinds of materials is obtained according to charging and discharging curve, it is clear that CS-650+850
Electric capacity multiplying power property preferably, in 50A g-1Under conditions of obtain specific capacitance be 108F g-1.But CS-650 and CS-850
Capacitance be 10F g-1With 93F g-1.It can be seen that, this example is by the first high component material with carbon element of atom doped amount and atom doped amount
The CS-650+850 carbon combined materials that the second low component material with carbon element is mixed obtain and higher ratio are used alone than both
Electric capacity.
Embodiment two
This example is calcined material with carbon element CS-650 at 1050 DEG C in step (b), the atom doped amount of acquisition it is low
Two component material with carbon elements are named as CS-1050.Remaining is identical with embodiment one.
Likewise, material with carbon element CS-1050 prepared by this example is observed using transmission electron microscope, as a result as shown in fig. 6, can
See, compared with material with carbon element CS-650, improving the material with carbon element CS-1050 obtained after calcining heat there are carbon layers to occur, stone
Blackization degree is higher, and electric conductivity is more preferable.
The N doping content of the material with carbon element CS-1050 of this example preparation is determined using X-ray photoelectron spectroscopic analysis, is as a result shown
Show, the N doping content of CS-1050 is 3.3%.
The carbon combined material CS-650+1050 of this example is prepared into by pole piece using the identical method of embodiment one, and with carbon
Material C S-1050 also makes pole piece for contrast, respectively the material with carbon element CS-850 systems of two pole pieces to this example and embodiment one
Into pole piece carry out high rate performance test, test result according to charging and discharging curve as shown in fig. 7, obtained the multiplying power of three kinds of materials
Performance, it is clear that the electric capacity multiplying power property of CS-650+1050 is best, in 50A g-1Under conditions of obtain specific capacitance be 100F g-1.But the capacitance of CS-650 and CS-850 is 10F g-1With 46F g-1。
Embodiment three
This example prepares carbon combined material using the carbon source sodium alginate containing oxygen atom, and concrete grammar is as follows：
A () weighs 0.06g sodium alginates and is placed in mortar, Deca 1ml water and 5ml ethanol, makes slurry；Weigh 0.3g vinegar
Sour ferrum, is added into being ground in prepared slurry, is subsequently placed in 4 hours in 80 DEG C of air dry ovens；Take out dried mixed
Raw material is closed, is calcined in a nitrogen environment, calcination condition is：Heated up with the speed of 2 DEG C/min, at 550 DEG C 6h is incubated；Calcine
Cheng Hou, naturally cools to room temperature, and the sample for obtaining is poured in concentrated sulphuric acid, and 80 DEG C are heated in the environment of stirring, and holding 12 is little
When, finally, sample being carried out into centrifuge washing drying, baking temperature is 80 DEG C, that is, obtain high first group of the oxygen doping amount of this example
Divide material with carbon element, be named as HZSN-550.
B () is calcined HZSN-550 at 850 DEG C, calcining whole process is carried out in argon, is incubated 6 hours, is obtained
To the second low component material with carbon element of oxygen doping amount, HZSN-850 is named as.
C the first component material with carbon element that () this example prepares step (a), the second component material with carbon element prepared with step (b), presses
According to 5:5 weight obtains the carbon combined material of this example than mixing, is named as HZSN-550+850.
The material with carbon element HZSN-550 and HZSN-850 prepared to this example using transmission electron microscope is observed, and is as a result shown, is carried
The material with carbon element HZSN-850 obtained after high calcining heat has carbon layers to occur, and degree of graphitization is higher, and electric conductivity is more
It is good.The oxygen doping content of the material with carbon element HZSN-550 and HZSN-850 of this example preparation is determined using X-ray photoelectron spectroscopic analysis,
As a result show, the oxygen doping content of HZSN-550 is 5% for the oxygen doping content of 20%, HZSN-850.
Pole piece is prepared using the identical method of embodiment one, and CV is tested with electrochemical workstation, use Maccor test cabinets
Capacitance under the different electric current densities of test.Also, as a comparison, respectively with material with carbon element HZSN-550 and HZSN-850 preparation pole
Piece, tests its high rate performance.As a result show, the high rate performance of three kinds of materials has been obtained according to charging and discharging curve, it is clear that HZSN-
The electric capacity multiplying power property of 550+850 is best, in 50A g-1Under conditions of obtain specific capacitance be 120F g-1.But HZSN-550
100F g are respectively with the capacitance of HZSN-850-1With 60F g-1.It can be seen that, this example is by the first high component of oxygen atom doping
The HZSN-550+850 carbon combined materials that the second low component material with carbon element of material with carbon element and oxygen atom doping is mixed are obtained
Higher specific capacitance is used alone than both.
Example IV
This example prepares carbon combined material using the carbon source thiophene of sulfur atom-containing, and concrete grammar is as follows：
A () weighs 0.06g thiophene and is placed in mortar, Deca 1ml water and 5ml ethanol, makes slurry；Weigh 0.3g acetic acid
Ferrum, is added into being ground in prepared slurry, is subsequently placed in 4 hours in 80 DEG C of air dry ovens；Take out dried mixing
Raw material, calcines in a nitrogen environment, and calcination condition is：Heated up with the speed of 2 DEG C/min, at 550 DEG C 6h is incubated；Calcining is completed
Afterwards, room temperature is naturally cooled to, the sample for obtaining is poured in concentrated sulphuric acid, 80 DEG C are heated in the environment of stirring, kept for 12 hours,
Finally, sample is carried out into centrifuge washing drying, baking temperature is 80 DEG C, that is, obtain the first high component carbon of the sulfur doping amount of this example
Material, is named as HZSN-550.
B () is calcined SF-550 at 850 DEG C, calcining whole process is carried out in argon, is incubated 6 hours, is obtained
The second low component material with carbon element of sulfur doping amount, is named as SF-850.
C the first component material with carbon element that () this example prepares step (a), the second component material with carbon element prepared with step (b), presses
According to 5:5 weight obtains the carbon combined material of this example than mixing, is named as SF-550+850.
The material with carbon element SF-550 and SF-850 prepared to this example using transmission electron microscope is observed, and is as a result shown, raising is forged
Burning the material with carbon element SF-850 obtained after temperature has carbon layers to occur, and degree of graphitization is higher, and electric conductivity is more preferable.Using X
Ray photoelectron spectroscopic analysis determines the sulfur doping content of the material with carbon element SF-550 and SF-850 of this example preparation, as a result shows, SF-
550 sulfur doping content is 3% for the sulfur doping content of 17%, SF-850.
Pole piece is prepared using the identical method of embodiment one, and CV is tested with electrochemical workstation, use Maccor test cabinets
Capacitance under the different electric current densities of test.Also, as a comparison, respectively pole piece prepared with material with carbon element SF-550 and SF-850,
Test its high rate performance.As a result show, the high rate performance of three kinds of materials has been obtained according to charging and discharging curve, it is clear that SF-550+850
Electric capacity multiplying power property preferably, in 50A g-1Under conditions of obtain specific capacitance be 140F g-1.But SF-550 and SF-850
Capacitance be 120F g-1With 80F g-1.It can be seen that, this example is by the first high component material with carbon element of sulphur atom doping and sulphur atom
The SF-550+850 carbon combined materials that the second low component material with carbon element of doping is mixed are obtained and are used alone more than both
High specific capacitance.
Embodiment five
This example prepares carbon combined material using the carbon source phytic acid containing phosphorus atoms, and concrete grammar is as follows：
A () weighs 0.06g phytic acids and is placed in mortar, Deca 1ml water and 5ml ethanol, makes slurry；Weigh 0.3g
Iron acetate, is added into being ground in prepared slurry, is subsequently placed in 4 hours in 80 DEG C of air dry ovens；Take out dried
Mixed material, calcines in a nitrogen environment, and calcination condition is：Heated up with the speed of 2 DEG C/min, at 550 DEG C 6h is incubated；Calcining
After the completion of, room temperature is naturally cooled to, the sample for obtaining is poured in concentrated sulphuric acid, 80 DEG C are heated in the environment of stirring, keep 12
Hour, finally, sample is carried out into centrifuge washing drying, baking temperature is 80 DEG C, that is, obtain the phosphorus doping amount of this example it is high first
Component material with carbon element, is named as JC-550.
B () is calcined SF-550 at 850 DEG C, calcining whole process is carried out in argon, is incubated 6 hours, is obtained
The second low component material with carbon element of phosphorus doping amount, is named as JC-850.
C the first component material with carbon element that () this example prepares step (a), the second component material with carbon element prepared with step (b), presses
According to 5:5 weight obtains the carbon combined material of this example than mixing, is named as SF-550+850.
The material with carbon element SF-550 and SF-850 prepared to this example using transmission electron microscope is observed, and is as a result shown, raising is forged
Burning the material with carbon element JC-850 obtained after temperature has carbon layers to occur, and degree of graphitization is higher, and electric conductivity is more preferable.Using X
Ray photoelectron spectroscopic analysis determines the phosphorus doping content of the material with carbon element JC-550 and JC-850 of this example preparation, as a result shows, SF-
550 phosphorus doping content is 3% for the phosphorus doping content of 12%, SF-850.
Pole piece is prepared using the identical method of embodiment one, and CV is tested with electrochemical workstation, use Maccor test cabinets
Capacitance under the different electric current densities of test.Also, as a comparison, respectively pole piece prepared with material with carbon element JC-550 and SF-850,
Test its high rate performance.As a result show, the high rate performance of three kinds of materials has been obtained according to charging and discharging curve, it is clear that JC-550+850
Electric capacity multiplying power property preferably, in 50A g-1Under conditions of obtain specific capacitance be 102F g-1.But JC-550 and JC-850
Capacitance be 80F g-1With 40F g-1.It can be seen that, this example mixes the first high component material with carbon element of phosphorus atoms doping and phosphorus atoms
The SF-550+850 carbon combined materials that the second low component material with carbon element of miscellaneous amount is mixed obtain higher than both exclusive uses
Specific capacitance.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Being embodied as please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of conceiving from the application, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. the carbon combined material of a kind of high specific capacitance, it is characterised in that：The carbon combined material is 10%- by atom doped amount
25% the first component material with carbon element, mixes with the second component material with carbon element of the atom doped amount for 0%-10%.
2. carbon combined material according to claim 1, it is characterised in that：Described atom doped repeatable mixes selected from nitrogen
At least one of miscellaneous, oxygen doping, sulfur doping and phosphorus doping.
3. carbon combined material according to claim 1 and 2, it is characterised in that：The first component material with carbon element and described
The weight ratio of two component material with carbon elements is 2:8-8:2.
4. application of the carbon combined material according to any one of claim 1-3 in ultracapacitor.
5. the pole piece that prepared by a kind of carbon combined material by described in any one of claim 1-3.
6. the ultracapacitor of the pole piece described in a kind of employing claim 5.
7. the preparation method of the carbon combined material according to any one of claim 1-3, it is characterised in that：Including following step
Suddenly,
(a) using carbon source with Prussian blue as raw material, or the carbon source containing foreign atom and iron acetate are used as raw material, dispersion
To in the mixed solution of water and ethanol, it is ground, grinding product is dried, as mixed material；By mixed material in nitrogen
Calcine under atmosphere, calcination condition is that the speed of 2-5 DEG C/min is warming up to 450 DEG C -650 DEG C, is incubated 4-10h；It is natural after the completion of calcining
Cooling, then, makes calcined product be exposed in air so as to spontaneous combustion；The product of spontaneous combustion is washed using concentrated acid solution
Wash, heat while stirring in washing process, heating-up temperature is 60 DEG C -90 DEG C；Rear centrifugal drying has been washed, atom doped amount has been obtained
For the first component material with carbon element of 10%-25%；
B the first component material with carbon element that () prepares step (a), in argon, and more than 650 DEG C at a temperature of calcine 6h, obtain
Atom doped amount is the second component material with carbon element of 0%-10%；
C the first component material with carbon element that () prepares step (a), the second component material with carbon element prepared with step (b) mixes, that is, obtain
The carbon combined material.
8. preparation method according to claim 7, it is characterised in that：The carbon source is glucose, described containing foreign atom
Carbon source be polyaniline, tripolycyanamide, sodium alginate, thiophene and phytic acid at least one.
9. preparation method according to claim 7, it is characterised in that：In the step (a), the concentrated acid solution is dense sulfur
Acid.
10. preparation method according to claim 7, it is characterised in that：In the step (b), the temperature calcined in argon
Spend for 850 DEG C -1050 DEG C.
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| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
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| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
| WO2015015386A1 (en) * | 2013-08-01 | 2015-02-05 | Basf Se | Two-dimensional graphene-based porous polymer and the preparation thereof |
| CN105702473A (en) * | 2014-11-26 | 2016-06-22 | 中国科学院上海硅酸盐研究所 | Carbon-based electrode material having super high specific capacitance and combined electrode material thereof |
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