CN109534337A - A kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode and its application - Google Patents
A kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode and its application Download PDFInfo
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- CN109534337A CN109534337A CN201811612409.3A CN201811612409A CN109534337A CN 109534337 A CN109534337 A CN 109534337A CN 201811612409 A CN201811612409 A CN 201811612409A CN 109534337 A CN109534337 A CN 109534337A
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- exchange resin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000009938 salting Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 150000003440 styrenes Chemical class 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000003729 cation exchange resin Substances 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 238000005530 etching Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 239000012190 activator Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- 238000005087 graphitization Methods 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to field of material technology more particularly to a kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode and its applications.The present invention provides a kind of preparation methods of graphitized stephanoporate material with carbon element, comprising the following steps: a) impregnates ion exchange resin in inorganic metal salting liquid, then is dried, obtains the first product；B) the first product is placed in nitrogen and/or inert gas atmosphere and carries out pre- carbonization treatment, obtain the second product；C) the second product is placed under carbon dioxide and the mixed atmosphere of nitrogen and/or inert gas and is activated, then cleaned, obtain graphitized stephanoporate material with carbon element.The result shows that the graphitized stephanoporate material with carbon element has porous microstructure, large specific surface area, has great application prospect, and the present invention uses etching agent of the inorganic metal salt as ion exchange resin, it is activated again using carbon dioxide as activator and pore creating material, it avoids using a large amount of etching agents, it is environmentally protective.
Description
Technical field
The invention belongs to field of material technology more particularly to a kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode
And its application.
Background technique
Energy shortage and environmental pollution are two hang-ups of the world today, to solve the above problems, develop wind energy, solar energy,
The renewable energy such as tide energy are an effective approach.But these energy can be made there is periodical and regional limitation
At the waste of resource, it is therefore desirable to seek suitable energy storage device.Supercapacitor is a kind of environmentally protective, safe recyclable
Energy storage device, power density is high, is able to achieve fast charging and discharging, causes everybody extensive concern.And the property of supercapacitor
It can be often heavily dependent on the performance of electrode material, so being badly in need of developing a kind of highly conductive, height ratio capacity electrode material
Material.
The common electrode material of supercapacitor is carbon material, the conductive good, stability of carbon material on the market at present
The advantages that high, cheap, widely used.Application in terms of energy storage can directly serve as active material and carry out energy storage, also can
Carbon skeleton is served as, other active materials are carried, composite material is formed, as active material using most commonly seen.
Although there are many relevant carbon materials to be applied to supercapacitor on the market now, performance much reaches not
To theoretical value, inefficiencies are caused.Such as existing technology is to utilize stalk, pitch etc. for carbon source at present, Pintsch process preparation
Carbon material, the carbon material specific surface area which is prepared is small, and relative availability is lower.
Summary of the invention
In view of this, being used the present invention provides a kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode and its application
In solving, existing carbon material specific surface area is not big enough, limits the capacitance value of electrode, causes supercapacitor inefficiencies
Technical problem.
The specific technical solution of the present invention is as follows:
A kind of preparation method of graphitized stephanoporate material with carbon element, comprising the following steps:
A) ion exchange resin is impregnated in inorganic metal salting liquid, then be dried, obtain the first product；
B) first product is placed in nitrogen and/or inert gas atmosphere and carries out pre- carbonization treatment, obtain the second production
Object；
C) second product is placed under the mixed atmosphere of carbon dioxide and nitrogen and/or inert gas and is carried out at activation
Reason, then cleaned, obtain graphitized stephanoporate material with carbon element.
The present invention the result shows that, the graphitized stephanoporate material with carbon element have porous microstructure, large specific surface area, have greatly
Application prospect.Existing preparation method mainly uses a large amount of pore creating material and etching agent, causes greatly to pollute to environment, this
Invention uses etching agent of the inorganic metal salt as ion exchange resin, then use carbon dioxide as activator and pore creating material into
Row is activated, environmentally protective, avoids obtaining graphitization porous carbon under conditions of environment friendly and pollution-free using a large amount of etching agents
Material, low energy consumption for preparation method provided by the invention, and using ion exchange resin as carbon source, raw material simplicity is easily taken, cheap,
Easy to operate, preparation process is easily controllable, it is easy to accomplish, it is suitble to large-scale production.
In the present invention, the first product can be the ion exchange resin after processing waste water.Step a) exists ion exchange resin
The ion exchange resin treatment waste water process that simulates is impregnated in inorganic metal salting liquid, the present invention can be by the ion after processing waste water
Exchanger resin prepares graphitized stephanoporate material with carbon element, can be realized the effect of waste material secondary use, scientific clean and environmental protection, so that graphite
The raw material simplicity for preparing for changing porous carbon materials easily takes, cheap.Also, it handles in the ion exchange resin after waste water, waste water
Metal ion can be as from etching agent, avoiding using a large amount of etching agent pollution on the environments.
Preferably, the step a) ion exchange resin is selected from D001 macropore strong acid styrene series anion exchange tree
Rouge, D201 macroporous strong basic styrene series anion exchange resin, D751 macropore chelating type styrene ion exchange resin,
D301 macroreticular weakly base styrene series anion exchange resin or D151/D152 weakly acidic cationic exchange resin of acrylic series.
Preferably, the metal salt of step a) the inorganic metal salting liquid is selected from nickel chloride, nickel nitrate, nickel acetate, chlorination
Cobalt, cobalt nitrate or cobalt acetate.
In the present invention, metal salt is preferably nickel chloride, nickel nitrate, nickel acetate, more preferably nickel acetate, further preferably
Nickel acetate tetrahydrate.
Preferably, the concentration ratio of the quality of the step a) ion exchange resin and the inorganic metal salting liquid is (1g
~10g): (0.05M~1M).
In the present invention, ion exchange resin is impregnated and then is dried in inorganic metal salting liquid by step a).Leaching
Bubble can also are as follows: is ultrasonically treated or is heated hydro-thermal process.The time of ultrasonic treatment is 1h~10h.Ultrasonic treatment is specially to adopt
Ultrasound is carried out with ultrasonic cell disruptor.The frequency of ultrasonic treatment is 15~30kHz, and the power of ultrasonic treatment is 1~2W
cm-3.The temperature for heating hydro-thermal process is 100~160 DEG C, and the time for heating hydro-thermal process is 4-10h.
Before drying, further includes: filtering removes filtrate.
Preferably, the temperature of step b) the pre- carbonization treatment is 100 DEG C~800 DEG C；
The time of the pre- carbonization treatment is 1h~10h.
Preferably, the temperature of the step c) activation processing is 500 DEG C~1000 DEG C；
The time of the activation processing is 1h~3h.
In the present invention, pre- carbonization treatment is carried out using tube furnace.
After step b), before step c), further includes: ground to the second product.
The partial size of the second product after grinding is 1~5 μm, and milling time is 20min~60min.
Preferably, in the mixed atmosphere of the step c) carbon dioxide and nitrogen and/or inert gas, carbon dioxide and nitrogen
The volume ratio of gas and/or inert gas is 1:4~1:1.
In the present invention, the cleaning agent of step c) cleaning is selected from one kind or more of dilute hydrochloric acid, dust technology, dilute sulfuric acid and spirit of vinegar
Kind and water will be activated the inorganic metal salt in product and remove.
After step c) is cleaned again, before obtaining graphitized stephanoporate material with carbon element, further includes: dry.
The present invention also provides graphitized stephanoporate material with carbon element made from preparation method described in above-mentioned technical proposal.
The present invention also provides a kind of electrodes, including graphitized stephanoporate material with carbon element described in above-mentioned technical proposal.
Electrodic electron transmission path of the present invention is short, and electric conductivity is strong, can effectively increase the capacitive property of supercapacitor, electricity
The charge transfer resistance of pole is smaller, and preferably, the present invention provides good electrode for energy storage problem for diffusion, has greatly
Application prospect.
In the present invention, graphitized stephanoporate material with carbon element and Kynoar (PVDF) are subjected to 3h~10h according to mass ratio 1:9
It after mixing, is applied in nickel foam, drying tabletting obtains electrode.
The present invention also provides the application of electrode described in above-mentioned technical proposal in the capacitor.
In the present invention, capacitor is supercapacitor.
In conclusion the present invention provides a kind of preparation methods of graphitized stephanoporate material with carbon element, comprising the following steps: a) will
Ion exchange resin impregnates in inorganic metal salting liquid, then is dried, and obtains the first product；B) first product is set
Pre- carbonization treatment is carried out in nitrogen and/or inert gas atmosphere, obtains the second product；C) second product is placed in dioxy
Change and be activated under carbon and the mixed atmosphere of nitrogen and/or inert gas, then cleaned, obtains graphitization porous carbon
Material.The result shows that the graphitized stephanoporate material with carbon element has porous microstructure, porous microstructure is porous nanometer structure, than
Surface area is big, and specific surface area is up to 402.88m2/g, and the peak D/G of Raman spectrum is than being only 0.66, and degree of graphitization is high, utilization rate
Height can be improved the benefit of supercapacitor, and the electrode conductivuty prepared by graphitized stephanoporate material with carbon element is strong, increase effectively electricity
The capacitive property of pole material provides good material for energy storage problem, has great application prospect.Also, this hair
The bright etching agent using inorganic metal salt as ion exchange resin, then using carbon dioxide as activator and pore creating material progress
It is activated, it is environmentally protective, it avoids obtaining graphitization porous carbon under conditions of environment friendly and pollution-free using a large amount of etching agents
Material, low energy consumption for preparation method provided by the invention, and using ion exchange resin as carbon source, raw material simplicity is easily taken, cheap,
Easy to operate, preparation process is easily controllable, it is easy to accomplish, it is suitble to large-scale production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the low range scanning electron microscope (SEM) photograph of the graphitized stephanoporate material with carbon element 5 provided in the embodiment of the present invention 1；
Fig. 2 is the high magnification scanning electron microscope (SEM) photograph of the graphitized stephanoporate material with carbon element 4 provided in the embodiment of the present invention 1；
Fig. 3 is that the AC impedance of the electrode prepared using the graphitized stephanoporate material with carbon element 4 provided in the embodiment of the present invention 1 is bent
Line；
Fig. 4 is that 0.15mol L is used in the embodiment of the present invention 2-1Nickel acetate, a series of electricity of 500 DEG C of pre- carbonization treatment 1h
The 100mVs of pole-1Sweep fast capacitive property figure.
Specific embodiment
The present invention provides a kind of graphitized stephanoporate material with carbon element and preparation method thereof, electrode and its applications, existing for solving
The technical issues of having carbon material specific surface area not big enough, limiting the capacitance value of electrode, cause supercapacitor inefficiencies.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Agents useful for same of the embodiment of the present invention and material are commercially available.
Embodiment 1
The present embodiment first carries out the preparation of graphitization porous carbon, includes the following steps:
1) it weighs 2g D001 macroporous strong acid styrene anion exchange resin, is added in Ni-acetate solution, using super
Sound wave cell disruptor, in 1.5W cm-3, ultrasonic mixing 1h under 20kHz refilters drying, obtains the first product.
2) the first product is placed in nitrogen atmosphere, carries out the pre- carbonization treatment of 1h with tube furnace, obtain the second product, then will
Second product is fully ground 30min.
3) the second product after grinding is placed under nitrogen and the gaseous mixture atmosphere of carbon dioxide (volume ratio 4:1) and is carried out
It is activated, then is cleaned with dilute hydrochloric acid and pure water, dried, obtain graphitization porous carbon.
Later, the present embodiment will obtain graphitization porous carbon and PVDF and carry out 3h~10h mixing according to mass ratio 1:9
Afterwards, it is applied in nickel foam, drying tabletting obtains electrode.
In the present embodiment, the concentration of Ni-acetate solution, the temperature of activation processing, is activated the temperature of pre- carbonization treatment
Time and electrode specific capacitance please refer to table 1, low range scanning electron microscope (SEM) photograph such as Fig. 1 of the present embodiment graphitized stephanoporate material with carbon element 5
Shown, the high magnification scanning electron microscope (SEM) photograph of the present embodiment graphitized stephanoporate material with carbon element 4 is as shown in Fig. 2, the present embodiment graphitization is porous
The specific surface area of carbon material 1 is 159.28m2/g, and the specific surface area of the present embodiment graphitized stephanoporate material with carbon element 4 is 402.88m2/
G, the specific surface area of the present embodiment graphitized stephanoporate material with carbon element 4 are 329.13m2/g.The result shows that the present invention is graphitized porous carbon
The specific area of material is big, and electrode specific capacitance is high.
Referring to Fig. 3, for the friendship of the electrode prepared using the graphitized stephanoporate material with carbon element 4 provided in the embodiment of the present invention 1
Flow impedance curve.Fig. 3 shows the R of electrodectFor 2.4 Ω, show that the charge transfer resistance of electrode is smaller, the oblique line slope of low frequency range
Larger, diffusion is preferable.
The parameter of 1 the present embodiment of table preparation graphitization porous carbon and the electrode being prepared using graphitization porous carbon are than electricity
Hold
Embodiment 2
The present embodiment first carries out the preparation of graphitization porous carbon, then carries out the preparation of electrode, is graphitized the preparation of porous carbon
With embodiment 1, but the concentration of Ni-acetate solution is 0.15mol L-1, the temperature of pre- carbonization treatment is 500 DEG C, pre- carbonization treatment
Time is 1h, and the temperature of activation processing is 800 DEG C, 900 DEG C or 1000 DEG C, and the time of activation processing is 1h or 2h.Using this reality
Apply the 100mVs of the electrode of example graphitization porous carbon preparation-1Fast capacitive property figure is swept as shown in figure 4, Fig. 4 shows the present embodiment stone
The electrode performance of inkization porous carbon preparation is good, and when the temperature of activation processing is 800 DEG C, and the time of activation processing is 1h
The electrode performance for being graphitized porous carbon preparation is best.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphitized stephanoporate material with carbon element, which comprises the following steps:
A) ion exchange resin is impregnated in inorganic metal salting liquid, then be dried, obtain the first product；
B) first product is placed in nitrogen and/or inert gas atmosphere and carries out pre- carbonization treatment, obtain the second product；
C) second product is placed under carbon dioxide and the mixed atmosphere of nitrogen and/or inert gas and is activated,
It is cleaned again, obtains graphitized stephanoporate material with carbon element.
2. preparation method according to claim 1, which is characterized in that it is big that the step a) ion exchange resin is selected from D001
Hole strongly acidic styrene's series anion exchange resin, D201 macroporous strong basic styrene series anion exchange resin, D751 macropore
Chelating type styrene ion exchange resin, D301 macroreticular weakly base styrene series anion exchange resin or D151/D152 third
Olefin(e) acid system weak-acid cation-exchange resin.
3. preparation method according to claim 1, which is characterized in that the metal salt of step a) the inorganic metal salting liquid
Selected from nickel chloride, nickel nitrate, nickel acetate, cobalt chloride, cobalt nitrate or cobalt acetate.
4. preparation method according to claim 1, which is characterized in that the quality of the step a) ion exchange resin and institute
The concentration ratio for stating inorganic metal salting liquid is (1g~10g): (0.05M~1M).
5. preparation method according to claim 1, which is characterized in that the temperature of step b) the pre- carbonization treatment is 100
DEG C~800 DEG C；
The time of the pre- carbonization treatment is 1h~10h.
6. preparation method according to claim 1, which is characterized in that the temperature of the step c) activation processing is 500 DEG C
~1000 DEG C；
The time of the activation processing is 1h~3h.
7. preparation method according to claim 1, which is characterized in that the step c) carbon dioxide and nitrogen and/or lazy
Property gas mixed atmosphere in, the volume ratio of carbon dioxide and nitrogen and/or inert gas is 1:4~1:1.
8. graphitized stephanoporate material with carbon element made from preparation method described in claim 1 to claim 7 any one.
9. a kind of electrode, which is characterized in that including graphitized stephanoporate material with carbon element described in claim 8.
10. the application of electrode described in claim 9 in the capacitor.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110790255A (en) * | 2019-11-25 | 2020-02-14 | 安徽理工大学 | Preparation method of pore-size-adjustable graphitized mesoporous carbon |
| CN112811423A (en) * | 2020-12-22 | 2021-05-18 | 河南省大潮炭能科技有限公司 | Method for removing carbon metal ions of super capacitor by using exchange resin |
| CN113955751A (en) * | 2021-11-09 | 2022-01-21 | 重庆科技学院 | Self-supporting porous dendritic graphite foam, preparation method and application |
| CN114188533A (en) * | 2021-12-20 | 2022-03-15 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
| CN114914101A (en) * | 2022-06-07 | 2022-08-16 | 西南交通大学 | Porous carbon energy storage material and preparation method thereof |
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| CN1315046A (en) * | 1998-08-25 | 2001-09-26 | 钟纺株式会社 | Electrode material and method for producing the same |
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| CN1315046A (en) * | 1998-08-25 | 2001-09-26 | 钟纺株式会社 | Electrode material and method for producing the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790255A (en) * | 2019-11-25 | 2020-02-14 | 安徽理工大学 | Preparation method of pore-size-adjustable graphitized mesoporous carbon |
| CN112811423A (en) * | 2020-12-22 | 2021-05-18 | 河南省大潮炭能科技有限公司 | Method for removing carbon metal ions of super capacitor by using exchange resin |
| CN113955751A (en) * | 2021-11-09 | 2022-01-21 | 重庆科技学院 | Self-supporting porous dendritic graphite foam, preparation method and application |
| CN113955751B (en) * | 2021-11-09 | 2023-12-22 | 重庆科技学院 | Self-supporting porous dendritic graphite foam, preparation method and application |
| CN114188533A (en) * | 2021-12-20 | 2022-03-15 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
| CN114914101A (en) * | 2022-06-07 | 2022-08-16 | 西南交通大学 | Porous carbon energy storage material and preparation method thereof |
| CN114914101B (en) * | 2022-06-07 | 2023-05-16 | 西南交通大学 | Porous carbon energy storage material and preparation method thereof |
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