CN110498413A - A kind of orientation regulation porous active Carbon Materials aperture and graphitizing method and its application in lithium-ion capacitor - Google Patents
A kind of orientation regulation porous active Carbon Materials aperture and graphitizing method and its application in lithium-ion capacitor Download PDFInfo
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- CN110498413A CN110498413A CN201910793064.4A CN201910793064A CN110498413A CN 110498413 A CN110498413 A CN 110498413A CN 201910793064 A CN201910793064 A CN 201910793064A CN 110498413 A CN110498413 A CN 110498413A
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- cobalt ions
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 93
- 239000003990 capacitor Substances 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000033228 biological regulation Effects 0.000 title claims abstract description 15
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 26
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 26
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005087 graphitization Methods 0.000 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000010668 complexation reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 238000001994 activation Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011701 zinc Substances 0.000 description 107
- 239000011148 porous material Substances 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 13
- 238000002336 sorption--desorption measurement Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013249 bimetallic zeolitic imidazolate framework Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of orientation regulation porous active Carbon Materials aperture and graphitizing method and its applications in lithium-ion capacitor.Organic ligand and zinc ion and cobalt ions are subjected to complexation reaction, obtain presoma；The presoma passes through calcination processing and pickling processes, obtains porous carbon materials；The porous carbon materials are activated with activator mixing, obtain porous active Carbon Materials；The aperture of porous active Carbon Materials and graphitization are regulated and controled by the molar ratio of zinc ion and cobalt ions, by adjusting the molar ratio of zinc ion and cobalt ions in 90%:10% or so, the porous active Carbon Materials taken into account suitable pore-size distribution and be graphitized effect can be obtained, as anode for constructing high performance lithium-ion capacitor.
Description
Technical field
The present invention relates to a kind of porous active Carbon Materials, and in particular to a kind of orientation regulation porous active Carbon Materials aperture
And graphitizing method, and a kind of porous active Carbon Materials with suitable aperture and degree of graphitization are synthesized by this method,
Application of the porous carbon materials in lithium-ion capacitor is further related to, electrochemical energy storage materials preparation technical field is belonged to.
Background technique
Lithium-ion capacitor is made of battery-type negative electrode and capacitive anode, and due to its high-energy density, high power is close
The advantage of degree and long circulating stability, in electric car, Medical Devices, national grid and field of aerospace with huge
Application prospect.However, the energy density and power density of current lithium-ion capacitor do not reach ideal degree also, mainly
Be limited to the unmatched problem of electrochemical kinetics and low capacity of cathode and anode the manufacture of positive bring electrode it is difficult and
The problems such as quality matches are difficult.Currently, commercialized active carbon is the common positive electrode of lithium-ion capacitor, although it possess compared with
Big specific surface area (about 1500m2 g-1), but its capacity is very undesirable, less than 40mAh g-1.This is because active carbon has
There is relatively narrow porosity, is unfavorable for the PF of storage of solvent6 -Anion.In order to promote the capacity of positive carbon material, promote lithium from
Corresponding research has been carried out in terms of the development of sub-capacitor, surface functionalization and introducing faraday's capacitor.Positive carbon material performance
Performance be the behavior based on electric double layer capacitance, and the basic reason for influencing electric double layer capacitance is pore property.However, many at present
Research emphasis be only limited only to the research of supercapacitor organic system, the research in terms of lithium-ion capacitor is very few.
Therefore, seeking suitable aperture is to promote positive carbon material performance, promotes the key factor of lithium-ion capacitor development.In order to than
The influence in aperture is systematically studied, early stage Yury Gogotsi reacts to obtain the carbon material of micropore by chlorine and titanium carbide,
Carbon material difference microporous properties are studied in the capacitance behavior of tetrafluoro boric acid tetraethyl amine electrolyte, obtain certain conclusion.But
This preparation method is than relatively hazardous and complicated for operation.In addition, there is presently no the apertures that report systematically studies porous carbon materials to exist
LiPF6The capacitance behavior of electrolyte.In addition, graphitization effect is also one ring of key for influencing carbon material performance, it is able to ascend
The conductivity of carbon material, to further promote the performance of carbon material.
Summary of the invention
In view of the defects existing in the prior art, the first purpose of this invention is to be that provide one kind is mixed by design zinc cobalt
Metal coordinating polymer is closed, and orients while regulating and controlling the specific surface area of porous active Carbon Materials by zinc cobalt mixed metal ratio
With the method for degree of graphitization.
Second object of the present invention is to be to provide a kind of while having both the porous of appropriate pore structure and degree of graphitization
Absorbent charcoal material, the carbon material are particularly suitable for the lithium-ion capacitor of preparation energy density height, good cycle.
Third object of the present invention is to be that providing a kind of pass through controls zinc cobalt mixed metal ratio in OK range,
The method with the porous active Carbon Materials of appropriate pore structure and degree of graphitization is prepared, which is conducive to industry
Metaplasia produces.
Fourth object of the present invention is to be to provide a kind of porous active with appropriate pore structure and degree of graphitization
The lithium-ion capacitor of the application of Carbon Materials, porous active Carbon Materials preparation shows high-energy density.
In order to achieve the above technical purposes, the present invention provides a kind of orientation regulation porous active Carbon Materials aperture and graphite
The method of change, this method are that organic ligand and zinc ion and cobalt ions are carried out complexation reaction, obtain presoma；The presoma
By calcination processing and pickling processes, porous carbon materials are obtained；The porous carbon materials are activated with activator mixing,
Obtain porous active Carbon Materials；The aperture of the porous active Carbon Materials and graphitization pass through the molar ratio of zinc ion and cobalt ions
Example is regulated and controled.
The ratio between integral molar quantity of preferred scheme, organic ligand mole and zinc ion and cobalt ions is 3~5:1.It is optimal
It is selected as 4:1.
Preferred scheme, the organic ligand are 2-methylimidazole, benzimidazole, terephthalic acid (TPA), 2,5- dihydroxy pair
Phthalic acid.Most preferably 2-methylimidazole.Stabilization can be formed with zinc ion and/or cobalt ions metal using 2-methylimidazole
ZIFs topological structure, be consistent using the topological structure that monometallic and bimetallic are formed with 2-methylimidazole.Pass through 2- first
Base imidazoles is that the porous active Carbon Materials of ligand preparation have special ordered porous structural, has higher specific surface area and biography
Matter rate.
Preferred scheme, the calcination processing process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to
750~850 DEG C, keep the temperature 1~3 hour.Can use metallic zinc volatilization under preferred calcination condition forms porous carbon materials
Micropore and pass through cobalt catalysis improve degree of graphitization.Most preferred calcination processing process: under protective atmosphere, with 10 DEG C of min-1
Heating rate is warming up to 800 DEG C, keeps the temperature 2 hours.
The mass ratio of preferred scheme, porous carbon materials and activator is 1:0.5~1.5.Most preferably 1:1.
Preferred scheme, the activator are potassium hydroxide.
Preferred scheme, the activation process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to
750~850 DEG C, keep the temperature 1~3 hour.By activation, the aperture increases of porous carbon materials, partial pore conversion can be made
At mesoporous.Most preferred activation process: under protective atmosphere, with 10 DEG C of min-1Heating rate is warming up to 800 DEG C, heat preservation 2
Hour.
Preferred scheme, cobalt ions accounts for zinc ion and the molar percentage of cobalt ions increases to 100% by 0%, corresponding to make
The I of standby porous active Carbon MaterialsD/IGRatio successively decreases, and specific surface area is successively decreased, and micropore ratio is successively decreased, and mesoporous and macropore ratio is passed
Increase.By adjusting the ratio of zinc ion and cobalt ions, the orientation of porous active Carbon Materials pore structure and specific surface area may be implemented
Regulation meets the preparation that different application requires porous carbon materials.
Preferred scheme, pickling processes are mainly to use acid solution to remove remaining elemental metals, mainly metallic cobalt.It adopts
Acid such as hydrofluoric acid.And dissolving acid and concentration needed for metallic cobalt is that those skilled in the art are easy to get.
Preferred scheme, protective gas are nitrogen or inert atmosphere.Inert atmosphere such as argon gas.
Preferred scheme, zinc ion and cobalt ions are provided by the ease of solubility salt of cobalt and zinc, such as nitrate, chlorate, acetic acid
Salt etc..
The present invention provides a kind of preparation method of porous active Carbon Materials, this method be by organic ligand and zinc ion and
Cobalt ions carries out complexation reaction, obtains presoma；The presoma passes through calcination processing, obtains porous carbon materials；It is described porous
Carbon material is activated with activator mixing, obtains porous carbon active material；Wherein, the molar ratio of zinc ion and cobalt ions
Example is 95~85%:5~15%.By controlling the ratio of zinc ion and cobalt ions in preferred range, ratio can be obtained
Surface area, pore structure and graphitization are most able to satisfy the positive electrode of lithium-ion capacitor application requirement.Zinc ion and cobalt ions
Molar ratio is most preferably 90%:10%.
Preferred scheme, the calcination processing process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to
750~850 DEG C, keep the temperature 1~3 hour.Most preferred calcination processing process: under protective atmosphere, with 10 DEG C of min-1Heating rate
800 DEG C are warming up to, keeps the temperature 2 hours.
The mass ratio of preferred scheme, porous carbon materials and activator is 1:0.5~1.5.Most preferably 1:1.
Preferred scheme, the activator are potassium hydroxide.
Preferred scheme, the activation process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to
750~850 DEG C, keep the temperature 1~3 hour.Most preferred activation process: under protective atmosphere, with 10 DEG C of min-1 heating rates
800 DEG C are warming up to, keeps the temperature 2 hours.
Preferred scheme, the ratio between the mole and zinc ion of organic ligand and the integral molar quantity of cobalt ions are 3~5:1；Most
Preferably 4:1.
Preferred scheme, the organic ligand are 2-methylimidazole, benzimidazole, terephthalic acid (TPA), 2,5- dihydroxy pair
At least one of phthalic acid.
Preferred scheme, protective gas are nitrogen or inert atmosphere.Inert atmosphere such as argon gas.
In a certain range, aperture 2~3nm range can be improved in ratio of the present invention by adjusting Zn ion and Co ion
Interior mesoporous ratio, while certain graphitization is obtained, and the aperture 2~3nm is in PF6 -Weight is played in the adsorption desorption behavior of ion
The effect wanted, and graphited raising is conducive to be promoted the high rate performance of positive carbon material, and porous active Carbon Materials anode
Surface capacitance behavior can be improved by promoting graphitization and increasing mesopore/macropore porosity.It is prepared by the present invention porous
Absorbent charcoal material can assemble to obtain the lithium-ion capacitor of energy density height, the preferable high capacity of cycle performance.
The present invention also provides a kind of porous active Carbon Materials, are obtained by the preparation method.
The present invention also provides a kind of application of porous active Carbon Materials in lithium-ion capacitor, are used as lithium-ion electric
Capacitor positive electrode material application.
Porous active Carbon Materials of the invention can obtain taking into account suitable pore-size distribution and graphitization effect, assemble
Lithium-ion capacitor show excellent electrochemical performance, especially Zn90Co10- APC (the molar ratio of zinc ion and cobalt ions
For the porous active Carbon Materials of 90%:10% preparation) in 300W kg-1Power density under show up to 108Wh kg-1's
Energy density.
Compared with the prior art, technical solution of the present invention has the advantage that
1, the present invention provides the methods that one kind can orient regulation carbon material pore structure and degree of graphitization simultaneously, to obtain
It obtains the carbon material that different application requires and provides theoretical direction；
2, the present invention obtains by regulating and controlling in a certain range carbon material pore structure and degree of graphitization and is particularly suitable for lithium
What ionistor used, the ideal lithium-ion capacitor positive electrode of absorbent charcoal material can be commercialized as substitution, and
And the lithium-ion capacitor constructed presents excellent performance, greatly promotes the application development of lithium-ion capacitor.
3, the present invention prepares a kind of porous active that can obtain taking into account suitable pore-size distribution and being graphitized effect
Carbon Materials show excellent electrochemical performance using the assembled lithium-ion capacitor of porous active Carbon Materials, especially
Zn90Co10- APC (the porous active Carbon Materials that the molar ratio of zinc ion and cobalt ions is 90%:10% preparation) is in 300W kg-1Power density under show up to 108Wh kg-1Energy density.
Detailed description of the invention
[Fig. 1] is ZnxCo100-xThe experiment XRD and simulation drawing of-ZIFs.
[Fig. 2] is that XRD and Raman schemes: (a, b) ZnxCo100-xPCs and (c, d) ZnxCo100-xAPCs。
[Fig. 3] is ZnxCo100-x- PCs and ZnxCo100-x(a, b) nitrogen adsorption desorption curve graph of-APCs, aperture (c, d) point
Butut and (e, f) normalize accumulative graph of pore diameter distribution.
[Fig. 4] is HRTEM figure: (a, b) Zn100- PC, (c, d) Co100- PC, (e, f) Zn100- APC and (g, h) Co100-
APC。
[Fig. 5] is ZnxCo100-x- PCs and ZnxCo100-xThe high rate performance figure of-APCs.
[Fig. 6] is ZnxCo100-x- PCs and ZnxCo100-xThe peak current of-APCs and the relational graph for sweeping speed.
[Fig. 7] is Zn90Co10(a) nitrogen adsorption desorption curve graph of-APC, (b) graph of pore diameter distribution (c) normalize accumulative hole
Diameter distribution map and (d) high rate performance figure.
[Fig. 8] is PLG//Zn90Co10(a) cyclic voltammetry curve figure of-APC LIC, (b) constant current charge-discharge figure and (c)
Ragone figure.
Specific embodiment
The content of present invention is described further below with reference to specific embodiment.These embodiments are interpreted as being only used for
Illustrate the present invention rather than limits the scope of the invention.After having read the content of the invention recorded, it is based on this hair
Bright principle equally falls into claims of the present invention limited range to the various changes of the invention made or modification.
Embodiment 1
1. the preparation of material
1.1 MOFs presoma (ZnxCo100-x- ZIFs) preparation:
Monometallic ZIF-8 (Zn100-) and ZIF-67 (Co ZIF100-ZIF preparation): Zn (NO3)2·6H2O(3mmol,
891mg) or Co (NO3)2·6H2O (3mmol, 873mg) is dissolved in respectively in 30mL methanol.Then, by 2-methylimidazole (984mg,
12mmol) it is dissolved in 30mL methanol respectively.Then, organic ligand solution is rapidly joined in metallic solution, is stirred while adding.
After stirring 15 minutes, by resulting solution left standstill 24 hours, product precipitating can be precipitated.Finally, by resulting product methanol
Repeatedly washing, is dried in vacuo 12 hours under the conditions of 80 DEG C.
The preparation of bimetallic ZIFs: the preparation method of bimetallic ZIFs and above-mentioned preparation method are much like, only change
Zn (NO is become3)2·6H2O Co(NO3)2·6H2The ratio of O.Therefore, Zn75Co25-ZIF,Zn50Co50- ZIF and Zn25Co50-
ZIF is respectively by being that 3:1,1:1 and 1:3 are obtained by the proportion adjustment of Zn/Co metal.
Porous carbon materials (Zn derived from 1.2MOFsxCo100-x- PCs) preparation:
By ZnxCo100-x- ZIFs is placed in tube furnace, with 10 DEG C of min under ar gas environment-1Heating rate is heated to 800 DEG C
And constant temperature 2 hours.After Temperature fall, resulting calcined product is repeatedly washed respectively by HF solution and distilled water to remove
Remaining metal impurities.Last resulting ZnxCo100-x- PCs product is dried in vacuo 12 hours under the conditions of 80 DEG C.
Porous active Carbon Materials (Zn derived from 1.3 MOFsxCo100-x- APCs) preparation:
The Zn originally preparedxCo100-x- PCs and KOH powder are added in the distilled water of 15mL with the condition of mass ratio 1:1
Stirring 12 hours, obtains uniformly mixed suspension.Then, the powder after dry out solvent by resulting drying is transferred to tube furnace
It is calcined, actual conditions: 10 DEG C of min-1Heating rate, 800 DEG C constant temperature 2 hours, ar gas environment.The sample dilute hydrochloric acid of activation
It is repeatedly washed with distilled water.Finally by obtained ZnxCo100-x- APCs product is dried in vacuo 12 hours under the conditions of 80 DEG C.
2. electro-chemical test:
Take carbon material (Zn derived from prepared 80wt%MOFsxCo100-x- PCs and ZnxCo100-x- APCs) as activity
Substance, 10wt%PVDF are placed in Ma as conductive agent and less N-Methyl pyrrolidone as viscous glutinous agent, the Super P of 10wt%
It is uniform that it is carefully ground to slurry in Nao mortar, acquired slurry is coated on Al foil, and is dried in vacuo 12 under the conditions of 80 DEG C
Hour, obtain anode pole piece to be tested.At the same time, preparation commercialization graphite cathode method and it is above-mentioned prepare carbon anode
Method is similar: the only active material by 70wt% of mixed slurry, the viscous glutinous agent of 15wt% carboxymethyl cellulose,
15wt%Super P conductive carbon and less distilled water grind to obtain, and are then coated on Cu foil.
In order to carry out the test of half-cell, the good carbon anode of cut-parts and graphite cathode as working electrode, metal Li piece is made
For to electrode and reference electrode, 1mol L-1 LiPF6Volume ratio 1:1:1 is ethylene carbonate, methyl ethyl carbonate and carbonic acid diformazan
The electrolyte of ester, Whatman GF/C glass fibre membrane select CR2016 battery case to carry out group as diaphragm in glove box
Dress.) in addition, being assembled into lithium-ion capacitor before, graphite cathode need under half-cell system in 0.1A g-1It is followed under current density
Ring 5 times.
3. result and analysis
It is generally known that ZIF-8 and ZIF-67 are isologs, constructed respectively by 2-methylimidazole and Zn ion and Co ion
It obtains.In addition, obtained bimetallic ZIFs topological structure will not change after changing Zn/Co source metal ratio, holding and Dan Jin
Belong to the same crystal form of ZIF.For the object phase and purity of verification sample, by prepared ZnxCo100-x- ZIFs presoma is first
XRD characterization test is carried out, as shown in Figure 1 as a result, it has been found that ZnxCo100-xThe XRD diagram of-ZIFs is consistent with computer analoging figure, illustrates
It has obtained uniform presoma and structure is consistent.As shown in Figure 2 a, two peaks for being clearly located in~25 ° and~44 ° respectively for
With (002) and (001) crystal face of carbon.Due to wider and more low intensive peak feature, Zn100- PC shows as indefiniteness carbon characteristic.
On the other hand, Co100The half-peak breadth at (002) peak of-PC obviously narrows, this illustrates the catalyzed graphitization effect due to Co metal
Carbon obtained by resulting in is transformed to graphited carbon.In addition, with the increase of Co ion, ZnxCo100-xThe crystallinity of-PCs has
It improves step by step.It is worth noting that, even across Zn after KOH chemical activationxCo100-x- APCs still remains original
ZnxCo100-xGraphited size order (Fig. 2 b) of-PCs is in order to further verify the graphitization of carbon material, to ZnxCo100-x-
PCs and ZnxCo100-x- APCs has carried out Raman test as shown in Fig. 2 c and Fig. 2 d, and there are two be significantly located at 1350 Hes in figure
1585cm-1Peak, be respectively belonging to the peak D of amorphous carbon and the peak G of graphitized carbon.Zn100-PC,Zn75Co25-PC,
Zn50Co50-PC,Zn25Co75- PC and Co100The I of-PCD/IGRatio is 1.46,1.34,1.27,1.15 and 1.05 respectively, this says
It is illustrated as the content of Co ion increases ZnxCo100-xThe graphitization of-PCs accordingly enhances.At the same time, for Zn100-APC,
Zn75Co25-APC,Zn50Co50-APC,Zn25Co75- APC and Co100- APC, corresponding ID/IGRatio is 1.86,1.51 respectively,
1.37,1.31 with 1.24.In addition, Zn100-PC,Zn75Co25-PC,Zn50Co50-PC,Zn25Co75- PC and Co100- PC sample difference
It is 0.1S cm-1,1.12S cm-1,5.42S cm-1,8.70S cm-1With 12.5S cm-1。Zn100-APC,Zn75Co25-APC,
Zn50Co50-APC,Zn25Co75- APC and Co100The conductivity of-APC sample is about 0.05S cm-1,0.89S cm-1,4.20S
cm-1,6.70S cm-1With 9.5S cm-1.The above results show graphitization of the promotion from enhancing of carbon material conductivity.
Therefore, the graphitization of carbon material can orient regulation by adjusting the molar ratio of Zn/Co ion.
ZnxCo100-x- PCs and ZnxCo100-xThe porosity characteristic of-APCs is obtained by nitrogen adsorption desorption curve post analysis,
Acquired parameter is summarised in table 1.As shown in Figure 3a, Zn100- PC presents typical I type curve, and it is obvious to illustrate that it has
Microcellular structure.And this microporous properties is caused by being volatilized under the high temperature conditions as Zn metallic vapour.It is worth noting that,
With the increase of Co source metal content, ZnxCo100-xThe curve of-PCs has gradually formed H3 hysteretic loop, and in the P/ of 0.45-1.0
P0It gradually broadens in range, illustrates that the generation in mesopore/macropore region and wide pore-size distribution are formed.This phenomenon mainly by
Caused by the metal Co simple substance for being retained in carbon substrate removes.Research finds ZnxCo100-xBET specific surface in-PCs system
Product gradually becomes smaller, sequence Zn100-PC(957m2 g-1)>Zn75Co25-PC(524m2 g-1)>Zn50Co50-PC(370m2 g-1)
>Zn25Co75-PC(367m2 g-1)>Co100-PC(332m2 g-1).Above results showed that specific surface area and the hole of carbon material
Diameter range can realize orientation regulation by changing Zn/Co ratio.It is generally known that KOH chemical activation is capable of increasing carbon material
BET specific surface area and change pore structure.Therefore, ZnxCo100-x- APCs presents with different levels porous structure and increase
Specific surface area and mesopore/macropore porosity (Fig. 3 b) abundant.In addition, Fig. 3 c and Fig. 3 d present the corresponding aperture of carbon material point
Cloth feature.In order to further preferably evaluate the otherness of pore-size distribution, ZnxCo100-x- PCs and ZnxCo100-xThe normalizing of-APCs
The accumulative pore size distribution figure changed has obtained analyzing (Fig. 3 e and Fig. 3 f) in detail.This can more intuitively provide pore structure micro-
Hole, mesoporous and macropore different degrees of change.Under normal circumstances, the average pore size d frequently referred to50It cannot reflect reality completely
Pore-size distribution situation on border.Therefore, d25And d75The addition energy of (respectively representing aperture when taking total pore volume 25 and 75%)
Enough pore property dispersion degrees for preferably reflecting carbon material.Significantly, this comprehensive pore property discrete results is for it
It inquires into pore-size distribution afterwards and capacitance behavior provides important parameter.
In order to intuitively observe Zn in more detail100- PC, Co100- PC, Zn100- APC, Co100The pattern and pore structure of-APC
Variation, has carried out TEM test.Fig. 4 a-4d is Zn100- PC and Co100The HRTEM of-PC schemes, it can be seen that Zn in figure100- PC is nothing
Shaping carbon and has significant microcellular structure, and Co100- PC is graphited carbon, and has biggish mesopore/macropore aperture.Through
After crossing KOH activation, Zn100There is the mesoporous of the apparent hole about 2~5nm size in-APC, and Co100The mesoporous distribution of-APC is more
Uniformly and the aperture of mesopore/macropore has become smaller (Fig. 4 e-4h).This result and above-mentioned XRD, Raman and pore property data one
It causes.
In order to evaluate the adsorption desorption PF of acquired carbon material6 -The capacitance behavior of anion, as lithium-ion capacitor
Anode has carried out half-cell test in 2.0-4.5V voltage range.Fig. 5 a and 5b show ZnxCo100-x- PCs and ZnxCo100-x-
High rate performance of the APCs under different current densities.It is worth noting that, Zn100Although-PC has biggish BET specific surface area,
But it shows worst chemical property (0.1A g-1Only has 15mAh g under current density-1Specific capacity).This be by
In Zn100- PC has a relatively narrow and inappropriate pore diameter range, and 80% Kong Rong is occupied by pore characteristics, to limit
Its chemical property.On the contrary, Co100Although-PC has lower BET specific surface area, due to its mesopore/macropore abundant
Porosity, so that its specific capacity Co100- PC is in 0.1A g-140mAh g can be reached under current density-1.In conjunction with Fig. 3 e and Fig. 3 f
It can be seen that Co100- PC possesses more appropriate pore diameter range (d50=2.07nm~d75=27.27nm), so as to cause compared with
Strong adsorption desorption PF6 -The behavior of ion.It is above-mentioned the result shows that adsorption desorption PF6 -The behavior of ion is the pore size of carbon material
Leading.It is interesting that after KOH is activated, Zn100The chemical property of-APC significantly improves, in 0.1A g-1Electric current is close
55mAh g can be played under degree-1Specific capacity.On the contrary, Co100The performance of-APC but substantially reduces.This result illustrates
Zn100- APC and Co100The chemical property of-APC is affected because of the pore size distribution range of change.It sends out after study
It is existing, Zn100The hole of-APC holds accounting and is reduced to 49%, d50And d75Aperture increase to 2.12 and 2.64nm respectively, illustrate
The pore diameter range of increase improves PF6 -The adsorption desorption behavior of ion.In addition, Co100The chemical property of-APC reduce this be by
Cause in the porosity reduction of 2nm or so.At the same time, Zn75Co25The d of-PC25, d50And d75Aperture is 10.06nm respectively,
33.75nm and 51.60nm, after chemical activation, Zn75Co25- APC changes into 2.11nm, 2.96nm and 17.37nm.Due to
The hole in the hole within the scope of 2-3nm holds accounting and increases, Zn75Co25The chemical property of-APC is significantly increased.On
It states results showed that the aperture of 2-3nm is in PF6 -It plays an important role in the adsorption desorption behavior of ion.Furthermore, it is possible to obvious
Find out due to ZnxCo100-xCo metal bring catalyzed graphitization effect in-ZIFs presoma, carbon material derived from MOFs its
High rate performance can get a promotion.
In order to better understand obtained carbon material to PF6 -The adsorption desorption behavior of ion, we are by carrying out its material
Cyclic voltammetry test.It chooses peak current i and sweeps the data of fast v, according to formula i=a νbWith log (i)=blog (ν)+loga
B value is calculated, wherein a and b is variable parameter.According to b value size, two different electrochemical energy storage rows can be divided into
For, when b value is closer to 0.5, energy storage behavior is mainly dominated by diffusion controlled process, on the contrary, if when b value is closer to 1,
Energy storage behavior is just dominated by the capacitance behavior of granule surface contral.Fig. 6 a and Fig. 6 b illustrate ZnxCo100-x- PCs and ZnxCo100-x-
The correlated fitting curve of APCs, corresponding b value also carefully calculate.Zn100-PC,Zn75Co25-PC,Zn50Co50-PC,
Zn25Co75-PC and Co100The b value of-PC is 0.73,0.75,0.80,0.88 and 0.94 respectively.This result illustrates graphite
The increase of change can promote the raising of surface capacitance behavior.Importantly, by KOH chemical activation Zn100-APC,
Zn75Co25-APC,Zn50Co50-APC,Zn25Co75- APC and Co100The b value of-APC is promoted to 0.76,0.81,0.94 respectively,
1.06 with 1.09.This result illustrates that being promoted for surface fake capacitance behavior can be by the mesopore/macropore hole of increase carbon material
Rate.Above result confirms that the surface capacitor behavior of carbon anode can be graphitized and increase mesopore/macropore by being promoted
Porosity improves, this helps preferably to provide theoretical direction for the positive carbon material of high-performance lithium ion capacitor.
According to obtained above about carbon positive electrode and adsorption desorption PF6 -The internal relation knot of the capacitance behavior of anion
By Zn90Co10- APC is dexterously designed to be synthesized.Since suitable pore-size distribution and the collaboration for being graphitized effect are made
With Zn90Co10- APC shows most excellent chemical property in all carbon materials synthesized, in 0.1A g-1Electric current
Nearly 60mAh g is able to maintain under density-1Reversible capacity (shown in Fig. 7).Commercialized lithium-ion capacitor is usually by graphite
Cathode and active carbon anode are constituted.In order to preferably evaluate the Zn of preparation90Co10- APC carbon material as lithium-ion capacitor just
The superiority of pole, Zn90Co10- APC is assembled into lithium-ion capacitor as anode and the graphite cathode (PLG) after prelithiation.Figure
8a-8b show the class rectangle CV curve that slightly deforms accordingly and and non-fully linear constant current charge-discharge curve graph,
This phenomenon shows in lithium-ion capacitor system that there are two kinds of energy storage mechnisms of faraday's behavior and non-faraday behavior.It is significant
, assembled PLG//Zn90Co10- APC lithium-ion capacitor is in 300W kg-1Power density under show to be up to
108Wh kg-1Energy density, and have excellent performance (Fig. 8 c) than PLG//AC lithium-ion capacitor.This patent provides one kind
The preparation method of orientation adjustment different pore size and graphitized carbon material can obtain taking into account suitable pore-size distribution according to the method
And the Zn of graphitization effect90Co10The carbon material of-APC, be used for constructing after lithium-ion capacitor present it is extremely excellent
Chemical property.
Claims (10)
1. a kind of orientation regulation porous active Carbon Materials aperture and graphitizing method, it is characterised in that: by organic ligand and zinc
Ion and cobalt ions carry out complexation reaction, obtain presoma；The presoma passes through calcination processing and pickling processes, obtains porous
Carbon material；The porous carbon materials are activated with activator mixing, obtain porous active Carbon Materials；The porous active
The aperture of Carbon Materials and graphitization are regulated and controled by the molar ratio of zinc ion and cobalt ions.
2. a kind of orientation regulation porous active Carbon Materials aperture according to claim 1 and graphitizing method, feature
Be: the ratio between the mole and zinc ion of organic ligand and the integral molar quantity of cobalt ions are 3~5:1；The organic ligand is 2-
At least one of methylimidazole, benzimidazole, terephthalic acid (TPA), 2,5- dihydric para-phthalic acid.
3. a kind of orientation regulation porous active Carbon Materials aperture according to claim 1 and graphitizing method, feature
It is: the calcination processing process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to 750~850 DEG C, heat preservation
1~3 hour.
4. a kind of orientation regulation porous active Carbon Materials aperture according to claim 1 and graphitizing method, feature
Be: the mass ratio of porous carbon materials and activator is 1:0.5~1.5；The activator is potassium hydroxide.
5. a kind of orientation regulation porous active Carbon Materials aperture according to claim 1 and graphitizing method, feature
It is: the activation process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to 750~850 DEG C, heat preservation
1~3 hour.
6. a kind of described in any item orientation regulation porous active Carbon Materials apertures and graphited side according to claim 1~5
Method, it is characterised in that: cobalt ions accounts for zinc ion and the molar percentage of cobalt ions increases to 100% by 0%, and what is accordingly prepared is more
The I of mesoporous activated carbon materialD/IGRatio successively decreases, and specific surface area is successively decreased, and micropore ratio is successively decreased, and mesoporous and macropore ratio is incremented by.
7. a kind of preparation method of porous active Carbon Materials, it is characterised in that: carry out organic ligand and zinc ion and cobalt ions
Complexation reaction obtains presoma；The presoma passes through calcination processing, obtains porous carbon materials；The porous carbon materials and work
Agent mixing is activated, and porous active Carbon Materials are obtained；Wherein, the molar ratio of zinc ion and cobalt ions be 95~
85%:5~15%.
8. a kind of preparation method of porous active Carbon Materials according to claim 7, it is characterised in that: the calcination processing
Process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to 750~850 DEG C, keeps the temperature 1~3 hour；
The mass ratio of porous carbon materials and activator is 1:0.5~1.5；The activator is potassium hydroxide；
The ratio between the mole and zinc ion of organic ligand and the integral molar quantity of cobalt ions are 3~5:1；
The organic ligand be 2-methylimidazole, benzimidazole, terephthalic acid (TPA), at least one in 2,5- dihydric para-phthalic acid
Kind；
The activation process: under protective atmosphere, with 5~15 DEG C of min-1Heating rate is warming up to 750~850 DEG C, heat preservation 1
~3 hours.
9. a kind of porous active Carbon Materials, it is characterised in that: the preparation method as described in claim 7 or 8 obtains.
10. a kind of application of porous active Carbon Materials in lithium-ion capacitor, it is characterised in that: just as lithium-ion capacitor
Pole material application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085691A (en) * | 2019-12-31 | 2020-05-01 | 上海应用技术大学 | Mesoporous activated carbon material containing Co @ C structure and preparation method and application thereof |
| CN113921810A (en) * | 2021-10-11 | 2022-01-11 | 中国科学技术大学 | Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof |
| CN114408893A (en) * | 2022-01-19 | 2022-04-29 | 佛山仙湖实验室 | Porous carbon material pore structure regulation method and application |
| CN114566657A (en) * | 2022-02-23 | 2022-05-31 | 福州大学 | Platinum-based ordered alloy catalyst for fuel cell and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013061789A1 (en) * | 2011-10-27 | 2013-05-02 | 住友電気工業株式会社 | Capacitor |
| US20130197235A1 (en) * | 2012-01-30 | 2013-08-01 | Georgia Tech Research Corporation | Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by a Mixed-Ligand Synthetic Approach |
| CN103833006A (en) * | 2014-03-06 | 2014-06-04 | 安徽工业大学 | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor |
| CN104916447A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | High-rate porous carbon electrode material for super capacitor and preparation method |
| CN106158413A (en) * | 2016-08-30 | 2016-11-23 | 湖北长海新能源科技有限公司 | Lithium-ion capacitor |
| CN106952736A (en) * | 2017-05-16 | 2017-07-14 | 中南大学 | Lithium-ion capacitor and preparation method thereof |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
| CN107895777A (en) * | 2017-11-07 | 2018-04-10 | 北京工业大学 | One kind is based on Co in situ (II) dopen Nano porous carbon materials CZIF‑67Lead carbon battery negative pole preparation method |
| CN109841410A (en) * | 2017-11-27 | 2019-06-04 | 李艳 | A kind of carbon-based preparation to electrode of quantum dot sensitized solar cell doping |
| CN109920655A (en) * | 2019-03-20 | 2019-06-21 | 北京理工大学 | Porous carbon electrodes preparation method derived from a kind of MOF |
-
2019
- 2019-08-27 CN CN201910793064.4A patent/CN110498413B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013061789A1 (en) * | 2011-10-27 | 2013-05-02 | 住友電気工業株式会社 | Capacitor |
| US20130197235A1 (en) * | 2012-01-30 | 2013-08-01 | Georgia Tech Research Corporation | Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by a Mixed-Ligand Synthetic Approach |
| CN103833006A (en) * | 2014-03-06 | 2014-06-04 | 安徽工业大学 | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor |
| CN104916447A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | High-rate porous carbon electrode material for super capacitor and preparation method |
| CN106158413A (en) * | 2016-08-30 | 2016-11-23 | 湖北长海新能源科技有限公司 | Lithium-ion capacitor |
| CN106952736A (en) * | 2017-05-16 | 2017-07-14 | 中南大学 | Lithium-ion capacitor and preparation method thereof |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
| CN107895777A (en) * | 2017-11-07 | 2018-04-10 | 北京工业大学 | One kind is based on Co in situ (II) dopen Nano porous carbon materials CZIF‑67Lead carbon battery negative pole preparation method |
| CN109841410A (en) * | 2017-11-27 | 2019-06-04 | 李艳 | A kind of carbon-based preparation to electrode of quantum dot sensitized solar cell doping |
| CN109920655A (en) * | 2019-03-20 | 2019-06-21 | 北京理工大学 | Porous carbon electrodes preparation method derived from a kind of MOF |
Non-Patent Citations (3)
| Title |
|---|
| CAINA JIAO ET AL: ""Preparation of a Co-doped hierarchically porous carbon from Co/ZnZIF: An efficient adsorbent for the extraction of trizine herbicides from environment water and white gourd samples"", 《TALANTA》 * |
| QINGFEI WANG ET AL: ""Functional Zeolitic-Imidazolate-Framework-Templated Porous Carbon Materials for CO2 Capture and Enhanced Capacitors"", 《CHEM. ASIAN J》 * |
| 周奇 等: ""热解法制备MOF衍生多孔碳材料研究进展"", 《科学通报》 * |
Cited By (7)
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| CN113921810B (en) * | 2021-10-11 | 2023-03-10 | 中国科学技术大学 | Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof |
| CN114408893A (en) * | 2022-01-19 | 2022-04-29 | 佛山仙湖实验室 | Porous carbon material pore structure regulation method and application |
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| CN114566657B (en) * | 2022-02-23 | 2024-05-10 | 福州大学 | Platinum-based ordered alloy catalyst for fuel cell and preparation method thereof |
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