CN109585181A - The preparation method of storage lithium nitrating porous carbon positive electrode based on brown alga egg-box structure - Google Patents
The preparation method of storage lithium nitrating porous carbon positive electrode based on brown alga egg-box structure Download PDFInfo
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- 230000000802 nitrating effect Effects 0.000 title claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title abstract description 20
- 238000003860 storage Methods 0.000 title description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 238000005554 pickling Methods 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 20
- 239000003990 capacitor Substances 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000001802 infusion Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 48
- 239000004202 carbamide Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001994 activation Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000013535 sea water Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000783 alginic acid Substances 0.000 claims description 5
- 229960001126 alginic acid Drugs 0.000 claims description 5
- 235000010443 alginic acid Nutrition 0.000 claims description 5
- 229920000615 alginic acid Polymers 0.000 claims description 5
- 150000004781 alginic acids Chemical class 0.000 claims description 5
- 210000002421 cell wall Anatomy 0.000 claims description 5
- 238000009396 hybridization Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002500 ions Chemical group 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000007605 air drying Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 241001519369 Sarcodia montagneana Species 0.000 description 7
- 241000512259 Ascophyllum nodosum Species 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002847 impedance measurement Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The preparation method for storing up lithium nitrating porous carbon positive electrode based on brown alga egg-box structure that the present invention provides a kind of, it include: that nitrogenous compound is supported in the brown alga presoma of precrosslink first with infusion method, then by carbonization, pickling in the way of be prepared into the mesoporous intermediate carbon of nitrating, finally obtain nitrating porous carbon materials using chemical activation.The present invention introduces orderly meso-hole structure using crosslinking in carbonization intermediate, these mesoporous activate for subsequent chemistry provide higher active area, simultaneously by immersing nitrogenous compound in presoma, traditional nitrating mode is simplified, the doping of nitrogen improves the surface chemical reaction activity of porous carbon materials.Therefore the nitrating porous carbon materials prepared both had passed on the original three-dimensional porous channel of brown alga, the speciality such as small mesoporous and nitrating graphitized carbon with artificial regulatory again, as lithium ion mixed capacitor anode, there is ion abundant and electron propagation ducts and good chemical mobility of the surface.
Description
Technical field
The present invention relates to storage lithium carbon material technical fields, and in particular, to a kind of storage lithium based on brown alga egg-box structure
With the preparation method of nitrating porous carbon positive electrode.
Background technique
A large amount of extensive style of the fossil fuels such as coal, petroleum consume, and not only bring the energy crisis in global range,
Bring serious problem of environmental pollution and climatic issues.The Novel cleans type energy such as solar energy, wind energy, geothermal energy, tide energy
It cannot be used continuously over time and space.Developing energy storage technology has been global research hotspot.Supercapacitor and lithium from
Sub- battery is current most widely used energy storage device.Supercapacitor using the electrostatic adsorption of electrode material come energy storage,
Reaction speed is fast, power density height (> 10kW kg-1), have extended cycle life (> 10 ten thousand times), but energy density is limited (to be based on water
Be electrolyte it is general < 10Wh kg-1).Lithium ion battery is converted energy storage using electric energy-chemical energy of electrode material, energy density
Height (150-200Wh kg-1), but reaction speed is slow, the low (< 1000W kg of power density-1)。
The advantages of lithium ion mixed capacitor is a kind of comprehensive lithium ion battery proposed in recent years and supercapacitor
New type of energy storage device.Lithium ion mixed capacitor is usually using faraday's reaction profile material as high-energy cathode, to adsorb profile
Material, using organic solution containing lithium salt as electrolyte, is expected to possess high-energy density simultaneously and high power is close as high power anode
Degree.Traditional absorbent-type positive electrode is usually pore type active carbon, and this material has the micropore knot that can not largely regulate and control
Structure (< 2nm), it is difficult to store.Therefore, in actual operation, traditional absorbent-type absorbent charcoal material is in lithium-ion electrolyte
Capacity is usually limited, significantly limits the energy density of entire lithium ion mixed capacitor.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of great Rong based on brown alga egg-box structure
The preparation method of amount storage lithium nitrating porous carbon positive electrode.
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, provide a kind of high capacity based on brown alga
The preparation method of the lithium ion mixed capacitor nitrating porous carbon positive electrode of egg-box structure；Utilize the egg- of brown alga
Box cross-linked structure prepares a kind of carbon material of surface N doping with even mesoporous structure.Specially it is directed to brown alga cell wall
In brown alga sour component and multivalent metal cation be cross-linked to form evenly dispersed " egg-box " nanostructure, utilize infusion method
The nitrogenous compounds such as urea are loaded in brown alga biological structure, by the method for carbonization, pickling, activation, to prepare novel nitrating more
Hole carbon material.The nitrating porous carbon materials of this method preparation had not only passed on the original mass transfer channel of brown alga, but also in brown alga
Carbon surface and inside introduce it is equally distributed small mesoporous, have classification hole path abundant.Meso-hole structure therein is by brown
It is formed after " egg-box " the structure carbonization pickling that alginic acid and metal cation are cross-linked to form, after these meso-hole structures can be
Continuous activation provides higher active area, therefore the carbon material hole path prepared is interconnected, and is more suitable lithium ion
Transimission and storage.Compared with traditional cocoanut active charcoal, carbon material of the invention is rich in Xiao Jie for being originated from " egg-box " structure
Hole is more suitable for the quick transimission and storage of lithium ion；Compared with mesoporous carbon, which has the macropore knot from brown alga itself
The microcellular structure that structure and post activation are formed, therefore there is the advantage in classification duct, more high-specific surface area, more quickly it can transmit and deposit
Store up more lithium ions.Porous carbon materials are first prepared with traditional, then are compared in the method for gained porous carbon materials surface nitrating, this
The preparation method of nitrating porous carbon just introduces source urea, thiocarbamide or the melamine of nitrogen in carbon matrix precursor in invention
Amine has simplified preparation process, and nitrating works well, and increases the surface-active of material.Therefore resulting nitrating porous carbon
Material in lithium-ion capacitor, has shown higher capacity and more preferably high rate performance as positive electrode.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of preparation method of nitrating porous carbon positive electrode, includes the following steps:
S1, brown alga and metal cation are subjected to precrosslink, brown alga presoma is made；Using infusion method by nitrogenous compound
(as nitrogen source) is supported on brown alga presoma surface, and the brown alga intermediate containing nitrogen source is made；
S2, the brown alga intermediate is carbonized, the mesoporous intermediate carbon of the obtained nitrating of pickling；It will be in the mesoporous carbon
Mesosome is activated to get nitrating porous carbon positive electrode.
Preferably, in step S1, the specific steps of the precrosslink include: by brown alga and seawater (at as where itself
Seawater) in multivalent metal cation carry out cross-linking reaction, or by brown alga immerse human configuration mass fraction be 0.1-
Cross-linking reaction is carried out in 20% metal salt solution.
Preferably, the multivalent metal cation includes Mg2+、Ca2+、Al3+、Zn2+、Fe2+、Fe3+、Sn2+、Sn4+In one
Kind is several；The metal salt solution of human configuration includes Mg2+、Ca2+、Al3+、Zn2+、Fe2+、Fe3+、Sn2+、 Sn4+In one
The metal salt solution or a variety of metal mixed salt solutions of kind.Selecting above-mentioned multivalent metal cation is due to: these metals sun
Ion can be crosslinked with alginic acid to react, and forms uniform egg-box structure；And it is formed in subsequent carbonisation
Metal simple-substance or oxide particle can be acid washed and be removed, to prepare porous carbon materials.
Preferably, in step S1, the specific steps of the infusion method include: that brown alga presoma is immersed in nitrogenous compound
In solution, the mass ratio of brown alga presoma and nitrogenous compound is 5:1-1:5, impregnates 1-2 days, then will under vacuum-pumping conditions
Sample after immersion is dried.The mass ratio of brown alga and nitrogenous compound can keep nitrating effect very faint lower than 5:1,
It will cause a large amount of nitrogen source wastes higher than 1:5.
Preferably, in step S1, the nitrogenous compound includes at least one of urea, thiocarbamide, melamine.
Preferably, in step S2, the specific steps of the carbonization include: by brown alga intermediate under inertia or vacuum atmosphere
Calcining 1-12 hours, calcination temperature are 600-1500 DEG C.Under the high carburizing temperature and long carbonization time, brown alga intermediate can
Fully it is converted into carbon material.
Preferably, in step S2, the specific steps of the pickling include: that the resulting nitrating intermediate that will be carbonized is placed in acidity
It is stirred in solution, filters to obtain precipitating, being cleaned with deionized water and being precipitated to pH is 7, is then dried.
Preferably, the acid solution includes hydrochloric acid solution.
Preferably, in step S1, the precrosslink refers to alginic acid and metal cation self assembly in brown alga cell wall
Reaction forms uniform " egg-box " nano hybridization structure in cell wall.
Preferably, in step S2, the meso-hole structure in the mesoporous intermediate carbon is by " egg-box " nano hybridization
It is made after structure carbonization, pickling." egg-box " nano hybridization structure is washed away in acid cleaning process, forms meso-hole structure.
Preferably, the activation is chemical activation, and specific steps include: by the mesoporous intermediate carbon and activating substance of nitrating
After mixing under inertia or vacuum atmosphere high-temperature process；The activating substance includes KOH, NaOH, K2CO3、CaCl2、H3PO4In
It is one or more of；The temperature of the high-temperature process is 700-1200 DEG C, and the time of processing is 0.5-12 hours.
Preferably, the mass ratio that the mesoporous intermediate carbon of the nitrating is mixed with activating substance is 1:1~1:4.
Preferably, the step of mixing includes: that the mesoporous intermediate carbon of nitrating and activating substance are dissolved in deionization
In water, heating stirring, until moisture is evaporated.
Preferably, after the chemical activation, with the alkaline product in acid solution and after activation, then repeatedly cleaning until gained sample
Product pH value is 7, dry, obtains nitrating porous carbon materials.
Preferably, the pore structure in the nitrating porous carbon materials is having a size of 1-50 nanometers.
The present invention also provides a kind of nitrating porous carbon positive electrodes prepared according to the method, and the nitrating porous carbon is just
In the material of pole, the load capacity of nitrogen is 0.1-5.0wt%；If the too low nitrating improving performance that will lead to of the load capacity of nitrogen is unobvious, mistake
The variation that height will lead to material pore structure influences its high rate performance.Pore structure is having a size of 1-50 nanometers.
The present invention also provides a kind of application of nitrating porous carbon positive electrode in lithium ion mixed capacitor.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) using nature, largely existing brown alga passes through the gold with seawater or human configuration as raw material to the present invention
Belong to the method for precrosslink, the nitrogen source immersion, carbonization, pickling, activation of salting liquid, the carbon material being prepared both remains brown alga
Biological graded porous structure, but on nanoscale combine the method for pickling on carbon materials surface by self assembly " Egg-box " and
Inside introduces meso-hole structure abundant, provides bigger active area for activation, so that resulting carbon material is classifying porous logical
Road is more abundant and is interconnected；In addition, the method by being immersed in nitrogen source presoma, after simplifying traditional first carbonization
The technique of nitrating improves the surface-active of gained carbon material.Therefore resulting nitrating porous carbon materials rely on its hole abundant
Channel and excellent surface-active have shown the specific capacity of superelevation and excellent forthright again in the anode of lithium-ion capacitor
Can, lithium-ion capacitor positive electrode is alleviated to the restricted problem of device energy density.
(2) step of the present invention is simple, easy to operate, and effect is obvious, has a good application prospect.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the shape appearance figure of the resulting nitrating porous carbon materials of the embodiment of the present invention 1；Wherein, Fig. 1 a and Fig. 1 b is brown alga
Shape appearance figure after carbonization；Fig. 1 c is the shape appearance figure after brown alga carbonization pickling；Fig. 1 d is that brown alga is carbonized after acid-wash activation
Shape appearance figure；
Fig. 2 is the nitrogen adsorption desorption curve of the resulting nitrating porous carbon materials of the embodiment of the present invention 1；
Fig. 3 is the graph of pore diameter distribution of the resulting nitrating porous carbon materials of the embodiment of the present invention 1；
Fig. 4 is the XPS analysis figure of the resulting nitrating porous carbon materials of the embodiment of the present invention 1；
Fig. 5 is the cyclic voltammogram of the resulting nitrating porous carbon materials of the embodiment of the present invention 1；
Fig. 6 is the high rate performance figure of the resulting nitrating porous carbon materials of the embodiment of the present invention 1.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to a kind of lithium ion mixed capacitor nitrating porous carbon materials based on brown alga egg-box structure
Preparation method, include the following steps:
(1) it takes the natural sea band harvested in seawater a certain amount of, dries.40g urea is taken to be dissolved in 360mL deionized water,
It is made into urea liquid.The kelp for taking 20g dry is immersed in prepared urea liquid, impregnates 24 hours, makes under vacuumized conditions
Urea is sufficiently submerged in into kelp.Then the kelp forced air drying of urea will be impregnated.
(2) dry kelp containing urea is placed in tube furnace, under the protection of nitrogen, in 1000 DEG C of temperature lower calcination
It 2 hours, is taken out after cooling.
(3) the resulting sample that will be carbonized is placed in the hydrochloric acid solution of 500mL (5mol/L), magnetic agitation 12 hours, is filtered,
It is cleaned repeatedly with deionized water again, until pH value is 7.By the sample forced air drying after pickling.
(4) the kelp carbon after taking 5g pickling dry, takes 10g potassium hydroxide (KOH), is dissolved in 20mL deionized water, adds
Mixture is placed in tube furnace by pyromagnetic force stirring until moisture is evaporated, and under the protection of nitrogen, 700 DEG C of heat preservations 2 are small
When, it is taken out after cooling.With in 500mL dilute hydrochloric acid and activation after alkaline product, then repeatedly cleaning until gained sample pH be
7, forced air drying obtains nitrating porous carbon materials.
Implementation result:
Resulting nitrating porous carbon pattern is as shown in Figure 1 according to the method described above, it can be seen that resulting materials are in micro-meter scale
On maintain the biological graded porous structure of natural sea band, a large amount of even mesoporous structures are contained on nanoscale；Fig. 1 d is brown
Shape appearance figure after algae carbonization acid-wash activation, dotted line therein have irised out apparent small meso-hole structure, and arrow therein is directed toward carbon
Carbonization structure in material.The mesopore size of the nitrating porous carbon positive electrode of this implementation preparation is 2-6 nanometers.Fig. 2 and figure
3 illustrate the nitrogen adsorption desorption curve and pore size distribution figure line of material, have apparent nitrogen under opposite pressure in as can be seen from Figure 2
Gas adsorbance corresponds to the presence of a large amount of meso-hole structures；The pore structure of the nitrating porous carbon materials concentrates on as can be seen from Figure 3
Between 1-6 nanometers.Fig. 4 illustrates the XPS spectrum of material, it was demonstrated that nitrogen is 2.6wt% by Effective Doping, the load capacity of nitrogen.
The 0.08g nitrating porous carbon materials are taken, are equably mixed into active material, conductive black, binder according to the ratio of 8:1:1
Slurry is coated on copper foil by slurry, and the electrode slice that diameter is 11mm is cut to after vacuum drying.Choosing lithium piece is to take to electrode
Celgard2500 is diaphragm, the lithium hexafluoro phosphate that electrolyte is 1mol/L (volume in ethylene carbonate and dimethyl carbonate
Than 1:1) solution.It is assembled into lithium ion half-cell in glove box, which is subjected to cyclic voltammetric, charge and discharge, exchange
Testing impedance.The cyclic voltammetry curve and high rate performance curve of the nitrating porous carbon materials are as shown in Figure 5, Figure 6, can from Fig. 5
Find out in the case where the different voltages of 1-20mV/s sweep speed, cyclic voltammetry curve is close to rectangle；As can be seen from Figure 6, in 0.1A/g
Current density under specific capacity be 110mAh/g, specific capacity at 5A/g is 81mAh/g.
Embodiment 2
The present embodiment is related to a kind of lithium ion mixed capacitor nitrating porous carbon materials based on brown alga egg-box structure
Preparation method, include the following steps:
(1) 25g calcium chloride is dissolved in 500mL deionized water, stirs evenly wiring solution-forming.The Hai Mu for taking 20g dry
Ear (a kind of brown alga) is dipped into calcium chloride solution, is allowed to that sufficient cross-linking reaction occurs, and dry.Take 100g urea molten
Solution is made into urea liquid in 180mL deionized water.Sarcodia montagneana after precrosslink is immersed in above-mentioned urea liquid, is taken out true
It is impregnated 24 hours under empty condition, keeps urea fully penetrated, then by sample drying.
(2) dry sarcodia montagneana containing urea is placed in tube furnace, under the protection of nitrogen, is calcined 2 hours at 800 DEG C
It is taken out after cooling.
(3) the resulting sample that will be carbonized is placed in the hydrochloric acid solution of 500mL (5mol/L), is heated to 60 DEG C, magnetic agitation
It 12 hours, filters, then cleaned repeatedly with deionized water, until pH value is 7.By the sample forced air drying after pickling.
(4) the sarcodia montagneana biomass carbon after taking 5g pickling dry, takes 20g sodium hydroxide (NaOH), be dissolved in 20mL go from
In sub- water, magnetic agitation is heated, until moisture is evaporated, mixture is placed in tube furnace, under the protection of nitrogen, 800 DEG C
Heat preservation 2 hours is taken out after cooling.With the alkaline product in 500mL dilute hydrochloric acid and after activation, then repeatedly cleaning until gained sample
PH value is 7, forced air drying, obtains nitrating porous carbon materials.
Implementation result: prepared nitrating porous carbon materials according to the method described above possess a large amount of even mesoporous, and nitrogen
Element has effectively been doped to material surface, maintains porosity and surface-active.The 0.08g nitrating porous carbon materials are taken, are pressed
Active material, conductive black, binder are equably mixed into slurry according to the ratio of 8:1:1, slurry is coated on copper foil, vacuum
The electrode slice that diameter is 11mm is cut to after drying.Choosing lithium piece is to electrode, and taking Celgard2500 is diaphragm, and electrolyte is
The lithium hexafluoro phosphate of 1mol/L in ethylene carbonate and dimethyl carbonate (volume ratio 1:1) solution.It is assembled in glove box
At lithium ion half-cell, which is subjected to cyclic voltammetric, charge and discharge, ac impedance measurement.The material is in different electric discharges times
Higher specific capacity is shown under rate.
Having a size of 2-10 nanometers, the load capacity of nitrogen is the pore structure of nitrating porous carbon positive electrode manufactured in the present embodiment
3.7 wt%.Specific capacity 105mAh/g under the current density of 0.1A/g, the specific capacity at 5A/g are 72mAh/g.
Embodiment 3
The present embodiment is related to a kind of lithium ion mixed capacitor nitrating porous carbon materials based on brown alga egg-box structure
Preparation method, include the following steps:
(1) it is a certain amount of to choose the thallus laminariae grown in seawater, weighs 50g after dry.It takes 10g urea to be dissolved in 300 mL to go
In ionized water, it is made into urea liquid.50g dry thallus laminariae is immersed in above-mentioned urea liquid, vacuumizes 24 hours, makes to urinate
Element is fully penetrated, then by sample drying.
(2) dry thallus laminariae containing urea is placed in tube furnace, under the protection of nitrogen, it is small that 2 is calcined at 600 DEG C
When, it is taken out after cooling.
(3) the resulting sample that will be carbonized is placed in the hydrochloric acid solution of 500mL (5mol/L), magnetic agitation 12 hours, is filtered,
It is cleaned repeatedly with deionized water again, until pH value is 7.By the sample forced air drying after pickling.
(4) the thallus laminariae biomass carbon after taking 10g pickling dry, takes 40g sodium hydroxide (NaOH), is dissolved in 40 mL and goes
In ionized water, magnetic agitation is heated, until moisture is evaporated, mixture is placed in tube furnace, under the protection of nitrogen, 750
It DEG C heat preservation 2 hours, is taken out after cooling.With the alkaline product in 500mL dilute hydrochloric acid and after activation, then repeatedly cleaning until gained sample
Product pH value is 7, and forced air drying obtains nitrating porous carbon materials.
Implementation result: prepared nitrating porous carbon materials, nitrogen have effectively been doped to material according to the method described above
Expect surface, the load capacity of nitrogen is 1.7wt%, maintains the porosity of material.The 0.08g nitrating porous carbon materials are taken, according to 8:
Active material, conductive black, binder are equably mixed into slurry by the ratio of 1:1, and slurry is coated on copper foil, vacuum drying
It is cut to the electrode slice that diameter is 11mm afterwards.Choosing lithium piece is to electrode, and taking Celgard2500 is diaphragm, electrolyte 1mol/L
Lithium hexafluoro phosphate in ethylene carbonate and dimethyl carbonate (volume ratio 1:1) solution.Be assembled into glove box lithium from
The half-cell is carried out cyclic voltammetric, charge and discharge, ac impedance measurement by sub- half-cell.The material is equal under different discharge-rates
Show higher specific capacity.
The mesopore size of nitrating porous carbon positive electrode manufactured in the present embodiment is 2-10 nanometers.It is close in the electric current of 0.1A/g
Specific capacity under degree is 92mAh/g, and the specific capacity at 5A/g is 60mAh/g.
Embodiment 4
The present embodiment is related to a kind of lithium ion mixed capacitor nitrating porous carbon materials based on brown alga egg-box structure
Preparation method, include the following steps:
(1) it takes 50g thiocarbamide to be dissolved in 300mL deionized water, is made into thiourea solution.By the thallus laminariae (seawater that 50g is dry
Middle growth) it immerses in above-mentioned urea liquid, it vacuumizes 24 hours, keeps thiocarbamide fully penetrated, then by sample drying.
(2) dry thallus laminariae containing thiocarbamide is placed in tube furnace, under the protection of nitrogen, it is small that 2 is calcined at 1400 DEG C
When, it is taken out after cooling.
(3) the resulting sample that will be carbonized is placed in the hydrochloric acid solution of 500mL (5mol/L), magnetic agitation 12 hours, is filtered,
It is cleaned repeatedly with deionized water again, until pH value is 7.By the sample forced air drying after pickling.
(4) the thallus laminariae biomass carbon after taking 10g pickling dry, takes 10g potassium carbonate (K2CO3), be dissolved in 20mL go from
In sub- water, magnetic agitation is heated, until moisture is evaporated, mixture is placed in tube furnace, under the protection of nitrogen, 1200 DEG C
Heat preservation 2 hours is taken out after cooling.With the alkaline product in 500mL dilute hydrochloric acid and after activation, then repeatedly cleaning until gained sample
PH value is 7, forced air drying, obtains nitrating porous carbon materials.
Implementation result: prepared nitrating porous carbon materials, nitrogen have effectively been doped to material according to the method described above
Expect surface, maintains the porosity of material.Take the 0.08g nitrating porous carbon materials, according to 8:1:1 ratio by active material,
Conductive black, binder are equably mixed into slurry, and slurry is coated on copper foil, and the electricity that diameter is 11mm is cut to after vacuum drying
Pole piece.Choosing lithium piece is to electrode, and taking Celgard2500 is diaphragm, and electrolyte is the lithium hexafluoro phosphate of 1mol/L in carbonic acid second
The solution of (volume ratio 1:1) in enester and dimethyl carbonate.Lithium ion half-cell is assembled into glove box, by the half-cell into
Row cyclic voltammetric, charge and discharge, ac impedance measurement.The material shows higher specific capacity under different discharge-rates.
The mesopore size of nitrating porous carbon positive electrode manufactured in the present embodiment is 2-10 nanometers, and the load capacity of nitrogen is 1.6
Wt%.Specific capacity under the current density of 0.1A/g is 95mAh/g, and the specific capacity at 5A/g is 65mAh/g.
Embodiment 5
The present embodiment is related to a kind of lithium ion mixed capacitor nitrating porous carbon materials based on brown alga egg-box structure
Preparation method, include the following steps:
(1) sarcodia montagneana for taking 20g dry is dipped into ferric chloride solution, is allowed to that sufficient cross-linking reaction occurs, and do
It is dry.It takes 10g melamine to be dissolved in 300mL deionized water, is made into melamine solution.By the sarcodia montagneana leaching after precrosslink
Enter in above-mentioned melamine solution, is impregnated 24 hours under vacuumized conditions, keep melamine fully penetrated, then do sample
It is dry.
(2) dry sarcodia montagneana containing melamine is placed in tube furnace, under the protection of nitrogen, is calcined at 1200 DEG C
It 2 hours, is taken out after cooling.
(3) the resulting sample that will be carbonized is placed in the hydrochloric acid solution of 500mL (5mol/L), magnetic agitation 12 hours, is filtered,
It is cleaned repeatedly with deionized water again, until pH value is 7.By the sample forced air drying after pickling.
(4) the sarcodia montagneana biomass carbon after taking 10g pickling dry, takes 10g potassium carbonate (K2CO3), be dissolved in 20mL go from
In sub- water, magnetic agitation is heated, until moisture is evaporated, mixture is placed in tube furnace, under the protection of nitrogen, 1200 DEG C
Heat preservation 2 hours is taken out after cooling.With the alkaline product in 500mL dilute hydrochloric acid and after activation, then repeatedly cleaning until gained sample
PH value is 7, forced air drying, obtains nitrating porous carbon materials.
Implementation result: prepared nitrating porous carbon materials, nitrogen have effectively been doped to material according to the method described above
Expect surface, the load capacity of nitrogen is 0.8wt%, maintains the porosity of material.The 0.08g nitrating porous carbon materials are taken, according to 8:
Active material, conductive black, binder are equably mixed into slurry by the ratio of 1:1, and slurry is coated on copper foil, vacuum drying
It is cut to the electrode slice that diameter is 11mm afterwards.Choosing lithium piece is to electrode, and taking Celgard2500 is diaphragm, electrolyte 1mol/L
Lithium hexafluoro phosphate in ethylene carbonate and dimethyl carbonate (volume ratio 1:1) solution.Be assembled into glove box lithium from
The half-cell is carried out cyclic voltammetric, charge and discharge, ac impedance measurement by sub- half-cell.The material is equal under different discharge-rates
Show higher specific capacity.
The mesopore size of nitrating porous carbon positive electrode manufactured in the present embodiment is 2-10 nanometers.It is close in the electric current of 0.1A/g
Specific capacity under degree is 88mAh/g, and the specific capacity at 5A/g is 62mAh/g.
Comparative example 1
This comparative example is related to a kind of preparation method of lithium ion mixed capacitor porous carbon materials, specific steps and implementation
Example 1 is almost the same, the difference is that only: without step (1) in this comparative example, i.e., kelp not being immersed urea liquid and carried out
Processing.
Implementation result: it is tested using test method same as Example 1.The porous carbon anode of this comparative example preparation
For the pore structure of material having a size of 2-4 nanometers, the load capacity of nitrogen is 0.Specific capacity under the current density of 0.1A/g is 80mAh/
G, the specific capacity at 5A/g are 55mAh/g.
Comparative example 2
This comparative example is related to a kind of preparation method of lithium ion mixed capacitor porous carbon materials, specific steps and implementation
Example 1 is almost the same, the difference is that only: this comparative example the step of in (1), urea liquid is to be dissolved in 100 grams of urea
It is obtained in the water of 100mL.
Implementation result: it is tested using test method same as Example 1.The porous carbon anode of this comparative example preparation
The pore structure of material is having a size of 5-20 nanometers, and the load capacity of nitrogen is 6.7wt%, more than 5.0wt%.It is close in the electric current of 0.1A/g
Specific capacity under degree is 92mAh/g, and the specific capacity at 5A/g is 57mAh/g.
The preparation side for the storage lithium nitrating porous carbon positive electrode that the present invention provides a kind of based on brown alga egg-box structure
Method specifically includes that the brown alga that the nitrogenous compounds such as urea, thiocarbamide, melamine are supported on to precrosslink first with infusion method
In presoma, then by carbonization, pickling in the way of the mesoporous intermediate carbon of nitrating is prepared, finally utilize chemical activation side
Method obtains nitrating porous carbon materials.The present invention introduces orderly meso-hole structure using cross-linking method in carbonization intermediate, this
A little mesoporous activate for subsequent chemistry provide higher active area, are simultaneously used in the side that nitrogenous compound is immersed in presoma
Method, has simplified traditional nitrating mode, and the doping of nitrogen improves the surface chemical reaction activity of porous carbon materials.Therefore it makes
Standby nitrating porous carbon materials out had not only passed on the original three-dimensional porous substance channel of brown alga, but also small mesoporous with artificial regulatory
With the speciality such as nitrating graphitized carbon, as lithium ion mixed capacitor anode, have ion abundant and electron propagation ducts and
Good chemical mobility of the surface can store more lithium ions under high magnification, show in lithium ion mixed capacitor
High capacity, high magnification and macrocyclic overall characteristic.
The present invention has unique meso-hole structure and high-specific surface area using the porous carbon of alginic acid crosslinking feature preparation；Benefit
The complicated preparation flow that tradition first prepares nitrating after carbon is shortened with the method for presoma nitrating；The nitrating porous carbon of comprehensive preparation
Material is used to have storage lithium characteristic outstanding when lithium-ion capacitor positive electrode, solves positive electrode current material to a certain extent
Expect the problem of specific capacity deficiency.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (11)
1. a kind of preparation method of nitrating porous carbon positive electrode, which comprises the steps of:
S1, brown alga and metal cation are subjected to precrosslink, brown alga presoma is made；Nitrogenous compound is loaded using infusion method
On brown alga presoma surface, the brown alga intermediate containing nitrogen source is made；
S2, the brown alga intermediate is carbonized, the mesoporous intermediate carbon of the obtained nitrating of pickling；By the mesoporous intermediate carbon
It is activated to get nitrating porous carbon positive electrode.
2. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that in step S1, institute
The specific steps for stating precrosslink include: that the multivalent metal cation in brown alga and seawater is carried out cross-linking reaction, or by brown alga
Cross-linking reaction is carried out in the metal salt solution that the mass fraction for immersing human configuration is 0.1-20%.
3. the preparation method of nitrating porous carbon positive electrode according to claim 2, which is characterized in that the polyvalent metal
Cation includes Mg2+、Ca2+、Al3+、Zn2+、Fe2+、Fe3+、Sn2+、Sn4+One or more of；The metal of human configuration
Salting liquid includes Mg2+、Ca2+、Al3+、Zn2+、Fe2+、Fe3+、Sn2+、Sn4+The metal salt solution or a variety of metal salts of middle one kind
Mixed solution.
4. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that in step S1, institute
The specific steps for stating infusion method include: that brown alga presoma is immersed in nitrogenous compound solution, brown alga presoma and nitrogen
The mass ratio for closing object is 5:1-1:5, impregnates 1-2 days, the sample after immersion is dried under vacuum conditions then；
The nitrogenous compound includes at least one of urea, thiocarbamide, melamine.
5. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that in step S2, institute
The specific steps for stating carbonization include: to calcine brown alga intermediate 1-12 hours under inertia or vacuum atmosphere, and calcination temperature is
600-1500℃。
6. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that in step S2, institute
The specific steps for stating pickling include: that the resulting nitrating intermediate that will be carbonized is placed in acid solution and stirs, and filter to obtain precipitating, spend
It is 7 that ionized water cleaning, which is precipitated to pH, is then dried.
7. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that in step S1, institute
It states precrosslink and refers to alginic acid in brown alga cell wall and metal cation self-assembling reaction, formed in cell wall uniform
" egg-box " nano hybridization structure；
In step S2, the meso-hole structure in the mesoporous intermediate carbon be by " egg-box " the nano hybridization structure through carbonization,
It is made after pickling.
8. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that the activation is change
Activation is learned, specific steps include: high under inertia or vacuum atmosphere after mixing the mesoporous intermediate carbon of nitrating with activating substance
Temperature processing；
The activating substance includes KOH, NaOH, K2CO3、CaCl2、H3PO4One or more of；
The temperature of the high-temperature process is 700-1200 DEG C, and the time of processing is 0.5-12 hours.
9. the preparation method of nitrating porous carbon positive electrode according to claim 1, which is characterized in that the nitrating is porous
Pore structure in carbon material is having a size of 1-50 nanometers.
10. a kind of nitrating porous carbon positive electrode of method according to claim 11 preparation, which is characterized in that described to mix
In nitrogen porous carbon positive electrode, the load capacity of nitrogen is 0.1-5.0wt%；Pore structure is having a size of 1-50 nanometers.
11. a kind of application of nitrating porous carbon positive electrode according to claim 10 in lithium ion mixed capacitor.
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