CN106910893A - A kind of rich N doping loose structure carbon material and its preparation method and application - Google Patents
A kind of rich N doping loose structure carbon material and its preparation method and application Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005011 phenolic resin Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003990 capacitor Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 238000000197 pyrolysis Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 122
- 229910052757 nitrogen Inorganic materials 0.000 claims description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 241000256844 Apis mellifera Species 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
- Y02E60/10—Energy storage using batteries
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- 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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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of rich N doping loose structure carbon material, is mixed by water soluble phenol resin, surfactant F127 and guanine, is prepared from by solvent evaporation self-assembly method.Its preparation method includes：（1）Surfactant F127 and guanine, water soluble phenol resin are obtained into nitrogenous precursor by evaporating self assembling process；（2）Nitrogenous precursor pyrolysis is obtained into rich nitrogen-doped modified porous carbon materials；（3）The porous carbon materials washing that will be obtained, filtering, drying obtains rich N doping loose structure carbon material.Material of the present invention as lithium ion battery negative material application, when current density be 100 mA g‑1When, specific capacity value is 607 mAh g‑1；As the application of super capacitor material, when current density is 0.5 A g‑1When, specific capacitance is 218 F g‑1.Carbon material prepared by the present invention has big specific surface area, and excellent chemical property, preparation process is simple, it is easy to mass produce have broad application prospects in fields such as electrochemistry.
Description
Technical field
The present invention relates to porous material technical field, and in particular to a kind of rich N doping loose structure carbon material and its preparation
Methods and applications.
Background technology
Lithium ion battery has high-energy-density, fast charging and discharging, high voltage that is easy to carry, comparing dry cell due to it
The features such as, it is widely used in various daily energy-storage travelling wave tubes.Negative material is filling as the important storage lithium main body of lithium ion battery
Insertion and abjection structure in discharge process with lithium ion are susceptible to cave in, and cause the continuous decay of capacity, reduction lithium from
The sub- original service life of battery, greatly limits its application in extensive energy storage.Carbon material is used as lithium ion battery battery
The important component of pole material, because it has wide source, preparation simplicity, good conductivity, aperture controllable and with low cost
The advantages of cause the extensive interest of researcher.
The good electric conductivity of carbon material, is conducive to the quick diffusion of lithium ion and electronics, can improve electrode reaction power.
Loose structure can also effectively alleviate volume and excessively expand, so as to realize lithium ion battery fast charging and discharging and long life
It is required that.Meanwhile, the carbon material with bigger serface, abundant pore structure is also the energy storage device-ultracapacitor of high-efficiency cleaning
A kind of promising selection.
The means that ordered mesoporous carbon material can generally be cast with nanometer such as dura mater plate methods synthesizes.Carbon source has been immersed in
In the aperture of sequence mesoporous silicon oxide, it is carbonized afterwards, removed template, so can be effectively replicated the pattern of template, but
It is that this method haves the shortcomings that time-consuming and is difficult volume production.Therefore, a kind of simple and reliable method is designed order mesoporous to prepare
Carbon is imperative.In recent years, a kind of self-assembly method by amphipathic nature block polymer and carbon source obtains the accreditation of people
Carry out synthesizing ordered mesoporous carbon material [Chem. Mater. 2006,18,4447-4464].Sun et al. utilizes this soft template
Method has synthesized 1-dimention nano carbon-point/fiber, and it has specific surface area 570-585 m higher2 g-1.But prepared by the method
There are two technical problems in material：
First, micropore amount contained by the material of method synthesis is more, and mesoporous amount is relatively fewer, and pore diameter range distribution is only 0.75-3.3
nm；
2nd, as lithium cell cathode material, in 100 mA g-1After lower 50 circulations of current density, specific capacity is only 476 mA h
g-1[J. Mater. Chem., 2012, 22, 17049]。
Heteroatomic doping can change the electronic environment of carbon atom, can significantly change the embedding lithium behavior of carbon material, wherein
N doping application is relatively broad.The doped forms that nitrogen-atoms is present mainly have pyridine type nitrogen, pyrroles's type nitrogen and graphite mould nitrogen etc., its
In can improve lithium ions embedded performance in the material and improve specific capacity for carbon material provides more surface defects in preceding two,
And graphite mould nitrogen can further improve electronic conductivity [Carbon, 2015,84 (1) of carbon material:335-346.].In carbon materials
In the preparation process of material, the compound of selection high nitrogen content can realize the high nitrogen doped amount of final carbon material as predecessor,
Extraly improve the lithium storage content of electrode material.Such as Zhu et al. using solvent-free mechanical attrition method with melamine as nitrogen source
The rich nitrogen ordered mesoporous carbon material of synthesis, with nitrogen content higher（24.4 %）, average pore size is 3.7 nm, and ought be used as lithium
Specific capacity during ion negative material is in 100 mA g-1506 mAh g are still kept after lower 300 circulations of current density-1.But
There are three technical problems in material prepared by the method：
First, when ultracapacitor is used as, in 0.2 A g-1Under current density, the specific capacity of the material is only 150 F g-1
[J. Mater. Chem. A, 2016, 4, 2286]；
2nd, the nitrogen source melamine that the method is selected can occur the phenomenon of distillation and thermal condensation being heated in the range of 297-390 DEG C,
The violent weight loss of simultaneous, when being further heated to 545 DEG C in open environment, has ammonation
Occur, therefore, in the case where nitrogen content high is kept, this method can consume more nitrogen sources [Langmuir 2009,25
(17), 10397–10401]；
3rd, the method needs to use ball-milling method to prepare persursor material, is not suitable for volume production.
In sum, therefore while nitrogen content high is controlled prepare with compared with high reversible capacity and suitable industrialization
The porous carbon materials of production are still a kind of very big challenge.
The content of the invention
The purpose of the present invention is the nitrogen content and specific surface area by improving cell negative electrode material, improves the ratio of negative material
Finite capacity, circulates unstable problem, while it is complicated to solve current high-capacity cathode material preparation process, it is difficult to extensive
The problem of production, proposes a kind of rich N doping loose structure carbon material and its preparation method and application.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is respectively carbon using phenolic resin, guanine
Source and nitrogen source, and it is template to use surfactant F127, using the three-dimensional porous carbon of solvent evaporation self-assembly method synthesizing stable
Material.Wherein, not only successfully can be entrained in carbon material nitrogen as the nitrogen source of high nitrogen content by guanine, may be used also
As pore creating material, there is pyrolytic reaction with presoma in carbonisation, so as to improve the mesoporous content and conduction of carbon material
Performance, is conducive to the transmission of lithium ion and electronics, further improves the chemical property of porous carbon negative pole material.
Realizing the concrete technical scheme of the object of the invention is：
Rich N doping loose structure carbon material is by rich N doping loose structure carbon material by water soluble phenol resin, surfactant
F127 and the guanine mixing as nitrogen source, are prepared from by solvent evaporation self-assembly method, and its micro content reduces, mesoporous to contain
Amount increases to 16%, and specific surface area scope is in 384 ~ 578 m2 g-1, the mass fraction of described water soluble phenol resin is 20 %,
The mean molecule quantity of surfactant F127 is 12600, EO106PO70EO106。
The preparation method of rich N doping loose structure carbon material, comprises the following steps：
Step（1）, in mass ratio it is 1 by surfactant F127 and guanine, water soluble phenol resin:0.5 ~ 3 is added to
Ionized water and absolute ethyl alcohol mass ratio are 1：In 2 mixed solution, nitrogenous precursor is obtained by evaporating self assembling process；
Step（2）, under nitrogen protection, nitrogenous precursor is put into tube furnace and is calcined, obtained with substantial amounts of honeybee through pyrolysis
Nest shape aperture, average pore size is distributed in the rich nitrogen-doped modified porous carbon materials of 3.77 nm, the porous carbon materials it is nitrogenous
Amount scope is 13.32 ~ 24.29%, and the porous carbon materials contain pyridine nitrogen and pyrroles's nitrogen total amount scope is 56.85 ~ 67.64 %；
Step（3）The nitrogen-doped modified porous carbon materials of above-mentioned richness are washed repeatedly respectively with deionized water and absolute ethyl alcohol
Wash, filter, drying obtains rich N doping loose structure carbon material.
Rich N doping loose structure carbon material as lithium ion battery negative material application, when current density be 100 mA
g-1When, specific capacity value is 607 mAh g-1。
Rich N doping loose structure carbon material as super capacitor material application, when current density be 0.5 A g-1
When, specific capacitance is 218 F g-1。
The elementary analysis of rich N doping loose structure carbon material of the invention is surveyed by German Elementar elemental analysers
Examination, nitrogen adsorption performance test is by Kang Ta companies of the U.S.（Quantachrome Instruments）Autosorb-1 type physics
Adsorption instrument is tested, and electrochemistry cycle performance is tested by Wuhan indigo plant electrical measurement test system and Chi660 electrochemical workstations.
Test result shows：The rich N doping loose structure carbon material has nitrogen content high（13.32~24.29 %）With
Abundant micropore and meso-hole structure, pore-size distribution increases with the increase of nitrogen source consumption, while there is specific surface area higher, model
It is trapped among 384 ~ 578 m2 g-1.When current density is 100 mA g-1When, specific capacity value is up to 607 mAh g-1, and with good
Cyclical stability and high rate performance.
The present invention relative to prior art, with advantages below：
First, the porous carbon materials of high nitrogen content are formed in the present invention using novel nitrogen source and pore creating material and carbon source, templating self-assembly,
Under the protection of nitrogen, during heating, because guanine is decomposed in carbon wall in 400 DEG C of heat absorptions and phenolic resin
It is upper to mix different types of nitrogen-atoms, for carbon material more avtive spots are provided to improve the storage lithium performance of carbon material；
2nd, a large amount of pore structures can be left while guanine is decomposed, further increases mesoporous content, it is appropriate mesoporous to be conducive to
The transmission of lithium ion, reduces its diffusional resistance, so as to the chemical property of material can be improved；
3rd, the method that this method directly mixes self assembly using carbon nitrogen source and template, can directly remove mould from carbonisation
Plate agent, synthesis technique is simple, time-consuming short, is obtained with high-quality product under low cost.
Therefore, the present invention has broad application prospects in fields such as the fields such as lithium ion battery, ultracapacitor.
Brief description of the drawings：
Fig. 1（a）It is the thermal gravimetric analysis curve of Nitrogen-rich porous carbon material,（b）For the means of differential scanning calorimetry of Nitrogen-rich porous carbon material is bent
Line；
Fig. 2 is the corresponding nitrogen high-resolution spectroscopy figure of x-ray photoelectron energy spectrum diagram of Nitrogen-rich porous carbon material；
Fig. 3 is the microstructure of porous carbon materials, scanning electron microscopy picture of (a) gained without nitrogen source loose structure carbon material
Figure,（b）Images of transmissive electron microscope without nitrogen source loose structure carbon material,（c）The scanning electron microscopy picture of Nitrogen-rich porous carbon material
Figure,（d）The images of transmissive electron microscope of Nitrogen-rich porous carbon material；
Fig. 4（a）It is the low temperature nitrogen adsorption isothermal curve without nitrogen source loose structure carbon material,（b）It is Nitrogen-rich porous carbon material
Low temperature nitrogen adsorption isothermal curve；
Fig. 5（a）It is the pore size distribution curve without nitrogen source loose structure carbon material,（b）It is the pore-size distribution of Nitrogen-rich porous carbon material
Curve；
Fig. 6 is the chemical property without nitrogen source loose structure carbon material,（a）It is 100 mA g in current density-1When discharge and recharge
Cycle performance curve,（b）High rate performance under different current densities；
Fig. 7 is the lithium ion battery chemical property of Nitrogen-rich porous carbon material,（a）It is 100 mA g in current density-1When
Charge-discharge performance curve,（b）High rate performance under different current densities；
Fig. 8 is the ultracapacitor chemical property of Nitrogen-rich porous carbon material,（a）In the charge and discharge cycles of different current densities
Performance curve,（b）In 10 A g-1Cyclical stability under current density.
Specific embodiment
The present invention is described in further detail, but be not right with reference to Figure of description by embodiment to present invention
Limitation of the invention.
Embodiment
A kind of preparation method of rich N doping loose structure carbon material is as follows：
Step（1）Take in 20 g phenol dissolving 4.26 g NaOH solutions of addition (20 wt%), 10 min are stirred at 50 DEG C, so
After be added dropwise over 35.4 g formalins (37 wt %), 60 min are reacted at 75 DEG C.After cooling, adjusted with 1 M watery hydrochloric acid
PH is then placed in being dried in 40 DEG C of vacuum drying chambers to neutrality, and the product dissolving for finally obtaining in ethanol, is configured to concentration
The Water-soluble phenolic resin solution of 20 wt%；
Step（2）1 g F127 and 2 g guanines are dissolved in the mixed solution of 10 g deionized waters and 20 g absolute ethyl alcohols, then
Take 5 g steps（1）Described in phenolic resin ethanol solution add above-mentioned solution, 30 min are stirred at 35 DEG C, after reaction
Pale yellow solution is imported and dries 6 h in culture dish at 50 DEG C, be then placed in solidifying 24 h in 100 DEG C of baking ovens；
Step（3）By the nitrogenous precursor grinding after solidification, tube furnace calcining in a nitrogen atmosphere is put into, is first 250
2 h are calcined at DEG C, 600 DEG C of calcinings 3 h, 1 DEG C/min of heating rate are then heated to, after cooling, black powder is obtained；
Step（4）, above-mentioned carbon material is carried out into cyclic washing, filtering with deionized water and absolute ethyl alcohol, drying obtains rich nitrogen and mixes
Miscellaneous loose structure carbon material.
In order to contrast the influence that addition nitrogen source guanine synthesizes to carbon material, further synthesize without nitrogen source loose structure carbon
Material, the specific steps of its preparation method if not otherwise specified the step of preparation method with rich N doping loose structure carbon material
Identical, difference is step（2）In without guanine, obtain without nitrogen source loose structure carbon material.
It is nitrogen source that guanine is added in the preparation method of rich N doping loose structure carbon material, through thermogravimetric analysis and differential
Scanning thermometric analysis is as shown in figure 1, in nitrogenous precursor carbonisation, guanine and phenolic resin absorb heat at 400 DEG C
Decompose, nitrogen is successfully mixed on carbon framework, and nitrogen content is up to 18.86 %, wherein containing substantial amounts of pyridine nitrogen, pyrroles's nitrogen and stone
Black type nitrogen, as shown in Figure 2.Detected through field emission scanning electron microscope and transmission electron microscope, test result such as Fig. 3 institutes
Show, as can be seen that what is prepared has bits and bobs to be distributed in its surface without nitrogen source loose structure carbon material surface is smooth from 3a, from
In Fig. 3 b it can be seen that its aperture is single.And the N doping loose structure carbon material for preparing contributes to expansion due to what guanine was decomposed
Big carbon materials blanking aperture, makes carbon material surface substantial amounts of cellular cavity such as Fig. 3 c occur, therefore with abundant pore-size distribution such as
Fig. 3 d.Micro content without nitrogen source loose structure carbon material more about 87 %, specific surface area greatly 578 m2 g-1, its aperture
It is mainly distributed in the range of micropores of 1.2 nm as shown in Figures 4 and 5.And N doping loose structure carbon material then contains substantial amounts of Jie
Hole, specific surface area is 455 m2 g-1, mesoporous content rises to 16 %, and aperture is mainly distributed in the macropore range of 5.3 nm.
The appropriate mesoporous transfer rate for being conducive to accelerating lithium ion, reduces its diffusional resistance, due to without the porous knot of nitrogen source
The mesoporous content of structure carbon material is relatively low, and participates in synthesizing without nitrogen source, therefore nitrogen content is extremely low, and its chemical property is also poor, such as Fig. 6
Shown specific capacity is 148 mAh g-1.But under identical current density, the specific capacitance of rich N doping loose structure carbon material
It is 607 mAh g-1As shown in fig. 7, illustrating that it has good chemical property.As shown in Figure 8 when as super capacitor equipment
It is 0.5 A g in current density during material-1Under, specific capacitance is 218 F g-1, in 10 A g-1Lower 5000 circulations of high current density
Specific capacitance conservation rate still has 89 % afterwards.
Claims (10)
1. a kind of rich N doping loose structure carbon material, it is characterised in that：Rich N doping loose structure carbon material is by water-soluble phenolic
Urea formaldehyde, surfactant F127 and the guanine as nitrogen source mix, and are prepared from by solvent evaporation self-assembly method.
2. rich N doping loose structure carbon material according to claim 1, it is characterised in that：The porous knot of rich N doping
The micro content of structure carbon material reduces, and mesoporous content increases to 16%, and specific surface area scope is in 384 ~ 578 m2 g-1。
3. rich N doping loose structure carbon material according to claim 1, it is characterised in that：Described water soluble phenolic resin
The mass fraction of fat is 20 %, and the mean molecule quantity of surfactant F127 is 12600, EO106PO70EO106。
4. the preparation method of rich N doping loose structure carbon material according to claim 1, it is characterised in that methods described bag
Include following steps：
Step（1）, surfactant F127 and guanine, water soluble phenol resin are added to deionized water by certain mass ratio
In the mixed solution of absolute ethyl alcohol, nitrogenous precursor is obtained by evaporating self assembling process；
Step（2）, under nitrogen protection, nitrogenous precursor is put into tube furnace and is calcined, obtain rich nitrogen-doped modified through pyrolysis
Porous carbon materials；
Step（3）The nitrogen-doped modified porous carbon materials of above-mentioned richness are washed repeatedly respectively with deionized water and absolute ethyl alcohol
Wash, filter, drying obtains rich N doping loose structure carbon material.
5. preparation method according to claim 4, it is characterised in that：Step（1）Described surfactant F127 and bird
The mass ratio of purine is 1：0.5 ~ 3, described deionized water and the mass ratio of the mixed solution of absolute ethyl alcohol are 1：2.
6. preparation method according to claim 4, it is characterised in that：Step（2）The nitrogen-doped modified porous carbon of the richness
Material has substantial amounts of cellular aperture, and average pore size is distributed in 3.77 nm.
7. preparation method according to claim 4, it is characterised in that：Step（2）The nitrogenous precursor is in high temperature cabonization
The nitrogen content scope of the rich nitrogen-doped modified porous carbon materials obtained after process is 13.32 ~ 24.29%.
8. preparation method according to claim 4, it is characterised in that：Step（2）The nitrogenous precursor is in high temperature cabonization
It is 56.85 ~ 67.64 that the rich nitrogen-doped modified porous carbon materials obtained after process contain pyridine nitrogen and pyrroles's nitrogen total amount scope
%。
9. according to claim 1 rich N doping loose structure carbon material as lithium ion battery negative material application, its
It is characterised by：When current density is 100 mA g-1When, specific capacity value is 607 mAh g-1。
10. according to claim 1 rich N doping loose structure carbon material as super capacitor material application, its feature
It is：When current density is 0.5 A g-1When, specific capacitance is 218 F g-1。
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