CN104795565A - Porous graphene powder rich in heteroatom and preparation method and application thereof - Google Patents
Porous graphene powder rich in heteroatom and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 150000001720 carbohydrates Chemical class 0.000 claims abstract 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 6
- -1 shitosan Polymers 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- 235000009973 maize Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005087 graphitization Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000012983 electrochemical energy storage Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000014633 carbohydrates Nutrition 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 239000005864 Sulphur Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001665 trituration Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 238000005234 chemical deposition Methods 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- H01G11/42—Powders or particles, e.g. composition thereof
-
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses porous graphene powder rich in heteroatom. The porous graphene powder is formed by gathering graphene doped with heteroatom, and the heteroatom comprises at least one of nitrogen, boron, oxygen and phosphorus, wherein the chemical bond type of the carbon comprises graphitized sp<2>C, sp<3> hybridized C, oxygen-bridged C, and heterocyclic ring C, the sp<3> hybridized C comprises C-N or C-O, and the heterocyclic ring C comprises C=N or C=O. A natural high polymer material and carbohydrate are used as a biomass resource model, urea is used as a solid-state nitrogen source, graphene, which is high in specific surface area, has a microporous-mesoporous structure and contains nitrogen atoms, oxygen atoms and boron atoms, is prepared through a free-standing pyrolysis one-step method under the condition of normal pressure and without protection atmosphere, the graphene has a good battery energy storage function. The graphene powder disclosed by the invention has the characteristics of being low in cost, recyclable, small in environment influence, free from secondary pollution and the like, and is suitable for actual production practice.
Description
Technical field
One of the present invention is rich in hetero-atom porous graphene powder and self-supporting pyrolysis preparation and electrochemical energy storage application thereof and belongs to Graphene two-dimension nano materials technical field.
Background technology
Graphene (Graphene, G) is a kind of by sp
2the two dimensional crystal material of hydbridized carbon atoms composition, has slightly wavy layered structure, is considered to the basic composition unit forming the allotropes such as graphite, carbon nano-tube, fullerene.The intensity of Graphene, up to 130GPa, is one of mechanical property best material found so far, and the thermal conductivity of Graphene reaches 5000W/ (mK), is good heat carrier.The carrier properties of Graphene uniqueness, makes its electron mobility reach 2 × 10
5cm
2/ (Vs), exceedes silicon 100 times, and varies with temperature hardly and change.Current graphene preparation method mainly contains: (1) crystal epitaxy method, this method is, under high vacuum degree, single crystal silicon carbide substrate is heated to 1200 ~ 1600 DEG C, silicon atom distillation in substrate is separated out, excessive carbon atom stays substrate and reconstruct generates Graphene, (2) chemical vapour deposition technique (CVD), the carbon compounds such as methane are carried out pyrolysis and reconstruct generation Graphene by this method in substrate, then remove metallic substrates and obtain Graphene, (3) chemical oxidation-reduction method, at present with the standby i.e. Brodie method of this legal system, Staudenmaier method and Hummers method.
Nitrogen-doped graphene (N-doped G) is containing very important one in hetero-atom Graphene, wherein the introducing of nitrogen-atoms can change spin density and the charge distribution state of electronics in around carbon atom, thus makes it have the potentiality of the application such as electro-catalysis, sensing and electronic device.At present, the synthetic method of nitrogen-doped graphene has two kinds: the chemical synthesis of (1) (bottom-up) from bottom to top, as CVD and solvent-thermal method, (2) under nitrogen or ammonia atmosphere, high temperature reprocessing Graphene or graphite oxide (graphite oxide).
Solid phase pyrolysis synthesis (Solid-state pyrolysis) belongs to chemical synthesis process from bottom to top, uses Nitrogen element carbon compound as precursors, certain atmosphere and catalyst auxiliary under react.Synthesis as, nitrogen-doped carbon nanometer pipe (N-doped Carbon nanotube) utilizes metal organic complex containing carbon, nitrogen and metal catalytic source as presoma, obtained in sealing system by solid phase pyrolytic reaction.
Carbon and nitrogen solid precursor compound can friendly, the cheap and agricultural biomass resource that is easy to get of environment for use and natural macromolecular materials, as cellulose, leaf, glucose, shitosan, starch etc.
As positive electrode, elemental sulfur has higher theoretical specific capacity 1675mAh/g, theoretical specific energy 2600Wh/Kg, is 3 ~ 5 times of lithium rechargeable battery, and in addition, elemental sulfur also has the advantages such as hypotoxicity, memory space be large, cheap.
In sulphur lithium battery, the electrochemical reaction process of sulfur-bearing positive pole complexity and the physical property such as non-conductive thereof determine the research and development difficult point of lithium-sulfur cell mainly at positive electrode, for realizing the application of lithium-sulfur cell, the conductivity of positive electrode will be improved on the one hand, improve the utilance of positive active material, improve the high rate performance of battery; Also to suppress can not losing of capacity, to improve the cycle performance of battery on the other hand.
And research in recent years mainly concentrates on organosulfur compound material and carbon composite material two kinds of positive electrodes.And the present invention is exactly the carrier using the Graphene of high-specific surface area, microcellular structure and nitrogenous, oxygen atom as sulphur (S), it is positive electrode that chemical deposition prepares sulphur/porous graphene composite material, apply its oxygen functional group and large specific area to sulphur load, and then the non-constant of the conductivity overcoming sulphur greatly, be unfavorable for that the high rate capability of battery and sulphur are in discharge process, the expansion of volume is reduced very large, likely causes cell expansion and the shortcoming damaged.
Summary of the invention
This research contents is for biomass resource model with cellulose, leaf, maize straw, glucose, shitosan, starch, gelatin (natural macromolecular material); urea is solid-state nitrogenous source; under the condition of normal pressure and unprotect atmosphere, prepare high-specific surface area, microcellular structure and containing heteroatomic Graphene by self-supporting pyrolysis one-step method.
To achieve these goals, technical scheme of the present invention is as follows:
One is rich in heteroatomic porous graphene powder, it forms by assembling doped with heteroatomic Graphene, the microscopic pattern of powder contains hetero-atom described in micropore-mesopore compound pore passage structure and comprises at least one in nitrogen, boron, oxygen and phosphorus, and wherein, the chemical bond types of carbon comprises: graphitization sp
2c, sp
3hydridization C, oxo bridge connection C, heterocycle C, described sp
3hydridization C comprises C-N or C-O, and described heterocycle C comprises C=N or C=O, and the chemical bond of nitrogen comprises pyridine N, pyrroles N or pyridone N, graphitization N, pyridine oxide N.
One is rich in heteroatomic porous graphene raw powder's production technology as described in the present invention, it is characterized in that, be with biomass resource and solid-state nitrogenous source for raw material, at ambient pressure, prepared by self-supporting pyrolysis one-step method.
Specifically comprise the steps:
By biomass resource with solid-state nitrogenous source with (0 ~ 2): the mass ratio of 20 mixes, and is ground to after granularity is less than 500 orders, obtains mixed powder;
Described mixed powder is dried at 85 DEG C to water content lower than 500ppm after, at 500 ~ 1300 DEG C, carry out pyrolysis 3 hours, obtain being rich in heteroatomic porous graphene powder;
Preferably, described biomass resource is natural macromolecular material; Described solid-state nitrogenous source is urea, melamine or thiocarbamide.
Preferably, described natural macromolecular material is at least one in cellulose, glucose, shitosan, starch, leaf, maize straw.
A kind ofly be rich in the application of heteroatomic porous graphene powder in electrochemical energy storage as described in the present invention.
Preferably, the electrode of the positive pole of lithium-sulfur cell, lithium ion battery negative, super capacitor is comprised.
Porous comprises micropore and mesoporous;
Content 1 ~ the 30wt% of what the present invention obtained be rich in hetero-atom porous graphene powder nitrogen, oxygen content 10 ~ 20wt%; Specific area 485.146 ~ 737.793m
2/ g, micropore pore volume 0 ~ 0.31cm
3/ g, average pore size is distributed as 2.2nm ~ 10.8nm.
To be rich in the carrier of heteroatomic porous graphene powder as sulphur (S), chemical deposition prepares sulphur/porous graphene composite material, with water-soluble LAX132 for binding agent makes sulphur positive pole.With lithium metal (Li) for negative pole, electrolyte is 1M lithium bis-(trifl uoromethanesulfonyl) imide (LiTFSI) in 1,3-dioxolane and 1,2-dimethoxy-ethane (volume ratio 1:1) processes lithium-sulphur electricity.
The present invention utilizes this nitrogenous exactly, the conductivity that the graphene carbon material of oxygen atom is superior, good chemical stability and thermal stability, large specific area, abundant pore structure and surface functional group, carried out on a microscopic scale carbon sulphur composite material design (nitrogen containing oxygen Graphene as the carrier of sulphur (S), chemical deposition prepares sulphur/porous graphene composite material) sulphur is limited in the micropore of carbon nano-material, defect and Adsorption, with 1M lithium bis-(trifl uoromethanesulfonyl) imide (LiTFSI) in 1, 3-dioxolane and 1, 2-dimethoxy-ethane (volume ratio 1:1) is electrolyte, effectively increase the conductivity of sulphur and limit the dissolving of many sulphions, significantly improve the performance of lithium-sulfur cell at electric automobile power battery, the application in the fields such as intelligent grid and the extensive energy-storage battery of clean energy resource, there is potential using value widely.
Content of the present invention is for biomass resource model with cellulose, leaf, maize straw, glucose, shitosan, starch, gelatin (natural macromolecular material); urea is solid-state nitrogenous source; under the condition of normal pressure and unprotect atmosphere; prepare high-specific surface area, microcellular structure and Graphene that is nitrogenous, oxygen atom by self-supporting pyrolysis one-step method, this Graphene has the function of good battery energy storage.And possess with low cost, recyclable recycling, have fewer environmental impacts, the feature such as non-secondary pollution, be suitable for actual production practices.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that hetero-atom porous graphene is rich in the present invention.
Fig. 2 is nitrogen adsorption-desorption curve figure that hetero-atom porous graphene is rich in the present invention.
Fig. 3 is that the cycle performance figure of hetero-atom porous graphene as Lithium-sulphur battery anode material is rich in the present invention.
Embodiment
For setting forth practical function of the present invention, below by reaction better and have the example of feature to be discussed.This process uses six kinds of natural products such as cellulose, leaf, maize straw, glucose, shitosan, starch, gelatin, there is wide material sources, renewable, wide variety, excellent performance, there are excellent biocompatibility, environmental friendliness, are easy to modification, broad-spectrum advantage.
Embodiment 1
Weigh urea 20g respectively, glucose 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10 ~ 12h.Black solid (Graphene) after pyrolysis is weighed, carries out the sign mensuration of XRD, SEM projection scanning, specific area respectively.
Embodiment 2
Weigh urea 20g respectively, cellulose 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10h ~ 12h.Black solid (Graphene) after pyrolysis is weighed, carries out the sign mensuration of XRD, SEM projection scanning, specific area respectively.
Embodiment 3
Weigh urea 20g respectively, shitosan 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10h ~ 12h.Black solid (Graphene) after pyrolysis is weighed, carries out the sign mensuration of XRD, SEM projection scanning, specific area respectively.
Embodiment 4
Weigh urea 20g respectively, edible corn starch 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10h ~ 12h.Black solid (Graphene) after pyrolysis is weighed, carries out the sign mensuration of XRD, SEM projection scanning, specific area respectively.
Embodiment 5
Weigh urea 20g respectively, gelatin 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10h ~ 12h.
Embodiment 6
Weigh urea 20g respectively, leaf powder 2g is in agate mortar, Homogeneous phase mixing, identical hand trituration is about 1h, till not having crystal to occur, by ground mixture in still, 85 DEG C without water oven in pyrolysis dry burning more than 3 days, the mixture be baked is placed in muffle furnace, and at the temperature of 900 DEG C and 1000 DEG C, carry out pyrolysis respectively, the time is about 10h ~ 12h.
Embodiment 7
It is nitrogenous that containing the carrier of oxygen Graphene as sulphur (S), chemical deposition prepares sulphur/porous graphene composite material, with water-soluble LAX132 for binding agent makes sulphur positive pole.With lithium metal (Li) for negative pole, electrolyte is 1M lithium bis-(trifl uoromethanesulfonyl) imide (LiTFSI) in 1,3-dioxolaneand 1,2-dimethoxy-ethane (volume ratio 1:1) processes lithium-sulfur cell.
Embodiment 8
Electrode preparation does not need binding agent and conductive filler, and 2mg powder sample is directly pressed onto (0.5cm*0.5cm) in nickel sheet and makes electrochemical capacitance electrode under 5MPa pressure.In 6M potassium hydroxide aqueous solution, be the electrochemical capacitance performance that reference electrode measures porous graphene electrode to electrode, saturated dry mercury electrode with Pt dish (1.5cm*1.5cm).
In sum, be only preferred embodiment of the present invention, not be used for limiting scope of the invention process, all equalizations of doing according to shape, structure, feature and the spirit described in the claims in the present invention scope change and modify, and all should be included in right of the present invention.
Claims (7)
1. be rich in a heteroatomic porous graphene powder, it is characterized in that, form by assembling doped with heteroatomic Graphene, described hetero-atom comprises at least one in nitrogen, boron, oxygen and phosphorus, and wherein, the chemical bond types of carbon comprises: graphitization sp
2c, sp
3hydridization C, oxo bridge connection C, heterocycle C, described sp
3hydridization C comprises C-N or C-O, and described heterocycle C comprises C=N or C=O, and the chemical bond of nitrogen comprises pyridine N, pyrroles N, pyridone N, graphitization N or pyridine oxide N.
2. be rich in a heteroatomic porous graphene raw powder's production technology as claimed in claim 1, it is characterized in that, be with biomass resource and solid-state nitrogenous source for raw material, at ambient pressure, prepared by self-supporting pyrolysis one-step method.
3. preparation method as claimed in claim 2, is characterized in that, specifically comprise the steps:
By biomass resource with solid-state nitrogenous source with (0 ~ 2): the mass ratio of 20 mixes, and is ground to after granularity is less than 500 orders, obtains mixed powder;
Described mixed powder is dried at 85 DEG C to water content lower than 500ppm after, at 500 ~ 1300 DEG C, carry out pyrolysis 3 hours, obtain being rich in heteroatomic porous graphene powder.
4. preparation method as claimed in claim 2 or claim 3, it is characterized in that, described biomass resource is natural macromolecular material; Described solid-state nitrogenous source is urea, melamine, thiocarbamide.
5. preparation method as claimed in claim 4, is characterized in that, described natural macromolecular material is cellulose, shitosan, leaf, maize straw, carbohydrate are at least one in starch, glucose.
6. one kind is rich in the application of heteroatomic porous graphene powder in electrochemical energy storage as claimed in claim 1.
7. apply as claimed in claim 6, it is characterized in that, comprise the electrode of the positive pole of lithium-sulfur cell, lithium ion battery negative, super capacitor.
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