CN104681823A - Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material - Google Patents
Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material Download PDFInfo
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- CN104681823A CN104681823A CN201510036178.6A CN201510036178A CN104681823A CN 104681823 A CN104681823 A CN 104681823A CN 201510036178 A CN201510036178 A CN 201510036178A CN 104681823 A CN104681823 A CN 104681823A
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- nitrogen
- doped graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000002077 nanosphere Substances 0.000 title claims abstract description 54
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 239000010411 electrocatalyst Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000004640 Melamine resin Substances 0.000 abstract 2
- 239000000758 substrate Substances 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- -1 Graphene compound Chemical class 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
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- 206010037844 rash Diseases 0.000 description 1
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Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a novel composite material, and particularly relates to a preparation method and application of a nitrogen-doped graphene and cobaltosic oxide hollow nanosphere composite material. The novel composite material comprises a doped graphene substrate and cobaltosic oxide hollow nanospheres which is attached to the surface of the doped graphene substrate. Melamine resin is taken as a cross-linking reagent for integrating graphite oxide with Co<2+> into a single coordination precursor. The preparation method comprises the following steps: in a pyrolysis process of the precursor, taking the melamine resin as a new nitrogen source to uniformly dope the graphene with nitrogen, fixing cobalt oxide which is generated in situ, and finally preparing the nitrogen-doped graphene/Co3O4 hollow nanosphere composite material with a sandwich structure. The composite material has a graded porous structure, is high in specific surface area, more in active sties, good in electron conductivity and ion conductivity, and good in application prospect in the field of new energy resources and catalysis.
Description
Technical field
The present invention relates to a kind of advanced composite material (ACM), particularly a kind of nitrogen-doped graphene is matrix, and is attached to the cobaltosic oxide hollow nano-sphere composite material on its surface, also comprises the preparation method and application of this composite material.
Background technology
New forms of energy and new material are the focuses that international community is paid close attention to, the new and high technology that Ye Shi China first develops.Lithium rechargeable battery is a kind of novel green energy-storing electric supply installation, is widely used in the portable type electronic product such as mobile phone, notebook.But the energy density of existing battery material is low, high rate performance is poor, the needs of vapour Vehicular dynamic battery can not be met.Therefore, research and development have that energy density is high, the battery material (comprising positive pole and negative pole) of high rate performance and good cycle is the emphasis of current lithium ion battery development, are also the difficult points of restriction high-energy, high-power battery development.
Bibliographical information, transition metal oxide Co
3o
4can pass through redox machinery reversible lithium storage, theoretical specific capacity is up to 890mAh g
-1, be expected to the graphite cathode replacing commodity lithium ion battery.But, Co in electrochemistry cyclic process
3o
4volume marked change, cause electrode efflorescence, come off, impedance obviously increases, and capacity is decayed rapidly, and cycle performance is poor.And, Co
3o
4be a kind of p-type semiconductor, poorly conductive, high rate performance is bad.For solving these difficulties, people have synthesized multiple Co
3o
4nano structural material and the composite material with carbon (comprising Graphene) thereof.These nano composite materials (particularly Co
3o
4with the composite material of Graphene) alleviate Co to a certain extent
3o
4the change in volume of electroactive material in charge and discharge process, also improves its conductivity, thus improves electrochemical lithium storage performance.But, Co in composite material
3o
4and lack enough interaction forces between the carbon matrix such as Graphene, be bonded to each other insecure.In electrochemistry cyclic process, Co
3o
4easily come off, reunite, cause the cycle performance of composite material still can not meet the demand of practical application.
In addition, oxygen reduction electro-catalyst is the critical material of the new energy devices such as fuel cell, metal-air battery development.At present, the oxygen reduction electro-catalyst mainly noble metal such as platinum.But noble metal catalyst cost is high, be subject to that methyl alcohol poisons, poor stability, significantly limit the development of fuel cell, metal-air battery.The Research Emphasis that catalytic activity is high, good stability, inexpensive non-precious metal catalyst are current electro-catalysis fields.
Nitrogen-doped graphene/Co prepared by prior art
3o
4co in composite material
3o
4be all solid nanoparticles, specific area is little, and avtive spot is few, so the chemical property of composite material still can not meet the needs of high-energy, high-power battery development.And its application is only confined to an aspect, or as lithium cell negative pole material, or as oxygen reduction electro-catalyst.
In sum, nitrogen-doped graphene/Co
3o
4the Synthesis and application of nano composite material becomes the study hotspot of current new forms of energy and field of new.Relevant nitrogen-doped graphene/Co in prior art data
3o
4the preparation method of nano composite material mainly contains two kinds.Method one for raw material, prepares nitrogen-doped graphene/Co by solvent thermal reaction with graphite oxide (GO), cobalt acetate, ammoniacal liquor
3o
4composite material (Nat.Mater.2011,10,780; RSC Adv.2013,3,5003).First the method prepares GO, then by made GO ultrasonic disperse in ethanolic solution, then adds the aqueous solution and the ammoniacal liquor of cobalt acetate, stirs 10 hours, finally proceed to reactor and react 3 hours obtained products at 150 DEG C at 80 DEG C.Method two with the Graphene of N doping, cobalt chloride and urea for raw material through multistep reaction preparation (Nano Energy 2014,3,134).The method needs 5 consecutive steps: 1) first prepare GO; 2) stripping of microwave irradiation method and reduction GO is adopted to prepare Graphene (MGO); 3) by MGO in the ammonia/argon-mixed atmosphere of flowing at 850 DEG C reaction within 1 hour, prepare nitrogen-doped graphene (NMGO); 4) a certain amount of MGO is dispersed in water, adds appropriate cobalt chloride and urea, and reflux 3 hours at 90 DEG C, preparation Co (OH)
2/ NMGO; 5) under the nitrogen protection of flowing, by Co (OH)
2/ NMGO, 300 DEG C of heat treated, finally obtains nitrogen-doped graphene/Co
3o
4compound.Nitrogen-doped graphene/Co prepared by said method
3o
4the specific capacity that composite material is used as lithium cell negative pole material is no more than 900mAh g
-1, and under big current, charge/discharge capacity is lower; During as oxygen reduction electro-catalyst, play spike potential low, differ greatly with commodity Pt/C catalyst, and hydrogen reduction current density is little.
But, nitrogen-doped graphene/Co
3o
4the preparation of hollow nano-sphere composite material and the rarely seen report of application in new forms of energy and catalytic field thereof.
Summary of the invention
The object of this invention is to provide a kind of nitrogen-doped graphene and Co
3o
4hollow nano-sphere composite material and its preparation method and application, as battery material negative pole, this composite material has that specific capacity is high, the feature of cycle performance and good rate capability, also solves the problem that in existing oxygen reduction electro-catalyst, preparation is difficult, activity is low, cost is high.
For solving the problems of the technologies described above, the invention provides a kind of nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material, comprises nitrogen-doped graphene matrix, and is attached to the Co in described nitrogen-doped graphene matrix
3o
4hollow nano-sphere.
This nitrogen-doped graphene/Co
3o
4the preparation method of hollow nano-sphere composite material comprises the following steps:
1) preparation of graphite oxide dispersion: be that graphite oxide (GO) prepared by raw material with graphite.Concrete grammar is as follows: by mass ratio (2 ~ 4): the graphite of 1 and sodium nitrate add in the concentrated sulfuric acid, 2 ~ 5 times are added to the potassium permanganate of described graphite quality under stirring, mix, 0.5 ~ 3h is stirred lower than 20 DEG C with ice-water bath control temperature, then raised temperature to 32 ~ 38 DEG C reaction 1 ~ 4h, slowly drips the deionized water of 35 ~ 50 times of graphite quality, stirs, when system temperature declines, add hydrogen peroxide cessation reaction, after suction filtration, washing, drying, namely obtain graphite oxide.
By the graphite oxide powder ultrasonic disperse of drying in water, be mixed with GO dispersion liquid.
2) preparation of nitrogenous precursor: be 1:(2 ~ 5 with formaldehyde by the ratio of amount of substance by melamine) mix soluble in water, heat at 50 ~ 90 DEG C, stir, obtain transparent nitrogenous precursor melmac (MR) solution;
3) by described GO dispersion liquid and described MR solution by volume (8 ~ 12): 1 mixes, and add described cobalt salt in the ratio that every gram of GO drops into (10 ~ 20) mmol cobalt salt, to stir or ultrasonic, make it form uniform dispersion; Wherein, described cobalt salt is the mixture of one or both and above arbitrary proportion in cobalt chloride, cobalt acetate, cobaltous sulfate or cobalt nitrate;
4) hydrothermal treatment consists: by described mixed dispersion liquid hydrothermal treatment consists 8 ~ 15 hours at 120 ~ 180 DEG C, precipitation and separation, washing, drying, obtain pressed powder;
5) pyrolysis: by the pyrolysis under nitrogen protection of described pressed powder, preferred pyrolysis temperature is 450 ~ 650 DEG C, and pyrolysis time is 1 ~ 2 hour, obtains nitrogen-doped graphene/cobalt composite material;
6) oxidation processes: by described nitrogen-doped graphene/cobalt composite material oxidation processes in atmosphere, preferential oxidation treatment temperature is 150 ~ 300 DEG C, oxidization time is 1 ~ 2 hour, obtains described nitrogen-doped graphene and cobaltosic oxide hollow nano-sphere composite material.
Nitrogen-doped graphene not only has higher conductivity than Graphene, and intercouples by coordination between itself and metal oxide nanoparticles, thus significantly can improve the physicochemical properties of composite material.Nitrogen-doped graphene prepared by the present invention and cobaltosic oxide nano ball composite material have hollow-core construction, the electroactive material of hollow-core construction not only has high-specific surface area, and have that avtive spot is many, the feature such as change in volume of material in available buffer charge and discharge process.
The present invention also protects the application of described nitrogen-doped graphene and cobaltosic oxide hollow nano-sphere composite material.
This nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material is preferentially used as lithium ion battery negative material.
Although Co
3o
4low to the catalytic activity of oxygen reduction reaction, but after the Graphene compound of it and Graphene or N doping, catalytic performance significantly strengthens.Therefore this nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material also can be used as oxygen reduction electro-catalyst, for fuel cell and metal-air battery.
This nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material also can be used as electrode material, for the electrochemical energy storage such as sodium-ion battery and ultracapacitor and conversion equipment.
This nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material also can be used as new catalyst, for fields such as meticulous chemicals synthesis, electrochemical sensor and biology sensors.
The present invention using melmac as cross-linking reagent by graphite oxide and Co
2+be integrated into a single precursor.In this presoma process of pyrolysis, melmac as a kind of novel nitrogenous source to graphene uniform nitrating, and fixing generated in-situ cobalt oxide, the final obtained nitrogen-doped graphene/Co with sandwich structure
3o
4nano-hollow ball composite material.This composite material has graded porous structure, and specific area is high, and avtive spot is many, electron conduction and ionic conductivity good, at new forms of energy and catalytic field, there is good application prospect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is nitrogen-doped graphene/Co of the present invention
3o
4the SEM figure of hollow nano-sphere composite material;
Fig. 2 is nitrogen-doped graphene/Co of the present invention
3o
4the TEM figure of hollow nano-sphere composite material;
Fig. 3 is nitrogen-doped graphene/Co of the present invention
3o
4the XRD figure of hollow nano-sphere composite material;
Fig. 4 is nitrogen-doped graphene/Co of the present invention
3o
4the N1s high-resolution XPS of hollow nano-sphere composite material schemes;
Fig. 5 is nitrogen-doped graphene/Co of the present invention
3o
4the TG figure of hollow nano-sphere composite material;
Fig. 6 is nitrogen-doped graphene/Co of the present invention
3o
4n2 adsorption/the desorption curve of hollow nano-sphere composite material;
Fig. 7 is nitrogen-doped graphene/Co of the present invention
3o
4the graph of pore diameter distribution of hollow nano-sphere composite material;
Fig. 8 is described nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material is as the charge-discharge performance of lithium cell negative pole material under 0.1C current density;
Fig. 9 is described nitrogen-doped graphene/Co
3o
4the charge-discharge performance of hollow nano-sphere composite material under different current density;
Figure 10 is described nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material is at N
2, O
2cV curve in saturated 0.1M KOH solution;
Figure 11 is nitrogen-doped graphene/Co of the present invention
3o
4hollow nano-sphere composite material is at O
2lSV figure in saturated 0.1MKOH solution;
Figure 12 is nitrogen-doped graphene/Co of the present invention
3o
4hollow nano-sphere composite material is at O
2electron transfer number under different potentials in saturated 0.1MKOH solution;
Figure 13 is nitrogen-doped graphene/Co of the present invention
3o
4the catalytic stability of hollow nano-sphere composite material and commodity Pt/C.
Embodiment
Embodiment 1:
Prepare nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material
1) preparation of graphite oxide (GO) dispersion liquid: 2g aquadag and 1g sodium nitrate are added in the concentrated sulfuric acid that 46mL cools through ice bath, gradation slowly adds 6g potassium permanganate, constantly stirs, and keeps temperature of reaction system lower than 20 DEG C.Subsequently temperature is increased to about 35 DEG C, continues to stir 20h.Add 92mL deionized water, temperature of reaction system raises rapidly.Stir after 30min, add the dilution of 142mL deionized water, and add 6mL hydrogen peroxide (30%) and obtain yellow dispersion liquid.Suction filtration, with watery hydrochloric acid (3.5%) washing extremely without SO
4 2-, then spending deionized water to neutral, at gained is deposited in 45 DEG C, namely vacuumize 24h obtains graphite oxide.By obtained graphite oxide ultrasonic disperse in water, be mixed with 2mg mL
-1graphite oxide dispersion is for subsequent use.
2) preparation of nitrogenous precursor melmac (MR): 1 gram of melamine and 1.8mL formaldehyde (37wt%) are added 10mL H
2in O, stir, at 80 DEG C, heating obtains transparent MR solution for 10 minutes;
3) GO and MR, cobalt salt solution Homogeneous phase mixing: to 20mL GO aqueous dispersions (2mg mL
-1) in add 3mL MR and 1mmol Co
2+salt (cobalt chloride, cobalt acetate, cobaltous sulfate or cobalt nitrate), fully stirs, and forms uniform dispersion;
4) hydrothermal treatment consists: above-mentioned mixed dispersion liquid is placed in reactor, react 8 ~ 15 hours at 120 ~ 180 DEG C, precipitation and separation, washing, drying, obtain pressed powder;
5) pyrolysis: by above-mentioned pressed powder under nitrogen protection in 450 ~ 650 DEG C of pyrolysis 1 ~ 2 hour, obtain N doping graphite/cobalt composite material;
6) oxidation processes: by above-mentioned N doping graphite/cobalt composite material in atmosphere in 150 ~ 300 DEG C of oxidations 1 ~ 2 hour, obtain described nitrogen-doped graphene and cobaltosic oxide hollow nano-sphere composite material.
Nitrogen-doped graphene/the Co of preparation
3o
4hollow nano-sphere composite material microstructure characterized by ESEM (SEM is shown in Fig. 1) and transmission electron microscope (TEM is shown in Fig. 2).Fig. 1 shows the sandwich lamellar structure that this composite material is porous; Fig. 2 shows Co
3o
4hollow nano-sphere is uniformly distributed in ultra-thin N doping graphite nano plate surface.
Nitrogen-doped graphene/Co of the present invention
3o
4the composition of hollow nano-sphere composite material and surface chemistry are characterized by x-ray diffractometer (XRD is shown in Fig. 3) and x-ray photoelectron spectroscopy (XPS is shown in Fig. 4).Fig. 3 shows Co in composite material
3o
4effectively prevent the stacking again of nitrogen-doped graphene; Fig. 4 is nitrogen-doped graphene/Co
3o
4the N1s high-resolution XPS of hollow nano-sphere composite material schemes, and shows nitrogen-atoms and embeds equably in graphene carbon skeleton with pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen three kinds of forms.Fig. 5 is Co in composite material
3o
4content by thermogravimetric analyzer (TG) quantitative assay, as shown in Figure 5, the Graphene of N doping and Co
3o
4content be respectively 27.5 and 72.5wt%.The specific area of composite material and pore-size distribution N2 adsorption ratio surface area instrument (BET) are tested.Fig. 6 and Fig. 7 is described nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material N2 adsorption/desorption curve and graph of pore diameter distribution, not only illustrate that composite material has higher specific area, also illustrate that in material exist a large amount of mesoporous.
Embodiment 2:
Nitrogen-doped graphene/Co of the present invention
3o
4the lithium electric performance test of hollow nano-sphere composite material.
1) preparation of electrode slice
By nitrogen-doped graphene/Co
3o
4hollow nano-sphere composite material, conductive black and Kynoar (PVDF) are 80:10:10 mixing in mass ratio, and add 1-METHYLPYRROLIDONE, furnishing slurry, is spread evenly across Copper Foil, dries, makes electrode slice.
2) battery assembling
With the positive pole that above-mentioned electrode slice is half-cell, lithium sheet is negative pole, and Celgard-2400 perforated membrane is barrier film, 1molL
-1liPF
6ethylene carbonate: dimethyl carbonate (volume ratio 1:1) is electrolyte, is assembled into CR2032 type button cell in the glove box being full of argon gas.
3) battery performance test
Adopt Neware BTS cell tester to carry out constant current charge-discharge test (see Fig. 8), cut-ff voltage scope is 0.005 ~ 2.5V.With CHI 760D electrochemical workstation (Shanghai Chen Hua instrument company) test loop volt-ampere curve, (CV, voltage scan range is 0.005 ~ 2.5V, and sweep speed is 0.1mVs
-1), see Fig. 9.Illustrate that this composite material has good high rate performance.
Embodiment 3:
Nitrogen-doped graphene/Co of the present invention
3o
4the electrocatalysis characteristic test of hollow nano-sphere composite material.
1) preparation of work electrode
Chamois leather is polished to minute surface with the glass-carbon electrode that diameter is 3mm by aluminium oxide powder, uses ethanol and deionized water ultrasonic cleaning 5min successively, naturally dry stand-by.By nitrogen-doped graphene/Co described in 1mg embodiment 2
3o
4hollow nano-sphere composite material or commodity Pt/C catalyst ultrasonic disperse are in the ethanolic solution (Nafion concentration is 0.05%) of 0.5mLNafion.Dripped by 5 μ L catalyst dispersion and be applied to preprepared glassy carbon electrode surface, naturally dry obtained work electrode, its catalyst loading is 141.6 μ gcm
-2.
2) hydrogen reduction electrocatalysis characteristic test
The glass-carbon electrode modified with catalyst is for work electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, and oxygen or the saturated 0.1M KOH of nitrogen are electrolyte, form three electrode test systems.The test of hydrogen reduction catalytic performance completes on the electrochemical workstation (CHI760D) being furnished with rotating circular disk device (ATA-1B).
At-1.0 ~ 0.2V potential range build-in test cyclic voltammetric (CV) curve, sweep speed for 100mV s
-1.Figure 10 is nitrogen-doped graphene/Co of the present invention
3o
4hollow nano-sphere composite material is at N
2, O
2cV curve in saturated 0.1MKOH solution, demonstrates it and has good catalytic activity to hydrogen reduction, and its activity is not by the impact of methyl alcohol.At 0.2 ~-0.8V potential range build-in test linear sweep voltammetry (LSV) curve, sweep speed for 10mV s
-1, electrode rotating speed is 1600rpm.Testing catalytic redox LSV curve under different rotating speeds, thus the electron transfer number under obtaining different potentials.Figure 11 and Figure 12 is nitrogen-doped graphene/Co of the present invention respectively
3o
4hollow nano-sphere composite material is at O
2lSV curve (background correction capacitive current) in saturated 0.1M KOH solution and the electron transfer number under different potentials, illustrate that a spike potential of this material catalyzes hydrogen reduction is high, hydrogen reduction current density large, four electronics (4e
-) reaction path selectivity is high;
Adopt the stability (see Figure 13) of current-vs-time method (I-t) detecting catalyst.Polarization potential is-0.36V, and electrode rotating speed is 1600rpm.Show the hydrogen reduction electrocatalysis characteristic good stability of composite material in the present invention.
Above-mentioned execution mode is intended to illustrate that the present invention can be professional and technical personnel in the field and realizes or use; modifying to above-mentioned execution mode will be apparent for those skilled in the art; therefore the present invention includes but be not limited to above-mentioned execution mode; any these claims or specification of meeting describes; meet and principle disclosed herein and novelty, the method for inventive features, technique, product, all fall within protection scope of the present invention.
Claims (10)
1. nitrogen-doped graphene and a cobaltosic oxide hollow nano-sphere composite material, it is characterized in that, described composite material comprises nitrogen-doped graphene matrix, and is attached to the cobaltosic oxide hollow ball in described nitrogen-doped graphene matrix.
2. prepare a method for nitrogen-doped graphene as claimed in claim 1 and cobaltosic oxide hollow nano-sphere composite material, it is characterized in that, comprise the following steps:
1) preparation of graphite oxide dispersion: be that graphite oxide prepared by raw material with graphite, and by obtained graphite oxide ultrasonic disperse in water, be mixed with graphite oxide dispersion for subsequent use;
2) preparation of nitrogenous precursor: be that 1:2 ~ 5 are soluble in water with formaldehyde by the ratio of amount of substance by melamine, heats, stirs, obtain transparent nitrogenous precursor melmac solution at 50-90 DEG C;
3) by described graphite oxide dispersion and described melmac solution by volume 8 ~ 12:1 mix, and add described cobalt salt in the ratio that every gram of graphite oxide drops into 10 ~ 20mmol cobalt salt, to stir or ultrasonic, make it form uniform dispersion; Wherein, described cobalt salt is the mixture of one or more arbitrary proportions in cobalt chloride, cobalt acetate, cobaltous sulfate or cobalt nitrate;
4) hydrothermal treatment consists: described mixed dispersion liquid reacted 8 ~ 15 hours at 120 ~ 180 DEG C, precipitation and separation, washing, drying, obtain pressed powder;
5) pyrolysis: by the pyrolysis under nitrogen protection of described pressed powder, obtain nitrogen-doped graphene/cobalt composite material;
6) oxidation processes: by described nitrogen-doped graphene/cobalt composite material oxidation processes in atmosphere, obtains described nitrogen-doped graphene and cobaltosic oxide hollow nano-sphere composite material.
3. the preparation method of nitrogen-doped graphene according to claim 2 and cobaltosic oxide hollow nano-sphere composite material, it is characterized in that, step 1) the concrete preparation method of described graphite oxide is: graphite and sodium nitrate added in the concentrated sulfuric acid with mass ratio 2 ~ 4:1, 2 ~ 5 times are added to the potassium permanganate of described graphite quality under stirring, mix, 0.5 ~ 3h is stirred lower than 20 DEG C with ice-water bath control temperature, then raised temperature to 32 ~ 38 DEG C reaction 1 ~ 4h, the deionized water of slow dropping 35 ~ 50 times of graphite quality, stir, hydrogen peroxide cessation reaction is added when system temperature declines, suction filtration, washing, namely graphite oxide is obtained after drying.
4. the preparation method of nitrogen-doped graphene according to claim 2 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, step 5) in, described pyrolysis temperature is 450-650 DEG C, and pyrolysis time is 1 ~ 2 hour.
5. the preparation method of nitrogen-doped graphene according to claim 2 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, step 6) in, described oxidation temperature is 150 ~ 300 DEG C, and oxidization time is 1 ~ 2 hour.
6. the application of nitrogen-doped graphene as claimed in claim 1 and cobaltosic oxide hollow nano-sphere composite material.
7. the application of nitrogen-doped graphene according to claim 6 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, described composite material is used as electrode material.
8. the application of nitrogen-doped graphene according to claim 7 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, described electrode material is used for lithium ion battery, sodium-ion battery or ultracapacitor.
9. the application of nitrogen-doped graphene according to claim 6 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, described composite material is used as catalyst.
10. the application of nitrogen-doped graphene according to claim 9 and cobaltosic oxide hollow nano-sphere composite material, is characterized in that, described catalyst is oxygen reduction electro-catalyst, for fuel cell or metal-air battery; Described catalyst or for catalyst preparation, electrochemical sensor and biology sensor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN102602917A (en) * | 2012-03-19 | 2012-07-25 | 华南理工大学 | Preparation method of nitrogen doped graphene/ metal oxide nanometer composite material |
| KR101466310B1 (en) * | 2013-09-09 | 2014-11-27 | 아주대학교산학협력단 | Manufacturing method of metal oxide/graphene nanocomposites and electrode manufacturing method of metal oxide/graphene nanocomposites |
-
2015
- 2015-01-23 CN CN201510036178.6A patent/CN104681823B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN102602917A (en) * | 2012-03-19 | 2012-07-25 | 华南理工大学 | Preparation method of nitrogen doped graphene/ metal oxide nanometer composite material |
| KR101466310B1 (en) * | 2013-09-09 | 2014-11-27 | 아주대학교산학협력단 | Manufacturing method of metal oxide/graphene nanocomposites and electrode manufacturing method of metal oxide/graphene nanocomposites |
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