CN113548655A - Preparation method of high-oxygen-content carbon black dispersion liquid and carbon black loaded iron oxide - Google Patents
Preparation method of high-oxygen-content carbon black dispersion liquid and carbon black loaded iron oxide Download PDFInfo
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- CN113548655A CN113548655A CN202110828257.6A CN202110828257A CN113548655A CN 113548655 A CN113548655 A CN 113548655A CN 202110828257 A CN202110828257 A CN 202110828257A CN 113548655 A CN113548655 A CN 113548655A
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- carbon black
- oxygen
- iron oxide
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- 239000006229 carbon black Substances 0.000 title claims abstract description 210
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000006185 dispersion Substances 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 121
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 121
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000002798 polar solvent Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 21
- 230000004580 weight loss Effects 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 241000872198 Serjania polyphylla Species 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- -1 iron oxide compound Chemical class 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- MAQAUGBCWORAAB-UHFFFAOYSA-N [C+4].[O-2].[Fe+2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Fe+2].[O-2].[O-2] MAQAUGBCWORAAB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention belongs to the technical field of carbon material modification, and discloses a method for preparing a high-oxygen-content carbon black dispersion liquid and an iron oxide-carbon black composite material, which is simple, efficient, safe and suitable for large-scale preparation. The carbon black is subjected to heat treatment in an oxygen-containing atmosphere with a certain flow rate at a certain heating rate, so that a large number of oxygen-containing groups are attached to the carbon black, then the carbon black is dispersed in a polar solvent to prepare a high-oxygen-containing carbon black dispersion liquid, and an iron oxide precursor is attached to the surface of the carbon black through electrostatic acting force between the oxygen-containing groups attached to the carbon black and the iron oxide precursor, so that the iron oxide precursor is converted into the iron oxide, and the carbon black iron-loaded compound is prepared. The carbon black dispersion liquid with high oxygen content can uniformly and stably exist, does not settle for a long time, and the iron oxide is uniformly attached to the surface of the carbon black in the form of nano particles. The invention avoids the use of corrosive strong acid and strong oxidizer; the compound has wide application potential in the fields of electromagnetic compatibility, lithium ion batteries, medicines and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation, relates to a technical process of a carbon material composite, and particularly relates to a preparation process and a method of a carbon black and iron oxide composite material.
Background
The carbon black is produced by incomplete combustion or cracking of many hydrocarbon substances (solid, liquid or gaseous), and the main component of the carbon black is carbon element, and in addition, the carbon black also contains 0.1-10 wt.% of oxygen, 0.2-1.0 wt.% of hydrogen, 0.01-0.2 wt.% of sulfur and other impurities. Carbon black has been widely used in rubber fillers, printing inks, coatings, paints, paper, chemicals, and the like. The consumption of carbon black in the rubber industry amounts to 94% of the total, of which 60% is used for the manufacture of tires. Carbon black is used as a filler in particular for the filling and reinforcement of rubbers. The addition of the carbon black enables the rubber product to reduce vibration and noise. In addition, the function can increase the toughness of the material, improve the capability of resisting external force damage, increase the gripping force of the tire on the road surface and greatly promote the development of the automobile industry. Among the functional groups on the surface of carbon black, the oxygen-containing functional group has the most significant influence on the surface properties of carbon black. The oxygen-containing groups on the surface of the carbon black can promote better dispersion in a medium, and the oxygen-containing groups are very important for the reinforcing effect of the nearly saturated elastomer such as butyl rubber. Chinese patent CN 110964349a discloses an oxidation modified carbon black and a preparation method thereof, wherein heteropoly acid is introduced into a hydrogen peroxide oxidation system, so that the oxidation capacity and efficiency of an oxidant are improved, the oxygen content of carbon black is increased from 0.1-2 wt.% to 5-20 wt.% after liquid phase heating and stirring reaction, and the dispersibility and stability of carbon black particles in an aqueous system are improved. Chinese patent CN 111423641a discloses that carbon black is treated with concentrated acid, potassium permanganate and hydrogen peroxide to finally prepare carbon black slurry, carbon black with attached hydroxyl and carboxyl is obtained by centrifugal washing, and modified carbon black is dispersed in water and mixed with styrene butadiene latex to finally prepare the highly dispersed carbon black/rubber nanocomposite. There are also many reports on the use of carbon black in the preparation of composites after attachment of oxygen-containing groups. Chinese patent CN 109908887B discloses a method for preparing carbon black attached with oxygen-containing groups by using 98% concentrated sulfuric acid and potassium permanganate as oxidants through an improved Hummer's method, then using bismuth nitrate pentahydrate as a precursor of bismuth, using ethylene glycol or glycerol as a reducing agent, and preparing the carbon black through hydrothermal reactionA micro-oxidation conductive carbon black supported metal bismuth catalyst is prepared. The iron oxide has low price, high storage capacity, environmental protection and electromagnetic wave absorption function, and the carbon black loaded iron oxide composite material can be used in the fields of antistatic materials, conductive materials, rubber heat-resistant materials, electromagnetic wave shielding and the like. Chinese patent CN 110614028A discloses carbon black-superparamagnetic Fe3O4A method for preparing a nanocomposite. The method is to use concentrated nitric acid to modify carbon black, and specifically comprises the steps of ultrasonically dispersing the carbon black in the concentrated nitric acid, enabling the carbon black to be attached with hydrophilic groups through hydrothermal reaction, then adding trivalent and divalent iron salts into modified carbon black dispersion liquid, taking polyacrylic acid as a stabilizing agent, and preparing the carbon black-superparamagnetic Fe through a coprecipitation method3O4A nanocomposite material.
However, the method uses corrosive strong acid and strong oxidizer when preparing the carbon black attached with the oxygen-containing group, has high risk coefficient, great harm to the environment, is not beneficial to large-scale preparation, and has complex preparation process. Therefore, it has been expensive to attach the oxygen-containing groups to the carbon black by a convenient method, obtain a uniform dispersion, and successfully use the dispersion for the preparation of a composite material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and seek to design a simple, efficient and safe method for preparing high-oxygen-content carbon black dispersion and an iron oxide-carbon black composite material on a large scale. The carbon black is subjected to heat treatment in an oxygen-containing atmosphere with a certain flow rate at a certain heating rate, so that a large number of oxygen-containing groups are attached to the carbon black, then the carbon black is dispersed in a polar solvent to prepare a high-oxygen-containing carbon black dispersion liquid, and an iron oxide precursor is attached to the surface of the carbon black through electrostatic acting force between the oxygen-containing groups attached to the carbon black and the iron oxide precursor, so that the iron oxide precursor is converted into the iron oxide, and the carbon black iron-loaded compound is prepared.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing carbon black-supported iron oxide, the method comprising the steps of:
(1) determination of the initial temperature of the reaction of carbon black with oxygen: firstly, performing thermogravimetric test on carbon black in an oxygen atmosphere at a certain heating rate to determine the initial weight loss temperature of the carbon black;
(2) attaching oxygen-containing groups to the surface of carbon black: putting a certain mass of carbon black into a high-temperature furnace, introducing a small flow of oxygen-containing atmosphere, raising the temperature to be at or above the initial weight loss temperature at a certain temperature rise rate, and carrying out heat treatment at the temperature for a certain time to ensure that a large amount of oxygen-containing groups are attached to the carbon black;
(3) preparation of carbon black dispersion liquid to which oxygen-containing group is attached: weighing a certain amount of carbon black, adding the carbon black into a polar solvent, and dispersing the carbon black in the polar solvent by ultrasonic to obtain a carbon black dispersion liquid with high oxygen content;
(4) preparation of carbon black loaded iron oxide with attached oxygen-containing group: adding an iron oxide precursor into the carbon black dispersion liquid attached with the oxygen-containing group, adsorbing the iron oxide precursor on the surface of the carbon black by utilizing the electrostatic adsorption effect between the oxygen-containing functional group and the iron oxide precursor, then adding an auxiliary agent into the carbon black, and preparing a carbon black loaded iron oxide compound by a liquid phase method;
(5) according to the requirements of the reduction degree of the carbon black and the crystallinity of the iron oxide in the prepared target product, the subsequent calcination in the inert atmosphere further reduces the carbon black, so that the conductivity of the composite material is improved, the crystallinity of the iron oxide is improved, and the composite material of the carbon black loaded with the iron oxide is obtained.
In a second aspect, the present invention provides a carbon black iron oxide-loaded composite material prepared by the above method.
The third aspect of the invention also provides a preparation method of the carbon black dispersion liquid with high oxygen content.
Through the technical scheme, the invention has the following beneficial effects:
the oxygen-containing group attached to the carbon black is obtained by a specific heat treatment in an oxygen-containing atmosphere, and the oxygen exists in a form mainly including a carbon-oxygen double bond connecting aromatic carbons, a carbon-oxygen single bond connecting aliphatic carbons, and a carbon-oxygen single bond connecting aromatic carbons. Further, the oxygen content in the carbon black is greatly improved through heat treatment, and the mass fraction of oxygen in the carbon black attached with oxygen-containing groups reaches more than 35.0 wt.%, and can reach 40-50 wt.%. The carbon black dispersion liquid with high oxygen content can exist uniformly and stably and does not settle for a long time.
The oxygen-containing groups on the surface of the carbon black help to load the iron oxide, and the iron oxide is uniformly attached on the surface of the carbon black in the form of nanoparticles, and the content of the attached iron oxide is up to 60 wt.%.
In addition, the method has simple, safe and environment-friendly process, is suitable for large-scale preparation, and avoids the use of corrosive strong acid and strong oxidant; the high-oxygen-content carbon black loaded iron oxide compound prepared by the invention has wide application potential in the fields of electromagnetic compatibility, lithium ion batteries, medicines and the like.
Description of the drawings:
FIG. 1 is a thermogravimetric plot of a conductive carbon black feedstock used in example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) chart of an oxygen-containing group-attached carbon black prepared in example 1 of the present invention and a raw material of the carbon black;
FIG. 3 is an XPS plot of O1s for oxygen containing group attached carbon black prepared in example 1 of the present invention;
FIG. 4 shows N of carbon black having oxygen-containing groups attached thereto prepared in example 1 of the present invention and its raw material2Adsorption and desorption graphs;
FIG. 5 is a graph showing the pore size distribution of the oxygen-containing group-attached carbon black prepared in example 1 of the present invention;
FIG. 6 is a photograph of the oxygen-containing group-attached carbon black prepared in example 1 of the present invention, uniformly dispersed in water (2mg/mL) for 3 months;
FIG. 7 shows Fe supported carbon black prepared in example 1 of the present invention2O3A Transmission Electron Microscope (TEM) image of (a);
FIG. 8 shows Fe supported carbon black prepared in example 1 of the present invention2O3X-ray diffractometer (XRD) pattern of (a);
FIG. 9 shows Fe loading of heat-treated carbon black prepared in example 1 of the present invention2O3Thermogravimetric plot of;
FIG. 10 shows Fe loading of carbon black prepared in example 2 of the present invention3O4XRD pattern of (a);
FIG. 11 shows Fe supported carbon black prepared in example 2 of the present invention3O4A TEM image of (B);
FIG. 12 shows N of the carbon black having oxygen-containing groups attached thereto prepared in example 3 of the present invention and a raw material therefor2Adsorption and desorption profiles.
The specific implementation mode is as follows:
the following examples further illustrate the details of the present invention.
The invention provides a preparation method of carbon black loaded iron oxide, which comprises the following steps:
the carbon black is subjected to heat treatment in an oxygen-containing atmosphere to increase a large number of oxygen-containing groups on the surface of the carbon black, so that uniform and stable dispersion liquid can be prepared, an iron oxide precursor is attached to the surface of the carbon black through the electrostatic interaction between the oxygen-containing groups and the iron oxide precursor, and the iron oxide precursor is further converted into the iron oxide in situ through a liquid phase method to prepare the carbon black loaded iron oxide composite material.
In the invention, the oxygen-containing atmosphere can be oxygen, air, or oxygen or a mixed gas of air and inert gas, and the heat treatment conditions are as follows: the flow rate of the oxygen-containing atmosphere is 0-5 mL/min, the temperature is raised to the initial weight loss temperature to be higher than the initial weight loss temperature by at most 100 ℃ at the temperature rise rate of 1-10 ℃/min, and the temperature is maintained for 0.1-5 h, preferably the heat treatment maintenance time is 1.5-3 h.
In the present invention, the inventors have studied and found that the oxygen-containing groups attached to the carbon black are obtained by heat treatment in an oxygen-containing atmosphere, the heat treatment is performed in an oxygen-containing atmosphere having a small flow rate in order to control the concentration of oxygen reacted in the oxygen-containing atmosphere and thereby control the reaction rate of the carbon black and oxygen, and the flow rate is 0 based on the volume of the oxygen-containing atmosphere contained in the furnace chamber; the heat treatment temperature is judged according to the initial weight loss temperature of the carbon black raw material, the heat treatment temperature is controlled to be the initial weight loss temperature which is at most 100 ℃ higher than the initial weight loss temperature, and the reaction of the carbon black and oxygen can be ensured and the reaction rate of the carbon black and the oxygen can be limited at the temperature; the heat treatment maintaining time is 0.1-5 h, the oxygen content of the carbon black is easy to be low when the time is too short, and the carbon black is difficult to keep a complete skeleton structure when the time is too long.
Further, the oxygen content in the carbon black can be greatly improved through heat treatment, and the mass fraction of oxygen in the carbon black attached with oxygen-containing groups reaches more than 35.0 wt.%, and can reach 40-50 wt.%. The oxygen exists in a form mainly including a carbon-oxygen double bond connecting aromatic carbons, a carbon-oxygen single bond connecting aliphatic carbons, and a carbon-oxygen single bond connecting aromatic carbons.
In the invention, the carbon black can be treated in a batch in a laboratory to reach 1kg, the oxygen content can be efficiently improved, and the method has the potential of large-scale commercial production.
Further, carbon black to which an oxygen-containing group is attached is added to a polar solvent, and is dispersed therein by ultrasonic waves, to obtain a carbon black dispersion liquid with high oxygen content. The high-oxygen-content carbon black dispersion can exist uniformly and stably and does not settle for a long time.
The polar solvent is one of water, N-dimethylformamide and N-methylpyrrolidone, the ultrasonic power is 300-1000W, and the ultrasonic dispersion time is 30-100 min;
the dosage ratio of the carbon black attached with the oxygen-containing group to the polar solvent is 30-60 mg: 20-70 mL.
In the present invention, the iron oxide precursor is selected from Fe (OH)3Sol, ferric nitrate, ferric acetate, FeCl3、FeCl2One or a mixture of two of them;
the dosage ratio of the carbon black attached with the oxygen-containing group to the iron oxide precursor is 30-60 mg: 30-200 mg.
According to the invention, the iron oxide precursor attached to the surface of the carbon black is converted in situ into iron oxide by a subsequent liquid phase method, wherein the iron oxide is Fe2O3Or Fe3O4Or a mixture of the two. The oxygen-containing groups on the surface of the carbon black help to load the iron oxide, and the iron oxide is uniformly attached on the surface of the carbon black in the form of nanoparticles, and the content of the attached iron oxide is up to 60 wt.%.
In the invention, the liquid phase method is mainly characterized in that the iron oxide precursor and ions in a liquid phase are subjected to chemical reaction under the liquid phase reaction condition of a certain temperature and finally converted into the iron oxide in situ; or the iron oxide precursor does not chemically react with ions in the liquid phase and is converted into the iron oxide in situ under the liquid phase reaction condition of a certain temperature.
According to the invention, the liquid phase method is a hydrothermal reaction or a coprecipitation reaction, the hydrothermal reaction is carried out for 10-14 h at 120-180 ℃, and the coprecipitation reaction is carried out for 2-5 min at 80 ℃.
In the invention, a reagent for adjusting the pH value of the solution, an auxiliary agent for reducing oxygen-containing groups on the surface of the carbon black and Fe are optionally added into the solution of the iron oxide precursor3+Conversion of ions to Fe2+A reducing agent for ions. The pH of the reaction solution is adjusted to be alkaline so as to provide OH needed by an intermediate of an iron oxide target product-Ions; mixing Fe3+Conversion of ions to Fe2+The ionic reducing agent will cause the iron oxide finally produced to be Fe2O3。
In the present invention, Fe is added3+Conversion of ions to Fe2+The reducing agent of the ions is selected from ascorbic acid or trisodium citrate, and the using amount of the reducing agent of the ions is 0.5-2 times of the molar amount of the iron oxide precursor; the auxiliary agent for reducing the oxygen-containing groups on the surface of the carbon black is selected from hydrazine hydrate or ethylene glycol, and the using amount of the auxiliary agent is 3-30 vol.% of the total volume of the solvent; the reagent for adjusting the pH value of the solution is selected from ammonia water, sodium hydroxide or sodium bicarbonate, and the pH value of the solution is adjusted to be about 11.
According to the requirements of the reduction degree of the carbon black and the crystallinity of the iron oxide in the prepared target product, the subsequent calcination in the inert atmosphere further reduces the carbon black, so that the conductivity of the composite material is improved, the crystallinity of the iron oxide is improved, and the composite material of the carbon black loaded with the iron oxide is obtained. The calcination temperature is 400-500 ℃, and the calcination time is 0.5-5 h.
Example 1:
(1) firstly, performing thermogravimetric test on carbon black (purity: 99%, model: XF115, manufacturer: Nanjing Xiancheng nano material science and technology Co., Ltd.) in an oxygen atmosphere to determine the initial weight loss temperature, wherein the thermogravimetric test curve is shown in figure 1, and the initial weight loss temperature of the carbon black is about 470 ℃ as can be seen from figure 1;
(2) weighing about 0.1g of the conductive carbon black, placing the conductive carbon black in a tubular furnace, introducing air at the flow rate of 0.5mL/min, heating to 475 ℃ at the heating rate of 5 ℃/min, maintaining for 3 hours, naturally cooling, and taking out to obtain carbon black loaded with a large amount of oxygen-containing groups;
it can be seen from fig. 2 that a large number of oxygen-containing functional groups are attached to the surface of the carbon black, and the mass fraction of oxygen is about 46.7 wt.% as calculated by the atomic number ratio of the carbon element, the nitrogen element and the oxygen element; while the original carbon black was also XPS tested, it can be seen from figure 2 that the oxygen content is significantly less than the treated carbon black, about 5.4 wt.%; this demonstrates that heat treatment in an air atmosphere causes carbon black to adhere a large amount of oxygen;
as can be seen from fig. 3, the oxygen-containing component in the carbon black attached with the oxygen-containing group mainly comprises a carbon-oxygen double bond connected with aromatic carbon, a carbon-oxygen single bond connected with aliphatic carbon and a carbon-oxygen single bond connected with aromatic carbon;
as can be seen from FIG. 4, the prepared carbon black having attached oxygen-containing group and N of the raw material thereof2Adsorption and desorption graphs show that the specific surface area of the carbon black attached with the oxygen-containing groups is greatly increased, and the specific surface area is 105.6m of the carbon black raw material2g-1Is increased to 773.4m2g-1；
As can be seen from FIG. 5, the pore size distribution curve of the oxygen-containing group-attached carbon black prepared, the increased specific surface area is mainly derived from micropores;
(3) weighing about 30mg of carbon black loaded with oxygen-containing groups in 15mL of ultrapure water, and performing ultrasonic dispersion for 30min to obtain an aqueous dispersion liquid in which the carbon black attached with the oxygen-containing groups is uniformly dispersed in the water, namely a high-oxygen-content carbon black dispersion liquid;
FIG. 6 is a photograph showing that the oxygen-containing group-attached carbon black prepared in example 1 of the present invention was uniformly dispersed in water for 3 months, from which it can be seen that the carbon black had very good dispersibility in water and did not undergo sedimentation even after 3 months;
(4) to the above-mentioned aqueous dispersion of carbon black having oxygen-containing groups attached thereto, 15mL of an aqueous dispersion containing about 50mg of Fe (OH) was added3Fe (OH) of colloidal particles3Adjusting the pH value of the reaction solution to about 11 by using ammonia water, and carrying out hydrothermal reaction for 12h at 180 ℃ to obtain carbon black loaded Fe2O3And (c) a complex.
Fe-loading of carbon black prepared by Transmission Electron Microscope (TEM) of FIG. 72O3As can be seen by the appearance characterization, Fe2O3The nanoparticles are clearly visible, while the part of them that is relatively light in color is carbon black.
Fe-loading of the prepared carbon black by FIG. 82O3Can be seen by the characterization of an X-ray diffractometer (XRD), the carbon black loaded nano particles are Fe2O3Position of diffraction peak and Fe2O3Corresponds one to one, and diffraction peaks at 24.1 °, 33.1 °, 35.6 °, 40.8 °, 49.5 °, 54.1 °, 57.6 °, 62.4 °, 64.0 °, 69.6 °, 71.9 °, and 75.4 ° of 2 θ respectively correspond to cubic α -Fe2O3The (012), (104), (110), (113), (024), (116), (018), (214), (300), (208), (1010), and (220) crystal planes of (a).
Fe-loading of the prepared heat-treated carbon black by FIG. 92O3The thermogravimetric test curve of the compound in an oxygen atmosphere shows that Fe2O3Loading of carbon black with Fe in heat treatment2O3The mass ratio in the composite was up to 59.8 wt.%.
Example 2:
the preparation process of this example is the same as that of example 1, except that 80mg of ascorbic acid is added to the reaction solution in step (4) to prepare a carbon black-loaded Fe oxide by a hydrothermal method3O4In which Fe3O4Is about 50 wt.%.
FIG. 10 carbon black loaded with Fe prepared by the present invention3O4The XRD pattern of (A) shows that the carbon black loaded nano particles are Fe3O4Position of diffraction peak and Fe3O4Standard of (2)The spectra correspond one to one, and the diffraction peaks at 2 θ of 30.1 °, 35.4 °, 43.1 °, 53.4 °, 56.9 ° and 62.5 ° correspond to the (220), (311), (400), (422), (511) and (440) crystal planes thereof, respectively.
FIG. 11 shows that the carbon black prepared in the present invention is loaded with Fe3O4In the TEM image of (1), wherein the darker substance is Fe3O4Nanoparticles, lighter in color, are carbon black substrates.
Example 3:
the preparation process of this example is the same as that of example 1, and a hydrothermal method is used to prepare carbon black loaded iron oxide, except that: 1) the carbon black used in this example (type: XC-72R, manufacturer: american cabot carbon black), the calcining temperature is 525 ℃, and the calcining time is 3 h; 2) adding 80mg of ascorbic acid into the reaction solution in the step (4), wherein the prepared compound is carbon black loaded Fe3O4In which Fe3O4The mass ratio of (A) is about 49 wt.%.
It is found from FIG. 12 that the specific surface area of the carbon black used in example 3 after heat treatment is from 254.2m2Per g, lift is 446.5m2/g。
Example 4:
this example is the same as example 1 except that ammonia water was not added in step (4) and 1.25mL of hydrazine hydrate was added, and the prepared composite was carbon black loaded Fe2O3In which Fe2O3Is about 59 wt.%.
Example 5:
this example is the same as example 2 except that Fe was not added in step (4)3O4Precursor Fe (OH)3Adding equal mole of FeCl3The prepared compound is carbon black loaded with Fe3O4In which Fe3O4Is about 50 wt.%.
Example 6:
the preparation process of this example is the same as that of example 2, except that: adding ammonia water, addingHydrazine hydrate, the prepared compound is carbon black loaded Fe3O4In which Fe3O4Is about 50 wt.%.
Example 7:
the preparation process of this example is the same as that of example 2, except that: loading the prepared carbon black with Fe3O4And then calcining the mixture for 2 hours at 500 ℃ under argon to enhance the reduction degree of the carbon black, thereby improving the conductivity of the composite and improving Fe3O4Crystallinity of nanoparticles, wherein Fe3O4The mass ratio of (A) is about 60 wt.%.
Example 8:
this example is the same as example 1 except that the liquid phase process used is a coprecipitation process. In the step (4), Fe is not added3O4Precursor Fe (OH)3An equimolar amount of FeCl is added in a 1:1 molar ratio3And FeCl2Heating the reaction container to 80 ℃ under stirring, adjusting the pH value of the reaction solution to about 11 by using ammonia water, continuously stirring for 3min at the temperature, and centrifuging, washing and drying to obtain the heat-treated graphene-loaded Fe3O4Composite of Fe3O4The mass ratio of (A) is about 40 wt.%.
Comparative example 1:
the difference from example 1 is that: the carbon black was not subjected to the heat treatment of the steps (1) and (2), and the oxygen content thereof was measured to be about 5.4 wt.% (see fig. 2), and the iron oxide precursor was directly attached, and only a small amount of Fe was loaded3O4And (3) nanoparticles.
Comparative example 2:
the difference from example 1 is that: heat-treating carbon black at 600 deg.C for 0.5h, the oxygen content in the carbon black after heat treatment is only about 6 wt.%, and part of the carbon black is collapsed and loaded with Fe3O4The content of nanoparticles is around 10 wt.%, which cannot form a payload.
Claims (10)
1. A method for preparing carbon black loaded iron oxide, characterized in that the method comprises the following steps:
(1) determination of the initial temperature of the reaction of carbon black with oxygen: firstly, performing thermogravimetric test on carbon black in an oxygen atmosphere at a heating rate of 5-10 ℃/min, and determining the initial weight loss temperature of the carbon black;
(2) attaching oxygen-containing groups to the surface of carbon black: putting a certain mass of carbon black into a high-temperature furnace, introducing a small flow of oxygen-containing atmosphere, raising the temperature to be at or above the initial weight loss temperature at a certain temperature rise rate, and carrying out heat treatment at the temperature for a certain time to ensure that a large amount of oxygen-containing groups are attached to the carbon black;
(3) preparation of carbon black dispersion liquid to which oxygen-containing group is attached: weighing a certain amount of carbon black, adding the carbon black into a polar solvent, and dispersing the carbon black in the polar solvent by ultrasonic to obtain a carbon black dispersion liquid with high oxygen content;
(4) preparation of carbon black loaded iron oxide with attached oxygen-containing group: adding an iron oxide precursor into the carbon black dispersion liquid attached with the oxygen-containing group, adsorbing the iron oxide precursor on the surface of the carbon black by utilizing the electrostatic adsorption effect between the oxygen-containing functional group and the iron oxide precursor, then adding an auxiliary agent into the carbon black, and preparing the carbon black loaded iron oxide compound by a liquid phase method.
2. The method of claim 1, wherein the oxygen-containing atmosphere is oxygen, air, oxygen or a mixture of air and an inert gas, and the heat treatment conditions are as follows: the flow rate of the oxygen-containing atmosphere is 0-5 mL/min, the temperature is increased to the initial weight loss temperature to be higher than the initial weight loss temperature by at most 100 ℃ at the heating rate of 1-10 ℃/min, and the temperature is maintained for 0.1-5 h.
3. The method for preparing carbon black supported iron oxide according to claim 1, wherein the mass fraction of oxygen in the carbon black attached with oxygen-containing groups is up to 35.0 wt.% or more, and can be up to 40-50 wt.%;
the oxygen exists in a form mainly including a carbon-oxygen double bond connecting aromatic carbons, a carbon-oxygen single bond connecting aliphatic carbons, and a carbon-oxygen single bond connecting aromatic carbons.
4. The method for preparing carbon black supported iron oxide according to claim 1, wherein the polar solvent is one of water, N-dimethylformamide and N-methylpyrrolidone;
the ultrasonic power is 300-1000W, and the ultrasonic dispersion time is 30-100 min;
the dosage ratio of the carbon black attached with the oxygen-containing group to the polar solvent is 30-60 mg: 20-70 mL.
5. The method of claim 1, wherein the iron oxide precursor is selected from the group consisting of Fe (OH)3Sol, ferric nitrate, ferric acetate, FeCl3、FeCl2One or a mixture of two of them;
the dosage ratio of the carbon black attached with the oxygen-containing group to the iron oxide precursor is 30-60 mg: 30-200 mg.
6. The method for preparing carbon black loaded iron oxide according to claim 1, wherein the liquid phase method is hydrothermal reaction or coprecipitation reaction, the hydrothermal reaction is carried out for 10-14 h at 120-180 ℃, and the coprecipitation reaction is carried out for 2-5 min at 80 ℃.
7. The method for preparing carbon black loaded iron oxide as claimed in claim 1, wherein an auxiliary agent is optionally added to the solution of the iron oxide precursor, wherein the auxiliary agent comprises an agent for adjusting the pH value of the solution, an auxiliary agent for reducing oxygen-containing groups on the surface of carbon black and an agent for reducing Fe3+Conversion of ions to Fe2+One or more ionic reducing agents;
said Fe3+Conversion of ions to Fe2+The reducing agent of the ions is selected from ascorbic acid or trisodium citrate, and the using amount of the reducing agent of the ions is 0.5-2 times of the molar amount of the iron oxide precursor;
the auxiliary agent for reducing the oxygen-containing groups on the surface of the carbon black is selected from hydrazine hydrate or ethylene glycol, and the using amount of the auxiliary agent is 3-30 vol.% of the total volume of the solvent;
the reagent for adjusting the pH value of the solution is selected from ammonia water, sodium hydroxide or sodium bicarbonate, and the pH value of the solution is adjusted to be about 11.
8. The method for preparing carbon black-loaded iron oxide according to claim 1, further comprising the step (5): according to the requirements of the reduction degree of the carbon black and the crystallinity of the iron oxide in the prepared target product, the subsequent calcination in the inert atmosphere further reduces the carbon black so as to improve the conductivity of the composite material and the crystallinity of the iron oxide, and the composite material of the carbon black loaded with the iron oxide is obtained;
the calcination temperature is 400-500 ℃, and the calcination time is 0.5-5 h.
9. The carbon black-loaded iron oxide composite material produced by the method of any one of claims 1 to 8, wherein the iron oxide is Fe2O3Or Fe3O4Or a mixture of the two; the iron oxide is uniformly attached on the surface of the carbon black in the form of nano particles, and the content of the attached iron oxide is up to 60 wt.%.
10. A method for preparing a high oxygen containing carbon black dispersion, comprising the steps of:
(1) determination of the initial temperature of the reaction of carbon black with oxygen: firstly, performing thermogravimetric test on carbon black in an oxygen atmosphere at a heating rate of 5-10 ℃/min, and determining the initial weight loss temperature of the carbon black;
(2) attaching oxygen-containing groups to the surface of carbon black: putting carbon black with a certain mass into a high-temperature furnace, introducing oxygen-containing atmosphere with a small flow of 0-5 mL/min, heating to the initial weight loss temperature to be higher than the initial weight loss temperature by at most 100 ℃ at a heating rate of 1-10 ℃/min, and maintaining for 0.1-5 h to attach a large amount of oxygen-containing groups to the carbon black;
(3) preparation of carbon black dispersion liquid to which oxygen-containing group is attached: weighing a certain amount of carbon black, adding the carbon black into a polar solvent, and dispersing the carbon black in the polar solvent by ultrasonic to obtain a carbon black dispersion liquid with high oxygen content;
the polar solvent is one of water, N-dimethylformamide and N-methylpyrrolidone, the ultrasonic power is 300-1000W, and the ultrasonic dispersion time is 30-100 min;
the dosage ratio of the carbon black attached with the oxygen-containing group to the polar solvent is 30-60 mg: 20-70 mL.
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