CN116443863A - 一种石墨化多级孔石墨烯及其制备方法和应用 - Google Patents
一种石墨化多级孔石墨烯及其制备方法和应用 Download PDFInfo
- Publication number
- CN116443863A CN116443863A CN202310461559.3A CN202310461559A CN116443863A CN 116443863 A CN116443863 A CN 116443863A CN 202310461559 A CN202310461559 A CN 202310461559A CN 116443863 A CN116443863 A CN 116443863A
- Authority
- CN
- China
- Prior art keywords
- graphitized
- fatty acid
- transition metal
- hierarchical
- preserving heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 fatty acid salt Chemical class 0.000 claims abstract description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 25
- 239000000194 fatty acid Substances 0.000 claims abstract description 25
- 229930195729 fatty acid Natural products 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 239000000295 fuel oil Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 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 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium 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
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000005087 graphitization Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种石墨化多级孔石墨烯的制备方法，将脂肪酸盐、过渡金属盐、模板前驱体加入到非极性溶剂中，混匀后加热至110‑180℃，保温5‑24h后冷却至室温，过滤并加入水，在190‑280℃下保温反应，结束后冷却，依次过滤、洗涤、干燥，得到油溶性过渡金属‑模板剂复合物，将其与重油残渣混匀，在氩气氛围下升温至500‑900℃，保温0.5‑3h后升温至900‑1600℃，保温0.5‑1h，最后冷却、洗涤、干燥，即得。与传统石墨化多孔碳的制备相比，该方法大大降低石墨化所需温度，节约能源，且程序简单。本发明制备的石墨烯具有多级孔结构，石墨化程度高，具有高导电率和比表面积，特别适合用作电容器电极材料。
Description
技术领域
本发明涉及一种石墨化多级孔石墨烯及其制备方法和应用，属于石墨烯材料技术领域。
背景技术
现有的电容器电极材料主要以碳材料为主，但商业生物质和煤基碳由于难以控制孔结构和较差的导电性，不能满足当下电容器的需求。一般是采用碳化-活化提高碳材料的比表面积，但具有程序繁琐、产率低、成本高、性能一般的缺点，不适合批量制备及商业化使用。
多孔石墨烯是一种新开发的碳材料，其具有良好的导电性，并具有多孔结构，比表面积相对较高。现有的多孔石墨烯的制备中，造孔主要依靠强酸(硫酸、氢氟酸)、强碱(氢氧化钾、氢氧化钠)等的活化作用，成本高，程序繁琐，石墨化温度在2000℃以上，存在制备成本高、产率低的问题，且难以平衡能量密度和功率密度，不适合批量制备使用。
围绕国家能源需求，我国传统能源需寻找新的低碳清洁利用模式。新能源开发利用快速发展并逐渐取代部分传统不可再生能源，因而对炭材料的需求量急剧上升，由于受到来源、转化技术和造孔工艺等限制，导致高品质活性炭成本较高，甚至需要依赖外国进口。重油残渣(例如减压渣油、油浆、煤焦油、沥青等)碳氢比较高且灰分较低，是大规模经济生产碳质材料的理想来源，将重油残渣从粗放式的利用模式向高值化低碳利用方式转变，有望进一步推进新能源材料的发展。
发明内容
本发明的目的在于解决现有技术的不足，提供一种石墨化多级孔石墨烯的制备方法，该方法以重油残渣为碳源，通过引入石墨化催化剂，原位制得石墨化多级孔石墨烯，制得的石墨化多级孔石墨烯具有孔结构丰富、比表面积大、导电率高的优点，并且制备方法简单，可低成本批量制备。
技术方案
一种石墨化多级孔石墨烯的制备方法，包括如下步骤：
(1)将脂肪酸盐、过渡金属盐、模板前驱体加入到非极性溶剂中，混合均匀后，加热至110-180℃，保温5-24h，然后冷却至室温，过滤后加入水，在190-280℃下保温反应，反应结束后冷却至室温，接着依次过滤、洗涤、干燥，得到油溶性过渡金属-模板剂复合物；
(2)将重油残渣与油溶性过渡金属-模板剂复合物混合均匀，然后在氩气氛围下升温至500-900℃，保温0.5-3h，接着升温至900-1600℃，保温0.5-1h，最后冷却至室温，洗涤后，干燥，得到石墨化多级孔石墨烯。
进一步，步骤(1)中，所述脂肪酸盐选自脂肪酸钾、脂肪酸钠、脂肪酸铵、脂肪酸锌、脂肪酸镁、脂肪酸钙、脂肪酸铜、脂肪酸铁中的一种或两种以上任意比例的组合物
进一步，步骤(1)中，所述过渡金属盐选自氯化铁、硫酸铁、硝酸铁、氯化镍、硝酸镍、硫酸镍、高锰酸钾、锰酸钾、氯化钴、硫酸钴或硝酸钴中的一种或两种以上任意比例的组合物。
进一步，步骤(1)中，所述模板前驱体选自氯化镁、硝酸镁、硫酸镁、氯化铝、硝酸铝中的一种或两种以上任意比例的组合物。
进一步，步骤(1)中，所述非极性溶剂选自四氯化碳、己烷、异辛烷或甲苯中的任意一种。更优选为四氯化碳。
进一步，步骤(1)中，所述脂肪酸盐、过渡金属盐和模板前驱体的质量比为(2-4)：(2-4)：3。
进一步，步骤(1)中，所述干燥温度为80-120℃，时间为8-24h。
进一步，步骤(2)中，所述重油残渣与油溶性过渡金属-模板剂复合物的质量比为1:5～5:1。
上述方法制备的石墨化多级孔石墨烯作为电容器电极材料的应用。
本发明的有益效果：
本发明提供了一种石墨化多级孔石墨烯的制备方法，与传统石墨化多孔碳的制备相比，该方法大大降低石墨化所需温度，节约能源，且石墨化与造孔同步完成，程序简单；与传统的氧化还原法制备的石墨烯相比，本发明提供的方法制备的石墨烯具有多级孔结构，石墨化程度高，具有高导电率和比表面积，其作为电容器电极材料具有高的能量密度、功率密度和优异的循环使用寿命，是一种理想的电容器电极材料。本发明制得的石墨化多级孔石墨烯成本低、可批量规模制备且表现出优异的电容性能，可用在新能源汽车上，进而推动石墨烯材料在新能源领域的应用。
附图说明
图1为实施例1制备的石墨化多级孔石墨烯的透射电镜照片；
图2为实施例2制备的石墨化多级孔石墨烯的透射电镜照片；
图3为实施例1制备的石墨化多级孔石墨烯的氮气吸脱附曲线；
图4为实施例1和实施例2制备的石墨化多级孔石墨烯与对比例1制备的石墨烯的电导率图；
图5为实施例1制备的石墨化多级孔石墨烯作为电极材料组装的超级电容器的循环稳定性测试图；
图6为实施例2制备的石墨化多级孔石墨烯作为电极材料组装的锂离子电容器的充放电曲线。
具体实施方式
下面结合附图和具体实施例对本发明的技术方案作清楚、完整的说明。
下述实施例中，采用的油浆来自于中石化秦皇岛炼厂，饱和酚(S)、芳香酚(A)、胶质(R)和沥青质(AT)的含量分别为31.1％、57.3％、10.1％、1.5％。
实施例1
一种石墨化多级孔石墨烯的制备方法，包括如下步骤：
(1)将20g脂肪酸钠、10g硝酸铁、10g硝酸镍、15g氯化镁加入到120mL四氯化碳中，搅拌溶解后，将溶液转移到反应釜中，再置于170℃的烘箱中保温10h，冷却到室温后，过滤，加入300mL水，超声2h后在油浴200℃下反应5h，冷却到室温后，常压过滤，用乙醇和水质量比1：1的混合液洗涤3次，得到的产物置于80℃烘箱12h，得到油溶性铁镍-氧化镁复合物；
(2)取60g油浆，加热至50℃使其具有流动性，加入100g油溶性铁镍-氧化镁复合物，混合均匀后，转入水平管式炉，通入氩气，从室温以3℃/min升至500℃并保温1h，再以1℃/min升至1000℃保温1h，自然冷却到室温，将反应产物分别用稀盐酸、醇水混合液(乙醇和水质量比1：1的混合液)洗涤3次，最后在80℃烘箱烘干，得到石墨化多级孔石墨烯。
实施例1制备的石墨化多级孔石墨烯比表面积为900m2/g，孔体积为1.7cm3/g。
实施例2
一种石墨化多级孔石墨烯的制备方法，包括如下步骤：
(1)将15g脂肪酸钠、5g硝酸铁、5g硝酸钴、15g硝酸铝加入到110mL四氯化碳中，搅拌溶解后，将溶液转移到反应釜中，再置于190℃的烘箱中保温6h，冷却到室温后，加入250mL水，在油浴210℃下反应4h，冷却到室温后，常压过滤，用乙醇和水质量比1：1的混合液洗涤3次，得到的产物置于80℃烘箱12h，得到油溶性铁钴-氧化铝复合物。
(2)取30g油浆，加热至60℃使其具有流动性，加入30g油溶性铁钴-氧化铝复合物，混合均匀后，转入水平管式炉，通入氩气，从室温以1℃/min升至600℃保温1h，再以2℃/min升至1200℃保温1h，自然冷却到室温，将反应产物分别用稀盐酸、醇水混合液(乙醇和水质量比1：1的混合液)洗涤3次，最后在80℃烘箱烘干，得到石墨化多级孔石墨烯。
实施例2制备的石墨化多级孔石墨烯比表面积为1060m2/g，孔体积为2.1cm3/g。
对比例1
传统氧化还原法制备石墨烯：
在250mL烧杯中加入1.5g鳞片石墨(300目)，0.75gNaNO3，35mL浓硫酸，冰浴2h，然后缓慢加入4.5gKMnO4，冰浴2h，缓慢加入80mL蒸馏水，转移至98℃水浴锅反应30min，加入7mL30％的双氧水，过滤，用蒸馏水洗涤3次，60℃烘箱烘干得到氧化石墨；取100mg氧化石墨加入100mL1mol/L的NaOH溶液，然后加入0.2gNaBH4，在80℃水浴锅中反应2h，冷却到室温，过滤，用蒸馏水洗涤3次，40℃烘箱烘干得到石墨烯。
该方法制备的石墨烯比表面积为180m2/g，孔体积为0.9cm3/g。
图1为实施例1制备的石墨化多级孔石墨烯的透射电镜照片，从该照片可以看到规整的边缘结构，说明石墨化程度高，表面可看到丰富的孔结构。
图2为实施例2制备的石墨化多级孔石墨烯的透射电镜照片，从该照片可以看到规整的边缘结构，说明石墨化程度高，表面可看到丰富的孔结构。
图3为实施例1制备的石墨化多级孔石墨烯的氮气脱附曲线，可以看出，该材料是具有微孔、中孔和大孔的多级孔石墨烯。
图4为实施例1和实施例2制备的石墨化多级孔石墨烯与对比例1制备的石墨烯的电导率图，从图中可以明显看出实施例1和实施例2制备的石墨化多级孔石墨烯的电导率大于对比例1传统氧化还原法制备石墨烯的电导率。
1.将实施例1制备的石墨化多级孔石墨烯、导电炭黑、聚偏氟乙烯(粘结剂PTFE)以8：1：1的比例，混合成浆料，涂覆在1cm×1cm的泡沫镍上，置于烘箱中，烘干后作为工作电极，铂片电极为对电极，饱和甘汞电极为参比电极，电解液为6mol/L的氢氧化钾水溶液，组装成超级电容器，测试其循环稳定性，结果如图5所示。
图5为实施例1制备的石墨化多级孔石墨烯作为电极材料组装的超级电容器的循环稳定性测试图，可以看出，循环20000次后，电容量仍能保持94.2％，这说明采用实施例1的石墨化多级孔石墨烯作为电极材料组装的电容器具有优异的循环稳定性能。
2.将实施例2制备的石墨化多级孔石墨烯、导电炭黑、聚偏氟乙烯(粘结剂PVDF)以7：1：2的比例混合成浆料，涂覆在铝箔上，制作成工作电极，锂片为对电极，电解液为1mol/L的LiPF6电解液(EC：EMC＝3：7，2％的VC)，组装成锂离子电容器，在工作电压为1.5V-4.5V时测试其倍率性能。测试结果见图6。
由图6可以看出，电压区间为1.5V-4.5V，在0.05A/g时的放电容量为600mAh/g，在0.1A/g时的放电容量为420mAh/g，具有优异的倍率性能。
Claims (9)
1.一种石墨化多级孔石墨烯的制备方法，其特征在于，包括如下步骤：
(1)将脂肪酸盐、过渡金属盐、模板前驱体加入到非极性溶剂中，混合均匀后，加热至110-180℃，保温5-24h，然后冷却至室温，过滤后加入水，在190-280℃下保温反应，反应结束后冷却至室温，接着依次过滤、洗涤、干燥，得到油溶性过渡金属-模板剂复合物；
(2)将重油残渣与油溶性过渡金属-模板剂复合物混合均匀，然后在氩气氛围下升温至500-900℃，保温0.5-3h，接着升温至900-1600℃，保温0.5-1h，最后冷却至室温，洗涤后，干燥，得到石墨化多级孔石墨烯；
步骤(2)中，所述重油残渣选自减压渣油、煤焦油、油浆或沥青中的一种。
2.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述脂肪酸盐选自脂肪酸钾、脂肪酸钠、脂肪酸铵、脂肪酸锌、脂肪酸镁、脂肪酸钙、脂肪酸铜、脂肪酸铁中的一种或两种以上任意比例的组合物。
3.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述过渡金属盐选自氯化铁、硫酸铁、硝酸铁、氯化镍、硝酸镍、硫酸镍、氯化铝、硝酸铝、氯化钴、硫酸钴或硝酸钴中的一种或两种以上任意比例的组合物。
4.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述模板前驱体选自氯化镁、硝酸镁、硫酸镁、氯化铝、硝酸铝中的一种或两种以上任意比例的组合物。
5.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述非极性溶剂选自四氯化碳、己烷、异辛烷或甲苯中的任意一种。
6.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述脂肪酸盐、过渡金属盐和模板前驱体的质量比为(2-4)：(2-4)：3。
7.如权利要求1所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(1)中，所述干燥温度为80℃-120℃，时间为8h-24h。
8.如权利要求1至7任一项所述石墨化多级孔石墨烯的制备方法，其特征在于，步骤(2)中，所述重油残渣与油溶性过渡金属-模板剂复合物的质量比为1:5～5:1。
9.权利要求1至8任一项所述方法制备的石墨化多级孔石墨烯作为电容器电极材料的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310461559.3A CN116443863B (zh) | 2023-04-26 | 2023-04-26 | 一种石墨化多级孔石墨烯及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310461559.3A CN116443863B (zh) | 2023-04-26 | 2023-04-26 | 一种石墨化多级孔石墨烯及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116443863A true CN116443863A (zh) | 2023-07-18 |
| CN116443863B CN116443863B (zh) | 2024-09-10 |
Family
ID=87130071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310461559.3A Active CN116443863B (zh) | 2023-04-26 | 2023-04-26 | 一种石墨化多级孔石墨烯及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116443863B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098091A (zh) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | 一种制备超级电容器用多孔石墨烯材料的方法 |
| CN106587017A (zh) * | 2016-12-14 | 2017-04-26 | 中国石油大学(北京) | 一种多孔石墨烯及其制备方法 |
| CN108002371A (zh) * | 2017-12-20 | 2018-05-08 | 中石油燃料油有限责任公司研究院 | 多孔石墨烯及其制备方法 |
| KR20180133063A (ko) * | 2017-06-05 | 2018-12-13 | 주식회사 엘지화학 | 촉매점, 이를 포함하는 양극 활물질 및 리튬-황 이차전지 |
| CN109626362A (zh) * | 2019-01-08 | 2019-04-16 | 新奥石墨烯技术有限公司 | 多孔石墨烯材料及其制备方法和超级电容器 |
| CN110265645A (zh) * | 2019-06-25 | 2019-09-20 | 郑州中科新兴产业技术研究院 | 一种沥青基碳纳米片复合负极材料、制备方法及其应用 |
-
2023
- 2023-04-26 CN CN202310461559.3A patent/CN116443863B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098091A (zh) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | 一种制备超级电容器用多孔石墨烯材料的方法 |
| CN106587017A (zh) * | 2016-12-14 | 2017-04-26 | 中国石油大学(北京) | 一种多孔石墨烯及其制备方法 |
| KR20180133063A (ko) * | 2017-06-05 | 2018-12-13 | 주식회사 엘지화학 | 촉매점, 이를 포함하는 양극 활물질 및 리튬-황 이차전지 |
| CN108002371A (zh) * | 2017-12-20 | 2018-05-08 | 中石油燃料油有限责任公司研究院 | 多孔石墨烯及其制备方法 |
| CN109626362A (zh) * | 2019-01-08 | 2019-04-16 | 新奥石墨烯技术有限公司 | 多孔石墨烯材料及其制备方法和超级电容器 |
| CN110265645A (zh) * | 2019-06-25 | 2019-09-20 | 郑州中科新兴产业技术研究院 | 一种沥青基碳纳米片复合负极材料、制备方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116443863B (zh) | 2024-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Recent advances and challenges in biomass-derived porous carbon nanomaterials for supercapacitors | |
| Wang et al. | A simple and universal method for preparing N, S co-doped biomass derived carbon with superior performance in supercapacitors | |
| WO2016184355A1 (zh) | 以煤炭为原料制备石墨烯的方法 | |
| Wu et al. | NiS nanoparticles assembled on biological cell walls-derived porous hollow carbon spheres as a novel battery-type electrode for hybrid supercapacitor | |
| Zhang et al. | Recent progress of transition metal-based biomass-derived carbon composites for supercapacitor | |
| CN106365163B (zh) | 一种剑麻纤维活性炭的制备方法及该剑麻纤维活性炭在锂离子电容器中的应用 | |
| Yang et al. | Cobalt–carbon derived from zeolitic imidazolate framework on Ni foam as high-performance supercapacitor electrode material | |
| CN112830472B (zh) | 一种多孔碳的制备方法及由其得到的多孔碳和应用 | |
| Zhao et al. | Sheet-like NiCo-layered double hydroxide anchored on N self-doped hierarchical porous carbon aerogel from chitosan for high-performance supercapacitors | |
| Xi et al. | Converting amorphous kraft lignin to hollow carbon shell frameworks as electrode materials for lithium-ion batteries and supercapacitors | |
| Zou et al. | Engineering of N, P co-doped hierarchical porous carbon from sugarcane bagasse for high-performance supercapacitors and sodium ion batteries | |
| Chen et al. | Wood-derived scaffolds decorating with nickel cobalt phosphate nanosheets and carbon nanotubes used as monolithic electrodes for assembling high-performance asymmetric supercapacitor | |
| Yin et al. | Synthesis of honeycomb-like hierarchical porous carbon via molten salt pyrolysis in a novel sequencing integration system for high-performance supercapacitors | |
| Shen et al. | Hierarchical porous carbon material regenerated from natural bamboo-leaf: How to improve the performance of lead-carbon batteries? | |
| CN111977651A (zh) | 碳酸钾化学活化低阶碳源基多孔碳的制备方法 | |
| Liu et al. | Modulating pore nanostructure coupled with N/O doping towards competitive coal tar pitch-based carbon cathode for aqueous Zn-ion storage | |
| CN111710530A (zh) | 一种低阶煤基多孔碳制备方法及在超级电容器中的应用 | |
| He et al. | Hierarchical tubular porous carbon derived from mulberry branches for long-life lead-carbon battery | |
| Wang et al. | A novel three-dimensional hierarchical porous lead-carbon composite prepared from corn stover for high-performance lead-carbon batteries | |
| Dong et al. | Facile synthesis of O and P co-doped hierarchical porous carbon nanosheets from biomass for high-performance supercapacitors | |
| CN110931267B (zh) | 一种镍钴钼三元金属硫化物及其制备方法和应用 | |
| Lu et al. | Pompon-like MnO2 and N/O doped nanoporous carbon composites with an ultrahigh capacity for energy storage | |
| Dong et al. | Facile wet mechanochemistry coupled K2FeO4 activation to prepare functional coal-derived hierarchical porous carbon for supercapacitors | |
| CN116443863B (zh) | 一种石墨化多级孔石墨烯及其制备方法和应用 | |
| US20230234851A1 (en) | Boron-sulfur-codoped porous carbon material and preparation method and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |