CN112349915B - Graphite composite material, preparation method and application thereof - Google Patents
Graphite composite material, preparation method and application thereof Download PDFInfo
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- CN112349915B CN112349915B CN202011168538.5A CN202011168538A CN112349915B CN 112349915 B CN112349915 B CN 112349915B CN 202011168538 A CN202011168538 A CN 202011168538A CN 112349915 B CN112349915 B CN 112349915B
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- graphite
- composite material
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- graphite composite
- nanosheets
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 158
- 239000010439 graphite Substances 0.000 title claims abstract description 158
- 239000002131 composite material Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011881 graphite nanoparticle Substances 0.000 claims abstract description 143
- 239000000463 material Substances 0.000 claims abstract description 119
- 239000002135 nanosheet Substances 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 239000011162 core material Substances 0.000 claims abstract description 55
- 239000000446 fuel Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 103
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims description 51
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 40
- 229910021389 graphene Inorganic materials 0.000 claims description 37
- 239000001301 oxygen Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 36
- 238000006722 reduction reaction Methods 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 32
- 230000001681 protective effect Effects 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 21
- 239000000981 basic dye Substances 0.000 claims description 20
- 229960003638 dopamine Drugs 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 18
- 230000003213 activating effect Effects 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 239000007770 graphite material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000002055 nanoplate Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical class CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- -1 p-isooctyl phenyl Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- ZQVKTHRQIXSMGY-UHFFFAOYSA-N 4-Ethylbenzoic acid Chemical compound CCC1=CC=C(C(O)=O)C=C1 ZQVKTHRQIXSMGY-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical class [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- UXEAWNJALIUYRH-UHFFFAOYSA-N [8-[(4-aminophenyl)hydrazinylidene]-7-oxonaphthalen-2-yl]-trimethylazanium;chloride Chemical compound [Cl-].C12=CC([N+](C)(C)C)=CC=C2C=CC(=O)\C1=N/NC1=CC=C(N)C=C1 UXEAWNJALIUYRH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Chemical class 0.000 claims description 3
- 229920002678 cellulose Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 3
- YYGBVRCTHASBKD-UHFFFAOYSA-M methylene green Chemical compound [Cl-].C1=CC(N(C)C)=C([N+]([O-])=O)C2=[S+]C3=CC(N(C)C)=CC=C3N=C21 YYGBVRCTHASBKD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical class [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical class CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001522 polyglycol ester Polymers 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 43
- 239000002184 metal Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000004576 sand Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 238000001338 self-assembly Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 5
- 239000002064 nanoplatelet Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002060 nanoflake Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ORLFVWPPBMVPNZ-UHFFFAOYSA-N 1-(6-methylheptyl)-4-[4-(6-methylheptyl)phenoxy]benzene Chemical compound C1=CC(CCCCCC(C)C)=CC=C1OC1=CC=C(CCCCCC(C)C)C=C1 ORLFVWPPBMVPNZ-UHFFFAOYSA-N 0.000 description 1
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical class CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical class CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
- C01B32/194—After-treatment
-
- 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
- C01B32/198—Graphene oxide
-
- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- 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
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
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Abstract
The application relates to the field of fuel cell catalysts, and provides a graphite composite material, a preparation method and application thereof, wherein the graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, the core material comprises a nano sheet material and graphite nano particles, and the core material has a sandwich structure; graphite nanoparticles are adhered between the nano flaky materials, and/or the graphite nanoparticles are adhered on the nano flaky materials. The graphite composite material, the preparation method and the application thereof have high catalytic activity, are durable and are not easily subjected to cross interference, and the preparation method can reduce the preparation cost.
Description
Technical Field
The present application relates to the field of fuel cell technology, and in particular, to graphite composite materials, methods of making, and uses thereof.
Background
The existing fuel cell, especially the hydrogen-oxygen fuel cell or proton exchange membrane fuel cell, has the characteristics of ultra-high energy conversion efficiency and zero pollution, so that the existing fuel cell undoubtedly generates great attraction when the energy is deficient and the environmental pollution is continuously intensified. However, the key catalyst for Oxygen Reduction Reaction (ORR) of fuel cell cathode is noble metal platinum (Pt), which is expensive and has limited global reserves, and the fuel cell is expected to be applied in large scale, and is necessarily limited by this catalyst. Meanwhile, the Pt catalyst also has the disadvantages of poor durability of catalyzing ORR, being easily interfered by alcohols, being easily poisoned by CO, and the like, and thus, an oxygen reduction reaction catalyst which is low in cost, durable, not easily interfered by cross and high in catalytic activity is urgently needed.
Disclosure of Invention
In view of this, the present application provides a graphite composite material, a preparation method and a use thereof, which has high catalytic activity, is durable and is not easily subjected to cross interference, and the preparation method can reduce the preparation cost.
In a first aspect, an embodiment of the present application provides a graphite composite material, where the graphite composite material includes a core material and a carbon layer coated on a surface of the core material, the core material includes a nano-sheet material and graphite nanoparticles, and the core material has a sandwich structure; the graphite nano-particles are adhered between the nano-flaky materials, and/or the graphite nano-particles are adhered on the nano-flaky materials.
According to the scheme, the graphite nanoparticles are adhered to the nano flaky material to form the core material with the sandwich structure, so that compared with the core material made of a single material, the core material has better catalytic durability and improves the catalytic activity of the material in the oxygen reduction reaction; and the surface of the core material with the sandwich structure is coated with a carbon layer, so that the volume expansion of the material is inhibited, and the cycle performance of the material is improved.
In one possible embodiment, the graphite composite material satisfies at least one of the following conditions a to f:
a. the graphite composite material comprises nitrogen, carbon and metal elements;
b. the mass percentage content of nitrogen in the graphite composite material is 0.1-20%;
c. the mass percentage content of carbon in the graphite composite material is 75-99%;
d. the mass percentage content of the metal elements in the graphite composite material is 0.01-5%;
e. the median particle size of the graphite composite material is 2.0-100.0 μm;
f. the specific surface area of the graphite composite material is 100.0m2/g～2000.0m2/g。
In one possible embodiment, the graphite composite material satisfies at least one of the following conditions a to i:
a. the nano flaky material comprises at least one of graphene nanosheets, graphene oxide nanosheets, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets;
b. the metal oxide nanoplates comprise Co3O4、MnO2、NiO2And CeO2At least one of;
c. the hydroxide nanosheets comprising La (OH)3、Co(OH)2、Ni(OH)2And Mn (OH)2At least one of;
d. the thickness of the nano flaky material is 1 nm-100 mu m;
e. the area of the nano sheet material is 1 mu m2～800μm2；
f. The number of the layers of the nano flaky material is 1-10;
g. the mass percentage content of carbon in the graphite nano-particles is 88-96%;
h. the mass percentage content of the metal elements in the graphite nano-particles is 0.01-5%;
i. the median particle size of the graphite nanoparticles is 50 nm-5000 nm.
In a second aspect, an embodiment of the present application further provides a method for preparing a graphite composite material, including the following steps:
adding a basic dye and/or dopamine into a solution containing graphite nanoparticles to obtain a mixed solution;
adding an activating agent and a nano flaky material into the mixed solution, mixing and dispersing, and then drying to obtain a precursor; and
carbonizing the precursor under protective gas to obtain a graphite composite material;
wherein the graphite nanoparticles are adhered to the nano-sheet material, and/or the graphite nanoparticles are adhered between the nano-sheet material sheets.
In the scheme, the graphite composite material is in a sandwich structure of graphite nanoparticles and graphene nanosheets by adsorbing alkaline dye or dopamine with positive charges through graphite nanoparticles through pi-pi conjugation, and then performing electrostatic adsorption and self-assembly with a nanosheet-shaped material, meanwhile, impurities such as various metal oxides rich in graphite form a plurality of single-atom metal active centers such as Fe, Co, Ni and the like in situ in the subsequent carbonization and reduction process, and the catalytic synergistic effect of the oxygen reduction reaction of pyrrole nitrogen formed in the reaction, so that the catalytic activity of the oxygen reduction reaction of the material is greatly improved, the specific surface area, the activity depression and the like are increased by using an activating agent, and the graphite composite material with a regular and stable multistage spherical structure is constructed by crushing treatment and spray drying.
In one possible embodiment, the graphite composite material satisfies at least one of the following conditions a to f:
a. the graphite composite material comprises nitrogen, carbon and metal elements;
b. the mass percentage content of nitrogen in the graphite composite material is 0.1-20%;
c. the mass percentage content of carbon in the graphite composite material is 75-99%;
d. the mass percentage content of the metal elements in the graphite composite material is 0.01-5%;
e. the median particle size of the graphite composite material is 2.0-100.0 μm;
f. the specific surface area of the graphite composite material is 100.0m2/g～2000.0m2/g。
In one possible embodiment, the method satisfies at least one of the following conditions a-h:
a. the graphite nano-particles are obtained by crushing a graphite material;
b. the mass percentage content of carbon in the graphite nano-particles is 88-96%;
c. the mass percentage content of the metal elements in the graphite nano-particles is 0.01-5%;
d. the median particle size of the graphite nanoparticles is 50 nm-5000 nm;
e. the mass ratio of the basic dye to the graphite nanoparticles is (0.1-5): 100, respectively;
f. the mass ratio of the dopamine to the graphite nanoparticles is (0.1-5): 100, respectively;
g. the basic dye comprises at least one of methylene blue, methylene green, basic red, basic black, basic brown, basic violet, basic yellow, basic green and basic orange;
h. the solvent of the mixed solution comprises at least one of water, methanol, ethanol, N-methyl pyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate and dimethylformamide.
In one possible embodiment, the method satisfies at least one of the following conditions a-g:
a. the mass ratio of the nano flaky material to the graphite nanoparticles is (0.1-20): 100, respectively;
b. the nano flaky material comprises at least one of graphene, graphene oxide, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets;
c. the metal oxide nanoplates comprise Co3O4、MnO2、NiO2And CeO2At least one of;
d. the hydroxide nanosheets comprising La (OH)3、Co(OH)2、Ni(OH)2And Mn (OH)2At least one of;
e. the thickness of the nano flaky material is 1 nm-100 mu m;
f. the area of the nano sheet material is 1 mu m2～800μm2；
g. The number of layers of the nano flaky material is 1-10.
In one possible embodiment, the method satisfies at least one of the following conditions a-d:
a. the mass ratio of the activating agent to the graphite nanoparticles is (0.1-40): 1;
b. the activating agent comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, phosphoric acid, nitric acid, sulfuric acid, lithium chloride, potassium chloride, sodium chloride, zinc chloride, potassium carbonate, lithium carbonate and sodium carbonate;
c. a dispersing agent is also added into the mixed solution, and the dispersing agent comprises at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyglycol ester, hexadecyl trimethyl ammonium bromide, polyethylene glycol p-isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid and polyetherimide;
d. the mass ratio of the dispersing agent to the graphite nanoparticles is (0.1-5): 100.
in one possible embodiment, the method satisfies at least one of the following conditions a-g:
a. the drying treatment mode comprises spray drying;
b. the temperature of the drying treatment is 150-300 ℃;
c. the carbonization temperature is 500-1100 ℃, and the heat preservation is carried out for 1-10 h;
d. the temperature rise rate of the carbonization is 0.5 ℃/min to 20.0 ℃/min;
e. the protective gas comprises at least one of nitrogen, helium, neon, argon and xenon;
f. the flow rate of the protective gas is 100mL/min-500 mL/min;
g. the protective gas also comprises ammonia gas, and the volume of the ammonia gas in the protective gas accounts for 10-40%.
In a third aspect, an embodiment of the present application further provides a use of the graphite composite material, where the graphite composite material is the graphite composite material described above, or the graphite composite material prepared by the method for preparing the graphite composite material described above, and the graphite composite material is used as an oxygen reduction catalyst and applied to an oxygen reduction reaction in a fuel cell.
The technical scheme of the application has at least the following beneficial effects:
firstly, graphite nanoparticles are selected to adsorb basic dye or dopamine to bring positive charge through pi-pi conjugation, then the graphite nanoparticles and a nano sheet material are subjected to electrostatic adsorption self-assembly to obtain a sandwich structure of the graphite nanoparticles and graphene nanosheets, meanwhile, impurities such as various metal oxides rich in graphite form a plurality of single-atom metal active centers such as Fe, Co and Ni in situ in the subsequent carbonization reduction process, and the single-atom metal active centers and the catalytic synergistic effect of the oxygen reduction reaction of pyrrole nitrogen formed in the reaction, so that the catalytic activity of the oxygen reduction reaction of the material is greatly improved, the specific surface area, the activity depression and the like are increased by using an activating agent, and the graphite composite material with a regular and stable multistage spherical structure is constructed by using crushing treatment and spray drying.
The graphite composite material is prepared by utilizing the graphite nano-particles and the nano-flake materials, the graphite composite material has high catalytic activity, is durable and is not easily subjected to cross interference, the preparation method can reduce the preparation cost, solves the problems of expensive sources of catalyst materials for oxygen reduction reaction, difficult process industrialization, unstable catalytic activity and the like, simultaneously changes waste into valuable, and realizes the comprehensive utilization of graphite grading materials.
Drawings
FIG. 1a is a schematic structural view of a graphite composite material provided in an embodiment of the present application;
FIG. 1b is a schematic illustration of a core material of a graphite composite material provided in an embodiment of the present application;
fig. 2 is a process flow diagram of a method for preparing a graphite composite material according to an embodiment of the present disclosure.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The existing fuel cell, especially the hydrogen-oxygen fuel cell or proton exchange membrane fuel cell, has the characteristics of ultra-high energy conversion efficiency and zero pollution, so that the existing fuel cell undoubtedly generates great attraction when the energy is deficient and the environmental pollution is continuously intensified. However, the key catalyst for Oxygen Reduction Reaction (ORR) of fuel cell cathode is noble metal platinum (Pt), which is expensive and has limited global reserves, and the fuel cell is expected to be applied in large scale, and is necessarily limited by this catalyst. Meanwhile, the Pt catalyst also has the disadvantages of poor durability of catalyzing ORR, being easily interfered by alcohols, being easily poisoned by CO, and the like, and thus, an oxygen reduction reaction catalyst which is low in cost, durable, not easily interfered by cross and high in catalytic activity is urgently needed.
The application provides a graphite composite material which can be used as an oxygen reduction reaction catalyst, as shown in fig. 1 a-1 b, the graphite composite material comprises a core material 10 and a carbon layer 20 coated on the surface of the core material 10, wherein the core material 10 comprises a nano sheet material 11 and graphite nano particles 12, and the core material 10 has a sandwich structure;
the graphite nanoparticles 12 are adhered between the nano-sheet materials 11, and/or the graphite nanoparticles 12 are adhered on the nano-sheet materials 11.
It should be noted that, compared with the core material made of a single material, the core material 10 of the sandwich structure can provide more pore structures, improve the specific surface area of the material, and the stability of the sandwich structure is stronger, so that the structural stability of the graphite composite material is improved, the catalytic sites of the material are increased, and the catalytic activity is enhanced while the catalytic durability is better.
The median particle diameter of the graphite composite material is 2.0 μm to 100.0 μm, and specifically, the median particle diameter of the graphite composite material may be 2.0 μm, 8.0 μm, 10.0 μm, 15.0 μm, 20.0 μm, 25.0 μm, 30.0 μm, 40.0 μm, 50.0 μm, 60.0 μm, 70.0 μm, 80.0 μm, 90.0 μm, 100.0 μm, or the like, which is not limited herein. Preferably, the graphite composite material has a median particle diameter of 10 to 25 μm. Through multiple experiments, the inventor finds that when the median particle size of the graphite composite material is controlled within the range of 2.0-100.0 microns, the catalyst sites of the material are increased, and the catalytic activity is enhanced. From the viewpoint of production cost and process difficulty, it is further preferable that the median particle diameter of the graphite composite material is 10.0 μm to 25.0 μm.
The specific surface area of the graphite composite material is 100.0m2/g～2000.0m2(ii) in terms of/g. Specifically, the specific surface area of the graphite composite material may be 100.0m2/g、200.0m2/g、500.0m2/g、800.0m2/g、900.0m2/g、 1000.0m2/g、1100.0m2/g、1200.0m2/g、1300.0m2/g、1400.0m2/g、1500.0m2/g、2000.0m2And/g, etc., without limitation thereto. Preferably, the specific surface area of the graphite composite material is 890.0m2/g～1100.0m2(ii) in terms of/g. The inventor finds that the specific surface area of the graphite composite material is controlled to be 100.0m through a plurality of experiments2/g～2000.0m2When the concentration is within the range of the concentration, the catalyst is beneficial to increasing the catalytic sites of the material, enhancing the catalytic activity, facilitating the diffusion of electrolyte or reactants of the fuel cell and promoting the reaction.
As an optional technical scheme of the application, the mass percent of nitrogen in the graphite composite material is 0.1-20%, the mass percent of carbon is 75-99%, and the mass percent of metal elements is 0.01-5%; among them, the metal elements include Fe, Co, Cu, Ni, and the like. It can be understood that the metal elements in the graphite composite material, such as metal elements of Fe, Co, Cu, Ni, etc., form a monatomic metal catalytic active center in the graphite composite material, and the catalytic activity of the material for oxygen reduction reaction is greatly improved under the synergistic effect with pyridine N.
Alternatively, the graphite composite material may contain nitrogen in an amount of, for example, 0.1%, 0.5%, 0.8%, 1%, 5%, 8.4%, 10%, 12%, 15%, or 20% by mass, carbon in an amount of, for example, 75%, 80%, 85%, 90%, 92%, 94%, 96%, 98%, or 99% by mass, and the metal element in an amount of, for example, 0.01%, 0.1%, 0.15%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, or 5% by mass, but not limited to, the recited values, and other values not recited in the above-mentioned range may be also used. The metal elements and the doped nitrogen elements in the graphite composite material can play a role in coordination, and the catalytic activity of the material in the oxygen reduction reaction is improved. The graphite composite material provided by the application has a spherical structure, developed pores, a large specific surface area and a plurality of active sites, can improve the N doping content, can be used as a cathode catalyst for the oxygen reduction reaction of a fuel cell, has catalytic activity comparable to that of a commercial Pt catalyst, has different adsorption and catalysis mechanisms of pyridine N, monoatomic metal and the like and Pt, and is stronger in tolerance, and the catalytic activity is not influenced by adsorption poisoning of alcohols, CO and the like.
Further, the nano-flake material includes at least one of a graphene nanoplate, a graphene oxide nanoplate, a metal oxide nanoplate, a hydroxide nanoplate, and a silicon carbide nanoplate. Optionally, the nanosheet material is graphene nanoplatelets or graphene oxide nanoplatelets.
The metal oxide nanoplates comprise Co3O4、MnO2、NiO2And CeO2At least one of (1).
The hydroxide nanosheets comprising La (OH)3、Co(OH)2、Ni(OH)2And Mn (OH)2At least one of (1).
The thickness of the nano sheet material is 1nm to 100 μm, and may be, for example, 1nm, 10nm, 50nm, 100nm, 1 μm, 10 μm or 100 μm; the area of the nano sheet material is 1 mu m2～800μm2And more specifically, may be 1 μm2、10μm2、20μm2、50μm2、100μm2、μm2、1μm2、1μm2、1μm2、1μm2Or 1 μm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
As an alternative embodiment of the present invention, the number of layers of the nanosheet-like material is 1 to 10, and for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers, etc., but the number is not limited to the recited values, and other values not recited within the range of the values are also applicable.
The graphite nanoparticles can be obtained by crushing a classified material in a spheroidization process of natural flake graphite, and exemplarily, the graphite classified material contains 4381ppm of Fe, 0.735ppm of Co, 11.96ppm of Cu and 12.65ppm of Ni. The median particle diameter of the graphite nanoparticles obtained by crushing is 50nm to 5000nm, and more specifically, it may be 50nm, 100nm, 150nm, 200nm, 300nm, 500nm, 600nm, 800nm, 1000nm, 2000nm, 3000nm, 5000nm or the like, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable. Preferably, the graphite nanoparticles have a median particle size of from 200nm to 800 nm. Through a plurality of experiments, the control of the median particle size of the graphite nanoparticles within the range is found to be beneficial to the graphite nanoparticles to be easily adhered to the nano flaky material in the self-assembly process, and the specific surface area and the catalytic activity can be increased.
Wherein, the carbon content in the graphite nanoparticles is 88 to 96 percent by mass, more specifically 88, 89, 90, 91, 92, 93, 94, 95 or 96 percent by mass; the content of the metal element may be, for example, 0.01%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% by mass or the like, in an amount of 0.01% to 5%. Among them, the metal elements include Fe, Co, Cu, Ni, and the like. Understandably, metal elements in the graphite nanoparticles, such as metal elements of Fe, Co, Cu, Ni, and the like, form a monoatomic metal catalytic active center, and the catalytic activity of the oxygen reduction reaction of the graphite composite material is greatly improved under the catalytic synergistic effect with pyridine N.
The graphite nanoparticles have a median particle diameter of 50nm to 5000nm, and more specifically, may be 50nm, 100nm, 200nm, 500nm, 800nm, 1000nm, 2000nm, 3000nm, 4000nm, 5000nm, or the like. Understandably, the smaller the particle size of the graphite nanoparticles, the larger the specific surface area of the graphite nanoparticles adsorbed on the nano-flake material, which can improve the catalytic activity, and in view of the process manufacturing cost and difficulty, the median particle size of the graphite nanoparticles is preferably 200nm to 800 nm.
The present application also provides a method for preparing a graphite composite material, as shown in fig. 2, the method comprising the steps of:
s100, adding a basic dye and/or dopamine into a solution containing graphite nanoparticles to obtain a mixed solution;
s200, adding an activating agent and a nano flaky material into the mixed solution, mixing and dispersing, and then drying to obtain a precursor; and
and S300, carbonizing the precursor under protective gas to obtain the graphite composite material.
According to the preparation method of the graphite composite material, graphite nanoparticles are selected to adsorb alkaline dye or dopamine through pi-pi conjugation to bring positive charge, and then the graphite nanoparticles and a nano sheet material are subjected to electrostatic adsorption and self-assembly to obtain a sandwich structure of the graphite nanoparticles and graphene nano sheets, meanwhile, various metal elements rich in graphite form a plurality of single-atom metal active centers of Fe, Co, Ni and the like in situ in the subsequent carbonization reduction and nitrogen doping processes, and the graphite nanoparticles and pyrrole nitrogen formed in the reaction play a catalytic synergistic effect in the oxygen reduction reaction, so that the oxygen reduction reaction catalytic activity of the material is greatly improved, the specific surface area, the activity depression and the like are increased by using an activating agent, and the graphite composite material with a regular and stable spherical structure is constructed by using pulverization treatment and spray drying.
Before adding a basic dye and/or dopamine to the solution containing the graphite nanoparticles to obtain a mixed solution at S100, the method further includes:
the preparation method comprises the steps of crushing and pretreating 88-96% of graphite material with carbon by mass to obtain micron-sized graphite particles, further grinding the micron-sized graphite particles to obtain graphite nanoparticles, and controlling the median particle size of the graphite nanoparticles to be 50-5000 nm.
Specifically, the graphite material can be a graphite grading material, the graphite grading material is a grading material in a spheroidization process of natural crystalline flake graphite, and the graphite material contains 88-96% of carbon by mass and 0.01-5% of metal elements by mass. It can be understood that the graphite graded material contains abundant metal elements such as Fe, Co, Ni and the like in the continuous spheroidization process, and the metal elements and other metal oxides and the like form in-situ metal monoatomic atoms and the like in the subsequent carbonization, activation and nitridation processes, and the in-situ metal monoatomic atoms and the like and have a catalytic synergistic effect with the formed pyrrole nitrogen in the oxygen reduction reaction, so that the catalytic activity of the oxygen reduction reaction of the material is greatly improved.
The graphite material can be pulverized by at least one of jet milling, mechanical milling, roll milling and roll milling, preferably, the mechanical milling can be adopted, so that the preparation cost can be reduced.
The median particle diameter of the crushed graphite nanoparticles may be 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 1000nm, 2000nm, 3000nm, 4000nm or 5000 nm. Understandably, the smaller the particle size of the graphite nanoparticles, the larger the specific surface area of the graphite nanoparticles adsorbed on the nano-flake material, which can improve the catalytic activity, and in view of the process manufacturing cost and difficulty, the median particle size of the graphite nanoparticles is preferably 200nm to 800 nm.
In one embodiment, the one-step milling may be performed using a sand mill to convert the micron-sized graphite particles into graphite nanoparticles. Wherein, the zirconium ball in the sand mill is more than or equal to 0.4 μm, the sand milling rotating speed is 500 rpm-2000 rpm, and the sand milling time is 60 min-300 min.
The sanding time can be 60min, 80min, 100min, 120min, 150min, 180min, 240min or 300min, and of course, the sanding time can have other values, and the specific value can be selected or set according to actual needs. The longer the milling time, the smaller the particle size of the particles.
And S100, adding a basic dye and/or dopamine into the solution containing the graphite nanoparticles to obtain a mixed solution.
Optionally, the mass ratio of the basic dye to the graphite nanoparticles is (0.1-5): 100.
specifically, the mass ratio of the basic dye to the graphite nanoparticles may be 0.1:100, 0.5:100, 1:100, 2:100, 3:100, 4:100, 5:100, or the like. Preferably, the mass ratio of the basic dye to the graphite nanoparticles is (0.5-2): 100. The basic dye comprises at least one of methylene blue, methylene green, basic red, basic black, basic brown, basic violet, basic yellow, basic green and basic orange.
The basic dye is also referred to as a basic dye. Dyes whose dye groups carry a positive charge, which are capable of dissociating in aqueous solution to form a cationic dye, are also known as cationic dyes. When the aqueous solution of the graphite nanoparticles is added with basic dye and ultrasonically stirred and dispersed, the graphite nanoparticles adsorb the basic dye through pi-pi conjugation to carry positive charges, which is beneficial to electrostatic adsorption and self-assembly of the graphite nanoparticles and the nano flaky material to form a sandwich structure.
The mass ratio of the dopamine to the graphite nanoparticles is (0.1-5): 100. specifically, the mass ratio of dopamine to graphite nanoparticles may be 0.1:100, 0.5:100, 1:100, 2:100, 3:100, 4:100, 5:100, and the like. Preferably, the mass ratio of the dopamine to the graphite nanoparticles is (0.5-2): 100.
It should be noted that dopamine is easily oxidized by dissolved oxygen in aqueous solution to initiate self-polymerization-crosslinking reaction, so as to form a tightly adhered composite layer on the surface of the graphite nanoparticles, which is beneficial to the graphite nanoparticles and the nano-sheet material to form a sandwich structure by adsorption and self-assembly.
Alternatively, the solvent of the mixed solution includes at least one of water, methanol, ethanol, N-methylpyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, and dimethylformamide.
And S200, adding an activating agent and a nano flaky material into the mixed solution, mixing and dispersing, and then drying to obtain a precursor.
Optionally, the mass ratio of the activating agent to the graphite nanoparticles is (0.1-40): 1; in specific embodiments, the mass ratio of the activating agent to the graphite nanoparticles may be 0.1:1, 0.5:1, 2:1, 5:1, 10:1, 20:1, 30:1, 40:1, etc., and preferably, the mass ratio of the activating agent to the graphite nanoparticles is (2-20): 1.
the activating agent comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, phosphoric acid, nitric acid, sulfuric acid, lithium chloride, potassium chloride, sodium chloride, zinc chloride, potassium carbonate, lithium carbonate and sodium carbonate. It can be understood that the activating agent can perform an etching reaction with the carbon material (such as graphite nanoparticles) during the carbonization process, so that the graphite nanoparticles form pores, the specific surface area and the depressions are further increased, the electrolyte diffusion contact is facilitated, and the catalytic sites and the catalytic activity are increased.
Optionally, the mass ratio of the nano flaky material to the graphite nanoparticles is (0.1-20): 100, in a specific embodiment, the mass ratio of the nano-platelet material to the graphite nanoparticles is 0.1:100, 0.5:100, 1:100, 2: 100. 5:100, 8:100, 10:100, 15:100, 20:100 and the like, preferably, the ratio of the nano flaky material to the graphite nanoparticles is (1-10): 100, which is not limited herein.
The nano flaky material comprises at least one of graphene nanosheets, graphene oxide nanosheets, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets.
It can be understood that the graphite nanoparticles have positive charges after adsorbing the basic dye, and a tightly attached composite layer is formed on the surfaces of the graphite nanoparticles after dopamine is self-polymerized and crosslinked, so that the nano flaky material and the graphite nanoparticles can be self-assembled to form a sandwich structure after the nano flaky material is added into the aqueous solution of the graphite nanoparticles.
Optionally, after adding the activator and the nanosheet material to the mixed solution, the method further comprises:
and adding a dispersing agent into the mixed solution, wherein the mass ratio of the dispersing agent to the graphite nanoparticles is (0.1-5): 100.
in specific embodiments, the mass ratio of the dispersant to the graphite nanoparticles may be 0.1:100, 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 4:100, 5:100, etc., and preferably, the mass ratio of the dispersant to the graphite sizing material is (0.5-3): 100.
Optionally, the dispersant comprises at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphoric acid, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, polyethylene glycol ester of fatty acid, cetyltrimethylammonium bromide, polyethylene glycol p-isooctylphenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid, and polyetherimide.
It is understood that the addition of the dispersing agent to the mixture can prevent the graphite nanoparticles and the nano flaky materials from settling and agglomerating and keep the dispersion system of the mixture relatively stable.
Alternatively, ultrasonic dispersion, stirring dispersion, grinding dispersion and the like can be used for mixing dispersion, and the drying treatment method can be oven drying, spray drying, vacuum drying, freeze drying and the like, in this embodiment, the spray drying method is used, the drying temperature is 150 ℃ to 300 ℃, the pressure in the drying tower is-0.13 kPa to 0.08kPa, and the rotation speed of the atomizing disk is 10000rpm to 20000 rpm. The frequency of the material conveying screw pump is 20 Hz-50 Hz when the spray drying and spraying are carried out.
The spherical precursor is prepared after spray drying, the precursor is a core material, as shown in fig. 1b, the core material 10 has a nano-scale sandwich structure, that is, the spherical precursor is the core material 10 of the graphite composite material.
Further, S300, carbonizing the precursor under a protective gas to obtain a graphite composite material, including:
heating the precursor to 500-1100 ℃ under the protection gas, and preserving heat for 1-10 h to carbonize the precursor;
and then preserving the heat for 1 to 10 hours under the protective gas with the ammonia gas content of 10 to 40 percent, and carrying out nitrogen doping to obtain the graphite composite material.
In other embodiments, the carbon fiber can be taken out after carbonization and then subjected to nitrogen doping, or the carbon fiber can be subjected to nitrogen doping immediately after carbonization; and nitrogen doping can be synchronously performed in the carbonization process, which is not limited herein.
Wherein the shielding gas comprises at least one of nitrogen, helium, neon, argon and xenon.
Alternatively, the ammonia content in the shielding gas may be 10%, 15%, 20%, 25%, 30%, 35% or 40%, although other values are possible, and the specific value may be selected or set according to actual needs.
The flow rate of the protective gas is 100mL/min-500 mL/min. Alternatively, the flow rate of the shielding gas may be 100mL/min, 200mL/min, 300mL/min, 400mL/min, or 500 mL/min. Preferably, the flow rate of the shielding gas may be 300 mL/min.
The temperature rise rate during carbonization is 0.5 ℃/min to 20.0 ℃/min. Alternatively, the rate of temperature rise may be 0.5 deg.C/min, 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 8 deg.C/min, 10 deg.C/min, 12 deg.C/min, 15 deg.C/min, 18 deg.C/min, 20 deg.C/min. Preferably, the heating rate is 3 ℃/min to 5 ℃/min. The inventor finds that the carbonization reaction can be effectively ensured and the time for heating to the preset temperature range can be shortened by controlling the heating rate to be 3-5 ℃/min through a plurality of tests.
Wherein the carbonization temperature is 500-1100 ℃, optionally 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or 1100 ℃. Preferably, the carbonization temperature is 700-900 ℃. Through multiple experiments, the inventor finds that the carbonization reaction efficiency can be improved by controlling the carbonization temperature within the range, so that the surface of the precursor is carbonized to form a uniform carbon layer, and the carbon layer can be amorphous carbon.
Furthermore, 10-40% ammonia gas can be added into the protective gas, so that the precursor is carbonized and nitrogen doping is carried out at the same time, the nitrogen content in the graphite composite material is improved, and the catalytic activity of the graphite composite material is improved.
In the nitrogen doping process and the carbonization process, the heat preservation time is 1h to 10h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, which is not limited herein. The heat preservation time is controlled within the range, so that the carbonization reaction and the nitrogen doping reaction can be fully performed, a uniform carbon layer is formed on the surface of the precursor, the nitrogen content in the carbon layer is increased, and the catalytic activity of the graphite composite material is improved.
The graphite composite material prepared by the method has catalytic activity comparable to that of a Pt catalyst, meanwhile, various metal elements rich in graphite form a plurality of single-atom metal active centers of Fe, Co, Ni and the like in situ in the carbonization reduction and nitridation processes, the graphite composite material is different from the adsorption catalytic mechanism of Pt, has stronger tolerance, is not influenced by adsorption poisoning of alcohols, CO and the like, and has a catalytic synergistic effect with the oxygen reduction reaction of pyrrole nitrogen formed by nitrogen doping, so that the catalytic activity of the oxygen reduction reaction of the material is greatly improved.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example 1
200g of graphite material with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the graphite nanoparticles with the median particle size of 300-600 nm are obtained by pulverization in a sand mill.
Adding 1g of methylene blue into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 0.5g of graphene oxide solution, ultrasonically stirring and dispersing for 30min, continuously stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump during spraying is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing turntable is 10000rpm, and drying to obtain a precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 6.2%, the mass percentage content of carbon is 93.1%, and the mass percentage content of the metal element is 0.4%. The graphite composite material has a median particle diameter of 22.5 μm and a specific surface area of 1008.1m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano flaky material (graphene oxide nano sheets) and graphite nano particles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 2
200g of graphite material with the carbon content of 92.95 percent and the metal content of 2.4 percent is crushed to the particle size of 25 to 50 mu m by a pair of rollers, added with aqueous solution and crushed in a sand mill to obtain graphite nano particles with the median particle size of about 800 nm.
Adding 1g of methylene blue into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 0.5g of graphene oxide solution, ultrasonically stirring and dispersing for 30min, continuously stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump during spraying is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing turntable is 10000rpm, and drying to obtain a precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 8.5%, the mass percentage content of carbon is 90.3%, and the mass percentage content of the metal element is 1.1%. The graphite composite material has a median particle diameter of 18.5 μm and a specific surface area of 1023.4m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano flaky material (graphene oxide nano sheets) and graphite nano particles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 3
1000g of graphite material with carbon content of 95.1% and metal content of 1.2% is rolled and ground to particle size of 200-450 μm, added with aqueous solution and ground in a sand mill to obtain graphite nanoparticles with median particle size of about 500 nm.
Adding 10g of alkaline black into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, then adding 100 g of LiOH, 10g of methyl amyl alcohol and 4g of graphene oxide solution, ultrasonically stirring and dispersing for 40min, further continuously stirring for 1.5h, then transferring into a transfer tank for spray drying, wherein the frequency of a pump during spraying is 39Hz, the drying temperature is 250 ℃, the pressure in a drying tower is-0.00 kPa, the rotating speed of an atomizing turntable is 16000rpm, and drying to obtain a precursor;
placing the precursor in a crucible, placing the crucible in a push plate furnace, and introducing nitrogen at a flow rate of 9m3And h, controlling the heating rate to be 8 ℃/min, heating to 950 ℃, preserving the heat for 2h, introducing protective gas with the ammonia content of 30%, preserving the heat for 3h, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 3.1%, the mass percentage content of carbon is 96.0%, and the mass percentage content of the metal element is 0.5%. The graphite composite material has a median particle diameter of 26 μm and a specific surface area of 919.9m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano flaky material (graphene oxide nano sheets) and graphite nano particles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 4
500g of graphite material with carbon content of 94.8% and metal content of 1.5% is airflow crushed to 600-1050 mu m, water solution is added, and the graphite material is crushed in a sand mill to obtain graphite nano-particles with median particle size of about 700 nm.
Adding 5g of dopamine into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, and then adding 50g of Na2CO34g of polyvinyl alcohol and 1.5g of graphene oxide solution, ultrasonically stirring and dispersing for 80min, and then continuously stirring for 0.5 h; then transferring the mixture into a transfer tank for spray drying, wherein the frequency of a pump is 45Hz, the drying temperature is 200 ℃, the pressure in a drying tower is-0.10 kPa, the rotating speed of an atomizing turntable is 12000rpm, and drying to obtain a precursor;
placing the precursor in a crucible, placing the crucible in a high-sand atmosphere furnace, introducing argon gas firstly, wherein the flow of the argon gas is 5m3Heating to 1050 deg.C/h at 4 deg.C/min, maintaining for 1h, introducing protective gas containing 50% ammonia gas, maintaining for 2h, and naturally cooling to room temperature, i.e. heating to 1050 deg.C/minObtaining the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 7.1%, the mass percentage content of carbon is 92.2%, and the mass percentage content of the metal element is 0.7%. The graphite composite material has a median particle diameter of 17.3 μm and a specific surface area of 892.3m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core comprises a nano flaky material (graphene oxide nano sheet) and graphite nano particles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 5
200g of graphite material with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the graphite nanoparticles with the median particle size of 300-600 nm are obtained by pulverization in a sand mill.
Adding 2g of dopamine into an aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 0.5g of graphene oxide solution, ultrasonically stirring and dispersing for 30min, continuously stirring for 2h, then transferring into a transfer tank for spray drying, wherein the frequency of a pump during spraying is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing turntable is 10000rpm, and drying to obtain a precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 6.8%, the mass percentage content of carbon is 90.6%, and the mass percentage content of the metal element is 0.8%. The graphite composite material has a median particle diameter of 18.5 μm and a specific surface area of 991.1m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano flaky material (graphene oxide nano sheets) and graphite nano particles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 6
200g of graphite material with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the graphite nanoparticles with the median particle size of 300-600 nm are obtained by pulverization in a sand mill.
Adding 1g of methylene blue into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, and then adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 1g of Co3O4And ultrasonically stirring and dispersing the solution for 30min, continuously stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing turntable is 10000rpm, and drying to obtain the precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 5.8%, the mass percentage content of carbon is 92.8%, and the mass percentage content of the metal element is 1.2%. The graphite composite material has a median particle diameter of 22.0 μm and a specific surface area of 1023.5m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano sheet material (Co)3O4Nanoplatelets) and graphite nanoparticles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Example 7
200g of graphite material with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the graphite nanoparticles with the median particle size of 300-600 nm are obtained by pulverization in a sand mill.
Adding 1g of methylene blue into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, and then adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 2g of La (OH)3And ultrasonically stirring and dispersing the solution for 30min, continuously stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing turntable is 10000rpm, and drying to obtain the precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 3.4%, the mass percentage content of carbon is 94.3%, and the mass percentage content of the metal element is 2.1%. The graphite composite material has a median particle diameter of 17.9 μm and a specific surface area of 930.5m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano sheet material (La (OH)3Nanoplatelets) and graphite nanoparticles. The graphite nano particles are adsorbed on the nano flaky materials, and the graphite nano particles are adsorbed among the nano flaky material sheets to form a sandwich structure.
Comparative example 1
The difference from the embodiment 1 is that the method does not add the nano flaky material, and specifically comprises the following steps:
200g of graphite material with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the graphite nanoparticles with the median particle size of 300-600 nm are obtained by pulverization in a sand mill.
Adding 1g of methylene blue into the aqueous solution containing the graphite nanoparticles, ultrasonically stirring for 1h, adding 50g of KOH and 2g of polyvinylpyrrolidone (PVP), ultrasonically stirring and dispersing for 30min, continuously stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump during spraying is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing rotary table is 10000rpm, and drying to obtain a precursor.
Placing the precursor in a crucible, placing the crucible in an atmosphere furnace, and introducing nitrogen with the flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 1.1%, the mass percentage content of carbon is 98.7%, and the mass percentage content of the metal element is 0.2%. The median particle diameter of the graphite composite material is 14.3 mu m, and the specific surface area is 773m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises graphite nanoparticles.
Comparative example 2
In contrast to example 1, no methylene blue was added
200g of graphite with carbon content of 94.5 percent and metal content of 5.4 percent is pulverized into particles with the particle size of 20-45 mu m by air flow, water is added, and the particles are pulverized in a sand mill to obtain graphite nanoparticles with the median particle size of 300-600 nm.
Adding 50g of KOH, 2g of polyvinylpyrrolidone (PVP) and 0.5g of graphene oxide solution into an aqueous solution containing the graphite nanoparticles, ultrasonically stirring and dispersing for 30min, further stirring for 2h, then transferring to a transfer tank for spray drying, wherein the frequency of a pump during spraying is 25Hz, the drying temperature is 180 ℃, the pressure in a drying tower is-0.13 kPa, the rotating speed of an atomizing rotary table is 10000rpm, and drying to obtain a precursor.
Placing the precursor in a crucible, and placing the crucible inIn the atmosphere furnace, nitrogen gas was introduced at a flow rate of 5m3Heating to 750 ℃ at a heating rate of 3 ℃/min for 3h, and keeping the temperature for 3 h; and introducing protective gas with the ammonia gas content of 40%, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the graphite composite material.
In the graphite composite material obtained in this example, the mass percentage content of nitrogen is 0.7%, the mass percentage content of carbon is 99.0%, and the mass percentage content of the metal element is 0.3%. The median particle diameter of the graphite composite material is 15.7 mu m, and the specific surface area is 755m2/g。
The graphite composite material comprises a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises graphite nanoparticles and a nano flaky material (graphene oxide nano sheets).
Comparative example 3
A fuel cell using Pt catalyst (wuhan himalaya platinum carbon catalyst, 40%).
The performance parameters of the materials prepared in examples 1 to 7 and comparative examples 1 to 3 are shown in the following table 1.
TABLE 1
The graphite composite materials prepared in examples 1-7 and comparative examples 1-2 are respectively used as Oxygen Reduction Reaction (ORR) key catalysts, and the Pt catalyst prepared in comparative example 3 is respectively prepared into slurry; and uniformly dripping the slurry on a pretreated glassy carbon electrode, and drying to obtain the electrode slice, wherein the counter electrode is a platinum wire, and the reference electrode is an Ag/AgCl electrode.
Performing linear volt-ampere scanning on the electrode plate by using 1M potassium hydroxide solution as electrolyte at a scanning speed of 10 mV/s;
0.1M potassium hydroxide solution is adopted as electrolyte for the electrode slice, and the ORR oxygen reduction current is tested by rotating the disc electrode;
TABLE 2 Performance comparison results Table
As can be seen from table 2 above, the difference between example 1 and comparative example 1 is that the nano-sheet material is not added during the preparation process, so that the core material with the sandwich structure cannot be formed, and the core material with the sandwich structure can provide more pores and a larger specific surface area during the nitrogen doping process, which is beneficial to increasing the nitrogen content of the material. The graphite composite material prepared in the comparative example 1 has relatively small specific surface area and lower nitrogen doping content, and the maximum power density, the oxygen reduction current density and the oxygen reduction current density retention rate of the fuel cell prepared from the material prepared in the comparative example 1 are all obviously reduced compared with those of the embodiment 1.
The difference between the embodiment 1 and the comparative example 2 is that the alkaline dye or dopamine is not added in the preparation process, the graphite nanoparticles are difficult to adsorb the alkaline dye or dopamine to carry positive charges, and a sandwich structure cannot be obtained through electrostatic adsorption self-assembly. The graphite composite material prepared in the comparative example 2 has a relatively small specific surface area and a lower nitrogen doping content, and the maximum power density, the oxygen reduction current density and the oxygen reduction current density retention rate of the fuel cell prepared from the graphite composite material are all obviously reduced compared with those in the example 1.
In a comparative example 3, Pt is used as a catalyst, although the maximum power density of the prepared fuel cell is superior to that of the fuel cell prepared in examples 1-7, the Pt catalyst is easily interfered by alcohol, and the current density after interference is greatly reduced, so that the oxygen reduction current density retention rate of the fuel cell is lower than that of the fuel cell prepared in examples 1-7.
In conclusion, the maximum power density of the fuel cell prepared by using the graphite composite material prepared by the preparation method as the catalyst is equivalent to that of the fuel cell prepared by using Pt as the catalyst; the catalytic activity of the graphite composite material is comparable to that of the graphite composite material in oxygen reduction reaction, the oxygen reduction current density of the battery is improved, the graphite composite material has high catalytic activity, is durable and is not easy to be subjected to cross interference, and the preparation method can reduce the preparation cost.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (10)
1. The graphite composite material is characterized by comprising a core material and a carbon layer coated on the surface of the core material, wherein the core material comprises a nano flaky material and graphite nano particles, and the core material has a sandwich structure;
the graphite nano particles are adhered between the nano flaky materials, and/or the graphite nano particles are adhered on the nano flaky materials;
the graphite composite material is prepared by the following method, and the method comprises the following steps:
adding a basic dye and/or dopamine into a solution containing graphite nanoparticles to obtain a mixed solution;
adding an activating agent and a nano flaky material into the mixed solution, mixing and dispersing, and then drying to obtain a precursor; and
and carbonizing the precursor under the protection gas to obtain the graphite composite material.
2. The graphite composite material according to claim 1, characterized in that it satisfies at least one of the following conditions a to f:
a. the graphite composite material comprises nitrogen, carbon and metal elements;
b. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percent of the nitrogen in the graphite composite material is 0.1-20%;
c. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percent of the carbon in the graphite composite material is 75-99%;
d. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percentage content of the metal elements in the graphite composite material is 0.01-5%;
e. the median particle size of the graphite composite material is 2.0-100.0 μm;
f. the specific surface area of the graphite composite material is 100.0m2/g～2000.0m2/g。
3. The graphite composite material according to claim 1 or 2, characterized in that it satisfies at least one of the following conditions a to i:
a. the nano flaky material comprises at least one of graphene nanosheets, graphene oxide nanosheets, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets;
b. the nano flaky material comprises at least one of graphene nanosheets, graphene oxide nanosheets, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets, and the metal oxide nanosheets comprise Co3O4、MnO2、NiO2And CeO2At least one of;
c. the nano flaky material comprises at least one of graphene nano sheets, graphene oxide nano sheets, metal oxide nano sheets, hydroxide nano sheets and silicon carbide nano sheets, wherein the hydroxide nano sheets comprise La (OH)3、Co(OH)2、Ni(OH)2And Mn (OH)2At least one of;
d. the thickness of the nano flaky material is 1 nm-100 mu m;
e. the area of the nano sheet material is 1 mu m2～800μm2；
f. The number of the layers of the nano flaky material is 1-10;
g. the mass percentage content of carbon in the graphite nano-particles is 88-96%;
h. the mass percentage content of the metal elements in the graphite nano-particles is 0.01-5%;
i. the median particle size of the graphite nanoparticles is 50 nm-5000 nm.
4. The preparation method of the graphite composite material is characterized by comprising the following steps:
adding a basic dye and/or dopamine into a solution containing graphite nanoparticles to obtain a mixed solution;
adding an activating agent and a nano flaky material into the mixed solution, mixing and dispersing, and then drying to obtain a precursor; and
carbonizing the precursor under protective gas to obtain a graphite composite material;
wherein the graphite nanoparticles are adhered to the nano-sheet material, and/or the graphite nanoparticles are adhered between the nano-sheet material sheets.
5. The production method according to claim 4, wherein the graphite composite material satisfies at least one of the following conditions a to f:
a. the graphite composite material comprises nitrogen, carbon and metal elements;
b. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percent of the nitrogen in the graphite composite material is 0.1-20%;
c. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percent of the carbon in the graphite composite material is 75-99%;
d. the graphite composite material comprises nitrogen, carbon and metal elements, wherein the mass percentage content of the metal elements in the graphite composite material is 0.01-5%;
e. the median particle size of the graphite composite material is 2.0-100.0 μm;
f. the specific surface area of the graphite composite material is 100.0m2/g～2000.0m2/g。
6. The production method according to claim 4 or 5, characterized in that it satisfies at least one of the following conditions a to h:
a. the graphite nano-particles are obtained by crushing a graphite material;
b. the mass percentage content of carbon in the graphite nano-particles is 88-96%;
c. the mass percentage content of the metal elements in the graphite nano-particles is 0.01-5%;
d. the median particle size of the graphite nanoparticles is 50 nm-5000 nm;
e. the mass ratio of the basic dye to the graphite nanoparticles is (0.1-5): 100, respectively;
f. the mass ratio of the dopamine to the graphite nanoparticles is (0.1-5): 100, respectively;
g. the basic dye comprises at least one of methylene blue, methylene green, basic red, basic black, basic brown, basic violet, basic yellow, basic green and basic orange;
h. the solvent of the mixed solution comprises at least one of water, methanol, ethanol, N-methyl pyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate and dimethylformamide.
7. The production method according to claim 4, characterized in that it satisfies at least one of the following conditions a to g:
a. the mass ratio of the nano flaky material to the graphite nanoparticles is (0.1-20): 100, respectively;
b. the nano flaky material comprises at least one of graphene, graphene oxide, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets;
c. the nano flaky material comprises at least one of graphene nanosheets, graphene oxide nanosheets, metal oxide nanosheets, hydroxide nanosheets and silicon carbide nanosheets, and the metal oxide nanosheets comprise Co3O4、MnO2、NiO2And CeO2At least one of;
d. the nano flaky material comprises graphene nano sheets and oxidationAt least one of graphene nanoplates, metal oxide nanoplates, hydroxide nanoplates, and silicon carbide nanoplates, the hydroxide nanoplates comprising La (OH)3、Co(OH)2、Ni(OH)2And Mn (OH)2At least one of;
e. the thickness of the nano flaky material is 1 nm-100 mu m;
f. the area of the nano sheet material is 1 mu m2～800μm2；
g. The number of layers of the nano flaky material is 1-10.
8. The production method according to claim 4, characterized in that it satisfies at least one of the following conditions a to d:
a. the mass ratio of the activating agent to the graphite nanoparticles is (0.1-40): 1;
b. the activating agent comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, phosphoric acid, nitric acid, sulfuric acid, lithium chloride, potassium chloride, sodium chloride, zinc chloride, potassium carbonate, lithium carbonate and sodium carbonate;
c. a dispersing agent is also added into the mixed solution, and the dispersing agent comprises at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyglycol ester, hexadecyl trimethyl ammonium bromide, polyethylene glycol p-isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid and polyetherimide;
d. and adding a dispersing agent into the mixed solution, wherein the mass ratio of the dispersing agent to the graphite nanoparticles is (0.1-5): 100.
9. the production method according to claim 4, characterized in that it satisfies at least one of the following conditions a to g:
a. the drying treatment mode comprises spray drying;
b. the temperature of the drying treatment is 150-300 ℃;
c. the carbonization temperature is 500-1100 ℃, and the heat preservation is carried out for 1-10 h;
d. the temperature rise rate of the carbonization is 0.5 ℃/min to 20.0 ℃/min;
e. the protective gas comprises at least one of nitrogen, helium, neon, argon and xenon;
f. the flow rate of the protective gas is 100mL/min-500 mL/min;
g. the protective gas also comprises ammonia gas, and the volume of the ammonia gas in the protective gas accounts for 10-40%.
10. Use of a graphite composite material, wherein the graphite composite material is the graphite composite material according to any one of claims 1 to 3 or the graphite composite material prepared by the method according to any one of claims 4 to 9, and the graphite composite material is used as an oxygen reduction catalyst and applied to an oxygen reduction reaction in a fuel cell.
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