CN109659574A - Composite positive pole and preparation method thereof, lithium-air battery - Google Patents
Composite positive pole and preparation method thereof, lithium-air battery Download PDFInfo
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- CN109659574A CN109659574A CN201811513929.9A CN201811513929A CN109659574A CN 109659574 A CN109659574 A CN 109659574A CN 201811513929 A CN201811513929 A CN 201811513929A CN 109659574 A CN109659574 A CN 109659574A
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 177
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 175
- 150000003839 salts Chemical class 0.000 claims abstract description 132
- 239000000243 solution Substances 0.000 claims abstract description 100
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011259 mixed solution Substances 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 42
- 229920005610 lignin Polymers 0.000 claims abstract description 38
- 238000006722 reduction reaction Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 238000012545 processing Methods 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 49
- 238000011282 treatment Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000009938 salting Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000003763 carbonization Methods 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- -1 hydrogen Sodium hydroxide Chemical class 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005275 alloying Methods 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 144
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 44
- 229910045601 alloy Inorganic materials 0.000 description 26
- 239000000956 alloy Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 17
- 229910002058 ternary alloy Inorganic materials 0.000 description 17
- 238000010792 warming Methods 0.000 description 16
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910001092 metal group alloy Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000826860 Trapezium Species 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000714 At alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005183 dynamical system Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of composite positive pole, comprising the following steps: the anhydrous alcohol solution of the aqueous solution of lignin salt and polyacrylonitrile is carried out mixed processing, is configured to the first mixed solution；Nano silica powder is dispersed in first mixed solution, the second mixed solution is obtained, program heat treatment is carried out, prepares char-forming material；Etching liquid is added in the char-forming material, N doping porous carbon is prepared；The N doping porous carbon is dispersed in deionized water or Organic Alcohol, the porous carbon solution of N doping is prepared；The mixing salt solution of alloying element is added in the porous carbon solution of N doping, third mixed solution is prepared；Adjust the third mixed solution pH make solution alkaline after, reducing agent is added, carries out reduction reaction, centrifuge separation is collected to precipitate and simultaneously be cleaned to neutrality, under an inert atmosphere calcination processing, and N doping porous carbon load Pd is preparedxFeyWzThe composite positive pole of Nanoalloy.
Description
Technical field
The invention belongs to lithium-air battery technical fields more particularly to a kind of N doping porous carbon to load PdxFeyWzNanometer
Composite positive pole of alloy and preparation method thereof, and the lithium-air battery containing the composite positive pole.
Background technique
In recent years, pure electric automobile development is getting faster, while country is increasing to the support dynamics of New Energy Industry,
The state of high speed development is presented as the lithium ion battery of New Energy Industry dynamical system.Conventional lithium ion battery capacity is limited,
Although as the development of technology, capacity is being gradually increased, but is also difficult to meet consumer demand, this can hinder new energy to produce
The further development of industry.Therefore the exploitation and application of new lithium battery system become increasingly it is necessary to.
Since the energy of lithium-air battery derives from inexhaustible oxygen, and the battery of its very small volume just has and vapour
The energy that oil compares favourably, lithium-air battery are concerned.But the kinetics that lithium-air battery oxygen is reduced is relatively more slow
Slowly, and then the overall performance of battery is influenced, becomes and restricts the main problem that further develops of lithium-air battery.Studies have shown that
Suitable oxygen reduction catalyst is added in air electrode, electric charge transfer rate and mass transfer rate in reaction process can be accelerated, had
Effect ground improves activation polarization phenomenon, improves the overall performance of battery.A kind of catalyst effective at present is noble metal platinum
Carbon (Pt/C).But the antitoxin sexuality of Pt is poor and expensive.Pd is because have similar electronic structure, electrification with Pt
Learn performance and its low-cost advantage, it is considered to be a kind of noble metal that can substitute platinum.But pure Pd catalytic activity is not good enough, far not
Such as Pt/C, and the cyclical stability of catalyst itself is also poor, to restrict the application of pure Pd catalyst.Therefore, existing
Technology also needs further to study.
Summary of the invention
The purpose of the present invention is to provide a kind of N doping porous carbons to load PdxFeyWzThe composite positive pole of Nanoalloy
And preparation method thereof, it is intended to solve Pd is not good enough as air electrode for lithium air battery catalyst activity, repeats itself stablize
Property difference problem.
Another object of the present invention is to provide one kind to load Pd containing N doping porous carbonxFeyWzNanoalloy is compound just
The lithium-air battery of pole material.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of composite positive pole, the composite positive pole are that N doping porous carbon loads PdxFeyWz
Nanoalloy, and the composite positive pole preparation method the following steps are included:
The aqueous solution of lignin salt and the anhydrous alcohol solution of polyacrylonitrile are provided, by the aqueous solution of the lignin salt and institute
The anhydrous alcohol solution for stating polyacrylonitrile carries out mixed processing, is configured to the first mixed solution；
Nano silica powder is provided, the nano silica powder is dispersed in first mixed solution,
The second mixed solution is obtained, second mixed solution is subjected to program heat treatment, prepares char-forming material；In the carbonization material
Etching liquid is added in material, etching removes the silica in the char-forming material, N doping porous carbon is prepared；Wherein, institute
State mixing sample progress pre-oxidation treatment that program heat treatment includes the steps that obtaining and by the sample after pre-oxidation treatment
The step of carrying out carbonization treatment；
The N doping porous carbon is dispersed in deionized water or Organic Alcohol, the porous carbon solution of N doping is prepared；It provides
The porous carbon solution of N doping is added in the salting liquid of the Pd salt, Fe salt and W salt by the salting liquid of Pd salt, Fe salt and W salt
In, prepare third mixed solution；Adjust the third mixed solution pH make solution alkaline after, be added reducing agent, stirring bar
Reduction reaction is carried out under part, centrifuge separation, which is collected, to precipitate and clean to neutrality, and calcination processing, is prepared nitrogen under an inert atmosphere
It adulterates porous carbon and loads PdxFeyWzThe composite positive pole of Nanoalloy, wherein the ratio of x, y, z is 1:(0.2-0.5):
(0.2-0.5)。
Preferably, the anhydrous alcohol solution of the aqueous solution of the lignin salt and the polyacrylonitrile is subjected to mixed processing,
It is the ratio of 10:(1-5) according to the mass ratio of lignin salt and polyacrylonitrile in the step of being configured to the first mixed solution, it will
The anhydrous alcohol solution of the aqueous solution of the lignin salt and the polyacrylonitrile carries out mixed processing.
Preferably, in the step of described program heats, the method for the pre-oxidation treatment are as follows: mixed described second
Under conditions of temperature is 180 DEG C~240 DEG C, heat preservation is pre-oxidized solution；The method of the carbonization treatment are as follows: will carry out pre-
In the case where temperature is 800 DEG C~1200 DEG C of inert atmosphere conditions, heat preservation is carbonized sample after oxidation processes.
Preferably, etching liquid is added in the char-forming material, etching removes the silica in the char-forming material
In step, the etching liquid is HF solution or the etching liquid is the sodium hydroxide of molten condition.
Preferably, the salting liquid of the Pd salt, Fe salt and W salt is added to the step in the porous carbon solution of the N doping
In, Pd is loaded by finally obtained N doping porous carbonxFeyWzIn Nanoalloy, PdxFeyWzThe weight percent of Nanoalloy contains
The salting liquid of the Pd salt, Fe salt and W salt is added in the porous carbon solution of N doping the ratio that amount is 10%~40%.
Preferably, adjust the third mixed solution pH make solution alkaline after, reducing agent is added, under stirring condition into
In the step of row reduction reaction, sodium hydroxide solution is used to adjust the pH of the third mixed solution as 9~12, boron hydrogen is added
Change sodium as reducing agent, carries out reduction treatment under agitation.
Preferably, adjust the third mixed solution pH make solution alkaline after, reducing agent is added, under stirring condition into
In the step of row reduction reaction, urea is used to adjust the pH of the third mixed solution as 9~12, ethylene glycol is added as reduction
Agent is stirred to react carry out reduction treatment under conditions of temperature is 70 DEG C~90 DEG C.
Preferably, under an inert atmosphere calcination processing the step of in, the calcination processing temperature be 300 DEG C~500 DEG C
Under conditions of carry out.
Preferably, the nano silica is mono-dispersed nano silica spheres, and the nanometer titanium dioxide silicon ball
Partial size be 150nm~250nm.
Correspondingly, a kind of composite positive pole, the composite positive pole is that N doping porous carbon loads PdxFeyWzNanometer
Alloy, wherein PdxFeyWzDoping weight percentage of the Nanoalloy in N doping porous carbon is 10%~40%, described
PdxFeyWzIn Nanoalloy, the ratio of x, y, z is 1:(0.2-0.5): (0.2-0.5).
And a kind of lithium-air battery, the lithium-air battery contain positive electrode active materials, and the positive electrode active materials
For composite positive pole of the present invention or the positive electrode active materials be the method for the invention be prepared it is compound just
Pole material.
It is porous first to prepare N doping using the method for going template for the preparation method of composite positive pole provided by the invention
Carbon, obtain to hole be uniformly dispersed, orderly N doping porous carbon；Then the simple and quick synthesis Pd of chemical reduction method is usedxFeyWzThree
First alloy is carried in the pore structure of N doping porous carbon, finally obtains the anode composite material that stability is strong, catalytic activity is good
Material-N doping porous carbon loads PdxFeyWzNanoalloy (PdxFeyWz-N/C).Specifically, the preparation of the composite positive pole
Method has the advantage that
Firstly, using silica template method can prepare aperture it is uniform, it is with higher repeatability, have it is abundant
The porous material of specific surface area and porosity.On the one hand, the N doping porous carbon being prepared using silica template method, tool
There is specific surface area abundant, can be PdxFeyWzTernary alloy three-partalloy nucleation provides more sites, is conducive to PdxFeyWzTernary is closed
Evenly dispersed, the increase Pd of goldxFeyWzThe exposure of ternary alloy three-partalloy improves catalysis to generate more active sites
Effect.Simultaneously as its hole of N doping porous carbon is relatively independent, alloy can be prevented to migrate reunion in cyclic process, very
To falling off, reinforce the stability of alloy.On the other hand, method provided by the invention can in C element Uniform Doped N element,
The N element of doping influence surrounding C atom spin density and institute's band it is charge, to increase the electric conductivity of carbon material and expedite the emergence of
More active sites.In addition, thus obtained N doping porous carbon, three-dimensional porous structure therein are conducive to active material oxygen
The transmission of gas.To sum up, the N doping porous carbon (N/C) that the present invention is prepared is a kind of good catalyst carrier.
Secondly, using the simple and quick synthesis Pd of chemical reduction methodxFeyWzTernary alloy three-partalloy is carried on the hole of N doping porous carbon
In gap structure, mild condition, and the Pd being preparedxFeyWzTernary alloy three-partalloy, dispersibility is very good, and shape is uniform, uniform particle diameter,
It is concentrated mainly between 5-10nm.It is compared with traditional business Pd/C, transition metal can be fast implemented using chemical reduction method
The codope of element of Fe, W, and then change the electronic structure of Pd.Fe, W, Pd three generate synergistic effect, and it is porous to improve N doping
Carbon loads PdxFeyWzCatalytic activity and stability when Nanoalloy is as lithium air battery positive electrode active material.In addition, N is first
Element doping can increase carbon carrier electric conductivity, and porous structure is conducive to the transmission of oxygen and huge specific surface is conducive to close
The dispersion of gold.Therefore, the present invention can not only reduce precious metals pd dosage under multi-level synergistic effect, but also in three electricity
In pole cyclic voltammetry and lithium-air battery limited capacity loop test, shows higher oxygen reduction catalytic activity and catalysis is steady
It is qualitative.
Again, the preparation method of composite positive pole provided by the invention, the method for going template prepare N doping porous carbon
When primary solvent be water；Using the simple and quick synthesis Pd of chemical reduction methodxFeyWzTernary alloy three-partalloy is carried on N doping porous carbon
When, it can be carried out in the aqueous solvent of room temperature, not use any surfactant, not will lead to environmental pollution；Fe, W money
Enrich and be widely used in industry, high conductivity, environmental-friendly characteristic in source.Therefore, composite positive pole provided by the invention
Preparation method, meet the theory of " Green Chemistry ".
In addition, the preparation method of composite positive pole provided by the invention, process is simple, easily operated, has lower
Cost is, it can be achieved that large-scale production.
Composite positive pole provided by the invention loads Pd for N doping porous carbonxFeyWzNanoalloy.
Firstly, using N doping porous carbon as carrier, N doping porous carbon Uniform Doped N element in C element is mixed
Miscellaneous N element influence surrounding C atom spin density and institute's band it is charge, to increase the electric conductivity of carbon material and expedite the emergence of more
More active sites.Meanwhile the N doping porous carbon has specific surface area abundant, can be PdxFeyWzTernary alloy three-partalloy at
Core provides more sites, is conducive to PdxFeyWzEvenly dispersed, the increase Pd of ternary alloy three-partalloyxFeyWzThe exposure of ternary alloy three-partalloy,
To generate more active sites, catalytic effect is improved.And N doping porous carbon provided by the invention, hole are opposite
It is independent, alloy can be prevented to migrate reunion in cyclic process, or even from falling off, reinforce the stability of alloy；Three-dimensional therein is more
Pore structure is conducive to the transmission of active material oxygen.
Secondly, Fe, W codope and Pd generate synergistic effect, improves N doping porous carbon and load PdxFeyWzNanoalloy is made
Catalytic activity and stability when for lithium air battery positive electrode active material.In addition, N element doping can increase carbon carrier conduction
Property, porous structure is conducive to the transmission of oxygen and huge specific surface is conducive to the dispersion of alloy.Therefore, the present invention is compound
Positive electrode is under multi-level synergistic effect, in the test of three electrode cycle volt-ampere and lithium-air battery limited capacity loop test
In, show higher oxygen reduction catalytic activity and catalytic stability.
The N doping porous carbon is loaded into PdxFeyWzNanoalloy is used for the positive electrode active materials of lithium-air battery, tool
Have the advantages that stability is good, chemical property is good, is expected to provide a kind of new positive material for the commercialization of later lithium-air battery
Material.
Lithium-air battery provided by the invention loads Pd with N doping porous carbonxFeyWzNanoalloy is as lithium air electricity
The positive electrode active materials in pond assign the advantage that lithium-air battery stability is good, chemical property is good.
The present invention synthesizes the preparation method of N doping porous carbon, and the by-product lignin-base for taking full advantage of papermaking is derivative
Object has reached waste utilization, meets the theory of " Green Chemistry ".
Detailed description of the invention
Fig. 1 is the N doping porous carbon load PdFe that the embodiment of the present invention 4 provides0.2W0.2The Flied emission of Nanoalloy scans
Electron microscope SEM figure；
Fig. 2 is the N doping porous carbon load PdFe that the embodiment of the present invention 4 provides0.2W0.2The XRD diagram of Nanoalloy；
Fig. 3 is the N doping porous carbon load PdFe that the embodiment of the present invention 4 provides0.2W0.2Nanoalloy is in the oxygen containing saturation
0.1MKOH solution in, the cyclic voltammetry figure of three-electrode electro Chemical work station；
Fig. 4 is the N doping porous carbon load PdFe that the embodiment of the present invention 4 provides0.2W0.2Nanoalloy is as positive-active
The cyclic curve figure of the lithium-air battery of material preparation.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of preparation method of composite positive pole, the composite positive pole is N doping
Porous carbon loads PdxFeyWzNanoalloy, and the composite positive pole preparation method the following steps are included:
S01. the aqueous solution of lignin salt and the anhydrous alcohol solution of polyacrylonitrile are provided, by the aqueous solution of the lignin salt
Mixed processing is carried out with the anhydrous alcohol solution of the polyacrylonitrile, is configured to the first mixed solution；
S02., nano silica powder is provided, the nano silica powder is dispersed in first mixed solution
In, the second mixed solution is obtained, second mixed solution is subjected to program heat treatment, prepares char-forming material；In the carbon
Change and etching liquid is added in material, etching removes the silica in the char-forming material, N doping porous carbon is prepared；Its
In, described program heat treatment includes the steps that the mixing sample that will be obtained progress pre-oxidation treatment and will be after pre-oxidation treatment
Sample carries out the step of carbonization treatment；
S03. the N doping porous carbon is dispersed in deionized water or Organic Alcohol, prepares the porous carbon solution of N doping；
The salting liquid of Pd salt, Fe salt and W salt is provided, it is molten that the N doping porous carbon is added in the salting liquid of the Pd salt, Fe salt and W salt
In liquid, third mixed solution is prepared；Adjust the third mixed solution pH make solution alkaline after, be added reducing agent, stirring
Under the conditions of carry out reduction reaction, centrifuge separation is collected to precipitate and simultaneously be cleaned to neutrality, and calcination processing, is prepared under an inert atmosphere
N doping porous carbon loads PdxFeyWzThe composite positive pole of Nanoalloy, wherein the ratio of x, y, z is 1:(0.2-0.5):
(0.2-0.5)。
The preparation method of composite positive pole provided in an embodiment of the present invention first prepares N doping using the method for going template
Porous carbon, obtain to hole be uniformly dispersed, orderly N doping porous carbon；Then the simple and quick synthesis of chemical reduction method is used
PdxFeyWzTernary alloy three-partalloy is carried in the pore structure of N doping porous carbon, finally obtains that stability is strong, catalytic activity is good answers
It closes positive electrode-N doping porous carbon and loads PdxFeyWzNanoalloy (PdxFeyWz-N/C).Specifically, the anode composite material
The preparation method of material, has the advantage that
Firstly, using silica template method can prepare aperture it is uniform, it is with higher repeatability, have it is abundant
The porous material of specific surface area and porosity.On the one hand, the N doping porous carbon being prepared using silica template method, tool
There is specific surface area abundant, can be PdxFeyWzTernary alloy three-partalloy nucleation provides more sites, is conducive to PdxFeyWzTernary is closed
Evenly dispersed, the increase Pd of goldxFeyWzThe exposure of ternary alloy three-partalloy improves catalysis to generate more active sites
Effect.Simultaneously as its hole of N doping porous carbon is relatively independent, alloy can be prevented to migrate reunion in cyclic process, very
To falling off, reinforce the stability of alloy.On the other hand, method provided in an embodiment of the present invention can in C element Uniform Doped N
Element, the N element of doping influence surrounding C atom spin density and institute's band it is charge, to increase the electric conductivity of carbon material
With expedite the emergence of more active sites.In addition, thus obtained N doping porous carbon, three-dimensional porous structure therein are conducive to activity
The transmission of substance oxygen.To sum up, the N doping porous carbon (N/C) that the present invention is prepared is a kind of good catalyst load
Body.
Secondly, using the simple and quick synthesis Pd of chemical reduction methodxFeyWzTernary alloy three-partalloy is carried on the hole of N doping porous carbon
In gap structure, mild condition, and the Pd being preparedxFeyWzTernary alloy three-partalloy, dispersibility is very good, and shape is uniform, uniform particle diameter,
It is concentrated mainly between 5-10nm.It is compared with traditional business Pd/C, transition metal can be fast implemented using chemical reduction method
The codope of element of Fe, W, and then change the electronic structure of Pd.Fe, W, Pd three generate synergistic effect, and it is porous to improve N doping
Carbon loads PdxFeyWzCatalytic activity and stability when Nanoalloy is as lithium air battery positive electrode active material.In addition, N is first
Element doping can increase carbon carrier electric conductivity, and porous structure is conducive to the transmission of oxygen and huge specific surface is conducive to close
The dispersion of gold.Therefore, the embodiment of the present invention can not only reduce precious metals pd dosage under multi-level synergistic effect, but also
Three electrode cycle volt-ampere test and lithium-air battery limited capacity loop test in, show higher oxygen reduction catalytic activity with
Catalytic stability.
Again, the preparation method of composite positive pole provided in an embodiment of the present invention, the method for going template prepare N doping
Primary solvent when porous carbon is water；Using the simple and quick synthesis Pd of chemical reduction methodxFeyWzTernary alloy three-partalloy is carried on N doping
It when porous carbon, can be carried out in the aqueous solvent of room temperature, not use any surfactant, not will lead to environmental pollution；
Fe, W are resourceful and are widely used in industry, high conductivity, environmental-friendly characteristic.Therefore, it is provided by the invention it is compound just
The preparation method of pole material meets the theory of " Green Chemistry ".
In addition, the preparation method of composite positive pole provided in an embodiment of the present invention, process is simple, easily operated, has
Lower cost is, it can be achieved that large-scale production.
Specifically, in above-mentioned steps S01, by the anhydrous alcohol solution of the aqueous solution of the lignin salt and the polyacrylonitrile
Mixed processing is carried out, is configured to the first mixed solution to get lignin/PAN precursor is arrived.Wherein, the lignin salt
The N doping porous carbon obtained for following step provides carbon source, and the polyacrylonitrile is the N doping porous carbon that following step obtains
Nitrogen source is provided.Compared to directly using carbon as catalyst carrier, due to introducing nitrogen, a side in carbon material in N doping porous carbon
Face, the N element of doping influence surrounding C atom spin density and institute's band it is charge, thus increase carbon material electric conductivity and
More active sites are expedited the emergence of, thus obtained N doping porous carbon is as aid dispersion PdxFeyWzThe carrier of Nanoalloy, can
Pd is loaded to improve obtained N doping porous carbonxFeyWzThe catalytic activity and stability of Nanoalloy.
In some embodiments, the lignin salt selects sodium lignin sulfonate, but not limited to this.In specific embodiment
In, the lignin salt selects papermaking wastewater lignin as presoma.Using papermaking wastewater lignin as synthesis N doping
The raw material of porous carbon can make full use of the by-product lignin-base derivative of papermaking, realize waste utilization, meet " greenization
The theory of ".
In the embodiment of the present invention, the aqueous solution of the lignin salt is prepared by the way that lignin salt to be dissolved in water.
In some embodiments, the solid content of the aqueous solution of the lignin salt is 10%~20%.Within this range, the lignin
The aqueous solution of salt has suitable viscosity after mixing with the anhydrous alcohol solution of polyacrylonitrile, is conducive to nano silica powder
Fully dispersed and infiltration.In particular preferred embodiment, the solid content of the aqueous solution of the lignin salt can for 12%, 13%,
15%, 16%, 18% etc..
In the embodiment of the present invention, the polyacrylonitrile is low in cost as nitrogen source presoma.Preferably, the polypropylene
The molecular weight of nitrile is 80000~15000.Specifically, the polyacrylonitrile of Aladdin purchase may be selected, but not limited to this.It is described poly-
The anhydrous alcohol solution of acrylonitrile realizes that the Organic Alcohol is selected by the way that polyacrylonitrile powder dissolution to be distributed in organic alcoholic solution
Liquid alcohol under normal temperature condition.In some embodiments, the Organic Alcohol for dissolving dispersion polyacrylonitrile powder is anhydrous
Ethyl alcohol or anhydrous propyl alcohol.
In some embodiments, the solid content of the anhydrous alcohol solution of the polyacrylonitrile is 10%~20%.In this range
Interior, the anhydrous alcohol solution of the polyacrylonitrile has suitable viscosity after mixing with the aqueous solution of lignin salt, is conducive to nanometer
The fully dispersed and infiltration of silicon-dioxide powdery.In particular preferred embodiment, the anhydrous alcohol solution of the polyacrylonitrile is consolidated
Content amount can be 12%, 13%, 15%, 16%, 18% etc..
On the basis of the above embodiments, in some embodiments, the solid content of the aqueous solution of the lignin salt is
10%~20%, concretely 10%, 12%, 13%, 15%, 16%, 18%, 20%, the absolute alcohol of the polyacrylonitrile is molten
The solid content of liquid is 10%~20%, concretely 10%, 12%, 13%, 15%, 16%, 18%, 20%.It is consequently formed
First mixed solution has suitable viscosity, can promote the evenly dispersed of nano silica powder, and then by subsequent pre-
Oxidation, carbonization treatment must arrive hole be uniformly dispersed, orderly N doping porous carbon.In particular preferred embodiment, the lignin
Salt selects sodium lignin sulfonate, and the solid content of the aqueous solution of the lignin salt is 15%, and the absolute alcohol of the polyacrylonitrile is molten
The solid content of liquid is 15%.At this point, the first obtained mixed solution is dispersed nano silica powder, there is optimum dispersion
Effect.It is further preferred that the lignin salt selects papermaking wastewater lignin, compound same cheap polyacrylonitrile, preparation
Lignin/polyacrylonitrile N doping porous carbon, it is not only low in cost, and also the effect for loading dispersion nanometer alloy catalyst is excellent
It is different.
In the embodiment of the present invention, it is preferred that the absolute alcohol of the aqueous solution of the lignin salt and the polyacrylonitrile is molten
It is 10 according to the mass ratio of lignin salt and polyacrylonitrile in the step of liquid carries out mixed processing, is configured to the first mixed solution:
The anhydrous alcohol solution of the aqueous solution of the lignin salt and the polyacrylonitrile is carried out mixed processing by the ratio of (1-5).If institute
It states in the first mixed solution, the content of the polyacrylonitrile is too low, then nitrogen-doping content in the N doping porous carbon obtained
Too low, number of nitrogen atoms is less, and the influence to carbon atom is relatively small, and the active site expedited the emergence of is reduced, and therefore, is unfavorable for significant
Improve catalytic effect.If in first mixed solution, the too high levels of the polyacrylonitrile, then carbon content lowers, then can shadow
Ring obtained N doping porous carbon load PdxFeyWzThe electric conductivity of Nanoalloy, and then influence to load N doping porous carbon
PdxFeyWzChemical property of the Nanoalloy as the lithium-air battery of positive electrode active materials.
In above-mentioned steps S02, nano silica powder is provided, the mould as three-dimensional porous structure in N doping porous carbon
Plate.Preferably, the nano silica is mono-dispersed nano silica spheres.On the one hand, the mono-dispersed nano two
Silicon oxide ball, not only good dispersion, is conducive to be dispersed in quality/PAN precursor solution i.e. the first mixed solution
In, and then pass through subsequent carbonization, etch to be uniformly dispersed to hole, orderly N doping porous carbon.On the other hand, it is received using spherical
Rice silica is conducive to obtain cellular pore structure, improves gap specific surface area as template, is conducive to raising alloy and urges
The dispersibility and stability of agent, and then improve catalytic activity and stability.It is further preferred that the nanometer titanium dioxide silicon ball
Partial size be 150nm~250nm.The nanometer titanium dioxide silicon ball of the particle size range can regulate and control pore size, available correspondence
The honeycomb structure of size, is conducive to PdxFeyWzThe dispersion of Nanoalloy.
In some embodiments, the mono-dispersed nano silica spheres, are prepared by following methods:
Using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, using biography in alkaline aqueous solution
It is prepared by the collosol and gel and precipitation from homogeneous solution combined techniques of system.
The nano silica powder is dispersed in first mixed solution, standing is sufficiently impregnated the two, obtains
To the second mixed solution.In some embodiments, it is slowly added to first mixed solution to be placed with nano-silica powder
In the container of body, promote nano silica powder it is abundant infiltration and it is evenly dispersed.Preferably, by the nano silica
Powder is dispersed in the step in first mixed solution, according to lignin salt and polyacrylonitrile total weight and nanometer two
The weight ratio of silica powder is 1:(1-10), the nano silica powder is dispersed in first mixed solution.
If lignin salt and polyacrylonitrile total weight content is very few, cause carbon wall excessively thin, hole configurations is easy to collapse；If lignin
Salt and polyacrylonitrile total weight content is excessive, and carbon wall is blocked up to cause hole to hold reduction, specific surface reduction, is unfavorable for point of alloy
It dissipates.It is specific preferred, the nano silica powder is dispersed in the step in first mixed solution, according to wooden
The weight ratio of plain salt and polyacrylonitrile total weight and nano silica powder can be 1:5,1:6,1:8, receive described
Rice silicon-dioxide powdery is dispersed in first mixed solution.
Further, second mixed solution is heated, lignin therein and polyethylene nitrile is made to be carbonized
Form char-forming material.In the embodiment of the present invention, it is real using program heat treatment that heat treatment is carried out to second mixed solution
It is existing, specifically, described program heat treatment includes the steps that the mixing sample that will be obtained carries out pre-oxidation treatment and will pre-oxidize
The step of sample progress carbonization treatment that treated.
The embodiment of the present invention first pre-oxidizes mixing sample, removes the solvent in liquid solution, is made by pre-oxidation
Chain is increasingly becoming structure and stablizes heat-resisting trapezium structure relatively, while making liquefied mixture solid state, and then after being able to bear
The carbonization of phase high temperature improves carbon yield.In some embodiments, in the step of described program heats, at the pre-oxidation
The method of reason are as follows: by second mixed solution under conditions of temperature is 180 DEG C~240 DEG C, heat preservation is pre-oxidized.At this
In temperature range, the solvent in second mixed solution volatilizees, while when initial stage low temperature pre-oxidation, the ring of the second mixed solution
Change reaction to start, temperature increases crosslinking cyclisation and improves rapidly, when temperature is to 240 DEG C, has reached cyclisation maximum temperature, has formd
Heat-resisting trapezium structure.Furthermore, it is possible to avoid the excessively high carbon caused in sample of temperature from directly generating carbon dioxide gas, to change
The carbon content changed in product, and avoid introducing other impurities.4 hours of the time of the pre-oxidation~10 hours.It is further excellent
Choosing, the method for the pre-oxidation treatment are as follows: first by second mixed solution under conditions of temperature is 180 DEG C~200 DEG C,
Heat preservation carries out first time pre-oxidation；Then under conditions of temperature is 220 DEG C~240 DEG C, heat preservation carries out second and pre-oxidizes, point
Section pre-oxidation can be such that substance is sufficiently oxidized, and oxidation, dehydrogenation and crosslinking cyclization, presoma viscosity gradually occur for presoma
It becomes larger, eventually becomes solid and lose flowability.On the basis of the above embodiments, in the step of pre-oxidation treatment,
After being warming up to pre-oxidation treatment temperature with the heating rate of 3~8 DEG C/min, pre-oxidation treatment is carried out, heating speed is thus avoided
It is too fast cause the first mixed solution be oxidized and its dehydrogenation and crosslinking cyclisation be not thorough influence the later period carbon yield.Specific excellent
It selects in embodiment, in the step of described program heats, the method for the pre-oxidation treatment are as follows: first with the heating of 5 DEG C/min
Rate is warming up to 180 DEG C, keeps the temperature 4 hours progress first time pre-oxidation treatments；Then it is warming up to the heating rate of 5 DEG C/min
240 DEG C, keep the temperature second of the pre-oxidation treatment of progress in 4 hours.
After pre-oxidation treatment, obtained solid sample, which is placed in, to carry out carbonization treatment in airtight heating device.
It is described can airtight heating device may be selected tube furnace.In some embodiments, in the step of described program heats, the carbon
Change the method for processing are as follows: by the sample after progress pre-oxidation treatment in the case where temperature is 800 DEG C~1200 DEG C of inert atmosphere conditions,
Heat preservation is carbonized, and obtains black powder.Carbonization treatment is carried out with this condition, and the crystallinity of carbon can be improved, promote carbon
Obtained N doping porous carbon to improve the electric conductivity of material, and then is loaded Pd by graphitizationxFeyWzNanoalloy is used as lithium
When air cell, its chemical property can be improved.Wherein, the inert atmosphere includes but is not limited to nitrogen atmosphere.Above-mentioned
On the basis of embodiment, the step of the carbonization treatment in, carbonization treatment temperature is warming up to the heating rate of 3~8 DEG C/min
Afterwards, carbonization treatment is carried out, thus avoids heating speed is too fast from leading to further to be crosslinked cyclisation unevenly, influences carbon atom
It resets, finally the orientation of carbon material, stability is all affected.In particular preferred embodiment, at described program heating
In the step of reason, the method for the carbonization treatment are as follows: be first warming up to 800 DEG C~1200 DEG C with the heating rate of 5 DEG C/min, heat preservation
4 hours progress carbonization treatments.
Further, etching liquid is added in the obtained char-forming material, etching removes two in the char-forming material
N doping porous carbon is prepared in silica.It is porous in the N doping porous carbon, what as former nano silica occupied
Site.Dispersibility, mode of appearance and the partial size of nano silica, directly affect the dispersion of porous structure in N doping porous carbon
Property, order, and influence porous structure pore size and shape, finally influence PdxFeyWzNanometer is closed porous in N doping
Supporting effect in carbon.
In some embodiments, etching liquid is added in the char-forming material, etching removes two in the char-forming material
In the step of silica, the etching liquid is HF solution.In some embodiments, etching liquid is added in the char-forming material,
Etching removed in the step of silica in the char-forming material, and the etching liquid is the sodium hydroxide of molten condition.Pass through
The corrasion of HF solution and the sodium hydroxide of molten condition, can be on the basis of not influencing char-forming material other compositions, will
Nano silica is removed, and site where nano silica forms corresponding hole, is finally obtained with three-dimensional porous
The N doping porous carbon of structure.
In above-mentioned steps S03, the N doping porous carbon is dispersed in deionized water or Organic Alcohol, it is more to prepare N doping
Hole carbon solution.As the deionized water or Organic Alcohol of solvent, there can not only be preferable dispersibility to N doping porous carbon, and
And also just there is preferable dispersibility to Pd salt, Fe salt and W salt.The Organic Alcohol selects under the conditions of room temperature (5 DEG C~40 DEG C) as liquid
The Organic Alcohol of state, more preferably ethyl alcohol, propyl alcohol.As particular preferred embodiment, the solvent that the N doping porous carbon is dispersed
Select cheap and environmentally friendly deionized water.
In the embodiment of the present invention, select Pd salt, Fe salt and W salt as precursor preparation PdxFeyWzNanoalloy.Pass through
Fe, W doping, the Pd that the cost of the pure palladium catalyst of script can not only be reduced, and obtainedxFeyWzNanoalloy, tool
There are preferable oxygen reduction catalytic activity and stability, is supported on positive electrode active materials of the N doping porous carbon as lithium-air battery
In use, can solve, existing oxygen reduction catalyst noble metal is at high cost, cyclical stability of catalytic activity and catalyst itself
Poor problem.
Specifically, PdxFeyWzThe preparation method of Nanoalloy includes: to provide the salting liquid of Pd salt, Fe salt and W salt.Pd salt,
The selection of Fe salt and W salt does not limit strictly, can use common Pd salt, Fe salt and W salt.In certain embodiments,
The Pd salt is palladium chloride；In some embodiments, the Fe salt is iron chloride；In some embodiments, the W salt is wolframic acid
Ammonium.In some embodiments, the Pd salt is palladium chloride, and the Fe salt is iron chloride or ferric sulfate, and the W salt is ammonium tungstate.
Preferably, the concentration of the Pd salt is 5~7mg/ml, concretely 5mg/ml, 6mg/ml, 7mg/ml；The concentration of the Fe salt
For 5~7mg/ml, concretely 5mg/ml, 6mg/ml, 7mg/ml；The concentration of the W salt is 5~7mg/ml, concretely
5mg/ml、6mg/ml、7mg/ml。
Further, the salting liquid of the Pd salt, Fe salt and W salt is added in the porous carbon solution of N doping, preparation
Third mixed solution.It is specific preferred, the salting liquid of Pd salt, Fe salt and W salt is separately added into the N doping porous carbon
In solution, the metal salt being added at first as a result, can be evenly dispersed and occupies gap site, after adding other metal salts,
It is uniformly arranged under the guidance for the metal salt being added at first, finally obtains finely dispersed metal salt.In a particular embodiment,
Pd salt is first added, then addition Fe salt and W salt, the order of addition of Fe salt and W salt does not have considered critical.In the base of above-described embodiment
On plinth, the salting liquid of Pd salt, Fe salt and W salt is slowly added and is such as added drop-wise in the porous carbon solution of N doping, promotes metal salt
Into in the pore structure of N doping porous carbon, and it is evenly dispersed.Further, after having added each metal salt, it is stirred place
Reason, so that Pd salt, Fe salt and W salt are evenly dispersed and be combined with each other, preferred mixing time is 2 hours~5 hours, more preferably
3 hours.
In a preferred embodiment, the salting liquid of the Pd salt, Fe salt and W salt is added in the porous carbon solution of N doping
The step of in, by finally obtained N doping porous carbon load PdxFeyWzIn Nanoalloy, PdxFeyWzThe weight of Nanoalloy
It is molten the N doping porous carbon to be added in the salting liquid of the Pd salt, Fe salt and W salt by the ratio that percentage composition is 10%~40%
In liquid.Control the PdxFeyWzWithin the above range, obtained N doping porous carbon loads Pd to NanoalloyxFeyWzNanometer is closed
Fitting has preferable redox catalysis effect.If the PdxFeyWzThe weight percentage of Nanoalloy is more than 40%, then
PdxFeyWzNanoalloy is unfavorable for the desorption of oxygen, causes redox reaction slack-off, and then reduces catalytic effect.More preferably
, Pd is loaded by finally obtained N doping porous carbonxFeyWzIn Nanoalloy, PdxFeyWzThe weight percent of Nanoalloy contains
The salting liquid of the Pd salt, Fe salt and W salt is added in the porous carbon solution of N doping the ratio that amount is 20%.
Adjust the third mixed solution pH make solution alkaline after, be added reducing agent, make the Pd salt, Fe salt and W
Reduction reaction occurs under normal temperature conditions for salt, generates PdxFeyWzNanoalloy.Preferably, the third mixed solution is adjusted
PH makes pH value of solution 9~12, is that the Pd salt, Fe salt and the reduction of W salt generate PdxFeyWzNanoalloy provides suitable alkaline item
Part.Reduction reaction preferably carries out under agitation, and being stirred to react the time is 20~48 hours.
In some embodiments, adjust the third mixed solution pH make solution alkaline after, be added reducing agent, stirring
Under the conditions of in the step of carrying out reduction reaction, use sodium hydroxide solution to adjust the pH of the third mixed solution as 9~12,
Sodium borohydride is added as reducing agent, carries out reduction treatment under agitation.This method can be by Pd salt, Fe salt and W salt also
Original is at PdxFeyWzNanoalloy.Preferably, the concentration of the sodium hydroxide solution is 0.5~1.5mol L-1, more preferably
1.0mol L-1。
In some embodiments, adjust the third mixed solution pH make solution alkaline after, be added reducing agent, stirring
Under the conditions of carry out reduction reaction the step of in, use urea adjust the pH of the third mixed solution be 8~10, addition ethylene glycol
Carry out reduction treatment is stirred to react under conditions of temperature is 70 DEG C~90 DEG C as reducing agent.This method can by Pd salt,
Fe salt and W salt are reduced into PdxFeyWzNanoalloy.
It in the above-described embodiments, is (4~6): 1 ratio according to the molar ratio of reducing agent and metal molar total amount, in institute
It states in third mixed solution and adds reducing agent.It is furthermore preferred that the ratio for being 5:1 according to the molar ratio of reducing agent and metal molar total amount
Example, adds reducing agent in the third mixed solution.
The sample that reduction reaction is obtained is centrifuged, and precipitating is collected, and be washed till neutrality, then at vacuum drying
Reason.Further, N doping porous carbon load Pd is prepared in calcination processing under an inert atmospherexFeyWzNanoalloy is answered
Close positive electrode.Preferably, under an inert atmosphere calcination processing the step of in, the calcination processing temperature be 300 DEG C~500
It is carried out under conditions of DEG C.By above-mentioned calcination processing, Pd can be improvedxFeyWzThe crystallinity of Nanoalloy, and then improve
PdxFeyWzThe stability of Nanoalloy.The calcination time is preferably 2~5 hours, and more preferably 3 hours.Inert atmosphere includes
But it is not limited to nitrogen atmosphere.
In the embodiment of the present invention, the PdxFeyWzIn Nanoalloy, the ratio of x, y, z is 1:(0.2-0.5): (0.2-
0.5).Within the above range, obtained alloying element is imitated with preferable redox catalysis for the constituent content control of Pd, Fe, W
Fruit.Specifically, the PdxFeyWzNanoalloy can be PdFe0.2W0.2Nanoalloy, PdFe0.5W0.5Nanoalloy,
PdFe0.2W0.3Nanoalloy, PdFe0.3W0.2Nanoalloy, PdFe0.2W0.2Nanoalloy, PdFe0.3W0.3Nanoalloy,
PdFe0.5W0.2Nanoalloy, PdFe0.2W0.5Nanoalloy, but not limited to this.
Correspondingly, the composite positive pole is that N doping is more the embodiment of the invention provides a kind of composite positive pole
Hole carbon loads PdxFeyWzNanoalloy, wherein PdxFeyWzDoping weight percent of the Nanoalloy in N doping porous carbon contains
Amount is 10%~40%, the PdxFeyWzIn Nanoalloy, the ratio of x, y, z is 1:(0.2-0.5): (0.2-0.5).
Composite positive pole provided in an embodiment of the present invention loads Pd for N doping porous carbonxFeyWzNanoalloy.
Firstly, using N doping porous carbon as carrier, N doping porous carbon Uniform Doped N element in C element is mixed
Miscellaneous N element influence surrounding C atom spin density and institute's band it is charge, to increase the electric conductivity of carbon material and expedite the emergence of more
More active sites.Meanwhile the N doping porous carbon has specific surface area abundant, can be PdxFeyWzTernary alloy three-partalloy at
Core provides more sites, is conducive to PdxFeyWzEvenly dispersed, the increase Pd of ternary alloy three-partalloyxFeyWzThe exposure of ternary alloy three-partalloy,
To generate more active sites, catalytic effect is improved.And N doping porous carbon provided in an embodiment of the present invention, hole
Hole is relatively independent, alloy can be prevented to migrate reunion in cyclic process, or even from falling off, reinforce the stability of alloy；It is therein
Three-dimensional porous structure is conducive to the transmission of active material oxygen.
Secondly, Fe, W codope and Pd generate synergistic effect, improves N doping porous carbon and load PdxFeyWzNanoalloy is made
Catalytic activity and stability when for lithium air battery positive electrode active material.In addition, N element doping can increase carbon carrier conduction
Property, porous structure is conducive to the transmission of oxygen and huge specific surface is conducive to the dispersion of alloy.Therefore, the present invention is implemented
Example composite positive pole is under multi-level synergistic effect, in the test of three electrode cycle volt-ampere and lithium-air battery limited capacity circulation
In test, higher oxygen reduction catalytic activity and catalytic stability are shown.
The N doping porous carbon is loaded Pd by the embodiment of the present inventionxFeyWzNanoalloy is used for the anode of lithium-air battery
Active material has the advantages that stability is good, chemical property is good, is expected to provide one kind for the commercialization of later lithium-air battery
New positive electrode.
It preferably, is the weight percent of N in terms of 100% by the total weight of N doping porous carbon in the N doping porous carbon
Content is 1%~5%.If the N element content is too low, unobvious to the effect for expediting the emergence of active site；If the N element contains
Excessively high, then carbon content attenuating is measured, then the N doping porous carbon load Pd that will affectxFeyWzThe electric conductivity of Nanoalloy, into
And it influences N doping porous carbon loading PdxFeyWzElectrochemistry of the Nanoalloy as the lithium-air battery of positive electrode active materials
Can, it is directly contacted in addition, N content has with carburizing temperature with carbonization time, if carburizing temperature is too high, carbonization time is too long
Final N element content is caused to tail off.
The N doping porous carbon loads PdxFeyWzNanoalloy, it is preferred that the diameter of porous structure be 150nm~
250nm, porous structure are preferably cellular porous.
N doping porous carbon described in the embodiment of the present invention loads PdxFeyWzNanoalloy can be prepared by the above method
It obtains.
And the embodiment of the invention also provides a kind of lithium-air battery, the lithium-air battery contains positive-active material
Material, and the positive electrode active materials are composite positive pole of the present invention or the positive electrode active materials are institute of the present invention
The composite positive pole that the method for stating is prepared.
Lithium-air battery provided in an embodiment of the present invention loads Pd with N doping porous carbonxFeyWzNanoalloy is as lithium
The positive electrode active materials of air cell assign the advantage that lithium-air battery stability is good, chemical property is good.
The case where composite positive pole, is as described above, and in order to save length, details are not described herein again.
Specifically, being deposited on plus plate current-collecting body after the composite positive pole is mixed with binder, anode is formed
Piece.The binder includes but is not limited to polyvinylidene fluoride, it is preferred that loads Pd according to N doping porous carbonxFeyWzNanometer
Alloy and polyvinylidene fluoride are in 9:(0.8~1.2) ratio, mixed, dispersion in a solvent, be further deposited on anode
On collector.It is furthermore preferred that loading Pd according to N doping porous carbonxFeyWzNanoalloy and polyvinylidene fluoride press the ratio of 9:1
Example, is mixed, and dispersion in a solvent, is further deposited on plus plate current-collecting body.The solvent includes but is not limited to anhydrous second
Alcohol.Conventional lithium air battery positive electrode collector, more preferably carbon paper/nickel foam/foam copper may be selected in the plus plate current-collecting body.
N doping porous carbon is loaded into PdxFeyWzNanoalloy is carried on N doping porous carbon, and deposits and be such as sprayed at carbon paper/foam
Nickel/foam copper surface has the advantages that oxidation catalytic activity and stability are good as lithium air battery positive electrode material.
It is further preferred that being the N doping porous carbon load in terms of 100% by the total weight of the positive plate
PdxFeyWzThe weight of Nanoalloy is 0.2-1mg cm-2, more preferably 0.4mg cm-2。
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of composite positive pole, comprising the following steps:
(1) using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, is used in alkaline aqueous solution
Traditional collosol and gel and precipitation from homogeneous solution combined techniques prepares the SiO that partial size concentrates on 150-200nm2Ball.
(2) sodium lignin sulfonate is dissolved into water, stirring forms uniform solution A, and the solid content of solution is 20%；It will
Polyacrylonitrile powder dissolution is dispersed in dehydrated alcohol, and stirring forms uniform solution B, and the solid content of solution is 20%.By solution A
It is uniformly mixed with B according to the amount that volume ratio is 10:1 and forms mixed solution C.
(3) preparation of N doping porous carbon N/C.Take the SiO in appropriate step (1)2Put 50mL corundum porcelain boat into, then
The solution C in appropriate step (2) is taken slowly to instill SiO2In powder, standing is sufficiently impregnated the two, then will mixing sample point
4h is not pre-oxidized successively in 180 DEG C and 220 DEG C of air；Pre-oxidize obtained solid N in tube furnace2Under atmosphere, with 3 DEG C/
The heating speed of min is warming up under 800 DEG C of heat preservation 4h and is carbonized, and obtains black powder；Finally prepared with HF solution etches template
N doping porous carbon (N/C).
(4)PdFe0.5W0.2Nanoalloy is carried on the porous carbon surface of N doping.Weigh 20mg N doping porous carbon support
(N/C), it is put into ultrasonic disperse 30min in 200mL deionized water and obtains solution D；It [is closed then according to designed alloy load capacity
Gold loading=alloy quality/(quality of alloy and the quality sum of N/C)] it is that 30wt% and scheduled Pd, Fe, W rub
You slowly drip respectively under stiring than 1:0.5:0.2, by three kinds of pre-configured palladium chloride, iron chloride, ammonium tungstate salting liquids
Enter in mixed solution D, continues to stir 3h, obtain mixed liquor E wait be sufficiently mixed；Then 1mol L is used-1Sodium hydrate aqueous solution
PH=11 is adjusted, then instills just prepared sodium borohydride aqueous solution (sodium borohydride is 5:2 with metal molar ratio), room temperature stirs
Mix 48h.Reaction terminates, and will contain PdFe0.5W0.2The mixed liquor of nano ternary metal alloy is centrifuged, and washs precipitating
It to neutrality, is dried in vacuo later, 300 DEG C of high temperature is finally warming up to the heating speed of 3 DEG C/min in nitrogen atmosphere of inert gases
3h is calcined, N doping porous carbon load PdFe is obtained0.5W0.2Nanoalloy.
Embodiment 2
A kind of preparation method of composite positive pole, comprising the following steps:
(1) using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, is used in alkaline aqueous solution
Traditional collosol and gel and precipitation from homogeneous solution combined techniques prepares the SiO that partial size concentrates on 150-200nm2Ball.
(2) sodium lignin sulfonate is dissolved into water, stirring forms uniform solution A, and the solid content of solution is 10%；It will
Polyacrylonitrile powder dissolution is dispersed in dehydrated alcohol, and stirring forms uniform solution B, and the solid content of solution is 10%.By solution A
It is uniformly mixed with B according to the amount that volume ratio is 10:2 and forms mixed solution C.
(3) preparation of N doping porous carbon N/C.Take the SiO in appropriate step (1)2Put 50ML corundum porcelain boat into, then
The solution C in appropriate step (2) is taken slowly to instill SiO2In powder, standing is sufficiently impregnated the two, then will mixing sample point
4h is not pre-oxidized successively in 200 DEG C and 240 DEG C of air；Pre-oxidize obtained solid N in tube furnace2Under atmosphere with 8 DEG C/
The heating speed of min is warming up under 1000 DEG C of heat preservation 4h and is carbonized, and obtains black powder；Finally prepared with HF solution etches template
N doping porous carbon (N/C).
(4)PdFe0.2W0.5Nanoalloy is carried on the porous carbon surface of N doping.Weigh 20mg N doping porous carbon support
(N/C), it is put into ultrasonic disperse 30min in 200mL deionized water and obtains solution D；It is then according to designed alloy load capacity
40wt% and scheduled Pd, Fe, W molar ratio 1:0.2:0.5, by pre-configured palladium chloride, iron chloride, ammonium tungstate three
Kind salting liquid is slowly dropped into mixed solution D respectively under stiring, is continued to stir 2h, is obtained mixed liquor E wait be sufficiently mixed；Then
With 1mol L-1Sodium hydrate aqueous solution adjust pH=10, then instill just prepared sodium borohydride aqueous solution (sodium borohydride
It is 5:1 with metal molar ratio), stirring at normal temperature is for 24 hours.Reaction terminates, and will contain PdFe0.2W0.5The mixing of nano ternary metal alloy
Liquid is centrifuged, and wash be precipitated to neutrality, be dried in vacuo later, finally in nitrogen atmosphere of inert gases with 8 DEG C/
The heating speed of min is warming up to 400 DEG C of high-temperature calcination 3h, obtains N doping porous carbon load PdFe0.2W0.5Nanoalloy.
Embodiment 3
A kind of preparation method of composite positive pole, comprising the following steps:
(1) using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, is used in alkaline aqueous solution
Traditional collosol and gel and precipitation from homogeneous solution combined techniques prepares the SiO that partial size concentrates on 150-200nm2Ball.
(2) sodium lignin sulfonate is dissolved into water, stirring forms uniform solution A, and the solid content of solution is 15%；It will
Polyacrylonitrile powder dissolution is dispersed in dehydrated alcohol, and stirring forms uniform solution B, and the solid content of solution is 15%.By solution A
It is uniformly mixed with B according to the amount that volume ratio is 10:3 and forms mixed solution C.
(3) preparation of N doping porous carbon N/C.Take the SiO in appropriate step (1)2Put 50mL corundum porcelain boat into, then
The solution C in appropriate step (2) is taken slowly to instill SiO2In powder, standing is sufficiently impregnated the two, then will mixing sample point
4h is not pre-oxidized successively in 180 DEG C and 200 DEG C of air；Pre-oxidize obtained solid N in tube furnace2Under atmosphere with 5 DEG C/
The heating speed of min is warming up under 1200 DEG C of heat preservation 4h and is carbonized, and obtains black powder；Finally prepared with HF solution etches template
N doping porous carbon (N/C).
(4)PdFe0.5W0.2Nanoalloy is carried on the porous carbon surface of N doping.Weigh 20mg N doping porous carbon support
(N/C), it is put into ultrasonic disperse 30min in 200mL deionized water and obtains solution D；It is then according to designed alloy load capacity
20wt% and scheduled Pd, Fe, W molar ratio 1:0.5:0.2, by pre-configured palladium chloride, iron chloride, ammonium tungstate three
Kind salting liquid is slowly dropped into mixed solution D respectively under stiring, is continued to stir 5h, is obtained mixed liquor E wait be sufficiently mixed；Then
With 1mol L-1Sodium hydrate aqueous solution adjust pH=9, then instill just prepared sodium borohydride aqueous solution (sodium borohydride
It is 5:1 with metal molar ratio), stirring at normal temperature 36h.Reaction terminates, and will contain PdFe0.5W0.2The mixing of nano ternary metal alloy
Liquid is centrifuged, and wash be precipitated to neutrality, be dried in vacuo later, finally in nitrogen atmosphere of inert gases with 5 DEG C/
The heating speed of min is warming up to 500 DEG C of high-temperature calcination 3h, obtains N doping porous carbon load PdFe0.5W0.2Nanoalloy.
Embodiment 4
A kind of preparation method of composite positive pole, comprising the following steps:
(1) using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, is used in alkaline aqueous solution
Traditional collosol and gel and precipitation from homogeneous solution combined techniques prepares the SiO that partial size concentrates on 150-200nm2Ball.
(2) sodium lignin sulfonate is dissolved into water, stirring forms uniform solution A, and the solid content of solution is 15%；It will
Polyacrylonitrile powder dissolution is dispersed in dehydrated alcohol, and stirring forms uniform solution B, and the solid content of solution is 15%.By solution A
It is uniformly mixed with B according to the amount that volume ratio is 10:5 and forms mixed solution C.
(3) preparation of N doping porous carbon N/C.Take the SiO in appropriate step (1)2Put 50mL corundum porcelain boat into, then
The solution C in appropriate step (2) is taken slowly to instill SiO2In powder, standing is sufficiently impregnated the two, then will mixing sample point
4h is not pre-oxidized successively in 190 DEG C and 220 DEG C of air；Pre-oxidize obtained solid N in tube furnace2Under atmosphere with 5 DEG C/
The heating speed of min is warming up under 800 DEG C of heat preservation 4h and is carbonized, and obtains black powder；Finally prepared with HF solution etches template
N doping porous carbon (N/C).
(4)PdFe0.2W0.2Nanoalloy is carried on the porous carbon surface of N doping.Weigh 20mg N doping porous carbon support
(N/C), it is put into ultrasonic disperse 30min in 200mL deionized water and obtains solution D；It is then according to designed alloy load capacity
30wt% and scheduled Pd, Fe, W molar ratio 1:0.2:0.2, by pre-configured palladium chloride, iron chloride, ammonium tungstate three
Kind salting liquid is slowly dropped into mixed solution D respectively under stiring, is continued to stir 3h, is obtained mixed liquor E wait be sufficiently mixed；Then
With 1mol L-1Sodium hydrate aqueous solution adjust pH=9, then instill just prepared sodium borohydride aqueous solution (sodium borohydride
It is 5:1 with metal molar ratio), stirring at normal temperature 20h.Reaction terminates, and will contain PdFe0.2W0.2The mixing of nano ternary metal alloy
Liquid is centrifuged, and wash be precipitated to neutrality, be dried in vacuo later, finally in nitrogen atmosphere of inert gases with 5 DEG C/
The heating speed of min is warming up to 400 DEG C of high-temperature calcination 3h, obtains N doping porous carbon load PdFe0.2W0.2Nanoalloy.
N doping porous carbon prepared by embodiment 4 loads PdFe0.2W0.2The field emission scanning electron microscope of Nanoalloy
SEM figure is as shown in Figure 1, as seen from the figure, N doping porous carbon loads PdFe0.2W0.2There are a large amount of size rules for Nanoalloy
Hole, it appears that just as honeycomb one by one, mutually indepedent between nest and nest, this can prevent the group that falls off of catalyst in the reaction
It is poly-.In addition, little by little the little particle of brilliant white is exactly PdFe0.2W0.2Nanoalloy, it is seen that it successfully loads to honeycomb carbon surface,
Alloy is loaded later there is no the structure and morphology for destroying honeycomb carbon script, shows that honeycomb carbon has good structural stability value
It obtains one to be mentioned that, N doping porous carbon loads PdFe0.2W0.2The alloy dispersion degree of Nanoalloy is higher, without agglomeration,
Uniform in size, granular size is all in 10nm or less.
N doping porous carbon prepared by embodiment 4 loads PdFe0.2W0.2The XRD diagram of Nanoalloy as shown in Figure 2 (while with
Porous carbon loads Pd as control), Fig. 2 illustrates Pd-/C and PdFe0.2W0.2There is apparent diffraction maximum, respectively corresponds Pd
(111), (200), (220), (311) crystal face, and do not find other miscellaneous peaks in entire XRD spectrum；And it clearly sees
Observe PdFe0.2W0.2XRD characteristic peak compared with Pd-/C, it is whole to be deviated to high angle, this is because the addition of Fe, W change
Pd crystal structure, results in palladium Lattice Contraction, illustrates Pd and Fe, W-shaped at alloy.
N doping porous carbon prepared by embodiment 4 loads PdFe0.2W0.2Nanoalloy is molten in the 0.1MKOH of the oxygen containing saturation
In liquid, (sweep speed is 50mV s respectively to the cyclic voltammetry figure of three-electrode electro Chemical work station-1) as shown in Figure 3 (simultaneously
Using porous carbon load Pd as compareing), PdFe as seen from Figure 30.2W0.2The take-off potential of-N/C, half wave potential and carrying current are close
Degree is shuffled than Pd-/C, therefore may determine that PdFe0.2W0.2The hydrogen reduction catalytic capability ratio Pd-/C of-N/C is more preferable.
N doping porous carbon prepared by embodiment 4 loads PdFe0.2W0.2The lithium-air battery of Nanoalloy preparation is constant
Size of current is 300mAh g-1, constant specific capacity is 500mAh g-1, under the conditions of charge and discharge protecting range is 5.0V-2.0V
Loop test, as a result as shown in Figure 4 (while loading Pd as control using porous carbon), as seen from Figure 4 in limitation lithium-air battery
Under capacity charge status, compared with business Pd/C cycle performance, PdFe0.2W0.2The overpotential of-N/C is smaller, in the electricity of restriction
Press the period recycled in range longer, far superior to the cycle performance of business Pd/C.
Embodiment 5
A kind of preparation method of composite positive pole, comprising the following steps:
(1) using tetraethyl orthosilicate as silicon source, cetyl trimethylammonium bromide is template, is used in alkaline aqueous solution
Traditional collosol and gel and precipitation from homogeneous solution combined techniques prepares the SiO that partial size concentrates on 150-200nm2Ball.
(2) sodium lignin sulfonate is dissolved into water, stirring forms uniform solution A, and the solid content of solution is 15%；It will
Polyacrylonitrile powder dissolution is dispersed in dehydrated alcohol, and stirring forms uniform solution B, and the solid content of solution is 15%.By solution A
It is uniformly mixed with B according to the amount that volume ratio is 10:4 and forms mixed solution C.
(3) preparation of N doping porous carbon N/C.Take the SiO in appropriate step (1)2Put 50mL corundum porcelain boat into, then
The solution C in appropriate step (2) is taken slowly to instill SiO2In powder, standing is sufficiently impregnated the two, then will mixing sample point
4h is not pre-oxidized successively in 180 DEG C and 240 DEG C of air；Pre-oxidize obtained solid N in tube furnace2Under atmosphere with 5 DEG C/
The heating speed of min is warming up under 1000 DEG C of heat preservation 4h and is carbonized, and obtains black powder；Finally carved with the NaOH solution of molten condition
Erosion template prepares N doping porous carbon (N/C).
(4)PdFe0.5W0.5Nanoalloy is carried on the porous carbon surface of N doping.Weigh the nitrogen co-doped honeycomb carbon carrier of 20mg
(N/C) it is scattered in 50mL urea liquid and forms mixed liquor D, be 40wt% and scheduled according to the alloy load capacity set in advance
Pd, Fe, W molar ratio 1:0.5:0.5 divide three kinds of pre-configured palladium chloride, iron chloride, ammonium tungstate salting liquids under stiring
It is not slowly dropped into mixed solution D, continues to stir 3h, obtain mixed liquor E wait be sufficiently mixed, mixed liquor E is transferred into three mouthfuls of burnings
In bottle, condensation reflux unit is built, temperature rises to 80 DEG C of oil bath heat preservation 1h.Room temperature to be cooled to is subsequently added into the ethylene glycol of 50mL,
Solution is warming up to 120 DEG C and keeps the temperature 12h under stirring condition.Reaction terminates, and will contain PdFe0.2W0.2Nano ternary metal alloy
Mixed liquor is centrifuged, and wash be precipitated to neutrality, be dried in vacuo later, finally nitrogen atmosphere of inert gases with 5 DEG C/
The heating speed of min is warming up to 400 DEG C of high-temperature calcination 3h, obtains N doping porous carbon load PdFe0.5W0.5Nanoalloy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of composite positive pole, which is characterized in that the composite positive pole is negative for N doping porous carbon
Carry PdxFeyWzNanoalloy, and the composite positive pole preparation method the following steps are included:
The aqueous solution of lignin salt and the anhydrous alcohol solution of polyacrylonitrile are provided, by the aqueous solution of the lignin salt and described poly-
The anhydrous alcohol solution of acrylonitrile carries out mixed processing, is configured to the first mixed solution；
Nano silica powder is provided, the nano silica powder is dispersed in first mixed solution, is obtained
Second mixed solution is carried out program heat treatment, prepares char-forming material by the second mixed solution；In the char-forming material
Etching liquid is added, etching removes the silica in the char-forming material, N doping porous carbon is prepared；Wherein, the journey
Sequence heat treatment includes the steps that the mixing sample that will be obtained carries out pre-oxidation treatment and carries out the sample after pre-oxidation treatment
The step of carbonization treatment；
The N doping porous carbon is dispersed in deionized water or Organic Alcohol, the porous carbon solution of N doping is prepared；Offer Pd salt,
The salting liquid of the Pd salt, Fe salt and W salt is added in the porous carbon solution of N doping the salting liquid of Fe salt and W salt, preparation
Third mixed solution；Adjust the third mixed solution pH make solution alkaline after, reducing agent is added, carries out under stirring condition
Reduction reaction, centrifuge separation, which is collected, to precipitate and cleans to neutrality, and calcination processing, it is porous to be prepared N doping under an inert atmosphere
Carbon loads PdxFeyWzThe composite positive pole of Nanoalloy, wherein the ratio of x, y, z is 1:(0.2-0.5): (0.2-0.5).
2. the preparation method of composite positive pole as described in claim 1, which is characterized in that by the water-soluble of the lignin salt
In the step of anhydrous alcohol solution of liquid and the polyacrylonitrile carries out mixed processing, is configured to the first mixed solution, according to wooden
The mass ratio of plain salt and polyacrylonitrile is 10:(1-5) ratio, by the aqueous solution of the lignin salt and the polyacrylonitrile
Anhydrous alcohol solution carries out mixed processing.
3. the preparation method of composite positive pole as described in claim 1, which is characterized in that the step of described program heat treatment
In rapid, the method for the pre-oxidation treatment are as follows: by second mixed solution under conditions of temperature is 180 DEG C~240 DEG C, protect
Temperature is pre-oxidized；The method of the carbonization treatment are as follows: by carry out pre-oxidation treatment after sample temperature be 800 DEG C~1200
DEG C inert atmosphere conditions under, heat preservation be carbonized.
4. the preparation method of composite positive pole as described in claim 1, which is characterized in that be added in the char-forming material
In the step of etching liquid, etching removes the silica in the char-forming material, the etching liquid is HF solution or the etching
Liquid is the sodium hydroxide of molten condition.
5. the preparation method of composite positive pole as described in claim 1, which is characterized in that by the Pd salt, Fe salt and W salt
Salting liquid be added in the step in the porous carbon solution of the N doping, by finally obtained N doping porous carbon load
PdxFeyWzIn Nanoalloy, PdxFeyWzThe weight percentage of Nanoalloy be 10%~40% ratio, by the Pd salt,
The salting liquid of Fe salt and W salt is added in the porous carbon solution of N doping.
6. such as the preparation method of composite positive pole described in any one of claim 1 to 5, which is characterized in that adjust described the
In the step of after the pH of three mixed solutions makes solution alkaline, reducing agent is added, reduction reaction is carried out under stirring condition, using hydrogen
Sodium hydroxide solution is 9~12 come the pH for adjusting the third mixed solution, and sodium borohydride is added as reducing agent, in stirring condition
Lower carry out reduction treatment；Or
It uses urea to adjust the pH of the third mixed solution as 9~12, ethylene glycol is added and is used as reducing agent, be 70 DEG C in temperature
Under conditions of~90 DEG C, it is stirred to react carry out reduction treatment.
7. such as the preparation method of composite positive pole described in any one of claim 1 to 5, which is characterized in that in inert atmosphere
In the step of lower calcination processing, the calcination processing carries out under conditions of temperature is 300 DEG C~500 DEG C.
8. such as the preparation method of composite positive pole described in any one of claim 1 to 5, which is characterized in that the nanometer two
Silica is mono-dispersed nano silica spheres, and the partial size of the nanometer titanium dioxide silicon ball is 150nm~250nm.
9. a kind of composite positive pole, which is characterized in that the composite positive pole is that N doping porous carbon loads PdxFeyWzIt receives
Meter He Jin, wherein PdxFeyWzDoping weight percentage of the Nanoalloy in N doping porous carbon is 10%~40%, institute
State PdxFeyWzIn Nanoalloy, the ratio of x, y, z is 1:(0.2-0.5): (0.2-0.5).
10. a kind of lithium-air battery, which is characterized in that the lithium-air battery contains positive electrode active materials, and the anode is living
Property material be composite positive pole as claimed in claim 9 or the positive electrode active materials for any one of claim 1~8 institute
The composite positive pole that the method for stating is prepared.
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Cited By (2)
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| CN115367745A (en) * | 2021-05-19 | 2022-11-22 | 北京化工大学 | Tungsten-containing substance hybrid and nitrogen-doped porous carbon material and preparation method thereof |
| CN117756111A (en) * | 2024-02-22 | 2024-03-26 | 鲁东大学 | Nitrogen-doped biochar with through mesoporous and preparation method and application thereof |
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Cited By (4)
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| CN115367745A (en) * | 2021-05-19 | 2022-11-22 | 北京化工大学 | Tungsten-containing substance hybrid and nitrogen-doped porous carbon material and preparation method thereof |
| CN115367745B (en) * | 2021-05-19 | 2023-11-24 | 北京化工大学 | Tungsten-containing substance hybridization and nitrogen-doped porous carbon material and preparation method thereof |
| CN117756111A (en) * | 2024-02-22 | 2024-03-26 | 鲁东大学 | Nitrogen-doped biochar with through mesoporous and preparation method and application thereof |
| CN117756111B (en) * | 2024-02-22 | 2024-05-14 | 鲁东大学 | Nitrogen-doped biochar with through mesoporous and preparation method and application thereof |
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