CN113506866A - Carbon-coated Fe2O3Hard carbon composite material and preparation method thereof - Google Patents
Carbon-coated Fe2O3Hard carbon composite material and preparation method thereof Download PDFInfo
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- CN113506866A CN113506866A CN202110720807.2A CN202110720807A CN113506866A CN 113506866 A CN113506866 A CN 113506866A CN 202110720807 A CN202110720807 A CN 202110720807A CN 113506866 A CN113506866 A CN 113506866A
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- carbon
- hard carbon
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- sintering
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 88
- 238000001354 calcination Methods 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 51
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000002505 iron Chemical class 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 11
- 239000001095 magnesium carbonate Substances 0.000 claims description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 21
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 15
- 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 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses carbon-coated Fe2O3A preparation method of a hard carbon composite material belongs to the technical field of sodium ion batteries. The method comprises the following steps: s1: washing leaves with water, drying and crushing to obtain leaf particles; s2: soaking the leaf particles in an iron salt solution, filtering the leaf particles, drying, calcining and crushing to obtain Fe2O3Hard carbon material of Fe2O3The grain diameter of the hard carbon material is 10-15 mu m, the porosity is 30-35 percent, and the pore diameter is 500nm-1 mu m; s3: subjecting said Fe to2O3Adding hard carbon material into organic carbon source liquid, mixing to obtain slurry, and subjecting the slurry to vacuum evaporationDrying, sintering and crushing the slurry to obtain the carbon-coated Fe2O3Hard carbon composite material, the carbon coated Fe2O3The grain diameter of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30nm-200 nm.
Description
Technical Field
The present application relates to a carbon-coated Fe2O3A hard carbon composite material and a preparation method thereof belong to the technical field of sodium ion batteries.
Background
In recent years, the output and sales of China new energy automobiles are continuously increased and stably live at the first place in the world. However, the traditional lead-acid battery and nickel-cadmium battery have low energy efficiency and serious pollution, the lithium ion battery has high cost and needs to be improved in safety, and the market demand of new energy automobiles is increased rapidly, so that the market demand is difficult to meet. The sodium ion battery has the advantages of high safety, low cost, environmental friendliness and the like, is favored by researchers, and promotes the application of the sodium ion battery in the aspect of power batteries.
The hard carbon material is a non-graphitizable amorphous carbon material, has a short-range order and a long-range disorder structure, and can be described as amorphous carbon formed by disordered stacking of countless tiny graphite-like nano chips, wherein defects and gaps are filled. The hard carbon material has good physical and chemical stability due to the unique disordered structure, the carbon-based material has good electrical conductivity, and in addition, the hard carbon material can be obtained by pyrolysis of a high polymer material and a biomass material, so that the structural design is easy to carry out, and the hard carbon material is a good composite material substrate. However, when the hard carbon material is used as a negative electrode material of a battery, the battery has disadvantages of low reversible capacity, low first efficiency, low discharge voltage, and the like, and the use of the hard carbon material is limited.
Disclosure of Invention
In order to solve the above problems, a carbon-coated Fe is provided2O3Method for preparing/hard carbon composite material, carbon-coated Fe prepared by the method2O3The/hard carbon composite material can improve the sodium storage capacity of the material, improve the first charge-discharge efficiency of the hard carbon material, improve the conductivity when used as a battery cathode material, increase the specific capacity and the absorbable stress of a battery, and further improve the cycle and rate performance of the battery.
The carbon-coated Fe2O3The preparation method of the/hard carbon composite material comprises the following steps:
s1: washing leaves with water, drying and crushing to obtain leaf particles;
s2: soaking the leaf particles in an iron salt solution, filtering the leaf particles, drying, calcining and crushing to obtain Fe2O3Hard carbon material, said Fe2O3The grain diameter of the hard carbon material is 10-15 mu m, the porosity is 30-35 percent, and the pore diameter is 50-250 nm;
s3: subjecting said Fe to2O3Adding a hard carbon material into an organic carbon source liquid, mixing to obtain slurry, drying, sintering and crushing the slurry to obtain carbon-coated Fe2O3Hard carbon composite material, said carbon coated Fe2O3The grain diameter of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30nm-200 nm.
Preferably, the carbon-coated Fe2O3The porosity of the hard carbon composite material is 28-30%, and the pore diameter is 50nm-150 nm.
More preferably, the carbon-coated Fe2O3The ratio of the pores with the pore diameter of 80nm-100nm of the/hard carbon composite material is more than 50%, preferably more than 60%, more preferably more than 70%, and most preferably more than 75%, so that more sodium storage space can be provided, and the specific capacity of the battery can be improved.
Fe obtained by immersing leaves in a solution of an iron salt and subsequently calcining them together2O3The hard carbon material has unique dendritic grains on leaves, can provide more sites for embedding sodium ions after being calcined, has strong physical and chemical stability and structural design and ultrahigh theoretical specific capacity, can increase the specific capacity of the hard carbon material, improves the sodium storage capacity of the hard carbon, and can also be used as Fe2O3The buffer matrix of the material reduces the damage of the composite material to the electrode structure caused by volume expansion in the charging and discharging process.
In the synthesis of Fe2O3Adding the hard carbon material into organic carbon source liquid, sintering and crushing to obtain carbon-coated Fe2O3Hard carbonThe coated carbon shell can maintain the stability of the iron oxide material, fully play the synergistic effect of the iron oxide and the carbon, improve the electronic conductivity of the battery, form a short-range ordered carbon layer with larger micropores at the sintering temperature, facilitate the transmission and the attachment of sodium ions with larger ionic radius, improve the first charge-discharge efficiency of the hard carbon and further improve the cycle and the rate performance of the battery.
Synthetic carbon coated Fe2O3Hard carbon composite vs. Fe2O3Carbon coated Fe for hard carbon materials2O3The particle size of the hard carbon composite material is increased, but the change is not large, the pore diameter and the porosity are reduced, the specific surface area of the composite material can be increased, the electrolyte can be favorably permeated into the composite material, the migration rate of sodium ions in the charging and discharging process is improved, the occurrence of dead sodium is avoided, and the first effect and the circulation rate of a sodium ion battery are improved. The porosity of the composite material is favorable for the adsorption of ferric oxide, the specific capacity of the composite material is improved, a small part of ferric oxide is embedded into the pores, and the influence on the embedding and the de-embedding of sodium ions is small; the aperture of the composite material is beneficial to the embedding and the de-embedding of sodium ions, the aperture is too small, the embedding and the de-embedding of the sodium ions in the charging and discharging process are not facilitated, the aperture is too large, the volume expansion is serious in the sodium embedding process, the space between pole pieces is reduced, and the capacity of a battery cannot be normally exerted.
Optionally, the calcination temperature in the step S2 is 300-500 ℃, and the time is 1.5-5 h;
preferably, the calcination in step S2 is a staged calcination, stage I: the calcination temperature is 300-: the calcination temperature is 350-450 ℃, the calcination time is 30-90min, and the stage III: the calcination time is 450-500 ℃, and the calcination time is 30-200 min.
More preferably, stage I: the calcination temperature is 320-350 ℃, the calcination time is 30-50min, and the stage II: the calcination temperature is 400-450 ℃, the calcination time is 50-70min, and the stage III: the calcination time is 470-500 ℃, and the calcination time is 90-120 min.
Most preferably, stage I: calcination temperature 350 ℃, calcination time 40min, stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: the calcination time is 480 ℃, and the calcination time is 100 min.
Calcining in stages at the temperature of 300-500 ℃ to obtain Fe2O3Hard carbon material, the calcining temperature is gradually increased, the initial calcining temperature is lower, the obtained ferric oxide and the components in the hard carbon material are incompletely reacted, the amorphous degree and the porosity of the hard carbon are increased, and the calcining temperature is increased later, so that Fe can be caused to be in an amorphous state2O3The porosity of the hard carbon material is ensured to be higher, and the ferric oxide and the components in the hard carbon material are further promoted to react, so that the obtained ferric oxide and the hard carbon material still keep amorphous, and the porosity can be in a higher range, so that the intercalation and deintercalation of sodium ions are facilitated, the migration rate of the sodium ions is facilitated to be improved, and the first efficiency of the battery is improved.
Optionally, the concentration of the iron salt solution is 2.5-3mol/L, preferably 2.5mol/L, the solvent in the iron salt solution is deionized water, and the weight ratio of the leaf particles to the iron salt solution is 0.01-0.5:1, preferably 0.2: 1.
Alternatively, the Fe2O3Fe in hard carbon material2O3The content of the iron salt solution is 2-5%, and the iron salt solution also comprises 1% of ethanol, 0.1-0.5% of magnesium carbonate and 0.2-1% of organic silicon resin.
The content of the ferric oxide is controlled to be 2% -5%, so that the high specific capacity of the ferric oxide can be exerted, and the over-high content can be avoided, so that the hard carbon sodium intercalation site is occupied, and the migration of sodium ions is not facilitated. The concentration of the iron salt solution is favorable for fully infiltrating leaf particles, magnesium carbonate and organic silicon resin are added into the iron salt, the magnesium carbonate and the organic silicon resin can be attached to the leaf particles together with the iron salt in the soaking process of the leaf particles, when the magnesium carbonate is calcined at the back, the magnesium carbonate can produce carbon dioxide, larger holes can be generated in the hard carbon material, sites are provided for the adsorption of the ferric oxide material, a magnesium oxide material is generated at the same time, and Fe can be stabilized2O3Hard carbon material structure, avoiding collapse of hard carbon material interior caused by over-high porosity, reducing hard carbon and electricityThe side reaction of the electrolyte can be cooperated with ferric oxide to further improve the specific capacity of the hard carbon material.
The organic silicon resin can increase the adsorption effect of the ferric oxide, improve the binding force of the ferric oxide and the hard carbon material, and avoid the ferric oxide from falling off in the charging and discharging processes, thereby influencing the specific capacity of the battery and improving the cycle rate of the battery. Meanwhile, part of the organic silicon resin is ablated in the sintering process of the step S3, and Fe coated with carbon2O3The hard carbon composite material generates holes inside and provides more sites for the intercalation and deintercalation of sodium ions, and preferably, the organic silicon resin is tetraethyl orthosilicate.
Optionally, the sintering temperature in the step S3 is 1000-1500 ℃, and the time is 5-15 h;
preferably, the sintering in the step S3 is staged sintering, and the step I: the sintering temperature is 1000-: the sintering temperature is 1100-: the sintering time is 1300-1500 ℃, and the sintering time is 1-1.5 h.
More preferably, stage I: sintering temperature 1050-: the sintering temperature is 1200-1250 ℃, the sintering time is 5-8h, and the stage III: the sintering time is 1350 ℃ and 1400 ℃, and the sintering time is 1-1.5 h.
Most preferably, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature 1200 ℃, sintering time 6h, stage III: the sintering time is 1350 ℃ and 1.5 h.
Sintering by stages to obtain carbon-coated Fe2O3The hard carbon composite material can enable hard carbon in the composite material to form a short-range ordered structure and a long-range disordered structure, the short-range ordered structure is favorable for adsorption of the surface of sodium ions, the long-range disordered structure is favorable for a large amount of embedding of the sodium ions, the sodium ions can be guaranteed to be rapidly separated in the discharging process of the sodium ion battery, and the first discharging efficiency of the battery is improved.
Optionally, the concentration of the organic carbon source solution is 1.0-2.0mol/L, preferably 1.5mol/L, and the Fe2O3Hard carbon material and the sameThe weight ratio of the organic carbon source solution is 1:5-10, preferably 1:6-8, and more preferably 1: 7. The proportion can ensure the uniform coating Fe of the carbon layer2O3Hard carbon material, forming a dense and uniform carbon layer.
Optionally, the carbon coating amount is 2% -8%, and the carbon-coated Fe2O3The thickness of the carbon coating layer in the hard carbon composite material is 20-50 nm. The carbon coating amount can promote Fe2O3And the composite material has enough sodium insertion sites under the synergistic action of the hard carbon, so that sodium ions can be conveniently inserted, and the capacity of the battery is further improved. The carbon coating amount is too small, the structure of the composite material is unstable, side reaction is easy to occur, the cycle performance of the battery is reduced, the carbon coating amount is too large, sodium intercalation sites can be occupied to a certain extent, and the specific capacity of the battery is reduced.
Optionally, the calcining in the step S2 and the sintering in the step S3 are both performed under a protective gas, and the protective gas is any one or more of nitrogen, argon and helium. Calcining and sintering under protective gas can reduce the adverse effect of harmful components (water and oxygen) in the atmosphere on the product, is helpful for removing impurities such as silicon, aluminum, magnesium, calcium and the like or oxides thereof, and plays a role of purifying materials.
Optionally, the leaf particles are mixed in the iron salt solution, then the iron salt solution is heated to 40-60 ℃, and is filtered after being soaked for 2-5h, wherein the mixing method is any one or more of ball milling, stirring and ultrasonic dispersion. The temperature of the ferric salt is controlled to be 40-60 ℃, which is beneficial to fully infiltrating leaf particles by the ferric salt solution and is convenient for the adsorption and combination of the ferric oxide and the hard carbon material.
Optionally, the negative ion of the iron salt is any one or more of acetate, propionate, oxalate, malonate, succinate, citrate, benzoic acid, phthalic acid, lactic acid, glycinate and salicylate, and is preferably citrate; the negative ions are stable and easy to dissolve in hot water, and the operation is simple.
The organic carbon source is any one or more of citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, asphalt, phenolic resin, epoxy resin and polyimide, preferably glucose, is easy to obtain and dissolve, has small influence on the environment, and is suitable for mass production.
According to yet another aspect of the present application, there is provided a carbon-coated Fe2O3A/hard carbon composite material prepared by the preparation method of any one of the above.
Benefits of the present application include, but are not limited to:
1. according to the preparation method of the composite material, the hard carbon material is obtained by calcining the unique dendritic grains in the leaves, more sites can be provided for the embedding of sodium ions, the iron oxide material is strong in physical and chemical stability and structural design, has ultrahigh theoretical specific capacity, can increase the specific capacity of the hard carbon material and improve the sodium storage capacity of the hard carbon, and meanwhile, the hard carbon material can also be used as Fe2O3The buffer matrix of the material reduces the damage of the composite material to the electrode structure caused by volume expansion in the charging and discharging process.
2. According to the method for preparing the composite material, the coated carbon shell can promote Fe2O3The hard carbon material plays a synergistic role, improves the specific capacity of the battery, stabilizes various performances of the battery, reduces the heat release of the battery during charging and discharging, improves the cycle performance of the battery, and prolongs the service life of the battery.
3. According to the preparation method of the composite material, the specific surface area of the composite material can be increased by 25-30% of the porosity, so that the migration of sodium ions in the composite material can be facilitated, the migration rate is increased, the occurrence of dead sodium is avoided, the energy density of a sodium ion battery is increased, the porosity is favorable for the adsorption of ferric oxide, and the specific capacity of the battery is increased.
4. According to the preparation method of the composite material, the small holes with the size of 30-50 nm are beneficial to the embedding and the de-embedding of sodium ions, the charging and discharging efficiency is improved, the holes with the size larger than 50nm are beneficial to the migration of the sodium ions in the hard carbon material, and the volume expansion in the sodium embedding is reduced.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially, and included iron salts, organic carbon sources, magnesium carbonate, and silicone resins.
The batteries manufactured in the examples and comparative examples of the present application were divided into three batches, five of which were manufactured for each batch, and the batteries were analyzed and tested after removing the defective products.
Analysis of the instrument information used for the test:
the types of the testing instruments of the grain diameter and the porosity are respectively as follows: mastersizer 3000, NOVA 2000e, pore size testing was performed using NOVA touch, a pore size analyzer, purchased from anto pa (shanghai) trade ltd, and the prepared composite material was subjected to electron microscope scanning to observe the pore size distribution.
The test uses the instrument model: CT-4008T-5V12A-S1-F, purchased from Shenzhen New Wille electronics, Inc.
Analysis and test conditions:
testing the first effect, the charge and discharge capacity and the energy density under the conditions that the voltage range is 1.0-4.2V and the current density is 0.1-5C;
and performing a discharge test of 100 cycles under the conditions that the voltage range is 1.0-4.2V and the current density is 1C to obtain the capacity retention rate after 100 cycles.
Example 1
(1) Washing leaves with water, drying and crushing to obtain leaf particles;
(2) and (2) placing the leaf particles in the step (1) in an iron salt solution, heating to 50 ℃ for soaking, wherein negative ions of iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the iron salt solution comprises 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, soaking for 4 hours, filtering out the leaf particles, drying, calcining and crushing, wherein the calcining is divided into three stages, and the stage I is as follows: calcination temperature 350 ℃, calcination time 40min, stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: the calcining time is 480 ℃, and the calcining time is 100 min;
(3) mixing the above Fe2O3Adding the hard carbon material into organic carbon source solution, and mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 1.5mol/L, and Fe2O3The weight ratio of the hard carbon material to the organic carbon source solution is 1:7, the slurry is dried, sintered and crushed, and the sintering is divided into three stages, namely stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature 1200 ℃, sintering time 6h, stage III: the sintering time is 1350 ℃, and the sintering time is 1.5 h;
thus obtaining the composite material 1 #.
Example 2
(1) Same as example 1;
(2) and (2) placing the leaf particles in the step (1) in an iron salt solution, heating to 50 ℃ for soaking, wherein negative ions of iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, soaking for 4 hours, filtering out the leaf particles, drying, calcining and crushing, wherein the calcining is divided into three stages, and stage I: calcination temperature 350 ℃, calcination time 40min, stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: the calcining time is 480 ℃, and the calcining time is 100 min;
(3) same as example 1;
thus obtaining the composite material No. 2.
Example 3
(1) Same as example 1;
(2) and (2) placing the leaf particles in the step (1) in an iron salt solution, heating to 50 ℃ for soaking, wherein negative ions of iron salt are citrate, the concentration of the iron salt solution is 0.5mol/L, the iron salt solution comprises 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.5:1, soaking for 4 hours, filtering out the leaf particles, drying, calcining and crushing, wherein the calcining is divided into three stages, and the stage I is as follows: calcination temperature 350 ℃, calcination time 40min, stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: the calcining time is 480 ℃, and the calcining time is 100 min;
(3) same as example 1;
thus obtaining the composite material No. 3.
Example 4
(1) (2) same as example 1;
(3) mixing the above Fe2O3Adding the hard carbon material into organic carbon source solution, and mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 1.5mol/L, and Fe2O3The weight ratio of the hard carbon material to the organic carbon source solution is 1:10, the slurry is dried, sintered and crushed, the sintering is divided into three stages, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature 1200 ℃, sintering time 6h, stage III: the sintering time is 1350 ℃, and the sintering time is 1.5 h;
thus obtaining the composite material No. 4.
Example 5
(1) (2) same as example 1;
(3) mixing the above Fe2O3Adding the hard carbon material into the organic carbon source solution, and mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 0.5mol/L, and Fe2O3The weight ratio of the hard carbon material to the organic carbon source solution is 1:3, the slurry is dried, sintered and crushed, and the sintering is divided into three stages, namely stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature 1200 ℃, sintering time 6h, stage III: the sintering time is 1350 ℃, and the sintering time is 1.5 h;
thus obtaining the composite material No. 5.
Comparative example 1
(1) Same as example 1;
(2) placing the leaf particles in the step (1) in an iron salt solution, heating to 50 ℃ for soaking, wherein negative ions of iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the leaf particles comprise 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, soaking for 4 hours, filtering out the leaf particles, drying, calcining and crushing, the calcining temperature is 500 ℃, and the calcining time is 3 hours;
(3) same as in example 1.
Thus obtaining the comparative composite material No. 1.
Comparative example 2
(1) Same as example 1;
(2) and (2) placing the leaf particles in the step (1) in an iron salt solution, heating to 50 ℃ for soaking, wherein negative ions of iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the iron salt solution comprises 1% of ethanol, 1% of magnesium carbonate and 5% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, soaking for 4 hours, filtering out the leaf particles, drying, calcining and crushing, wherein the calcining is divided into three stages, and the stage I is as follows: calcination temperature 350 ℃, calcination time 40min, stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: the calcining time is 480 ℃, and the calcining time is 100 min;
(3) same as example 1;
thus obtaining the comparative composite material No. 2.
Comparative example 3
(1) (2) same as in example 1
(3) Mixing the above Fe2O3Adding the hard carbon material into organic carbon source solution, and mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 1.5mol/L, and Fe2O3The weight ratio of the hard carbon material to the organic carbon source solution is 1:7, and the slurry is dried, sintered and crushed, wherein the sintering temperature is 1200 ℃, and the sintering time is 9 hours;
thus obtaining the comparative composite material No. 3.
The prepared composite material 1# -5# and the comparative composite material 1# -3# were tested for particle size, pore size and porosity, and the results are shown in table 1:
TABLE 1
Examples of the experiments
Respectively mixing the composite material No. 1-5 prepared in the embodiment and the comparative composite material No. 1-3 prepared in the comparative example, conductive carbon black and sodium carboxymethylcellulose according to a mass ratio of 80: 10: 10 mixing in deionized water, grinding into paste, coating on copper foil current collector, drying at 80 deg.C for 12 hr, cutting into pieces with diameter of 12mm, weighing, calculating the mass of hard carbon material (active substance), and adding argonIn the gas-shielded glove box, a metal sodium sheet is used as a positive electrode, glass fiber is used as a diaphragm, and 1mol/L NaClO is used4And the/PC solution is used as electrolyte, a 2032 button type half cell is assembled, and a sodium ion half cell is subjected to charge-discharge test in a constant current charge-discharge mode, wherein the voltage range is 1.0-4.2V. The test results are shown in table 2:
TABLE 2
The experimental data show that when the composite material prepared by the invention is used as the cathode material of the sodium ion battery, the side reaction of the cathode material and the electrolyte can be reduced, the cycle performance of the battery is improved, meanwhile, the pore diameter of the composite material is beneficial to the permeation of the electrolyte, the migration rate of sodium ions in the electrolyte is improved, the phenomenon of dead sodium is reduced, the first effect and the energy density of the sodium ion battery are improved, the adsorption of ferric oxide is facilitated, the specific capacity of the composite material is improved, the service life of the sodium ion battery is prolonged, and the large-scale production is facilitated.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. Carbon-coated Fe2O3The preparation method of the/hard carbon composite material is characterized by comprising the following steps:
s1: washing leaves with water, drying and crushing to obtain leaf particles;
s2: soaking the leaf particles in an iron salt solution, filtering the leaf particles, drying, calcining and crushing to obtain Fe2O3Hard carbon material, said Fe2O3The grain diameter of the hard carbon material is 10-15 mu m,the porosity is 30-35%, and the pore diameter is 50-250 nm;
s3: subjecting said Fe to2O3Adding a hard carbon material into an organic carbon source liquid, mixing to obtain slurry, drying, sintering and crushing the slurry to obtain carbon-coated Fe2O3Hard carbon composite material, said carbon coated Fe2O3The grain diameter of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30nm-200 nm.
2. Carbon-coated Fe according to claim 12O3The preparation method of the hard carbon composite material is characterized in that the calcination temperature in the step S2 is 300-500 ℃, and the time is 1.5-5 h;
preferably, the calcination in step S2 is a staged calcination, stage I: the calcination temperature is 300-: the calcination temperature is 350-450 ℃, the calcination time is 30-90min, and the stage III: the calcination time is 450-500 ℃, and the calcination time is 30-200 min.
3. Carbon-coated Fe according to claim 22O3The preparation method of the hard carbon composite material is characterized in that the concentration of the ferric salt solution is 2.5-3mol/L, preferably 2.5mol/L, and the solvent in the ferric salt solution is deionized water;
the weight ratio of the leaf particles to the iron salt solution is 0.01-0.5:1, preferably 0.2: 1.
4. Carbon-coated Fe according to claim 12O3The preparation method of the hard carbon composite material is characterized in that the sintering temperature in the step S3 is 1000-1500 ℃, and the time is 5-15 h;
preferably, the sintering in the step S3 is staged sintering, and the step I: the sintering temperature is 1000-: the sintering temperature is 1100-: the sintering time is 1300-1500 ℃, and the sintering time is 1-1.5 h.
5. Carbon-coated Fe according to claim 42O3The preparation method of the hard carbon composite material is characterized in that the concentration of the organic carbon source solution is 1.0-2.0mol/L, preferably 1.5 mol/L;
said Fe2O3The weight ratio of the hard carbon material to the organic carbon source solution is 1:5-10, preferably 1: 7.
6. Carbon-coated Fe according to claim 52O3The preparation method of the hard carbon composite material is characterized in that the carbon coating amount is 2% -8%, and the carbon-coated Fe2O3The thickness of the carbon coating layer in the hard carbon composite material is 20-50 nm.
7. Carbon-coated Fe according to claim 12O3A method for producing a hard carbon composite material, characterized in that Fe is used2O3Fe in hard carbon material2O3The content of the iron salt solution is 2-5%, and the iron salt solution also comprises 1% of ethanol, 0.1-0.5% of magnesium carbonate and 0.2-1% of organic silicon resin.
8. Carbon-coated Fe according to claim 12O3The preparation method of the hard carbon composite material is characterized in that the calcination in the S2 step and the sintering in the S3 step are both carried out under a protective gas, and the protective gas is any one or more of nitrogen, argon and helium; and/or
The leaf particles are mixed in the ferric salt solution, then the ferric salt solution is heated to 40-60 ℃, soaked for 2-5h and then filtered, and the mixing method is any one or more of ball milling, stirring and ultrasonic dispersion.
9. Carbon-coated Fe according to claim 12O3The preparation method of the hard carbon composite material is characterized in that the negative ions of the ferric salt are acetate, propionate, oxalate, malonate, succinate, citrate, benzoic acid and phthalic acidAny one or more of lactic acid, glycinate and salicylate, preferably citrate;
the organic carbon source is any one or more of citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, asphalt, phenolic resin, epoxy resin and polyimide, and is preferably glucose.
10. Carbon-coated Fe2O3A/hard carbon composite material, characterized in that it is produced by the production method according to any one of claims 1 to 9.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101699640A (en) * | 2009-10-26 | 2010-04-28 | 湖南大学 | Fe/FeO composite negative electrode material of power lithium ion battery and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN102790217A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof |
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| CN105355908A (en) * | 2011-12-12 | 2016-02-24 | 浙江大学 | Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery |
| CN106299365A (en) * | 2016-11-04 | 2017-01-04 | 郑州大学 | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery |
| CN106558685A (en) * | 2015-09-30 | 2017-04-05 | 比亚迪股份有限公司 | Porous core shell structure negative material and preparation method thereof and battery |
| CN106848277A (en) * | 2017-01-22 | 2017-06-13 | 曲阜师范大学 | A kind of magnesium iron oxygen/carbon composite and preparation method thereof |
| CN107611419A (en) * | 2017-08-22 | 2018-01-19 | 武汉理工大学 | Alkaline-earth metal ferrite electrode material and its preparation method and application |
| WO2018126818A1 (en) * | 2017-01-04 | 2018-07-12 | 华南理工大学 | Three-dimensional structured carbonized plant-fiber material serving as negative electrode material for sodium-ion battery and lithium-ion battery, and preparation method thereof |
| CN109360935A (en) * | 2018-09-28 | 2019-02-19 | 桑顿新能源科技有限公司 | A kind of lithium ion battery cellular hard carbon coated LiFePO 4 for lithium ion batteries positive electrode, preparation method, porous electrode and lithium battery |
| CN110350179A (en) * | 2019-07-17 | 2019-10-18 | 中国科学院福建物质结构研究所 | A kind of Fe2O3Nano carbon composite material and its preparation method and application |
| WO2020019311A1 (en) * | 2018-07-27 | 2020-01-30 | 辽宁星空钠电电池有限公司 | Polyanionic sodium ion battery anode material and preparation method thereof |
| CN111554885A (en) * | 2019-02-12 | 2020-08-18 | 成都佰思格科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN113036099A (en) * | 2021-02-22 | 2021-06-25 | 武汉纺织大学 | Biomass-based graphitized carbon/Fe7S8Method for preparing composite material |
-
2021
- 2021-06-28 CN CN202110720807.2A patent/CN113506866B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101699640A (en) * | 2009-10-26 | 2010-04-28 | 湖南大学 | Fe/FeO composite negative electrode material of power lithium ion battery and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN105355908A (en) * | 2011-12-12 | 2016-02-24 | 浙江大学 | Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery |
| CN102790217A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof |
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| CN106558685A (en) * | 2015-09-30 | 2017-04-05 | 比亚迪股份有限公司 | Porous core shell structure negative material and preparation method thereof and battery |
| CN106299365A (en) * | 2016-11-04 | 2017-01-04 | 郑州大学 | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery |
| WO2018126818A1 (en) * | 2017-01-04 | 2018-07-12 | 华南理工大学 | Three-dimensional structured carbonized plant-fiber material serving as negative electrode material for sodium-ion battery and lithium-ion battery, and preparation method thereof |
| CN106848277A (en) * | 2017-01-22 | 2017-06-13 | 曲阜师范大学 | A kind of magnesium iron oxygen/carbon composite and preparation method thereof |
| CN107611419A (en) * | 2017-08-22 | 2018-01-19 | 武汉理工大学 | Alkaline-earth metal ferrite electrode material and its preparation method and application |
| WO2020019311A1 (en) * | 2018-07-27 | 2020-01-30 | 辽宁星空钠电电池有限公司 | Polyanionic sodium ion battery anode material and preparation method thereof |
| CN109360935A (en) * | 2018-09-28 | 2019-02-19 | 桑顿新能源科技有限公司 | A kind of lithium ion battery cellular hard carbon coated LiFePO 4 for lithium ion batteries positive electrode, preparation method, porous electrode and lithium battery |
| CN111554885A (en) * | 2019-02-12 | 2020-08-18 | 成都佰思格科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN110350179A (en) * | 2019-07-17 | 2019-10-18 | 中国科学院福建物质结构研究所 | A kind of Fe2O3Nano carbon composite material and its preparation method and application |
| CN113036099A (en) * | 2021-02-22 | 2021-06-25 | 武汉纺织大学 | Biomass-based graphitized carbon/Fe7S8Method for preparing composite material |
Non-Patent Citations (2)
| Title |
|---|
| NA NA LI ET AL: "《Fe2O3 nanoparticles encapsulated with N-doped porous graphitic shells approached by oxidizing Fe3C@C precursor for high-performance sodium-ion batteries》", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 792 * |
| 吴宏照;李海鹏;: "碳包覆Fe_3O_4纳米负极材料的制备及电化学性能", 电源技术, no. 04 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114420938A (en) * | 2022-03-31 | 2022-04-29 | 河北坤天新能源科技有限公司 | Metal oxide amorphous carbon coated hard carbon composite material and preparation method and application thereof |
| CN114420938B (en) * | 2022-03-31 | 2022-06-21 | 河北坤天新能源股份有限公司 | Metal oxide amorphous carbon coated hard carbon composite material and preparation method and application thereof |
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