CN108807919B - Preparation method of three-dimensional carbon skeleton - Google Patents
Preparation method of three-dimensional carbon skeleton Download PDFInfo
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- CN108807919B CN108807919B CN201810630253.5A CN201810630253A CN108807919B CN 108807919 B CN108807919 B CN 108807919B CN 201810630253 A CN201810630253 A CN 201810630253A CN 108807919 B CN108807919 B CN 108807919B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 25
- 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 abstract description 19
- 239000008103 glucose Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 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 abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000012298 atmosphere Substances 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000004222 ferrous gluconate Substances 0.000 claims description 3
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 3
- 229960001645 ferrous gluconate Drugs 0.000 claims description 3
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 12
- 230000010287 polarization Effects 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 238000003763 carbonization Methods 0.000 abstract description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 41
- 239000002243 precursor Substances 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 239000002131 composite material Substances 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 4
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 4
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- H01M4/362—Composites
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- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- 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
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method of a three-dimensional carbon skeleton. The method comprises the steps of mixing glucose and ferrous sulfate, then ball-milling the mixture and sodium chloride, tabletting by using an infrared tablet press, and washing away the sodium chloride after sintering and carbonization to obtain the three-dimensional carbon skeleton. The material obtained by the invention can realize the conduction of electrons from points to a three-dimensional space, can improve the electron conduction capability among particles of the anode material, reduce polarization and further enhance the electrochemical performance of the anode material.
Description
The application is a divisional application of the original application of 'a preparation method of a lithium iron manganese phosphate/three-dimensional carbon frame/carbon composite material' (application number 201610841343X, application date 2016, 09 and 23).
Technical Field
The invention relates to the field of preparation of lithium ion battery anode materials, in particular to a preparation method of a lithium iron manganese phosphate/three-dimensional carbon frame/carbon composite material.
Background
Since sony corporation introduced commercial lithium ion batteries for the first time in 1991, lithium ion batteries have been widely used in various aspects of people's work, study, and life due to their advantages of high open circuit voltage, long cycle life, high energy density, low self-discharge, no memory effect, and environmental friendliness. In recent years, with increasing market demands for power batteries and large-scale power storage devices, power and energy storage power sources using lithium ion batteries as carriers have been developed.
The lithium iron phosphate is commercially applied at present primarily due to low cost, higher specific capacity and excellent safety, and the lithium manganese phosphate which belongs to the olivine structure with the lithium iron phosphate has the same specific capacity as the lithium iron phosphate, higher working voltage (4.IV, the lithium iron phosphate is 3.4V), higher specific energy (701Wh/Kg, the lithium iron phosphate is 586Wh/Kg), lower cost, but compared with the lithium iron phosphate, the lithium manganese phosphate has large internal resistance of crystal lattices, slower electron/ion conduction rate and less than 10 electrical conductivity-10S/cm is more than two orders of magnitude lower than that of lithium iron phosphate. The energy gap of electrons in transition in the lithium iron phosphate is 0.3eV, and the lithium iron phosphate has semiconductor characteristics; lithium manganese phosphate has an energy gap of 2eV, and is poor in electron conductivity, and thus it is an insulator.
For LiMnPO4The modification research generally adopts three modes of carbon coating, metal ion doping and material nanocrystallization. The carbon coating can effectively improve LiMnPO4The conductivity of the particles. But LiMnPO4The carbon coated on the surface is an inactive substance, and the excessive addition of the carbon not only influences the tap density and the processing performance of the material, but also reduces LiMnPO to a certain extent4Contact area with electrolyte, block Li+The movement of (2). The porous carbon material is adopted for open coating, so that the electronic conductivity of the material can be improved, and Li is not influenced+At present, the research on the porous coating carbon material is less, and the porous coating carbon is a direction with development prospect for improving the material performance. At present, much work has been done on carbon coating processes. For example, chinese patent (publication No. CNIO5390682A, publication No. 2016.03.09) discloses a preparation method of a lithium iron phosphate microsphere/three-dimensional graphene composite electrode material, which comprises the steps of: weighing 1g of ferric phosphate and 1g of glucose, dispersing in 80ml of deionized water, placing in a 100ml hydrothermal reaction kettle, reacting at 120 ℃ for 5h, washing and dryingDrying to obtain the 'spherical iron source' polyhydroxy ferric phosphate microspheres. Dispersing 2g of polyhydroxy ferric phosphate microspheres (based on the mass of iron metal), 0.3g of lithium acetate (based on the mass of lithium metal) and 0.6g of graphene oxide in deionized water, and drying; placing the mixture in a high-temperature tube furnace, and carrying out high-temperature thermal reaction under the nitrogen atmosphere, wherein the reaction temperature is 750 ℃, the reaction time is 8h, and the heating speed is 2 ℃/min; thus obtaining LiFePO4Micro/three-dimensional graphene composite materials. In the method, graphene oxide is used as a raw material of the three-dimensional conductive framework, the graphene oxide is expensive firstly, the industrial application is not facilitated, and the basic principle of constructing the three-dimensional graphene is that the layered graphene oxide is self-assembled in a hydrothermal reaction and is assembled into a three-dimensional porous structure from a layered structure. Chinese patent (publication CNIO557622OA, published 2016.05.11) discloses a preparation of a porous carbon-coated lithium iron phosphate positive electrode material, comprising the steps of: dissolving 136.2g of absolute ethyl alcohol in 136.2g of deionized water, and pouring the deionized water into a reaction kettle; 157g of LiFePO were weighed419.4g of glucose and 88.2g of ammonium bicarbonate are mixed uniformly and then put into a reaction kettle, and the mixture is stirred fully for lh. And (3) putting the uniformly stirred slurry into a vacuum freeze dryer, freezing the slurry for lh at the temperature of minus 10 ℃, and then drying the slurry for 5h in a vacuum environment of 13 Pa. And (3) drying the solid, putting the dried solid into an oven at 100 ℃, drying for lh, and sintering for 2h at 750 ℃ in a nitrogen protection atmosphere. Cooling to room temperature, grinding, and sieving with 325 mesh sieve to obtain porous carbon-coated LiFePO4and/C. The principle of preparing the porous carbon by the method is that porous carbon is obtained by pore-forming through ammonium salt gas phase decomposition, but the porous carbon and LiFePO4By merely physically mixing another LiFePO4The porous carbon does not exist in the pore structure of the porous carbon, and the porous carbon only plays a role in electric conduction and cannot play a role in limiting the particle size.
Disclosure of Invention
The invention aims at the existing LiMnPO in the prior art4The material has poor electronic conductivity, the carbon material is coated on the surface of the material by the conventional carbon coating method, the polarization of the material is serious in the charge and discharge processes of the coating method,high rate performance is poor, and the adoption of a three-dimensional porous carbon frame for LiMnPO is provided4And constructing a three-dimensional conductive network among the particles. The invention utilizes the characteristic that the three-dimensional porous carbon skeleton can transmit electrons in three dimensions to increase the electrons in LiMnPO4And the inter-particle transmission path ensures higher ion conductivity while improving the electronic conductivity of the material. The partially open incomplete carbon-coated lithium manganese iron phosphate/three-dimensional carbon frame/carbon composite material is constructed, the polarization degree of the material during charging and discharging is reduced, and the electrochemical performance is improved.
The technical scheme of the invention is as follows:
a method of preparing a three-dimensional carbon skeleton comprising the steps of:
1) adding a carbon source and a catalyst into ethanol, stirring, and then carrying out vacuum drying at 30-90 ℃ to obtain a mixture A;
wherein, the mass ratio of the carbon source to the catalyst is 5-50: 1; each gram of carbon source corresponds to 1-3ml of ethanol; the carbon source is one or more of glucose, sucrose, starch, oxalic acid, cellulose, ferrous gluconate and ferrous oxalate; the catalyst is one or more of ferrous sulfate, ferric chloride, ferrous chloride, nickel sulfate, nickel chloride and cobalt sulfate;
2) mixing the mixture A obtained in the step 1) with a pore-forming agent, and then carrying out ball milling for 1-9h, wherein the mass ratio of the mixture A to the pore-forming agent is 1: 100-; obtaining a mixture B; the ball milling rotating speed is 100-;
3) pressing the mixture B obtained in the step 2) into tablets by using an infrared tablet press under the pressure of 1-50MPa in a size of 1-2g at a time;
4) sintering the tablets obtained in the step 3) in an inert atmosphere, and comprises the following steps:
A. heating from room temperature to 350-400 ℃ at the heating rate of 2-5 ℃/min under the inert atmosphere, wherein the end temperature is named as T1; and keeping the temperature at T1 for 60-120 min;
B. heating from T1 to 600-700 ℃ at a heating rate of 1-4 ℃/min under an inert atmosphere, wherein the end temperature is T2; keeping the temperature at T2 for 60-180 min;
C. heating from T2 to 700 ℃ and 900 ℃ at the heating rate of 1-3 ℃/min under the inert atmosphere, wherein the end temperature is named as T3; preserving the heat at the temperature of T3 for 120-;
D. the temperature is reduced from T3 to 600-700 ℃ in the inert atmosphere at the temperature reduction rate of 0.2-1 ℃/min, and the end temperature is T4;
E. cooling from T4 to 500-600 ℃ in inert atmosphere at a cooling rate of 0.2-1 ℃/min, wherein the end temperature is T5;
F. cooling from T5 to 350-450 ℃ in an inert atmosphere at a cooling rate of 1-1.5 ℃/min, wherein the end temperature is T6;
G. naturally cooling to room temperature from T6 under inert atmosphere to obtain a mixture C;
wherein the inert atmosphere is nitrogen or argon atmosphere.
5) And (4) putting the mixture C obtained in the step (4) into distilled water, taking out the solid after the pore-forming agent is completely dissolved, and drying in vacuum to obtain the three-dimensional carbon skeleton.
The pore-making agent in the step 2) is one or more of sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate and calcium carbonate.
The invention has the substantive characteristics that:
the invention prepares the three-dimensional carbon frame (the process is simple and is easy to be better than the preparation of the current three-dimensional ordered macroporous and three-dimensional mesoporous materials), and then uses the three-dimensional carbon frame as the matrix of the hydrothermal reaction, and the pores on the three-dimensional carbon frame limit the growth of the grain diameter in the hydrothermal process to a certain extent. On the other hand, the three-dimensional carbon frame has three-dimensional conductivity compared with a one-dimensional carbon layer coated on the surface of the material conventionally.
In the prior art, a precursor prepared by a hydrothermal method adopts a carbon source to coat a layer of amorphous carbon (the amorphous carbon has poor conductivity) on the surface of a material, and electron conduction can only be conducted through point-to-point contact among particles. Or the precursor is compounded with a sheet-layer conductor such as graphene, so that the electron point-to-surface conduction is realized. The invention can realize the conduction of electrons from points to three-dimensional space, improve the electron conduction capability among particles of the anode material, reduce polarization and further enhance the electrochemical performance of the anode material.
The invention has the beneficial effects that:
the invention discloses a preparation method of a lithium iron manganese phosphate/three-dimensional carbon skeleton/carbon composite material. Firstly mixing glucose and ferrous sulfate, then ball-milling the mixture and sodium chloride, tabletting by using an infrared tablet press, and washing away the sodium chloride after sintering and carbonization to obtain the three-dimensional carbon skeleton. And (3) taking the obtained three-dimensional carbon skeleton as a matrix of the lithium manganese iron phosphate hydrothermal reaction to prepare the lithium manganese iron phosphate/three-dimensional carbon skeleton/carbon composite material.
The carbon source, catalyst and pore-forming agent adopted in the preparation of the three-dimensional carbon skeleton are glucose, ferrous sulfate and sodium chloride which are common in industry, and the selection of the raw materials can reduce the production cost.
The use of ferrous sulphate in the preparation of the three-dimensional carbon skeleton serves two purposes: firstly, trace addition of ferrous sulfate is reduced into Fe simple substance by carbon simple substance along with the sintering process, the Fe simple substance is in a 'nano island' structure at high temperature, and the graphitization degree of carbon can be improved by a mechanism that amorphous carbon is dissolved in the 'nano island' structure and then separated out along with the programmed temperature rise and programmed slow temperature reduction processes of a tubular furnace during sintering, so that the conductivity of a three-dimensional carbon frame is enhanced. And secondly, the conductivity of the carbon skeleton can be enhanced after ferrous sulfate is converted into Fe simple substance.
In the hydrothermal process, lithium manganese iron phosphate firstly nucleates and grows on the hole wall of the three-dimensional carbon frame under the action of Gibbs free energy, and finally a lithium manganese iron phosphate/three-dimensional carbon frame structure is formed. In addition, due to the existence of the three-dimensional carbon skeleton, electrons conducted from the lithium manganese iron phosphate in the discharging process are transmitted from a point to a three-dimensional space, and the polarization phenomenon in the charging and discharging process of the material can be reduced by the effective electron transmission mechanism.
As described in example 1, when the mass of the added three-dimensional carbon skeleton is 3% of that of the lithium iron manganese phosphate, the specific capacity of the material under the 0.1C rate is 160.2mAh/g and reaches 94.23% of the theoretical specific capacity of 170mAh/g, the specific capacity of the material after 30 cycles is 151.8mAh/g, and the capacity retention rate is 94.47%. The capacity retention rate is 91.91 percent after 30 times of circulation, and the capacity retention rate is better than 155.8mAh/g under 0.1C multiplying power of the same carbon content without adding a three-dimensional carbon frame material. When the mass of the added three-dimensional carbon frame is 3% of that of the lithium iron manganese phosphate, the difference value between the charging platform and the discharging platform of the material which is charged and discharged for the first time under the multiplying power of 0.1C is 0.1708V, the difference value of the material platform without the added three-dimensional carbon frame is 0.2095V, and the lower difference value indicates that the polarization of the material is smaller during charging and discharging.
Drawings
FIG. 1 is an SEM photograph of a three-dimensional carbon skeleton and lithium manganese phosphate/three-dimensional carbon skeleton/carbon composite material obtained in example 1;
fig. 2 is a graph showing the cycle charge and discharge curves of the lithium iron manganese phosphate/three-dimensional carbon skeleton/carbon composite material obtained in example 1 and the lithium iron manganese phosphate/carbon composite material obtained in example 3;
fig. 3 is a first charge-discharge curve diagram of the lithium iron manganese phosphate/three-dimensional carbon skeleton/carbon composite material obtained in example 1 and the lithium iron manganese phosphate/carbon composite material obtained in example 3;
fig. 4 is an XRD spectrum of the obtained lithium iron manganese phosphate/three-dimensional carbon skeleton/carbon composite in example 1.
The specific implementation mode is as follows:
the invention is further illustrated with reference to the following figures and examples.
The reaction equation in the hydrothermal process of the invention is as follows:
3LiOH+XMnSO4+(1-X)FeSO4+H3PO4→LiMnxFe1-xPO4+Li2SO4+3H2O
wherein X is 0.1-0.9;
example 1:
manganese sulfate (0.0384mol), ferrous sulfate (0.0096mol), phosphoric acid (0.048mol) and ascorbic acid (0.014mol) according to LiMnxFe1-xPO4(X is 0.8), and the solution is weighed and dissolved in 200ml of a mixed solvent composed of water and ethylene glycol in a volume ratio of 1:2, and the solution is called solution a; dispersing a three-dimensional carbon skeleton in 120ml of a mixed solvent containing water and ethylene glycol with a volume ratio of 1:2, wherein the volume ratio of the water to the ethylene glycol is 1:0.03, the mixed solvent contains lithium hydroxide (0.144mol), magnetically stirring for 12h to obtain a solution B, dropwise adding the solution B into the solution A for 20min to obtain a precursor solution of the lithium manganese iron phosphate, and placing the precursor solution into a high-temperature high-pressure reaction kettle, wherein the lithium ion concentration in the precursor solution is 0.45 mol/L; the volume of the precursor solution is 80 percent of the volume of the reaction kettle, the precursor solution is heated to 240 ℃,the reaction time is 4 hours, after the reaction kettle is naturally cooled to room temperature, the reaction kettle is centrifugally washed by distilled water and ethanol for three times respectively, and vacuum drying is carried out to obtain a lithium iron manganese phosphate precursor;
weighing 0.8640g of glucose according to the mass ratio of the precursor lithium manganese iron phosphate to the glucose of 15:4, and ball-milling for 6 hours at 300r/min by taking 5ml of ethanol as an auxiliary agent.
Thirdly, drying the mixture obtained in the second step, then placing the dried mixture into a tubular furnace, sintering the mixture in an inert gas atmosphere, pre-sintering the mixture for 3 hours at 350 ℃, cooling the mixture to room temperature along with the furnace, then grinding and crushing the mixture (until no blocky particles are obviously agglomerated together, the same is carried out in the following embodiment), adding the mixture into the tubular furnace, sintering the mixture in the inert atmosphere, wherein the sintering processes are respectively 650 ℃ and 6 hours, and cooling the mixture to room temperature along with the furnace to finally obtain the manganese iron phosphate composite material of the three-dimensional conductive network formed by the three-dimensional carbon frame and the carbon;
wherein the inert atmosphere is a nitrogen atmosphere.
The carbon content in the final product is 9% of the mass of the lithium manganese iron phosphate, and 9% of carbon respectively comes from 3% of three-dimensional carbon skeleton added in the hydrothermal process and 6% of carbon obtained after carbonization of glucose added in the precursor ball milling process.
The preparation method of the three-dimensional carbon skeleton comprises the following steps:
1) fully stirring and dispersing glucose and ferrous sulfate in ethanol (1.5 ml of ethanol corresponding to each gram of carbon source) according to the mass ratio of 22:1, and performing vacuum drying at 60 ℃ to obtain a mixture A;
2) ball-milling the mixture A obtained in the step 1) and sodium chloride for 6 hours at a mass ratio of 1:240 and 300r/min to obtain a mixture B;
3) pressing the mixture B obtained in the step 2) into tablets by using an infrared tablet press under the pressure of 1g at a time of 20 MPa;
4) sintering the tablets obtained in the step 3) in an inert atmosphere, wherein the process comprises the following steps:
A. a temperature rising process, wherein the temperature is raised from room temperature to 400 ℃ at a temperature rising rate of 4 ℃/min under an inert atmosphere, and the end temperature is called T1; and keeping the temperature at T1 for 60 min;
B. a temperature rise process, wherein the temperature is raised from T1 to 650 ℃ at the temperature rise rate of 2 ℃/min under the inert atmosphere, and the end temperature is named as T2; and keeping the temperature at T2 for 120 min;
C. a temperature rise process, wherein the temperature is raised from T2 to 750 ℃ at the temperature rise rate of 1 ℃/min under the inert atmosphere, and the end temperature is called T3; and preserving the heat for 180min at the temperature of T3;
D. a temperature reduction process, wherein the temperature is reduced from T3 to 650 ℃ at a temperature reduction rate of 0.5 ℃/min under an inert atmosphere, and the end temperature is T4;
E. a temperature reduction process, wherein the temperature is reduced from T4 to 550 ℃ at a temperature reduction rate of 1 ℃/min under an inert atmosphere, and the end temperature is T5;
F. a temperature reduction process, wherein the temperature is reduced from T5 to 400 ℃ at a temperature reduction rate of 1.5 ℃/min in an inert atmosphere, and the end temperature is T6;
G. a cooling process, wherein the temperature is naturally cooled to room temperature from T6 under inert atmosphere to obtain a mixture C;
wherein the inert atmosphere is a nitrogen atmosphere.
5) Adding the mixture C obtained in step 4) into distilled water until the pore-forming agent is completely dissolved (replacing distilled water in the midway, and dripping a small amount of distilled water for soaking the three-dimensional carbon skeleton into AgNO3Solution, no white precipitate is generated, which proves that the pore-making agent is completely dissolved), solid is fished out, and the three-dimensional carbon skeleton is obtained after vacuum drying.
It can be seen from a in fig. 1 that the three-dimensional carbon frame prepared by the invention has an irregular three-dimensional pore layer structure, the pore diameter is between 100nm and 1 mu m, lithium iron manganese phosphate particles grow in the pores of the three-dimensional carbon frame after hydrothermal reaction, and the particle diameter is between 100nm and 300 nm. The lithium manganese iron phosphate is incompletely coated by a three-dimensional carbon frame capable of conducting electricity through multiple paths, so that a lithium manganese iron phosphate/three-dimensional carbon frame/carbon composite material with partially opened and incompletely coated carbon is constructed, the excessive growth of lithium manganese iron phosphate material particles in the hydrothermal process is limited by the addition of the three-dimensional carbon frame, and the conductivity among the material particles is enhanced.
FIG. 2 is a curve of performance of a CT2001A model LAND tester for charging and discharging a battery, wherein the voltage range is 2.0-4.6V and the testing temperature is 25 ℃. It can be seen that the specific capacity of the lithium manganese iron phosphate added with 3% of three-dimensional carbon skeleton + 6% of carbon (carbonized by glucose) under the rate of 0.1C can reach 160.2mAh/g, while the specific capacity of the lithium manganese iron phosphate added with 9% of carbon (carbonized by glucose-example 3) under the rate of 0.1C by adopting the same preparation process is 155.8 mAh/g.
FIG. 3 shows the charging and discharging curve of a battery using a CT2001A model LAND tester, with a voltage range of 2.0-4.6V and a testing temperature of 25 ℃. It can be seen that the difference between the charging and discharging platforms of lithium iron manganese phosphate with 3% three-dimensional carbon skeleton + 6% carbon (carbonized by glucose) added under 0.1C rate is 0.1708V, while the same preparation process is only added with 9% carbon (carbonized by glucose)
The difference between the charge and discharge platforms at 0.1C magnification of lithium manganese iron phosphate of example 3) was 0.2095V, indicating that the addition of a three-dimensional carbon skeleton reduced the polarization of the material.
Fig. 4 shows that the XRD spectrogram of the lithium iron manganese phosphate prepared by the method coincides with the standard spectrogram, and the peak type is sharp without the occurrence of an impurity peak, which indicates that the lithium iron manganese phosphate material with a complete crystal form can be prepared by the method.
Example 2:
firstly, manganous sulfate (0.0096mol), ferrous sulfate (0.0384mol), phosphoric acid (0.048mol) and ascorbic acid (0.018mol) are mixed according to LiMnxFe1-xPO4Weighing and dissolving the mixture in 200ml of a mixed solvent composed of water and ethylene glycol according to the volume ratio of 1:2, wherein the solution is called solution A; dispersing a three-dimensional carbon skeleton in 120ml of a mixed solvent of water containing lithium hydroxide (0.1584mol) and ethylene glycol according to the volume ratio of 1:2 according to the mass ratio of theoretical manganese lithium iron phosphate to the three-dimensional carbon skeleton of 1:0.1, magnetically stirring for 10h to obtain a solution B, dropwise adding the solution B into the solution A for 15min to obtain a precursor solution of the manganese lithium iron phosphate, placing the precursor solution into a high-temperature high-pressure reaction kettle, wherein the concentration of lithium ions in the precursor solution is 0.495 mol/L; heating the precursor solution to 200 ℃ with the volume of 60% of the volume of the reaction kettle, reacting for 6 hours, naturally cooling the reaction kettle to room temperature, centrifugally washing the reaction kettle with distilled water and ethanol for three times, and drying the reaction kettle in vacuum to obtain a lithium iron manganese phosphate precursor;
weighing 0.8640g of glucose according to the mass ratio of the precursor lithium manganese iron phosphate to the glucose of 15:8, and ball-milling for 1h by taking ethanol as an auxiliary agent at a speed of 400 r/min.
Thirdly, drying the mixture obtained in the second step, then placing the dried mixture into a tubular furnace, sintering the mixture in an inert gas atmosphere, pre-sintering the mixture for 2 hours at 390 ℃, cooling the mixture to room temperature along with the furnace, then grinding and crushing the mixture, then adding the ground mixture into the tubular furnace, sintering the mixture in the inert atmosphere at 700 ℃ and 4 hours along with the furnace, and cooling the mixture to room temperature along with the furnace to finally obtain the lithium iron manganese phosphate composite material with a three-dimensional conductive network formed by a three-dimensional carbon frame and carbon;
wherein the inert atmosphere is argon atmosphere.
The carbon content in the final product is 22% of the mass of the lithium iron manganese phosphate, and the 22% carbon is respectively from 10% of carbon skeleton added in the hydrothermal process and 12% of carbon carbonized by glucose added in the precursor ball milling process. .
The preparation method of the three-dimensional carbon skeleton comprises the following steps:
1) fully stirring and dispersing ferrous gluconate and cobalt sulfate in ethanol (2 ml of ethanol corresponding to each gram of carbon source) according to the mass ratio of 10:1, and performing vacuum drying at 50 ℃ to obtain a mixture A;
2) ball-milling the mixture A obtained in the step 1) and sodium carbonate for 4 hours according to the mass ratio of 1:1000 and 200r/min to obtain a mixture B;
3) pressing the mixture B obtained in the step 2) into tablets by 1.5g at a pressure of 10MPa by using an infrared tablet press;
4) sintering the tablets obtained in the step 3) in an inert atmosphere, wherein the process comprises the following steps:
A. a temperature rising process, wherein the temperature is raised from room temperature to 350 ℃ at a temperature rising rate of 5 ℃/min under an inert atmosphere, and the end temperature is called T1; and keeping the temperature at T1 for 120 min;
B. a temperature rise process, wherein the temperature is raised from T1 to 700 ℃ at the temperature rise rate of 1 ℃/min under the inert atmosphere, and the end temperature is named as T2; and preserving the heat for 180min at the temperature of T2;
C. a temperature rise process, wherein the temperature is raised from T2 to 800 ℃ at the temperature rise rate of 2 ℃/min under the inert atmosphere, and the end temperature is named as T3; and keeping the temperature at T3 for 240 min;
D. a temperature reduction process, wherein the temperature is reduced from T3 to 700 ℃ at a temperature reduction rate of 0.2 ℃/min under an inert atmosphere, and the end temperature is T4;
E. a temperature reduction process, wherein the temperature is reduced from T4 to 600 ℃ at a temperature reduction rate of 0.5 ℃/min under an inert atmosphere, and the end temperature is T5;
F. a temperature reduction process, wherein the temperature is reduced from T5 to 350 ℃ at a temperature reduction rate of 1 ℃/min under an inert atmosphere, and the end temperature is T6;
G. a cooling process, wherein the temperature is naturally cooled to room temperature from T6 under inert atmosphere to obtain a mixture C;
wherein the inert atmosphere is an argon atmosphere.
5) Adding the mixture C obtained in step 4) into distilled water until the pore-forming agent is completely dissolved (replacing distilled water in the midway, and dripping a small amount of distilled water for soaking the three-dimensional carbon skeleton into AgNO3Solution, no precipitate is generated, and the pore-making agent is proved to be completely dissolved), and solid is fished out and dried in vacuum to obtain the three-dimensional carbon skeleton.
Example 3:
manganese sulfate (0.0384mol), ferrous sulfate (0.0096mol), phosphoric acid (0.048mol) and ascorbic acid (0.014mol) according to LiMnxFe1-xPO4(X ═ 0.8). Weighing, dissolving in 200ml of mixed solvent composed of water and ethylene glycol according to the volume ratio of 1:2, and obtaining solution A; dispersing lithium hydroxide (0.144mol) in 120ml of mixed solvent containing water and ethylene glycol according to the volume ratio of 1:2 to obtain a solution B, dropwise adding the solution B into the solution A for 20min to obtain a precursor solution of lithium manganese iron phosphate, and placing the precursor solution into a high-temperature high-pressure reaction kettle, wherein the concentration of lithium ions in the precursor solution is 0.45 mol/L; heating the precursor solution to 240 ℃ with the volume of 80% of the volume of the reaction kettle, reacting for 4h, naturally cooling the reaction kettle to room temperature, centrifugally washing the reaction kettle with distilled water and ethanol for three times, and drying the reaction kettle in vacuum to obtain a lithium iron manganese phosphate precursor;
weighing 0.7960g of glucose according to the mass ratio of the precursor lithium manganese iron phosphate to the glucose of 5:2, and ball-milling for 6 hours at 300r/min by using ethanol as an auxiliary agent.
Thirdly, drying the mixture obtained in the second step, then placing the dried mixture into a tubular furnace, sintering the mixture in an inert gas atmosphere, pre-sintering the mixture for 3 hours at 350 ℃, cooling the mixture to room temperature along with the furnace, then grinding and crushing the mixture, then adding the ground mixture into the tubular furnace, sintering the mixture in the inert atmosphere at 650 ℃ for 6 hours along with the furnace, and finally obtaining the lithium iron manganese phosphate/carbon composite material;
wherein the inert atmosphere is a nitrogen atmosphere.
The carbon content in the final product is 9% of the mass of the lithium manganese iron phosphate.
The invention is not the best known technology.
Claims (2)
1. A method for producing a three-dimensional carbon skeleton, characterized by comprising the steps of:
1) adding a carbon source and a catalyst into ethanol, stirring, and then carrying out vacuum drying at 30-90 ℃ to obtain a mixture A;
wherein, the mass ratio of the carbon source to the catalyst is 5-50: 1; each gram of carbon source corresponds to 1-3ml of ethanol; the carbon source is one or more of glucose, sucrose, starch, oxalic acid, cellulose, ferrous gluconate and ferrous oxalate; the catalyst is one or more of ferrous sulfate, ferric chloride, ferrous chloride, nickel sulfate, nickel chloride and cobalt sulfate;
2) mixing the mixture A obtained in the step 1) with a pore-forming agent, and then carrying out ball milling for 1-9h, wherein the mass ratio of the mixture A to the pore-forming agent =1: 100-; obtaining a mixture B; the ball milling rotating speed is 100-;
3) pressing the mixture B obtained in the step 2) into tablets by using an infrared tablet press under the pressure of 1-50MPa in a size of 1-2g at a time;
4) sintering the tablets obtained in the step 3) in a nitrogen or argon atmosphere, and comprising the following steps:
A. heating from room temperature to 350-400 ℃ at the heating rate of 2-5 ℃/min under the atmosphere of nitrogen or argon, wherein the end temperature is named as T1; and keeping the temperature at T1 for 60-120 min;
B. heating from T1 to 600-700 ℃ at a heating rate of 1-4 ℃/min in the nitrogen or argon atmosphere, wherein the end temperature is T2; keeping the temperature at T2 for 60-180 min;
C. heating from T2 to 700-900 ℃ at a heating rate of 1-3 ℃/min in the nitrogen or argon atmosphere, wherein the end temperature is T3; preserving the heat at the temperature of T3 for 120-;
D. cooling from T3 to 600-700 ℃ in the nitrogen or argon atmosphere at the cooling rate of 0.2-1 ℃/min, wherein the end temperature is T4;
E. cooling from T4 to 500-600 ℃ in the nitrogen or argon atmosphere at the cooling rate of 0.2-1 ℃/min, wherein the end temperature is T5;
F. cooling from T5 to 350-450 ℃ in nitrogen or argon atmosphere at a cooling rate of 1-1.5 ℃/min, wherein the end temperature is T6;
G. naturally cooling to room temperature from T6 under nitrogen or argon atmosphere to obtain a mixture C;
5) and (4) putting the mixture C obtained in the step (4) into distilled water, taking out the solid after the pore-forming agent is completely dissolved, and drying in vacuum to obtain the three-dimensional carbon skeleton.
2. The method for preparing a three-dimensional carbon skeleton as set forth in claim 1, wherein the pore-forming agent in the step 2) is one or more of sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate and calcium carbonate.
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| CN110690424A (en) * | 2019-09-27 | 2020-01-14 | 天津大学 | Preparation method of three-dimensional carbon-coated nano lithium iron phosphate lithium ion battery positive electrode material |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5571617A (en) * | 1978-11-27 | 1980-05-29 | Ebara Infilco Co Ltd | Activated carbon regenerator |
| WO2008120979A1 (en) * | 2007-04-03 | 2008-10-09 | Stichting Deltares | Microbiologically induced carbonate precipitation |
| CN102674291A (en) * | 2012-05-25 | 2012-09-19 | 广西诺方储能科技有限公司 | Preparation method of superfine nanometer lithium iron phosphate electrode material and application thereof |
| EP2679219A1 (en) * | 2007-04-06 | 2014-01-01 | Activus Pharma Co., Ltd. | Method for producing finely pulverized organic compound particle |
| CN103855413A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Porous carbon material used for lithium-air cell anode |
| CN104538595A (en) * | 2014-12-10 | 2015-04-22 | 南京师范大学 | Lithium ion battery cathode material embedded nano metal loaded carbon nanosheet as well as preparation method and application thereof |
| CN105006575A (en) * | 2015-06-23 | 2015-10-28 | 西安博纳材料科技有限公司 | Method for preparing metallic oxide-carbon composite material |
| CN105293470A (en) * | 2015-11-12 | 2016-02-03 | 天津大学 | Template preparation method for hierarchical porous structure three-dimensional carbon nanometer net electrode material of supercapacitor |
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| CN105449214A (en) * | 2016-01-12 | 2016-03-30 | 广西师范大学 | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material |
| CN105810924A (en) * | 2016-04-21 | 2016-07-27 | 北京大学深圳研究生院 | Carbon-clad alloy material and fabrication method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100420787B1 (en) * | 2001-04-30 | 2004-03-02 | 한국과학기술원 | Carbon Molecular Sieve and Process for Preparing the Same |
| CN103482597B (en) * | 2012-06-14 | 2017-08-25 | 中国人民解放军63971部队 | A kind of preparation method of middle macropore carbon |
| CN103346319B (en) * | 2013-07-04 | 2015-06-24 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
-
2016
- 2016-09-23 CN CN201810630253.5A patent/CN108807919B/en not_active Expired - Fee Related
- 2016-09-23 CN CN201610841343.XA patent/CN106129387B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5571617A (en) * | 1978-11-27 | 1980-05-29 | Ebara Infilco Co Ltd | Activated carbon regenerator |
| WO2008120979A1 (en) * | 2007-04-03 | 2008-10-09 | Stichting Deltares | Microbiologically induced carbonate precipitation |
| EP2679219A1 (en) * | 2007-04-06 | 2014-01-01 | Activus Pharma Co., Ltd. | Method for producing finely pulverized organic compound particle |
| CN102674291A (en) * | 2012-05-25 | 2012-09-19 | 广西诺方储能科技有限公司 | Preparation method of superfine nanometer lithium iron phosphate electrode material and application thereof |
| CN103855413A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Porous carbon material used for lithium-air cell anode |
| CN104538595A (en) * | 2014-12-10 | 2015-04-22 | 南京师范大学 | Lithium ion battery cathode material embedded nano metal loaded carbon nanosheet as well as preparation method and application thereof |
| CN105006575A (en) * | 2015-06-23 | 2015-10-28 | 西安博纳材料科技有限公司 | Method for preparing metallic oxide-carbon composite material |
| CN105293470A (en) * | 2015-11-12 | 2016-02-03 | 天津大学 | Template preparation method for hierarchical porous structure three-dimensional carbon nanometer net electrode material of supercapacitor |
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| CN105449214A (en) * | 2016-01-12 | 2016-03-30 | 广西师范大学 | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material |
| CN105810924A (en) * | 2016-04-21 | 2016-07-27 | 北京大学深圳研究生院 | Carbon-clad alloy material and fabrication method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| In-situ growth of graphene decorations for high-performance LiFePO4 cathode through solid-state reaction;Jing Li;《Journal of Power Sources》;20131105;全文 * |
| Porous Graphitic Carbon Nanosheets as a High-Rate Anode Material for Lithium-Ion Batteries;Long Chen;《ACS Applied Materials & Interfaces》;20130909;全文 * |
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| Publication number | Publication date |
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| CN106129387A (en) | 2016-11-16 |
| CN106129387B (en) | 2018-12-07 |
| CN108807919A (en) | 2018-11-13 |
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