CN106129388A - A kind of preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite - Google Patents
A kind of preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite Download PDFInfo
- Publication number
- CN106129388A CN106129388A CN201610841800.5A CN201610841800A CN106129388A CN 106129388 A CN106129388 A CN 106129388A CN 201610841800 A CN201610841800 A CN 201610841800A CN 106129388 A CN106129388 A CN 106129388A
- Authority
- CN
- China
- Prior art keywords
- lifepo4
- protective atmosphere
- carbon skeleton
- temperature
- dimensional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 64
- 230000001681 protective effect Effects 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 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 21
- 239000008103 glucose Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 13
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 10
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 8
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 8
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 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
- 238000005406 washing Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- -1 iron ion Chemical class 0.000 claims description 5
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 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
- 238000013019 agitation Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 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
- 229910052742 iron Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 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
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 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
- 239000010452 phosphate Substances 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
- 240000000111 Saccharum officinarum Species 0.000 claims 1
- 235000007201 Saccharum officinarum Nutrition 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 239000000126 substance Substances 0.000 abstract description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 11
- 238000005253 cladding Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 230000001413 cellular effect Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000009392 Vitis Nutrition 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001338 self-assembly 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
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005553 drilling Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration 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
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention is the preparation method of a kind of LiFePO4/three-dimensional carbon skeleton/carbon composite.The method comprises the following steps: 1. ferrous sulfate, phosphoric acid, dissolution of ascorbic acid are obtained in mixed solvent A liquid；Three-dimensional carbon skeleton is dispersed in the mixed solvent containing Lithium hydrate and obtains B liquid, then B liquid add to obtain in A liquid the precursor solution of LiFePO4；2. step is used ball milling after 1. gained ferric lithium phosphate precursor mixes with glucose；3., under protective gas atmosphere, sintering finally obtains LiFePO4/three-dimensional carbon skeleton/carbon composite.The material that the present invention obtains can realize electronics by putting three-dimensional conduction, can improve the intergranular electronic conduction ability of positive electrode and then enhancing positive electrode chemical property.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries preparation field, in particular to a kind of LiFePO4/three-dimensional carbon skeleton/carbon
The preparation method of composite.
Background technology
Since sony company in 1991 releases commodity lithium ion battery first, lithium ion battery is with its open-circuit voltage
High, have extended cycle life, energy density is high, self discharge is low, memory-less effect, the advantage such as environmentally friendly are widely used in people's work
The various aspects make, learn, lived.In recent years, constantly increase along with the market demand of electrokinetic cell and large-scale power energy storage device
Add, occur in that the power using lithium ion battery as carrier and accumulation power supply successively.
LiFePO4As a member in positive electrode material of lithium secondary cell, because it is cheap, environmental friendliness, voltage platform are smooth,
The advantages such as safety is good are considered as one of the most promising anode material for lithium-ion batteries.But due to LiFePO4Not there is layer
Shape LiCoO2、LiMnO2With spinelle shape LiMn2O4Two dimension or three-dimensional Li+Migrating channels, its ionic conductance and electronic conductance
Rate is the most on the low side, and wherein ionic conductance is 10-11cm2/ S electronic conductivity is 10-9S/cm, during high current charge-discharge, capacity can not
All play and affect its application.
Do many research for solving above-mentioned two shortcoming people, such as coated with conductive agent, metal ion mixing, passed through
Different synthetic methods reduce particle size etc..Wherein carbon cladding is exactly a kind of important modification means.Carbon cladding can effectively carry
High LiFePO4The electric conductivity of granule.But LiFePO4Surface coated carbon is inert matter, and carbon addition the most not only can shadow
Ring tap density and the processing characteristics of material, reduce LiFePO to a certain extent simultaneously4With the contact area of electrolyte, resistance
Hinder Li+Motion.And use porous carbon materials to carry out open cladding and both can improve material electronics electrical conductivity and do not affect
Li+Motion, the research that carbon coated material carries out porous at present is the most less, is to improve material property very by carbon coated porous
A promising direction.At present, do a lot of work in terms of carbon cladding process.Such as, Chinese patent (publication No.
CNIO5390682A, date of publication 2016.03.09) system of a kind of LiFePO4 microsphere/three-dimensional grapheme combination electrode material is disclosed
Preparation Method, step is: weigh 1g iron phosphate and 1g glucose is scattered in 80ml deionized water, be placed in 100ml hydrothermal reaction kettle
In 120 DEG C reaction 5h, washing be dried prepare " spherical source of iron " polyhydroxy iron phosphate microsphere.2g polyhydroxy iron phosphate microsphere (is pressed
Ferrous metal quality), 0.3g lithium acetate (by lithium metal quality) and 0.6g graphene oxide be scattered in deionized water, be dried；Will
Said mixture is placed in high temperature process furnances, carries out high-temperature hot reaction in a nitrogen atmosphere, and reaction temperature is 750 DEG C, during reaction
Between be 8h, programming rate is 2 DEG C/min；I.e. prepare " LiFePO4Micro-/three-dimensional grapheme " composite.Said method uses oxygen
Functionalized graphene is unfavorable for industrial applications as the raw material first graphene oxide of three-dimensional conductive skeleton is expensive, the most above-mentioned
It is that layered graphite oxide alkene carries out self assembly by layer structure in hydro-thermal reaction that method builds the ultimate principle of three-dimensional grapheme
Be assembled into three-dimensional cavernous structure, but when said method is one-step method i.e. graphene oxide hydro-thermal self assembly can by solution its
The impact of his ion, easily causes the three-dimensional grapheme structure obtained imperfect.Chinese patent (announce CNIO557622OA, public
Open a day 2016.05.11) preparation of a kind of cellular carbon-coated LiFePO 4 for lithium ion batteries positive electrode is disclosed, step is: the anhydrous second of 136.2g
Alcohol is dissolved in 136.2g deionization, pours reactor into；Weigh 157gLiFePO4, 19.4g glucose and 88.2g ammonium hydrogen carbonate
Putting into after mix homogeneously in reactor, mixture is sufficiently stirred for lh.Vacuum freeze drier put into by slurry after stirring
In, freeze lh at-10 DEG C, under vacuum 13Pa environment, be then dried 5h.100 DEG C of baking ovens put into by dried solid, dry lh, nitrogen
The lower 750 DEG C of sintering 2h of gas shielded atmosphere.It is cooled to room temperature, after grinding, crosses 325 mesh sieves, obtain cellular carbon cladding LiFePO4/C。
It is that ammonium salt gas-phase decomposition carries out pore-creating and obtained cellular carbon that said method prepares the principle of porous carbon, but cellular carbon with
LiFePO4The simply other LiFePO of physical mixed4Being not present in the pore space structure of cellular carbon, cellular carbon only plays and leads
Electro ultrafiltration, can not play the effect limiting particle diameter.
Summary of the invention
The present invention is directed to LiFePO present in current techniques4Material electronics poorly conductive, conventional bag carbon is at material list
Bread covers material with carbon element, serious polarization in this cladding mode material charge and discharge process, and big high rate performance is poor, it is proposed that use three-dimensional
Porous carbon skeleton is at LiFePO4Three-dimensional conductive network is built between granule.The present invention utilizes three-dimensional porous carbon skeleton three-dimensional can transmit electronics
Characteristic, increase electronics at LiFePO4Transmission channel between granule, improve guarantee while material electronics electrical conductivity higher from
Sub-conductivity.Construct the LiFePO4/three-dimensional carbon skeleton/carbon composite of fractional open incomplete carbon cladding, improve material
Chemical property.
Technical solution of the present invention is:
The preparation method of a kind of LiFePO4/three-dimensional carbon skeleton/carbon composite, comprises the following steps:
1. ferrous sulfate, phosphoric acid, dissolution of ascorbic acid are obtained A liquid in mixed solvent；Three-dimensional carbon skeleton is dispersed in and contains
Have in the mixed solvent of Lithium hydrate, obtain B liquid through magnetic agitation 2-12h, then B liquid 15-20min is dropped in A liquid
Obtain the precursor solution of LiFePO4, be then placed in high-temperature high-pressure reaction kettle, be heated to 160-300 DEG C, during reaction
Between be 1-20h, after question response axe naturally cools to room temperature, respectively with distilled water, ethanol centrifuge washing, after vacuum drying, prepare phosphorus
Acid ferrum lithium presoma；
Wherein, described ion mol ratio is lithium ion: iron ion: phosphate anion=3-3.3:1:1；Precursor solution
Middle lithium concentration is 0.1-1mol/L；In precursor solution, ascorbic acid concentrations is 0.03-0.2mol/L；Quality compares theoretical amount
LiFePO4: three-dimensional carbon skeleton=1:0.1-0.005；Volume ratio A liquid: B liquid=5:3；Mixed solvent in A liquid and B liquid is water
With the mixture of ethylene glycol, volume ratio is water: ethylene glycol=1:2；
2. by step after 1. gained ferric lithium phosphate precursor mixes with glucose with ball milling, auxiliary agent is that ethanol is mixed
Compound；Wherein, every gram of presoma adds 0.5-10ml ethanol；
Wherein, mass ratio is ferric lithium phosphate precursor: glucose=1-10:1, rotational speed of ball-mill 200-500r/min, ball milling
Time 2-10h；
3. step 2. gained mixture is put in tube furnace after drying, under protective atmosphere atmosphere, first at 240-390 DEG C
Under the conditions of pre-burning 1-5h, cool to room temperature with the furnace, then ground broken, add in tube furnace, equally at protective atmosphere
Under, 450-780 DEG C of sintering 3-12h, cool to room temperature with the furnace, finally obtain LiFePO4/three-dimensional carbon skeleton/carbon composite；
The 30-90% that volume is reactor volume of described step 1. middle precursor solution.
Described protective atmosphere is one or more gaseous mixture atmosphere in nitrogen, argon, hydrogen.
In end product, phosphorus content is the 5-30% of LiFePO4 quality, and institute's carbon containing is respectively from addition in water-heat process
Carbon after the glucose carbonization that three-dimensional carbon skeleton and presoma mechanical milling process add.
The preparation method of described three-dimensional carbon skeleton, comprises the following steps:
1) carbon source, catalyst are joined in ethanol and stir, then in 30-90 DEG C of vacuum drying, obtain mixture A；
Wherein, quality is than carbon source: catalyst=5-50:1；Every gram of carbon source adds 1-3ml ethanol；Described carbon source is Fructus Vitis viniferae
In sugar, sucrose, starch, oxalic acid, cellulose, ferrous gluconate, Ferrox. one or more；Catalyst is ferrous sulfate, chlorine
Change one or more in ferrum, ferrous chloride, nickel sulfate, Nickel dichloride. and cobaltous sulfate；
2) by step 1) gained mixture A mix with perforating agent after ball milling 1-9h, mass ratio is mixture A: drilling
Agent=1:100-5000；Obtain mixture B；Rotational speed of ball-mill 100-500r/min；
3) by step 2) gained mixture B is compressed to being pressed into of 1-2g size with infrared tablet machine under 1-50MPa pressure
Tablet；
4) by step 3) gained tablet sinters in protective atmosphere, comprises the following steps:
A, being warmed up to 350-400 DEG C with 2-5 DEG C/min heating rate from room temperature under protective atmosphere, outlet temperature is referred to as
T1；And at a temperature of T1, it is incubated 60-120min；
B, being warmed up to 600-700 DEG C with 1-4 DEG C/min heating rate from T1 under protective atmosphere, outlet temperature is referred to as T2；
60-180min it is incubated at a temperature of T2；
C, being warmed up to 700-900 DEG C with 1-3 DEG C/min heating rate from T2 under protective atmosphere, outlet temperature is referred to as T3；
120-240min it is incubated at a temperature of T3；
D, from T3 with 0.2-1 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 600-700 DEG C, outlet temperature is T4；
E, from T4 with 0.2-1 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 500-600 DEG C, outlet temperature is T5；
F, from T5 with 1-1.5 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 350-450 DEG C, outlet temperature is T6；
G, to room temperature, obtain mixture C from T6 Temperature fall under protective atmosphere；
Wherein, the protective atmosphere in step A-F is nitrogen or argon gas atmosphere.
5) by 4) mixture C that obtains puts in distilled water, treats that perforating agent is completely dissolved, pull solid out, after vacuum drying
Obtain three-dimensional carbon skeleton.
Described step 2) in perforating agent be a kind of in sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate, calcium carbonate or
Multiple.
The substantive distinguishing features of the present invention is:
By preparing three-dimensional carbon skeleton, (its technique is simple, easy is better than the most three-dimensional ordered macroporous, three-dimensional meso-hole to the present invention
The preparation of material), it is then used as the matrix of hydro-thermal reaction, the hole on three-dimensional carbon skeleton limits hydro-thermal to a certain extent
During the growth of particle diameter.The most three-dimensional carbon skeleton has three-dimensional conductive compared with the one-dimensional carbon-coating that material surface routine is coated with
Ability.
In prior art, presoma prepared by hydro-thermal method uses carbon source to be coated with one layer of agraphitic carbon (without fixed at material surface
Type carbon conductive is poor), electronics conduction can only be by the point-to-point contact conduction between granule.Or by presoma and Graphene etc.
Lamella conducting objects is combined, and is achieved in that the conduction to face of the electronics point.And the present invention can to realize electronics three-dimensional by putting
Conduction, can improve the intergranular electronic conduction ability of positive electrode and reduce polarization and then strengthen positive electrode chemical property.
The invention have the benefit that
The invention discloses the preparation method of a kind of LiFePO4/three-dimensional carbon skeleton/carbon composite.First Fructus Vitis viniferae is mixed
Sugar, ferrous sulfate, then by mixture and sodium chloride ball milling, then use infrared tabletting machine, wash away chlorine after sintered carbonization
Change sodium and prepare three-dimensional carbon skeleton.Using the three-dimensional carbon skeleton that obtains as the matrix of LiFePO4 hydro-thermal reaction, prepare LiFePO4/tri-
Dimension carbon skeleton/carbon composite.
The carbon source that uses when the three-dimensional carbon skeleton of preparation, catalyst, perforating agent are that glucose common in industry, sulphuric acid are sub-
Ferrum, sodium chloride, the selection of above raw material all can reduce production cost.
Ferrous sulfate is used to have two purposes when the three-dimensional carbon skeleton of preparation: the first trace of ferrous sulfate adds along with sintering
Process is reduced into Fe simple substance by carbon simple substance, is the structure of a kind of " nano island " under high temperature, during sintering in along with tube furnace program liter
Temperature and program slow cooling process agraphitic carbon dissolve in this " nano island " structure and separate out the machine-processed stone that can improve carbon again
Inkization degree, and then strengthen the electric conductivity of three-dimensional carbon skeleton.Secondly ferrous sulfate can strengthen leading of carbon skeleton after being converted into Fe simple substance
Electrically.
LiFePO4 first nucleation on the hole wall of three-dimensional carbon skeleton under the effect of Gibbs free energy in water-heat process
Growth, ultimately forms LiFePO4/three-dimensional carbon shelf structure, and owing to growing in aperture, three-dimensional carbon skeleton can play control particle diameter
Effect.Additionally, due to the existence of three-dimensional carbon skeleton transfer out from LiFePO4 in discharge process electrically realized by o'clock to three
The transmission of dimension space, this effective mechanisms of electronic can reduce the polarization phenomena in material charge and discharge process.
As described in Example 1, when adding three-dimensional carbon skeleton quality and being LiFePO4 3%, material is specific volume under 0.2C multiplying power
Amount reaches the 92.18% of theoretical specific capacity 170mAh/g for 156.7mAh/g.It is better than same carbon content but is not added with three-dimensional carbon skeleton material
151.6mAh/g under the 0.2C multiplying power of material.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the LiFePO4/three-dimensional carbon skeleton/carbon composite obtained in embodiment 1；
Fig. 2 is the phosphoric acid obtained in the LiFePO4/three-dimensional carbon skeleton/carbon composite and embodiment 3 obtained in embodiment 1
Ferrum lithium/carbon composite material cycle charge-discharge curve chart；
Fig. 3 is the XRD spectra of the LiFePO4 obtained in embodiment 1/three-dimensional carbon skeleton/carbon composite.
Detailed description of the invention:
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
Reaction equation in the water-heat process of the present invention is:
3LiOH+FeSO4+H3PO4→LiFePO4+Li2SO4+3H2O
Embodiment 1:
1. ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.014mol), be dissolved in after weighing
200ml water and ethylene glycol by volume=mixed solvent of 1:2 composition in, referred to as A liquid；According to theoretical amount LiFePO4: three-dimensional
The mass ratio of carbon skeleton=1:0.03, is dispersed in, by three-dimensional carbon skeleton, water and the ethylene glycol that 120ml contains Lithium hydrate (0.144mol)
In by volume=1:2 mixed solvent, magnetic agitation 12h obtains B liquid, then drops to obtain phosphoric acid in A liquid by B liquid 20min
The precursor solution of ferrum lithium, is placed in high-temperature high-pressure reaction kettle, and in precursor solution, lithium concentration is 0.45mol/L；
The volume of precursor solution is the 80% of reactor volume, is heated to 240 DEG C, and the response time is 4h, question response still natural cooling
After distilled water, three vacuum drying of each centrifuge washing of ethanol, ferric lithium phosphate precursor is prepared to room temperature；
2. by presoma LiFePO4: the mass ratio of glucose=15:2 weighs glucose 0.4320g, with 5ml ethanol it is
Auxiliary agent 300r/min ball milling 6h.
3. step 2. gained mixture is put in tube furnace after drying, sinter under protective atmosphere atmosphere, first at 350 DEG C
Under the conditions of pre-burning 3h, cool to room temperature with the furnace, then ground broken (until without the blocky-shaped particle substantially reunited together,
Following example are same), add in tube furnace, sinter under protective atmosphere equally, sintering process is respectively 650 DEG C, and 6h, with stove
It is cooled to room temperature, finally obtains the composite ferric lithium phosphate material being constituted three-dimensional conductive network with three-dimensional carbon skeleton and carbon；
Wherein, protective atmosphere is nitrogen atmosphere.
In end product, phosphorus content is the 6% of LiFePO4 quality, and 6% carbon is respectively from 3% added in water-heat process
Carbon 3% after the glucose carbonization that three-dimensional carbon skeleton and presoma mechanical milling process add.
The preparation method of described three-dimensional carbon skeleton, comprises the following steps:
1) by glucose, ferrous sulfate 22:1 in mass ratio, it is sufficiently stirred for being scattered in ethanol (every gram of carbon source correspondence 1.5ml
Ethanol) in, 60 DEG C of vacuum drying, obtain mixture A；
2) by step 1) gained mixture A and sodium chloride 1:240 in mass ratio, 300r/min ball milling 6h, obtain mixture
B；
3) by step 2) gained mixture B with infrared tablet machine on 20MPa pressure once 1g be pressed into tablet；
4) by step 3) gained tablet sinters in protective atmosphere, and its processing step is:
A, heating process, be warmed up to 400 DEG C from room temperature with 4 DEG C/min heating rate under protective atmosphere, and outlet temperature claims
For T1；And at a temperature of T1, it is incubated 60min；
B, heating process, be warmed up to 650 DEG C from T1 with 2 DEG C/min heating rate under protective atmosphere, and outlet temperature is referred to as
T2；And at a temperature of T2, it is incubated 120min；
C, heating process, be warmed up to 750 DEG C from T2 with 1 DEG C/min heating rate under protective atmosphere, and outlet temperature is referred to as
T3；And at a temperature of T3, it is incubated 180min；
D, temperature reduction technology, from T3 with 0.5 DEG C/min rate of temperature fall in protective atmosphere borehole cooling to 650 DEG C, outlet temperature be
T4；
E, temperature reduction technology, from T4 with 1 DEG C/min rate of temperature fall at protective atmosphere borehole cooling to 550 DEG C, outlet temperature is T5；
F, temperature reduction technology, from T5 with 1.5 DEG C/min rate of temperature fall in protective atmosphere borehole cooling to 400 DEG C, outlet temperature be
T6；
G, temperature reduction technology, to room temperature, obtain mixture C from T6 Temperature fall under protective atmosphere；
Wherein the protective atmosphere in step A-F is nitrogen atmosphere.
5) by 4) mixture C that obtains puts in distilled water, treat perforating agent be completely dissolved (distilled water that midway more renews,
Take a small amount of distilled water soaking three-dimensional carbon skeleton and instill AgNO3Solution, produces without white precipitate, it was demonstrated that perforating agent is completely dissolved), drag for
Go out solid, after vacuum drying, obtain three-dimensional carbon skeleton.
From Fig. 1, can be seen that the three-dimensional carbon skeleton prepared by the present invention presents irregular three-dimension hole Rotating fields, hole
Footpath is between 100nm-1 μm, and in hydro-thermal reaction, lithium iron phosphate particles grows in three-dimensional carbon frame aperture hole.LiFePO4 is more than enough by energy
The three-dimensional carbon skeleton of path conduction is not exclusively coated with, and constructs the LiFePO4/three-dimensional carbon skeleton/carbon of fractional open incomplete carbon cladding
Composite, on the one hand adding of three-dimensional carbon skeleton limit the undue growth of LiFePO 4 material granule in water-heat process, another
Aspect enhances the electric conductivity between material granule.
Fig. 2 is for utilizing CT2001A type LAND tester that battery is carried out charge-discharge test performance curve, and voltage range is
2.5-4.2V, test temperature 25 DEG C.Can be seen that and be used under 0.2C multiplying power three-dimensional carbon skeleton+3% carbon (the glucose carbonization of addition 3%
) LiFePO4 specific capacity can reach 156.7mAh/g, and use identical preparation technology simply to add 6% carbon (glucose
Carbonization-embodiment 3) lithium ferric manganese phosphate 0.2C multiplying power under specific capacity be 151.6mAh/g.
Fig. 3 is it can be seen that the XRD spectra of the LiFePO4 that a process for preparing matches with standard spectrogram, and peak type point
Sharp free from admixture peak occurs, the LiFePO 4 material that crystal formation is complete can be prepared by explanation this method.
Embodiment 2:
1. ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.018mol), be dissolved in after weighing
200ml water and ethylene glycol by volume=mixed solvent of 1:2 composition in, referred to as A liquid；According to theoretical amount LiFePO4: three-dimensional
Three-dimensional carbon skeleton is dispersed in water that 120ml contains Lithium hydrate (0.1584mol) by the mass ratio of carbon skeleton=1:0.1 and ethylene glycol is pressed
In volume ratio=1:2 mixed solvent, magnetic agitation 10h obtains B liquid, then drops to obtain iron phosphate in A liquid by B liquid 15min
The precursor solution of lithium, is placed in high-temperature high-pressure reaction kettle, and in precursor solution, lithium concentration is 0.495mol/L；Before
Driving volume is reactor volume the 60% of liquid solution, be heated to 200 DEG C, the response time is 6h, and question response still naturally cools to
After distilled water, three vacuum drying of each centrifuge washing of ethanol, ferric lithium phosphate precursor is prepared after room temperature；
2. by presoma LiFePO4: the mass ratio of glucose=15:8 weighs glucose 0.8640g with 8ml ethanol for helping
Agent 400r/min ball milling 1h.
3. step 2. gained mixture is put in tube furnace after drying, sinter under protective atmosphere atmosphere, first at 390 DEG C
Under the conditions of pre-burning 2h, cool to room temperature with the furnace, then ground broken, add in tube furnace, equally under protective atmosphere
Sintering, sintering process is respectively 700 DEG C, and 4h cools to room temperature with the furnace, finally obtains and is constituted three-dimensional conductive with three-dimensional carbon skeleton and carbon
The composite ferric lithium phosphate material of network；
Wherein, protective atmosphere is hydrogen atmosphere.
In end product, phosphorus content is the 22% of LiFePO4 quality, and 22% carbon is respectively from addition in water-heat process
Carbon 12% after the glucose carbonization that 10% carbon skeleton and presoma mechanical milling process add..
The preparation method of described three-dimensional carbon skeleton, comprises the following steps:
1) by Ferrous gluconate, cobaltous sulfate 10:1 in mass ratio, it is sufficiently stirred for being scattered in ethanol (every gram of carbon source correspondence
2ml ethanol) in, 50 DEG C of vacuum drying, obtain mixture A；
2) by step 1) gained mixture A and sodium carbonate 1:1000 in mass ratio, 200r/min ball milling 4h, obtain mixture
B；
3) by step 2) gained mixture B with infrared tablet machine on 10MPa pressure once 1.5g be pressed into tablet；
4) by step 3) gained tablet sinters in protective atmosphere, and its processing step is:
A, heating process, be warmed up to 350 DEG C from room temperature with 5 DEG C/min heating rate under protective atmosphere, and outlet temperature claims
For T1；And at a temperature of T1, it is incubated 120min；
B, heating process, be warmed up to 700 DEG C from T1 with 1 DEG C/min heating rate under protective atmosphere, and outlet temperature is referred to as
T2；And at a temperature of T2, it is incubated 180min；
C, heating process, be warmed up to 800 DEG C from T2 with 2 DEG C/min heating rate under protective atmosphere, and outlet temperature is referred to as
T3；And at a temperature of T3, it is incubated 240min；
D, temperature reduction technology, from T3 with 0.2 DEG C/min rate of temperature fall in protective atmosphere borehole cooling to 700 DEG C, outlet temperature be
T4；
E, temperature reduction technology, from T4 with 0.5 DEG C/min rate of temperature fall in protective atmosphere borehole cooling to 600 DEG C, outlet temperature be
T5；
F, temperature reduction technology, from T5 with 1 DEG C/min rate of temperature fall at protective atmosphere borehole cooling to 350 DEG C, outlet temperature is T6；
G, temperature reduction technology, to room temperature, obtain mixture C from T6 Temperature fall under protective atmosphere；
Wherein the protective atmosphere in step A-F is argon gas atmosphere.
5) by 4) mixture C that obtains puts in distilled water, treat perforating agent be completely dissolved (distilled water that midway more renews,
Take a small amount of distilled water soaking three-dimensional carbon skeleton and instill AgNO3Solution, produces without precipitation, it was demonstrated that perforating agent is completely dissolved), pull out solid
Body, obtains three-dimensional carbon skeleton after vacuum drying.
Embodiment 3:
1. ferrous sulfate (0.048mol), phosphoric acid (0.048mol), ascorbic acid (0.014mol), be dissolved in after weighing
200ml water and ethylene glycol by volume=mixed solvent of 1:2 composition in, referred to as A liquid；Lithium hydrate (0.144mol) is disperseed
The water contained at 120ml and ethylene glycol by volume=1:2 mixed solvent in, obtain B liquid, then B liquid 20min dropped to A
Liquid obtains the precursor solution of LiFePO4, is placed in high-temperature high-pressure reaction kettle, lithium concentration in precursor solution
For 0.45mol/L；The volume of precursor solution is the 80% of reactor volume, is heated to 240 DEG C, and the response time is 4h, treats anti-
After distilled water, three vacuum drying of each centrifuge washing of ethanol, ferric lithium phosphate precursor is prepared after answering still to naturally cool to room temperature；
2. by presoma LiFePO4: the mass ratio of glucose=15:4 weighs glucose 0.8640g with 5ml ethanol for helping
Agent 300r/min ball milling 6h.
3. step 2. gained mixture is put in tube furnace after drying, sinter under protective atmosphere atmosphere, first at 350 DEG C
Under the conditions of pre-burning 3h, cool to room temperature with the furnace, then ground broken, add in tube furnace, equally under protective atmosphere
Sintering, sintering process is respectively 650 DEG C, and 6h cools to room temperature with the furnace, finally obtains lithium iron phosphate/carbon composite material；
Wherein, protective atmosphere is nitrogen atmosphere.
In end product, phosphorus content is the 6% of LiFePO4 quality.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a preparation method for LiFePO4/three-dimensional carbon skeleton/carbon composite, is characterized by that the method comprises the following steps:
1. ferrous sulfate, phosphoric acid, dissolution of ascorbic acid are obtained A liquid in mixed solvent；Three-dimensional carbon skeleton is dispersed in containing hydrogen
In the mixed solvent of lithium oxide, obtain B liquid through magnetic agitation 2-12h, then drop to A liquid obtains by B liquid 15-20min
The precursor solution of LiFePO4, is then placed in high-temperature high-pressure reaction kettle, is heated to 160-300 DEG C, and the response time is
1-20h, after question response axe naturally cools to room temperature, respectively with distilled water, ethanol centrifuge washing, prepares iron phosphate after vacuum drying
Lithium presoma；
Wherein, described ion mol ratio is lithium ion: iron ion: phosphate anion=3-3.3:1:1；Lithium in precursor solution
Ion concentration is 0.1-1mol/L；In precursor solution, ascorbic acid concentrations is 0.03-0.2mol/L；Quality is than theoretical amount phosphoric acid
Ferrum lithium: three-dimensional carbon skeleton=1:0.1-0.005；Volume ratio A liquid: B liquid=5:3；Mixed solvent in A liquid and B liquid is water and second
The mixture of glycol, volume ratio is water: ethylene glycol=1:2；
2. by step after 1. gained ferric lithium phosphate precursor mixes with glucose with ball milling, auxiliary agent is that ethanol is mixed
Thing；Wherein, every gram of presoma adds 0.5-10ml ethanol；
Wherein, mass ratio is ferric lithium phosphate precursor: glucose=1-10:1, rotational speed of ball-mill 200-500r/min, Ball-milling Time
2-10h；
3. step 2. gained mixture is put in tube furnace after drying, under protective atmosphere atmosphere, first 240-390 DEG C of condition
Lower pre-burning 1-5h, cools to room temperature with the furnace, is then ground broken, adds in tube furnace, equally under protective atmosphere,
450-780 DEG C of sintering 3-12h, cools to room temperature with the furnace, finally obtains LiFePO4/three-dimensional carbon skeleton/carbon composite.
2. the preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite as claimed in claim 1, is characterized by described
Protective atmosphere is one or more gaseous mixture atmosphere in nitrogen, argon, hydrogen.
3. the preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite as claimed in claim 1, is characterized by described
The 30-90% that volume is reactor volume of step 1. middle precursor solution.
4. the preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite as claimed in claim 1, is characterized by described three
The preparation method of dimension carbon skeleton, comprises the following steps:
1) carbon source, catalyst are joined in ethanol and stir, then in 30-90 DEG C of vacuum drying, obtain mixture A；
Wherein, quality is than carbon source: catalyst=5-50:1；Every gram of carbon source adds 1-3ml ethanol；Described carbon source is glucose, sugarcane
In sugar, starch, oxalic acid, cellulose, ferrous gluconate, Ferrox. one or more；Catalyst be ferrous sulfate, iron chloride,
One or more in ferrous chloride, nickel sulfate, Nickel dichloride. and cobaltous sulfate；
2) by step 1) gained mixture A mix with perforating agent after ball milling 1-9h, mass ratio be mixture A: perforating agent=
1:100-5000；Obtain mixture B；Rotational speed of ball-mill 100-500r/min；
3) by step 2) gained mixture B is pressed into tablet with what infrared tablet machine was compressed to 1-2g size under 1-50MPa pressure；
4) by step 3) gained tablet sinters in protective atmosphere, comprises the following steps:
A, being warmed up to 350-400 DEG C with 2-5 DEG C/min heating rate from room temperature under protective atmosphere, outlet temperature is referred to as T1；And
60-120min it is incubated at a temperature of T1；
B, being warmed up to 600-700 DEG C with 1-4 DEG C/min heating rate from T1 under protective atmosphere, outlet temperature is referred to as T2；At T2
At a temperature of be incubated 60-180min；
C, being warmed up to 700-900 DEG C with 1-3 DEG C/min heating rate from T2 under protective atmosphere, outlet temperature is referred to as T3；At T3
At a temperature of be incubated 120-240min；
D, from T3 with 0.2-1 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 600-700 DEG C, outlet temperature is T4；
E, from T4 with 0.2-1 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 500-600 DEG C, outlet temperature is T5；
F, from T5 with 1-1.5 DEG C/min rate of temperature fall protective atmosphere borehole cooling to 350-450 DEG C, outlet temperature is T6；
G, to room temperature, obtain mixture C from T6 Temperature fall under protective atmosphere；
5) by 4) mixture C that obtains puts in distilled water, treats that perforating agent is completely dissolved, pull solid out, obtain after vacuum drying
Three-dimensional carbon skeleton.
5. the preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite as claimed in claim 4, is characterized by described step
Rapid 2) during in, perforating agent is sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate, calcium carbonate one or more.
6. the preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite as claimed in claim 4, is characterized by step A-F
In protective atmosphere be nitrogen or argon gas atmosphere.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256960A (en) * | 2017-08-06 | 2017-10-17 | 长沙小新新能源科技有限公司 | A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole |
| CN107394139A (en) * | 2017-07-05 | 2017-11-24 | 东莞中汽宏远汽车有限公司 | Compound anode material of lithium battery and preparation method thereof and lithium battery anode, lithium battery |
| CN107394114A (en) * | 2017-07-05 | 2017-11-24 | 东莞中汽宏远汽车有限公司 | Anode material of lithium battery and preparation method thereof and lithium battery anode, lithium battery |
| CN109860572A (en) * | 2019-03-01 | 2019-06-07 | 沈阳国科金能科技有限公司 | The preparation method of the compound carbon-coated nano-scale lithium iron phosphate of three-dimensional net structure |
| CN113511641A (en) * | 2021-07-04 | 2021-10-19 | 桂林理工大学 | Method for preparing three-dimensional porous carbon/iron phosphate compound by salt crystal foaming with glucose as carbon source |
Citations (3)
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| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN103482597A (en) * | 2012-06-14 | 2014-01-01 | 中国人民解放军63971部队 | Mesoporous-macroporous carbon production method |
| 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 |
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| CN103482597A (en) * | 2012-06-14 | 2014-01-01 | 中国人民解放军63971部队 | Mesoporous-macroporous carbon production method |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394139A (en) * | 2017-07-05 | 2017-11-24 | 东莞中汽宏远汽车有限公司 | Compound anode material of lithium battery and preparation method thereof and lithium battery anode, lithium battery |
| CN107394114A (en) * | 2017-07-05 | 2017-11-24 | 东莞中汽宏远汽车有限公司 | Anode material of lithium battery and preparation method thereof and lithium battery anode, lithium battery |
| CN107256960A (en) * | 2017-08-06 | 2017-10-17 | 长沙小新新能源科技有限公司 | A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole |
| CN109860572A (en) * | 2019-03-01 | 2019-06-07 | 沈阳国科金能科技有限公司 | The preparation method of the compound carbon-coated nano-scale lithium iron phosphate of three-dimensional net structure |
| CN113511641A (en) * | 2021-07-04 | 2021-10-19 | 桂林理工大学 | Method for preparing three-dimensional porous carbon/iron phosphate compound by salt crystal foaming with glucose as carbon source |
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