CN111446429A - Poly-polyanion cathode material and preparation method and application thereof - Google Patents
Poly-polyanion cathode material and preparation method and application thereof Download PDFInfo
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- CN111446429A CN111446429A CN202010232297.XA CN202010232297A CN111446429A CN 111446429 A CN111446429 A CN 111446429A CN 202010232297 A CN202010232297 A CN 202010232297A CN 111446429 A CN111446429 A CN 111446429A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010406 cathode material Substances 0.000 title claims description 21
- 229920000447 polyanionic polymer Polymers 0.000 title abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims description 68
- 229910021389 graphene Inorganic materials 0.000 claims description 54
- 239000011572 manganese Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 17
- 238000001694 spray drying Methods 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 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 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 description 53
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000011162 core material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 238000004729 solvothermal method Methods 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910017677 NH4H2 Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 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 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020509 Na4Mn3 (PO4)2P2O7 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 229910010446 TiO2-a Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005641 tunneling Effects 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
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of anode materials, and provides a poly-polyanion anode material, a preparation method and application thereof4MnxCo3‑x(PO4)2P2O7(3>x>0) The positive electrode material is characterized in that the surface of the core is coated with a first coating layer and a second coating layer, the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; wherein the first coating layer is coated on the surface of the core, and the second coating layer is coated on the first coating layerCoating the surface of the coating layer; or the second coating layer is coated on the surface of the core, and the first coating layer is coated on the surface of the second coating layer. The positive electrode material can increase Na4MnxCo3‑x(PO4)2P2O7Discharge plateau of (3), increase of Na4MnxCo3‑x(PO4)2P2O7The electronic conductivity and the ionic conductivity of the composite lead to have excellent rate performance and cycle stability. The preparation method has the characteristics of good repeatability and high reliability.
Description
Technical Field
The invention belongs to the technical field of anode materials, and particularly relates to a poly-polyanion anode material and a preparation method and application thereof.
Background
Lithium ion batteries have the characteristics of high energy density, good cycle performance, high safety and the like, and have been used as main power sources of portable equipment in the last thirty years. In recent years, its application has been expanded as an important energy source for hybrid electric vehicles, plug-in electric vehicles, pure electric and energy storage-based power stations. However, lithium element is low in storage amount in the earth crust, and sodium element is abundant and environment-friendly, so that many researchers focus on the research of the sodium ion battery.
The research on sodium ion batteries began in the eighties of the last century but developed less well than lithium ion batteries. The radius (0.102nm) of sodium ions is far larger than that (0.076nm) of lithium ions, so that the change of the material structure is large in the charging and discharging process, and the cycle life of the sodium ion battery is seriously influenced. The structure of the polyanion compound is stable and controllable, and the cycling stability and the thermal stability are also higher, so that the polyanion compound becomes a research hotspot of the anode material of the sodium-ion battery.
In the existing research on polyanion sodium ion batteries, Na4Fe3(PO4)2P2O7As a typical material, the theoretical specific capacity is 129mAh/g, the discharge platform voltage is 3.2V, and the material is widely concerned due to excellent comprehensive electrical property. But the electronic conductivity and the ionic conductivity of the material are low, so that the actual discharge capacity is small, the 0.05C rate discharge specific capacity is only 106mAh/g, the large rate discharge performance is worse, and the energy density is extremely low. Another typical material Na4Mn3(PO4)2P2O7The theoretical specific capacity of the manganese-based lithium ion battery is 129mAh/g, the voltage of a discharge platform can be increased to 3.84V, the energy density is improved, but the problem that the ginger-Taylor effect of manganese is easy to dissolve is solved, so that the cycle and rate performance of the manganese-based lithium ion battery are poorer.
Disclosure of Invention
In order to solve the defect problem of the conventional polyanion sodium-ion battery cathode material, the invention provides a polyanion cathode material, a preparation method and application thereof, wherein the polyanion cathode material is coated Na with excellent electrochemical performance4MnxCo3-x(PO4)2P2O7(3>x>0) Positive electrode material, the coated Na4MnxCo3-x(PO4)2P2O7The positive electrode material can increase Na4MnxCo3-x(PO4)2P2O7Discharge plateau of (3), increase of Na4MnxCo3-x(PO4)2P2O7The electronic conductivity and the ionic conductivity of the composite lead to have excellent rate performance and cycle stability. The preparation method has the characteristics of good repeatability and high reliability.
Specifically, the invention provides a positive electrode material, wherein the positive electrode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7(3>x>0) A material; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; wherein the first coating layer is coated on the nuclear surfaceThe second coating layer is coated on the surface of the first coating layer; or the second coating layer is coated on the surface of the core, and the first coating layer is coated on the surface of the second coating layer.
Preferably, the first coating layer is coated on the surface of the core, and the second coating layer is coated on the surface of the first coating layer.
According to the invention, the positive electrode material is used in a sodium ion battery, for example in a positive electrode of a sodium ion battery.
According to the invention, the core comprises Na4MnxCo3-x(PO4)2P2O7The material comprises manganese ions and cobalt ions at the same time, and the oxidation-reduction potentials of the manganese ions and the cobalt ions are higher, so that the discharge platform voltage is higher (about 3.86V), and according to a formula, the mass (volume) energy density is equal to the capacity × discharge platform voltage/mass (volume), so that the discharge platform voltage is improved, the energy density (mass energy density or volume energy density) of the material is also improved, and the application of the material is widened.
According to the invention, said Na4MnxCo3-x(PO4)2P2O7The material is crystalline, the median particle size of the crystals being 5 to 12 μm, preferably 5 to 9 μm.
According to the invention, said Na4MnxCo3-x(PO4)2P2O7In the material, x is, for example, 1 or 2, preferably Na4MnCo2(PO4)2P2O7。
According to the invention, said Na4MnxCo3-x(PO4)2P2O7The material is a secondary particle having a median particle diameter of 5 to 12 μm, preferably 5 to 9 μm, assembled from primary particles.
According to the invention, the first coating layer is a carbon coating layer, the thickness of which is 0.01-8nm, preferably 0.1-6nm, and more preferably 1-5 nm.
According to the present invention, the carbon coating layer may be coated directly on Na4MnxCo3-x(PO4)2P2O7The surface of the material, or the carbon coating layer is coated on the surface of the second coating layer.
In the cathode material, the introduction of the carbon coating layer can inhibit Na on one hand4MnxCo3-x(PO4)2P2O7The abnormal growth of primary particles in the preparation process of the material, the primary particle granularity of the roasted product is refined, and Na is favorably used+Diffusing; on the other hand, the carbon coating is on Na4MnxCo3-x(PO4)2P2O7The conductive network formed on the surface of the material can increase the conductivity between particles, and is Na4MnxCo3-x(PO4)2P2O7The material provides electron tunneling to compensate for Na+Dynamic charge balance during de-intercalation and further increase Na4MnxCo3-x(PO4)2P2O7Electrochemical properties of the material. The TiO is2The introduction of the modified graphene coating layer also has the same effect.
According to the invention, the carbon of the first coating layer is amorphous carbon.
According to the invention, the second coating layer is TiO2Modified graphene coating, denoted TiO2A graphene coating with a thickness of 0.01-10nm, preferably 0.1-8 nm.
According to the invention, the TiO2The modified graphene coating layer is coated on the carbon-coated Na4MnxCo3-x(PO4)2P2O7The surface of the material, or, the TiO2The modified graphene coating layer is directly coated on Na4MnxCo3-x(PO4)2P2O7The surface of the material.
According to the invention, in the second coating layer, TiO2Bound to graphene in the form of a chemical bond, denoted TiO2-graphene. In particular, the graphene oxide surface containsMany oxygen-containing functional groups such as carboxyl, hydroxyl and carbonyl groups; by solvothermal method, TiO2The oxygen-containing groups can be combined with graphene in a chemical bond mode, and simultaneously, the oxygen-containing groups can be reduced to obtain TiO2A modified graphene coating layer. In the second coating layer, TiO2The content of (A) is 50-70 wt%, and the content of graphene is 30-50 wt%.
According to the invention, in the second coating layer, the carbon atom in the graphene is sp2Hybridization, faster electron transfer rate, TiO2The modified graphene serving as a coating layer can obviously improve Na4MnxCo3-x(PO4)2P2O7The electronic conductivity of the material; however, when only graphene is used as a coating layer, the graphene and the core material or the core material coating the first coating layer are likely to form an absolute coating shape, and particularly when the coating layer is thick, although electron conductivity is significantly improved, lithium ion transport is significantly inhibited, and performance such as capacity is significantly reduced. Thus, by selecting the TiO of the present application2And the modified graphene is used as a second coating layer, and the thickness of the second coating layer is controlled to realize the regulation and control of the performance of the second coating layer.
TiO2Is a rich, low-cost and environment-friendly material, and has high conductivity and stable structure. Thus, TiO is added2Preparing TiO by compounding with graphene2A graphene material, which will have a stronger electronic conductivity. In addition, as a coating material, TiO2Graphene is a three-dimensional structure whose thickness can be controlled below 10nm, thus not hindering ion transport and avoiding Na4MnxCo3-x(PO4)2P2O7The direct contact of the material and the electrolyte reduces the violent degree of the contact reaction of the anode and the electrolyte, reduces the dissolution of transition metal, and improves Na4MnxCo3-x(PO4)2P2O7Structural stability and cycle performance of the material.
According to the present invention, the carbon coating layer accounts for 0.1 to 2.5 wt%, more preferably 0.8 to 1.5 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, or 2.5 wt% of the positive electrode material.
According to the invention, in the positive electrode material, the TiO2The mass percentage of the graphene coating layer is 0.1 to 3 wt%, more preferably 0.5 to 1.5 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, or 3 wt%.
According to the invention, the median particle diameter of the cathode material is 5-12 μm, preferably 5-9 μm, and the specific surface area is 7-11g/m2And the powder resistivity of the anode material is less than or equal to 5.0 omega cm.
According to the invention, the morphology structure of the cathode material is secondary spherical particles with the median particle size of 5-12 μm, preferably 5-9 μm, which are assembled by primary particles with the median particle size of 100-300nm, and the morphology is favorable for the rapid transfer of charges, and improves Na+And (3) the de-intercalation dynamics optimizes the rate performance of the material.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
(1) mixing a carbon source, a phosphorus source, a cobalt source, a manganese source and a sodium source, spray drying and carrying out heat treatment;
(2) mixing the product of step (1) with TiO2Mixing, drying and sintering the modified graphene to prepare the cathode material, wherein the cathode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7(3>x>0) A material; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; wherein the first coating layer is coated on the coreThe surface of the second coating layer is coated on the surface of the first coating layer.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
(i) adding TiO into the mixture2Mixing the modified graphene, a phosphorus source, a cobalt source, a manganese source and a sodium source, spray drying and carrying out heat treatment;
(ii) mixing the product obtained in the step (i) with a carbon source, spray-drying, and sintering to obtain the cathode material, wherein the cathode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7(3>x>0) A material; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; the second coating layer is coated on the surface of the core, and the first coating layer is coated on the surface of the second coating layer.
According to the present invention, in the step (1) and the step (ii), the carbon source is at least one selected from the group consisting of glucose, citric acid, chitosan, urea, sucrose, polyacrylamide, polyvinyl alcohol, phenol resin, and epoxy resin.
According to the invention, in step (1), the carbon source is added in an amount of Na4MnxCo3-x(PO4)2P2O71-10 wt%, such as 2-8 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt% of the mass of the material.
According to the invention, in step (ii), the TiO2The addition amount of the modified graphene is Na4MnxCo3-x(PO4)2P2O70.1-3 wt%, such as 0.5-1.5 wt%, such as 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, or 3.0 wt% of the mass of the material.
According to the invention, in step (1) and step (i), the phosphorus source is selected from ammonium dihydrogen phosphate, pyrophosphoric acidAt least one of sodium, ammonium pyrophosphate, phosphoric acid, sodium dihydrogen phosphate and disodium hydrogen phosphate; the cobalt source is selected from at least one of cobalt acetate, cobalt sulfate, cobalt nitrate, cobalt oxide, cobalt oxalate and cobalt chloride; the manganese source is selected from at least one of manganese nitrate, manganous acetate, manganese dioxide and manganese hydroxide, and the sodium source is selected from at least one or more of sodium pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium acetate, sodium nitrate and sodium citrate; the molar ratio of the phosphorus source, the cobalt source, the manganese source and the sodium source to Na4MnxCo3-x(PO4)2P2O7The molar ratio of each substance in the material is the same.
According to the invention, in the step (1) and the step (i), the mixing is carried out in a ball mill, for example, deionized water is added in the mixing process, and various materials can be fully mixed in the material mixing process; wherein the deionized water is added in an amount of 20 to 40 wt% of the solid component, for example, 30 wt%.
According to the invention, in the step (1) and the step (i), the temperature of the spray drying is 180-220 ℃, for example 200 ℃, and spherical particles with the median diameter of 5-12 μm are prepared by spray drying; the purpose of the spray drying is to dry and granulate the mixed material to obtain spherical particles.
According to the invention, in steps (1) and (i), the heat treatment is carried out under an inert atmosphere, such as argon.
According to the invention, in the step (1) and the step (i), the temperature of the heat treatment is 250-350 ℃, and the time of the heat treatment is 4-8 h. During the heat treatment, a carbon source or TiO2And mixing the modified graphene with a phosphorus source, a cobalt source, a manganese source and a sodium source, and carrying out preliminary pre-reaction to obtain an intermediate.
According to the invention, in step (2), the mixing is carried out under stirring, for example, by mixing TiO2Ultrasonically dispersing the modified graphene in an aqueous solution to obtain a dispersion system, adding the product obtained in the step (1), and stirring and mixing.
According to the invention, in the step (ii), the carbon source is added into the product obtained in the step (i), and then a proper amount of water is added, and the mixture is subjected to ball milling and uniform mixing.
According to the invention, in the step (ii), the temperature of the spray drying is 180-220 ℃, for example 200 ℃, and spherical particles with the median diameter of 5-12 μm are prepared through the spray drying; the purpose of the spray drying is to dry and granulate the mixed material to obtain spherical particles.
According to the invention, in step (2), the product of step (1) is mixed with TiO2The mass ratio of the modified graphene is 100 (0.1-3), and more preferably 100 (0.5-1.5).
According to the present invention, in the step (ii), the mass ratio of the product of the step (i) to the carbon source is 1 to 10 wt%, and more preferably 2 to 8 wt%.
According to the invention, in steps (2) and (ii), the sintering is carried out, for example, under an inert atmosphere, such as argon.
According to the invention, in step (2) and step (ii), the sintering temperature is 500-700 ℃, such as 550 ℃, 600 ℃, 650 ℃, 700 ℃; the sintering time is 8-14h, such as 8h, 10h, 12h or 14 h.
According to the invention, in step (2) and step (i), the TiO2The modified graphene is prepared by a solvothermal method, for example, comprising the following steps:
a) mixing graphene oxide with TiO2Mixing powder materials, adding a solvent, and carrying out a solvothermal reaction;
b) optionally, the method also comprises the steps of cooling, centrifuging, washing and drying after the reaction is finished.
According to the invention, in step a), the graphene oxide is, for example, graphene oxide prepared by Hummers method. The TiO is2The powder being, for example, commercially available TiO type P252。
According to the invention, in step a), the graphene oxide is mixed with TiO2The mass ratio of the powder is 5:5 to 3:7, for example 5:5, 4:6 or 3: 7.
According to the invention, in the step a), the solvent is a mixed solvent of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is (1-4):1, such as 2: 1.
According to the invention, in step a), the temperature of the solvothermal reaction is 110-130 ℃, for example 120 ℃; the solvothermal reaction time is 12 to 36h, for example 24 h.
In the invention, the oxygen-containing functional group in the graphene oxide can be reduced to form graphene by adopting a solvothermal method, and meanwhile, TiO is reduced2Chemically bonded to oxygen-containing functional groups to form TiO2-graphene。
The invention also provides application of the cathode material as a cathode active material of a sodium-ion battery.
The invention also provides a positive electrode for the sodium-ion battery, which comprises the positive electrode material.
The invention also provides a sodium ion battery which comprises the positive electrode.
The invention has the beneficial effects that:
the invention provides a polyanion anode material, a preparation method and application thereof, and the anode material and a sodium ion battery comprising the anode material have the following advantages:
1) lithium ions in the lithium ion battery only have one-dimensional channels, while sodium ions in the sodium ion battery are 3-dimensional channels, and have higher ionic conductivity compared with the lithium battery.
2)Na4Fe3(PO4)2P2O7The discharge plateau voltage of (1) is only 3.2V, while Na4MnxCo3-x(PO4)2P2O7In particular Na4MnCo2(PO4)2P2O7The voltage of the discharge platform is increased to 3.86V, so that the energy density is improved, and the application of the discharge platform is expanded.
3)TiO2The introduction of the graphene coating layer and the carbon coating layer improves the electronic conductivity of the material, so that the material has better rate performance and meets the requirement of large scaleMultiplying power charge and discharge, the structure is more stable, and the cycle life is longer.
4) The anode material is secondary spherical particles assembled by primary particles with the median particle size of 100-300nm, and the structure is more beneficial to the desorption of sodium ions due to TiO2The introduction of the graphene coating layer and the carbon coating layer inhibits the growth of the nucleus, so that the particle size of the nucleus material particles is reduced, the extraction path of sodium ions is shortened, and the ion conductivity is further improved.
5) The preparation process has high operation reliability, rich raw material resources and wide industrial application prospect.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first", "second", etc. are used for descriptive purposes only and do not indicate or imply relative importance.
Example 1:
the method comprises the following steps: TiO 22Preparation of graphene
Taking 0.3g of graphene oxide prepared by a Hummers method, adding the graphene oxide into 100g of a mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 2:1, performing ultrasonic dispersion for 1 hour, and then adding 0.7g of TiO2Powder (commercially available P25) was stirred continuously for 2h to give a homogeneous dispersion.
Then transferring the suspension into a polytetrafluoroethylene kettle for hydrothermal treatment, and heating for 24 hours at 120 ℃; cooling, centrifuging, washing with water, and vacuum drying at 60 deg.C to obtain TiO2Modified graphene, denoted TiO2-graphene。
Step two: na (Na)4MnCo2(PO4)2P2O7Preparation of the/C intermediate
Weighing Na according to the molar ratio of 1.02:1:2:2.044P2O7、Mn(NO)3、(CH3COO)2Co and NH4H2PO4Adding citric acid and deionized water for ball milling, wherein the adding amount of citric acid is theoretically capable of generating Na4MnCo2(PO4)2P2O75 wt% of the mass (calculated as the content of Co or Mn) and the amount of deionized water added was 30 wt% of the solid content. Spray drying the mixture after ball milling at 200 deg.C, and heating at 300 deg.C under argon protection for 6h to obtain Na4MnCo2(PO4)2P2O7a/C intermediate.
Step three: TiO 22-graphene@Na4MnCo2(PO4)2P2O7Preparation of/C
0.15g of TiO was weighed2Adding graphene into 15m L deionized water, performing ultrasonic dispersion for 2h, and adding 10g Na4MnCo2(PO4)2P2O7The intermediate/C is continuously stirred for 5 hours, centrifuged and dried in vacuum for 12 hours to obtain solid; sintering the obtained solid for 10h at 600 ℃ under the protection of argon atmosphere to obtain TiO2-graphene@Na4MnCo2(PO4)2P2O7/C。
Step four: electrical property detection of finished product
The positive electrode material prepared by the embodiment and the sodium sheet are assembled into the button cell, and the charge and discharge performance of the button cell is tested, wherein the voltage range is 1.7-4.6V.
Example 2:
the procedure is as in example 1, except that TiO is present in step III2The amount of graphene added was 0.05 g.
Example 3:
the operation process is the same as that of the embodiment1, with the difference that TiO is in step III2-graphene is added in an amount of 0.30 g.
Example 4:
the procedure is as in example 1, except that in step three the solid is sintered for 14h at 500 ℃ under argon.
Example 5:
the procedure is as in example 1, except that in step three the solid is sintered at 700 ℃ for 8h under argon.
Example 6:
the procedure is as in example 1, except that the amount of citric acid added in step two is such that Na is theoretically formed4MnCo2(PO4)2P2O710 wt% of the mass (calculated as Co or Mn content).
Example 7:
the procedure is as in example 1, except that the amount of citric acid added in step two is such that Na is theoretically formed4MnCo2(PO4)2P2O71 wt% of the mass (calculated as Co or Mn content).
Example 8:
the operation process is the same as that of example 1, except that the carbon source in the second step is glucose, the heat treatment temperature is 250 ℃, and the sintering time is 4 h.
Example 9:
the operation process is the same as that of example 1, except that the carbon source in the second step is urea, the heat treatment temperature is 350 ℃, and the sintering time is 8 hours.
Example 10:
the operation process is the same as that of example 1, except that the step one:
taking 0.4g of graphene oxide prepared by a Hummers method, adding the graphene oxide into 100g of a mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 6:3, performing ultrasonic dispersion for 1 hour, and then adding 0.6g of TiO2The powder (commercially available P25) was continuously stirred for 2h to give a uniformly dispersed suspension.
Then transferring the suspension into a polytetrafluoroethylene kettle for hydrothermal treatment, and heating for 24 hours at 120 ℃; after being cooled, the mixture is centrifuged,washing with water, and vacuum drying at 60 deg.C to obtain TiO2Modified graphene, denoted TiO2-graphene。
Example 11:
the operation process is the same as that of example 1, except that the step one:
taking 0.5g of graphene oxide prepared by a Hummers method, adding the graphene oxide into 100g of a mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 6:3, performing ultrasonic dispersion for 1 hour, and then adding 0.5g of TiO2The powder (commercially available P25) was continuously stirred for 2h to give a uniformly dispersed suspension.
Then transferring the suspension into a polytetrafluoroethylene kettle for hydrothermal treatment, and heating for 24 hours at 120 ℃; cooling, centrifuging, washing with water, and vacuum drying at 60 deg.C to obtain TiO2Modified graphene, denoted TiO2-graphene。
Example 12:
the operation process is the same as that of example 1, except that the steps two and three:
step two: na (Na)4MnCo2(PO4)2P2O7/TiO2Preparation of-graphene intermediates
0.15g of TiO was weighed2Adding graphene into 15m L deionized water, performing ultrasonic dispersion for 2h, recording as a solution A, and weighing 4.31g of Na4P2O7、2.31g Mn(NO)3、5.63g(CH3COO)2Co and 3.73g NH4H2PO4Then, the solution A is added into the powder, 38.77g of deionized water is additionally added, and then ball milling dispersion is carried out. After uniform dispersion, spray drying is carried out at 200 ℃ to obtain solid powder. Heating the solid powder under the protection of argon at 300 ℃ for 6h to obtain Na4MnCo2(PO4)2P2O7/TiO2-a graphene intermediate.
Step three: c @ Na4MnCo2(PO4)2P2O7/TiO2Preparation of graphene
Weighing 10g of Na4MnCo2(PO4)2P2O7/TiO2-graphene intermediate, 0.5g citric acid and 35g deionized water, ball milled and mixed, and spray dried at 200 ℃. Finally sintering the obtained solid for 10h at 600 ℃ under the protection of argon atmosphere to obtain C @ Na4MnCo2(PO4)2P2O7/TiO2-graphene。
Comparative example 1:
the method comprises the following steps: na (Na)4MnCo2(PO4)2P2O7Preparation of
Weighing Na according to the molar ratio of 1.02:1:2:2.044P2O7、Mn(NO)3、(CH3COO)2Co and NH4H2PO4And adding deionized water for ball milling, wherein the deionized water is added according to the solid-liquid mass ratio of 7: 3. Spray drying the mixture after ball milling at 200 ℃, keeping the temperature of 300 ℃ under the protection of argon, heating for 6h, and sintering at 600 ℃ for 10h to obtain Na serving as a product4MnCo2(PO4)2P2O7。
Step two: electrical property detection of finished product
The button cell is assembled by adopting the anode material prepared by the comparative example and the sodium sheet, and the charge and discharge performance of the button cell is tested, wherein the voltage range is 1.7-4.6V.
Comparative example 2:
the method comprises the following steps: na (Na)4MnCo2(PO4)2P2O7Preparation of/C
Weighing Na according to the molar ratio of 1.02:1:2:2.044P2O7、Mn(NO)3、(CH3COO)2Co and NH4H2PO4Adding citric acid and deionized water for ball milling, wherein the adding amount of citric acid is theoretically capable of generating Na4MnCo2(PO4)2P2O75 wt% of the mass (calculated by the content of Co or Mn), deionized water was added in a solid-liquid mass ratio of 7: 3. Spraying the mixture after ball milling at 200 DEG CDrying, heating at 300 deg.C under the protection of argon for 6 hr, and sintering at 600 deg.C for 10 hr to obtain Na product4MnCo2(PO4)2P2O7/C。
Step two: electrical property detection of finished product
The button cell is assembled by adopting the anode material prepared by the comparative example and the sodium sheet, and the charge and discharge performance of the button cell is tested, wherein the voltage range is 1.7-4.6V.
Table 1 comparison of electrical properties of the batteries prepared in example 1 and comparative examples 1 to 2
As can be seen from Table 1 above, the TiO of example 12-graphene@Na4MnCo2(PO4)2P2O7The gram capacity exertion, rate capability and cycling stability of the/C cathode material are obviously improved compared with those of the cathode materials prepared in comparative examples 1 and 2.
Table 2 comparison of electrical properties of batteries prepared in examples 1-3
As can be seen from Table 2 above, when TiO is used2The amount of graphene added was 3.0 wt%, and both the discharge capacity and rate capability were reduced, probably because of TiO2Graphene on Na4MnCo2(PO4)2P2O7The excessive enrichment of the surface of the/C hinders the transmission of ions to a certain extent, so that the transmission of electrons and ions is unbalanced, the gram capacity is reduced, and the multiplying power performance is reduced. When the addition amount is 0.5 wt%, the conductivity improvement is limited, so that the gram capacity exertion and rate capability are not as good as 1.5 wt%.
Table 3 comparison of electrical properties of the batteries prepared in examples 1, 4 to 5
As can be seen from Table 3, the difference between the properties of the products obtained by sintering at low temperature for a long time and sintering at high temperature for a short time is substantially equivalent.
Table 4 comparison of electrical properties of the batteries prepared in examples 1, 6 to 7
As can be seen from Table 4 above, too much or too little carbon source can seriously affect the performance of the material. This is probably because Na when the amount of carbon added is too small4MnCo2(PO4)2P2O7The particle size is not easy to control, the particles are larger, and the ionic conductivity is reduced; when the amount of carbon added is too high, the surface coating layer prevents the migration of sodium ions, and thus the performance is degraded.
Table 5 comparison of electrical properties of the batteries prepared in examples 1, 8-9
As can be seen from Table 5 above, the electrical properties of the final product obtained from different carbon sources at different heat treatment temperatures and times are substantially equivalent. Wherein, the heat treatment temperature and the heat preservation time of the carbon source are mainly determined according to the temperature and the time required by the carbonization of the carbon source.
Table 6 comparison of electrical properties of batteries prepared in examples 1, 10-11
As can be seen from Table 6 above, in the preparation of TiO2In graphene, the electrical properties decrease as the amount of graphene oxide added increases. This may be due to an increased amount of graphene oxide and TiO2The amount is reduced, so that TiO is formed2The worse the 3-dimensional structure of graphene; and the increase of the graphene oxide can cause the increase of Na4MnCo2(PO4)2P2O7the/C forms a complete coating, thereby reducing ionic conductance, resulting in a reduction in gram capacity, rate capability, and the like.
Table 7 comparison of electrical properties of batteries prepared in examples 1 and 12
As can be seen from Table 7 above, the reaction product of TiO2The graphene coating layer is directly coated on the surface of the core material, and the carbon coating layer is coated on the TiO2Capacity and rate of the battery (example 12) made of the positive electrode material on the surface of graphene coating are improved compared with the battery without coating (comparative example 1) or only coated with carbon layer (comparative example 2), and TiO is coated on the surface of the core material directly compared with the carbon coating layer under the same coating amount2The capacity and rate of the battery composed of the positive electrode material with the carbon coating layer coated on the surface of the carbon coating layer are slightly reduced. This is probably because TiO2When the graphene coating layer is directly coated on the surface of the core material, the coating uniformity is inferior to that of the carbon coating layer, so that the effect of inhibiting the growth of the nuclear crystal particles is not good, and the improvement of the ion conductivity is not obvious.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive electrode material, wherein the positive electrode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7A material wherein 3>x>0; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; wherein the first coating layer is coated on the surface of the core, and the second coating layer is coated on the surface of the first coating layer; or, the second coating layerThe first coating layer is coated on the surface of the core, and the second coating layer is coated on the surface of the first coating layer.
2. The positive electrode material according to claim 1, wherein the Na is4MnxCo3-x(PO4)2P2O7The material is Na4MnCo2(PO4)2P2O7。
3. The positive electrode material according to claim 1 or 2, wherein the first coating layer is a carbon coating layer having a thickness of 0.01 to 8 nm; the carbon of the first coating layer is amorphous carbon.
4. The positive electrode material according to any one of claims 1 to 3, wherein the second coating layer is TiO2Modified graphene coating layer, the TiO2The thickness of the modified graphene coating layer is 0.01-10 nm;
in the second coating layer, TiO2The content of (A) is 50-70 wt%, and the content of graphene is 30-50 wt%.
5. The positive electrode material according to any one of claims 1 to 4, wherein the carbon coating layer accounts for 0.1 to 2.5 wt% of the positive electrode material; TiO 22The modified graphene coating layer accounts for 0.1-3 wt%.
6. The method for producing a positive electrode material according to any one of claims 1 to 5, wherein the method comprises the steps of:
(1) mixing a carbon source, a phosphorus source, a cobalt source, a manganese source and a sodium source, spray drying and carrying out heat treatment;
(2) mixing the product of step (1) with TiO2Mixing, drying and sintering the modified graphene to prepare the cathode material, wherein the cathode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7Materials, 3>x>0; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; wherein the first coating layer is coated on the surface of the core, and the second coating layer is coated on the surface of the first coating layer; or,
the method comprises the following steps:
(i) adding TiO into the mixture2Mixing the modified graphene, a phosphorus source, a cobalt source, a manganese source and a sodium source, spray drying and carrying out heat treatment;
(ii) mixing the product obtained in the step (i) with a carbon source, spray-drying, and sintering to obtain the cathode material, wherein the cathode material has a core-shell structure; the core comprises Na4MnxCo3-x(PO4)2P2O7Materials, 3>x>0; coating a first coating layer and a second coating layer on the surface of the core, wherein the first coating layer and the second coating layer form a shell, the first coating layer is a carbon coating layer, and the second coating layer is TiO2A modified graphene coating layer; the second coating layer is coated on the surface of the core, and the first coating layer is coated on the surface of the second coating layer.
7. The preparation method according to claim 6, wherein in the step (1) and the step (i), the temperature of the heat treatment is 250 ℃ to 350 ℃, and the time of the heat treatment is 4h to 8 h;
in the step (2) and the step (ii), the sintering temperature is 500-700 ℃, and the sintering time is 8-14 h.
8. Use of the positive electrode material as claimed in any one of claims 1 to 5 as a positive electrode active material for a sodium ion battery.
9. A positive electrode for a sodium-ion battery, comprising the positive electrode material according to any one of claims 1 to 5.
10. A sodium ion battery comprising the positive electrode of claim 9.
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