CN116864684A - Positive electrode material for lithium ion battery - Google Patents
Positive electrode material for lithium ion battery Download PDFInfo
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- CN116864684A CN116864684A CN202210311032.8A CN202210311032A CN116864684A CN 116864684 A CN116864684 A CN 116864684A CN 202210311032 A CN202210311032 A CN 202210311032A CN 116864684 A CN116864684 A CN 116864684A
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- Prior art keywords
- nitrogen
- positive electrode
- iron phosphate
- doped composite
- composite carbon
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 90
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 157
- 239000000463 material Substances 0.000 claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 82
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 79
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 77
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 57
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000013543 active substance Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- 239000011149 active material Substances 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 14
- 229910011980 LiFe0.4Mn0.6PO4 Inorganic materials 0.000 claims description 13
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- 238000009396 hybridization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 68
- 239000012298 atmosphere Substances 0.000 description 23
- 238000002156 mixing Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011261 inert gas Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910011849 LiFe0.2Mn0.8PO4 Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910017221 Ni0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage 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
- H01M4/62—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
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Abstract
The invention relates to a positive electrode material for a lithium ion battery. The positive electrode material comprises an active substance loaded in a nitrogen-doped composite carbon material, the nitrogen-doped composite carbon material has a three-dimensional porous structure, the nitrogen-doped composite carbon material comprises three-dimensional graphene and carbon nanotubes, the carbon nanotubes are intertwined on the surface of a sheet layer of the three-dimensional graphene, a hybrid structural unit is formed between the carbon nanotubes and the three-dimensional graphene, the active substance is loaded in pores of the nitrogen-doped composite carbon material, and the active substance comprises a lithium iron phosphate material. The battery containing the positive electrode material has improved rate performance and cycle stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries. In particular, the present invention relates to a positive electrode material for a lithium ion battery.
Background
Lithium ion batteries have the advantages of high voltage, high energy density, environmental protection, no pollution and the like, and are currently mainstream energy storage systems, and the application of the lithium ion batteries has been developed from portable electronic equipment to vehicles.
Many researches are focused on developing lithium ion batteries suitable for electric vehicles and large-scale power grid energy storage, wherein safety problems are of great concern, and thus phosphate-based cathode materials which do not release oxygen at high temperature and have stable structures are widely used.
However, phosphate-based cathode materials have two obvious disadvantages, one of which is low electron conductivity and ion conductivity, which not only is unfavorable for the rate performance of the battery, but also causes poor low-temperature performance of the battery due to retarded electrode dynamics, limiting further large-scale application of the battery; another disadvantage is poor processability, affecting the preparation and electrochemical properties of the electrode.
Aiming at the two problems, the most commonly used improvement method is to carry out surface carbon coating, ion doping and morphology optimization on the phosphate positive electrode material, wherein the carbon coating and morphology optimization can obviously improve the electrochemical performance of the phosphate positive electrode material, so that the phosphate positive electrode material is widely studied. Currently, the most commonly used means is to coat an amorphous carbon layer on the surface of a phosphate-based positive electrode material.
For example, CN108682787B discloses a lithium ion battery pole piece and a preparation method thereof. Wherein the positive electrode active material is prepared by the steps of: (1) Adding graphene and carbon nanotubes into ethanol, performing ultrasonic primary crushing treatment, mixing at normal temperature, heating to 40-60 ℃ under the protection of inert gas, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution; the graphene is multilayer graphene, the inside of the multilayer graphene is of a three-dimensional conductive network structure, the carbon nanotubes are inserted into the three-dimensional conductive network, and particle sizes formed after the action of the multilayer graphene and the carbon nanotubes are 700 nm-22 mu m; (2) Crushing lithium iron phosphate, putting the lithium iron phosphate into a stirring kettle, adding distilled water, a coupling agent and acetylene black, rapidly stirring, and then adding the mixed solution in the step (1) into the stirring kettle, and uniformly stirring to obtain a modified intermediate; (3) Adding the modified intermediate prepared in the step (2) into an atomizer for spray drying treatment, wherein a gaseous carbon source is blown in under the action of protective gas in the process, so that the gaseous carbon source is cracked on the surface of the modified intermediate to form amorphous carbon, and the amorphous carbon is coated on the surface of the modified intermediate to form a uniform coating layer; (4) And (3) drying the powder particles obtained in the step (3) in vacuum, and calcining for 3-4 hours at the temperature of 250-350 ℃ under the action of protective gas to obtain the modified lithium iron phosphate anode material.
However, it is difficult to achieve a uniform coating effect of the coated amorphous carbon layer, and the improvement of the conductivity thereof is limited, and still further improvement is required.
Accordingly, there remains a need in the art for further improvements in phosphate-based cathode materials to increase their electron conductivity as well as the rate performance and cycling stability of lithium ion batteries comprising the same.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a phosphate positive electrode material which has improved electron conductivity, and a lithium ion battery comprising the phosphate positive electrode material has improved rate performance and cycle stability.
The invention solves the problems by the following technical proposal:
according to a first aspect of the present invention, there is provided a positive electrode material for a lithium ion battery, characterized by comprising an active material supported in a nitrogen-doped composite carbon material,
the nitrogen-doped composite carbon material has a three-dimensional porous structure, the average pore diameter of the nitrogen-doped composite carbon material is 15-60 mu m, the porosity is not lower than 90 percent, the nitrogen-doped composite carbon material comprises three-dimensional graphene and carbon nano tubes, the carbon nano tubes are mutually wound on the surface of a sheet layer of the three-dimensional graphene, a hybridization structural unit is formed between the carbon nano tubes and the three-dimensional graphene,
The active material is loaded in the pores of the nitrogen-doped composite carbon material, the mass ratio of the active material in the positive electrode material is not less than 60%,
the active substance comprises a lithium iron phosphate material, wherein the lithium iron phosphate material has a chemical formula of LiFe x M (1-x) PO 4 Wherein 0 is<x is less than or equal to 1, and M is one or more of Mn, co, ti, mg, ca elements.
According to a second aspect of the present invention, there is provided a method for producing the above positive electrode material, characterized by comprising the steps of:
1) Dispersing graphene oxide, carbon nanotubes, a nitrogen dopant, a raw material selected from a lithium iron phosphate material and a lithium iron phosphate precursor, and an optional ternary material in water to obtain a mixture A;
2) Lyophilizing the mixture A obtained in the step 1) to obtain three-dimensional graphene oxide loaded with the raw materials and optional ternary materials; and
3) And (3) placing the three-dimensional graphene oxide obtained in the step (2) in an inert gas atmosphere and at a sintering temperature in the range of 500-800 ℃ for 5-30 hours to obtain the positive electrode material.
According to a third aspect of the present invention, there is provided a method for producing the above-mentioned positive electrode material, characterized by comprising the steps of:
1) Dispersing graphene oxide, carbon nanotubes, lithium iron phosphate material and optional ternary material in water to obtain a mixture B;
2) Lyophilizing the mixture B obtained in the step 1) to obtain three-dimensional graphene oxide loaded with a lithium iron phosphate material and an optional ternary material; and
3) And (3) placing the three-dimensional graphene oxide in a hydrazine hydrate atmosphere and at a temperature within a range of 75-110 ℃ for 10-36 hours, and then drying at 120-200 ℃ for 12-48 and h to obtain the positive electrode material.
According to a fourth aspect of the present invention, there is provided a lithium ion battery cell, characterized in that the positive electrode is prepared by using the positive electrode material.
According to a fifth aspect of the present invention, there is provided a battery module comprising the above lithium ion battery cell.
According to a sixth aspect of the present invention, there is provided a battery pack comprising the above battery module.
According to a seventh aspect of the present invention, there is provided a vehicle characterized by comprising the above-described battery pack.
The positive electrode material has improved electron conductivity, and the battery core containing the positive electrode material has improved rate performance and cycle stability.
Drawings
The invention is described and explained in more detail below with reference to the attached drawing figures, wherein:
fig. 1 shows a topography of the three-dimensional pores of the nitrogen-doped composite carbon material prepared in example 1.
Fig. 2 shows a topography of three-dimensional graphene sheets of the nitrogen-doped composite carbon material prepared in example 1.
Fig. 3 shows a topography of the positive electrode material prepared in example 2.
Fig. 4 shows the morphology of the positive electrode material prepared in example 7.
Fig. 5 shows charge and discharge curves at 0.1C of a battery respectively including the positive electrode material prepared in example 7 and the positive electrode material prepared in comparative example 2.
Fig. 6 shows the rate performance graphs at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, and 10C of the battery respectively including the positive electrode material prepared in example 7 and the positive electrode material prepared in comparative example 2.
Fig. 7 shows XPS spectra of the nitrogen-doped composite carbon material prepared in example 8.
Detailed Description
Various aspects, as well as further objects, features, and advantages of the present invention will be more fully apparent hereinafter.
Positive electrode material
According to a first aspect of the present invention, there is provided a positive electrode material for a lithium ion battery, characterized by comprising an active material supported in a nitrogen-doped composite carbon material,
the nitrogen-doped composite carbon material has a three-dimensional porous structure, the average pore diameter of the nitrogen-doped composite carbon material is 15-60 mu m, the porosity is not lower than 90 percent, the nitrogen-doped composite carbon material comprises three-dimensional graphene and carbon nano tubes, the carbon nano tubes are mutually wound on the surface of a sheet layer of the three-dimensional graphene, a hybridization structural unit is formed between the carbon nano tubes and the three-dimensional graphene,
The active material is loaded in the pores of the nitrogen-doped composite carbon material, the mass ratio of the active material in the positive electrode material is not less than 60%,
the active substance comprises a lithium iron phosphate material, wherein the lithium iron phosphate material has a chemical formula of LiFe x M (1-x) PO 4 Wherein 0 is<x is less than or equal to 1, and M is one or more of Mn, co, ti, mg, ca elements.
Advantageously, in the nitrogen-doped composite carbon material, the carbon nanotubes have a mass ratio of between 2 and 60%, preferably between 2 and 20%, more preferably between 5 and 10%.
Advantageously, the graphene oxide has a size in the range of 2-400 μm and an average size in the range of 15-30 μm.
Preferably, the average pore diameter of the nitrogen-doped composite carbon material is 15-30 μm.
Preferably, the porosity of the nitrogen-doped composite carbon material is above 95%.
The carbon nanotubes are selected from the group consisting of multi-walled carbon nanotubes, single-walled carbon nanotubes, and combinations thereof.
Preferably, in the nitrogen-doped composite carbon material, the nitrogen doping amount is 0.1 to 10 wt%, preferably 0.5 to 7wt%.
The lithium iron phosphate material may be selected from the group consisting of nanoscale particles, microscale particles, and combinations thereof.
Preferably, the lithium iron phosphate material has a chemical formula of LiFe x Mn (1-x) PO 4 Wherein 0.ltoreq.x<1, M is Mn element.
In some embodiments, the lithium iron phosphate material has a chemical formula of LiFe 0.4 Mn 0.6 PO 4 。
Preferably, the lithium iron phosphate material has an average particle size of 0.03-2 μm.
Preferably, the active substance further comprises a ternary material, wherein the ternary material has a chemical formula of LiNi y Co z N (1-y-z) O 2 Wherein y is more than or equal to 0.5 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and N is one or more of Mn, al, mg, ca, zr, mo, nb.
When the ternary material exists, the lithium iron phosphate material is coated on the surface of the ternary material or the ternary material and the lithium iron phosphate material are in a mixing state.
Preferably, the ternary material is single crystal particles having an average diameter of 1-10 μm or polycrystalline particles having an average diameter of 3-25 μm.
Preferably, the amount of ternary material is 10-90% relative to the total weight of the active material.
The nitrogen doped composite carbon material is coated on the outer surface of the lithium iron phosphate material, so that the problem of poor processability of the lithium iron phosphate material can be solved, and the problem of poor dispersibility of the cathode material is solved.
Preparation method of positive electrode material
In the method for preparing the cathode material of the present invention, the lithium iron phosphate material may be generated in situ in the pores of the three-dimensional graphene or the graphene oxide, the carbon nanotubes and the lithium iron phosphate material may be directly mixed.
According to a second aspect of the present invention, there is provided a method for producing the above-described positive electrode material, characterized by comprising the steps of:
1) Dispersing graphene oxide, carbon nanotubes, a nitrogen dopant, a raw material selected from a lithium iron phosphate material and a lithium iron phosphate precursor, and an optional ternary material in water to obtain a mixture A;
2) Lyophilizing the mixture A obtained in the step 1) to obtain three-dimensional graphene oxide loaded with the raw materials and optional ternary materials; and
3) And (3) placing the three-dimensional graphene oxide obtained in the step (2) in an inert gas atmosphere and at a sintering temperature in the range of 500-800 ℃ for 5-30 hours to obtain the positive electrode material.
Preferably, the step 1) includes mixing graphene oxide and carbon nanotubes in water to obtain a mixture A1, and then adding a nitrogen dopant and the raw materials and optional ternary materials to the mixture A1 to obtain a mixture a.
Preferably, the nitrogen dopant is selected from urea, melamine, and combinations thereof.
Preferably, the mass ratio of the nitrogen dopant to the graphene oxide is between 1.1 and 5, preferably between 1.5 and 3.
The graphene oxide may be prepared by itself (e.g., by modified Hummers method) or purchased.
The graphene oxide has a size ranging from 2 to 400 μm and an average size ranging from 15 to 30 μm.
The carbon nanotubes are selected from the group consisting of multi-walled carbon nanotubes, single-walled carbon nanotubes, and combinations thereof.
The carbon nanotubes can be prepared by themselves or purchased.
The amount of the raw materials selected from the group consisting of lithium iron phosphate materials and lithium iron phosphate precursors, and the optional ternary materials, is such that the mass ratio of the active material in the resulting cathode material is not less than 60%.
Preferably, the lithium iron phosphate material has a chemical formula of LiFe x Mn (1-x) PO 4 Wherein 0.ltoreq.x<1, M is Mn element.
In some embodiments, the lithium iron phosphate material has a chemical formula of LiFe 0.4 Mn 0.6 PO 4 。
Preferably, the lithium iron phosphate material has an average particle size of 0.03-2 μm.
In some embodiments, ternary materials are included in the mixture a.
The chemical general formula of the ternary material is LiNi y Co z N (1-y-z) O 2 Wherein y is more than or equal to 0.5 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and N is one or more of Mn, al, mg, ca, zr, mo, nb.
Preferably, the ternary material is single crystal particles having an average diameter of 1-10 μm or polycrystalline particles having an average diameter of 3-25 μm.
In some embodiments, the mixture A includes a lithium source compound, an iron source compound, a metal M compound, and a phosphorus source compound as lithium iron phosphate precursors in amounts such that the molar ratio of the Li element, the Fe element, the M element, and the P element in the mixture A is (1 to 1.1): x (1-x): 1, where x is in the range of 0< x.ltoreq.1, and the sum of the concentrations of the Fe element and the M element is 0.5 to 6.0 mol/L.
Preferably, the lithium source compound is selected from the group consisting of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate, and combinations thereof.
Preferably, the iron source compound is selected from the group consisting of ferrous sulfate, ferrous oxalate, and ferrous sulfate heptahydrate, and combinations thereof.
Preferably, the phosphorus source compound is selected from the group consisting of phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and combinations thereof.
Where the starting materials include a lithium iron phosphate precursor, mixing may be performed in a manner well known in the art (e.g., stirring or sonication).
In the case of mixing with stirring, the person skilled in the art can choose a suitable stirring speed, for example 50-800 rpm, preferably 50-200rpm.
Preferably, the mixing is performed under an inert gas atmosphere.
Preferably, the inert gas atmosphere is a nitrogen atmosphere or an argon atmosphere.
Preferably, the mixing is carried out at a temperature in the range of 40-200 ℃.
More preferably, the mixing is performed at a temperature in the range of 60-80 ℃.
More preferably, the mixing is performed under a nitrogen atmosphere at a temperature in the range of 60-80 ℃.
Preferably, in step 3), the three-dimensional graphene oxide is maintained under an inert gas atmosphere and at a sintering temperature in the range of 500-800 ℃ for 10-15 hours.
Preferably, in step 3), the three-dimensional graphene oxide is maintained under an inert gas atmosphere and at a sintering temperature in the range of 650-750 ℃ for 5-30 hours.
Preferably, in step 3), the three-dimensional graphene oxide is maintained under an inert gas atmosphere and at a sintering temperature in the range of 650-750 ℃ for 10-15 hours.
Preferably, in step 3), the three-dimensional graphite oxide obtained in step 2) is brought to the sintering temperature at a heating rate of 3-10 ℃/min or the three-dimensional graphite oxide obtained in step 2) is directly placed at the sintering temperature.
Preferably, in step 3), the inert gas atmosphere is a nitrogen atmosphere or an argon atmosphere.
In some embodiments, the mixture a includes the lithium iron phosphate material.
The lithium iron phosphate material may be selected from the group consisting of nanoscale particles, microscale particles, and combinations thereof.
In some embodiments, the mixture a comprises phosphorusLithium iron acid material and ternary material, wherein the chemical general formula of the ternary material is LiNi y Co z N (1-y-z) O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, and N is one or more of Mn, al, mg, ca, zr, mo, nb.
The lithium iron phosphate material is coated on the surface of the ternary material or the ternary material and the lithium iron phosphate material are in a mixed state, and preferably, the lithium iron phosphate material is coated on the surface of the ternary material.
Where the starting materials include lithium iron phosphate materials, mixing may be performed in a manner well known in the art (e.g., stirring or sonication).
In the case of mixing by sonication, the skilled person can choose a suitable ultrasonic power, for example 100-500W.
The mixing may be performed under an air atmosphere or an inert gas atmosphere.
Preferably, the inert gas atmosphere is a nitrogen atmosphere or an argon atmosphere.
The mixing may be performed at room temperature.
Preferably, the mixing is performed under an air atmosphere and at room temperature.
Preferably, in step 3), the three-dimensional graphene oxide is maintained under an inert gas atmosphere and at a sintering temperature in the range of 500-800 ℃ for 5-30 hours.
Preferably, in step 3), the three-dimensional graphene oxide is maintained under an inert gas atmosphere and at a sintering temperature in the range of 650-750 ℃ for 10-15 hours.
Preferably, in step 3), the inert gas atmosphere is a nitrogen atmosphere or an argon atmosphere.
According to a third aspect of the present invention, there is provided a method for producing the above-described positive electrode material, characterized by comprising the steps of:
1) Dispersing graphene oxide, carbon nanotubes, lithium iron phosphate material and optional ternary material in water to obtain a mixture B;
2) Lyophilizing the mixture B obtained in the step 1) to obtain three-dimensional graphene oxide loaded with a lithium iron phosphate material and an optional ternary material; and
3) And (3) placing the three-dimensional graphene oxide in a hydrazine hydrate atmosphere and at a temperature within a range of 75-110 ℃ for 10-36 hours, and then drying at 120-200 ℃ for 12-48 and h to obtain the positive electrode material.
Preferably, the step 1) includes mixing graphene oxide and carbon nanotubes in water to obtain a first mixture B1, and then adding a lithium iron phosphate material and an optional ternary material to the mixture B1 to obtain a mixture B.
Preferably, the carbon nanotubes account for 2-60%, preferably 2-20%, more preferably 5-10% of the total mass of the graphene oxide and the carbon nanotubes.
The graphene oxide may be prepared by itself (e.g., by modified Hummers method) or purchased.
The carbon nanotubes can be prepared by themselves or purchased.
The lithium iron phosphate material and the optional ternary material are present in amounts such that the mass fraction of active material in the resulting positive electrode material is not less than 60%.
Preferably, the lithium iron phosphate material has a chemical formula of LiFe x Mn (1-x) PO 4 Wherein 0.ltoreq.x<1, M is Mn element.
In some embodiments, the lithium iron phosphate material has a chemical formula of LiFe 0.4 Mn 0.6 PO 4 。
Preferably, the lithium iron phosphate material has an average particle size of 0.03-2 μm.
The lithium iron phosphate material may be selected from the group consisting of nanoscale particles, microscale particles, and combinations thereof.
In some embodiments, ternary materials are included in mixture B.
The chemical general formula of the ternary material is LiNi y Co z N (1-y-z) O 2 Wherein y is more than or equal to 0.5 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and N is one or more of Mn, al, mg, ca, zr, mo, nb.
Preferably, the ternary material is single crystal particles having an average diameter of 1-10 μm or polycrystalline particles having an average diameter of 3-25 μm.
In some embodiments, the mixture B comprises a lithium iron phosphate material and a ternary material having the chemical formula LiNi y Co z N (1-y-z) O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, and N is one or more of Mn, al, mg, ca, zr, mo, nb.
The lithium iron phosphate material is coated on the surface of the ternary material or the ternary material and the lithium iron phosphate material are in a mixed state, and preferably, the lithium iron phosphate material is coated on the surface of the ternary material.
The mixing may be performed in a manner well known in the art, such as stirring or sonication.
In the case of mixing by sonication, the skilled person can choose a suitable ultrasonic power, for example 100-500W.
The mixing may be performed under an air atmosphere or an inert gas atmosphere.
The mixing may be performed at room temperature.
Preferably, in step 3), the three-dimensional graphene oxide is kept under a hydrazine hydrate atmosphere and at a temperature ranging from 85 to 95 ℃ for 10 to 20 hours.
Lithium ion battery cell, battery module, battery pack and vehicle
According to a fourth aspect of the present invention, there is provided a lithium ion battery cell, characterized in that the positive electrode is prepared by using the positive electrode material.
According to a fifth aspect of the present invention, there is provided a battery module comprising the above lithium ion battery cell.
According to a sixth aspect of the present invention, there is provided a battery pack comprising the above battery module.
According to a seventh aspect of the present invention, there is provided a vehicle characterized by comprising the above-described battery pack.
The vehicle may be, for example, an electric vehicle, such as an electric car.
The positive electrode may be prepared according to a method commonly used in the art.
The slurry preparation, coating, drying, rolling and slitting in the positive electrode preparation process can be performed according to the process parameters known in the art.
The lamination and assembly of the lithium ion battery cell, the battery module and the battery pack in the preparation process can be performed according to the process parameters known in the art.
The present application provides at least the following embodiments:
1. a positive electrode material for a lithium ion battery, characterized by comprising an active material supported in a nitrogen-doped composite carbon material,
the nitrogen-doped composite carbon material has a three-dimensional porous structure, the average pore diameter of the nitrogen-doped composite carbon material is 15-60 mu m, the porosity is not lower than 90 percent, the nitrogen-doped composite carbon material comprises three-dimensional graphene and carbon nano tubes, the carbon nano tubes are mutually wound on the surface of a sheet layer of the three-dimensional graphene, a hybridization structural unit is formed between the carbon nano tubes and the three-dimensional graphene,
the active material is loaded in the pores of the nitrogen-doped composite carbon material, the mass ratio of the active material in the positive electrode material is not less than 60%,
the active substance comprises a lithium iron phosphate material, wherein the lithium iron phosphate material has a chemical formula of LiFe x M (1-x) PO 4 Wherein 0 is<x is less than or equal to 1, and M is one or more of Mn, co, ti, mg, ca elements.
2. The positive electrode material according to embodiment 1, wherein the mass ratio of the carbon nanotubes in the nitrogen-doped composite carbon material is 2 to 60%, preferably 2 to 20%, more preferably 5 to 10%.
3. The positive electrode material according to embodiment 1 or 2, wherein the graphene oxide has a size in the range of 2 to 400 μm and an average size in the range of 15 to 30 μm.
4. The positive electrode material according to any one of embodiments 1 to 3, characterized in that the nitrogen-doped composite carbon material has an average pore diameter of 15 to 30 μm.
5. The positive electrode material according to any one of embodiments 1 to 4, wherein the porosity of the nitrogen-doped composite carbon material is 95% or more.
6. The positive electrode material according to any one of embodiments 1 to 5, characterized in that the nitrogen-doped composite carbon material has a nitrogen doping amount of 0.1 to 10 wt%, preferably 0.5 to 7wt%.
7. The positive electrode material of any one of embodiments 1 to 6, having a chemical formula of LiFe x Mn (1-x) PO 4 Wherein 0.ltoreq.x<1, M is Mn element, preferably, the chemical formula of the lithium iron phosphate material is LiFe 0.4 Mn 0.6 PO 4 。
8. The positive electrode material according to any one of embodiments 1 to 7, characterized in that the lithium iron phosphate material has an average particle diameter of 0.03 to 2 μm.
9. The positive electrode material according to any one of embodiments 1 to 8, wherein the active material further comprises a ternary material having a chemical formula of LiNi y Co z N (1-y-z) O 2 Wherein 0.5.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.0.2, N is one or more of Mn, al, mg, ca, zr, mo, nb, preferably the amount of ternary material is 10-90% relative to the total weight of the active material.
10. The positive electrode material according to embodiment 9, wherein the lithium iron phosphate material is coated on the surface of the ternary material or the ternary material and the lithium iron phosphate material are in a mixed state.
11. The positive electrode material according to embodiment 9 or 10, characterized in that the ternary material is single crystal particles having an average diameter of 1 to 10 μm or polycrystalline particles having an average diameter of 3 to 25 μm.
12. A lithium ion battery cell, characterized in that a positive electrode thereof is prepared using the positive electrode material according to any one of embodiments 1 to 11.
13. A battery module comprising the lithium-ion cell of embodiment 12.
14. A battery pack comprising the battery module of embodiment 13.
15. A vehicle comprising the battery pack of embodiment 14.
The terms "comprising" and "including" as used in the present application encompass the situation in which other elements not explicitly mentioned are also included or included as well as the situation in which they consist of the elements mentioned.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this application pertains, the definitions described herein control.
Unless otherwise indicated, all numbers expressing quantities of ingredients, temperatures, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
Examples
The conception, specific structure, and technical effects of the present invention will be further described with reference to the embodiments and drawings so as to fully understand the objects, features, and effects of the present invention by those skilled in the art. It will be readily appreciated by those skilled in the art that the embodiments herein are for illustrative purposes only and that the scope of the present invention is not limited thereto. The raw materials used in the examples are those commonly used in the art, if not explicitly stated.
Example 1
A certain amount of carbon nano tube aqueous dispersion is measured and added into graphene oxide aqueous dispersion, and the mixture is stirred at room temperature for 1.5 and h to obtain a first mixture, wherein the content of graphene oxide in the first mixture is controlled to be 2.5 mg/mL, and the content of carbon nano tubes is controlled to be 1.5 mg/mL. Wherein the average particle diameter of the graphene oxide is 19.7 mu m, and the size distribution is varied from 2.3 mu m to 400 mu m; the carbon nanotubes are carboxylated multiwall carbon nanotubes.
Freezing the first mixture prepared by liquid nitrogen, transferring into a vacuum freeze dryer, setting the vacuum pressure to 45 Pa, and drying at-40 ℃ for 48 hours to obtain the three-dimensional graphene oxide compounded with the carbon nano tubes, wherein the appearance of the three-dimensional graphene oxide is dark brown.
Placing the three-dimensional graphene oxide in a hydrazine hydrate atmosphere, reacting at 95 ℃ for 35 h, in the step, reducing oxygen-containing functional groups on graphene oxide sheets and carboxyl groups on carbon nanotubes to generate partial nitrogen-containing functional groups, completing the nitrogen doping process of the composite carbon material, then raising the temperature to 160 ℃, and vacuum drying for 24 h to obtain the nitrogen doped composite carbon material.
As can be seen by a scanning electron microscope, the average pore size of the prepared nitrogen-doped composite carbon material is about 25 mu m, and the porosity of the prepared nitrogen-doped composite carbon material is 98.58% by a mercury intrusion method.
The nitrogen-doped composite carbon material prepared in the embodiment has a nitrogen atom content of 0.5wt% as measured by an X-ray photoelectron spectroscopy at 0-1200 eV.
Fig. 1 and 2 are SEM images of the nitrogen-doped composite carbon material of the present embodiment at different magnifications. From fig. 1, it can be observed that the obtained nitrogen-doped composite carbon material has a rich and communicated three-dimensional network structure inside, the communicated network structure is formed by three-dimensional graphene sheets, the formed pores are more regular in shape, take on a honeycomb shape, have uniform pore size distribution, and have an average pore size of about 25 mu m. From fig. 2, it can be observed that the carbon nanotubes are adsorbed on the surface of the three-dimensional graphene sheet, and the carbon nanotubes are mutually entangled and cover the surface of the three-dimensional graphene to form a hybrid structural unit.
Example 2
A certain amount of carbon nano tube aqueous dispersion is measured and added into graphene oxide aqueous dispersion, and the mixture is stirred at room temperature for 1.5 and h to obtain a first mixture, wherein the content of graphene oxide in the first mixture is controlled to be 4.0 mg/mL, and the content of carbon nano tubes is controlled to be 1.0 mg/mL. Wherein the average size of the graphene oxide is 18.6 mu m, and the size distribution is varied from 2.3 mu m to 400 mu m; the carbon nanotubes are carboxylated single-walled carbon nanotubes.
Weighing phosphorusAnd adding a lithium iron phosphate material into the first mixture, and then carrying out ultrasonic treatment under the atmosphere, wherein the ultrasonic power is 150W, and the ultrasonic treatment time is 1.5 and h, so that the lithium iron phosphate material and graphene oxide are uniformly mixed to obtain a second mixture, and the content of the lithium iron phosphate material in the second mixture is controlled to be 7.5 and mg/mL. Wherein the chemical general formula of the lithium iron phosphate material is LiFe 0.4 Mn 0.6 PO 4 The average diameter was 0.65. Mu.m.
Placing the second mixture in a refrigerator, freezing, transferring to vacuum freeze dryer, setting vacuum pressure at 40 Pa, drying at-40deg.C for 48 h to obtain LiFe-loaded material 0.4 Mn 0.6 PO 4 The appearance of the three-dimensional graphene oxide is dark brown.
Will be loaded with LiFe 0.4 Mn 0.6 PO 4 Placing the three-dimensional graphene oxide in a hydrazine hydrate atmosphere, reacting at 95 ℃ for 36 h, in the step, reducing oxygen-containing functional groups on graphene oxide sheets and carboxyl groups on carbon nanotubes into nitrogen-containing functional groups to complete the nitrogen doping process of the composite carbon material, then raising the temperature to 200 ℃, and vacuum drying for 12 h to obtain the nitrogen-doped composite carbon material loaded LiFe 0.4 Mn 0.6 PO 4 Is a positive electrode material of (a).
According to observation of a scanning electron microscope, the average pore diameter of the prepared nitrogen-doped composite carbon material is 40 mu m, and the porosity of the nitrogen-doped composite carbon material measured by a mercury intrusion method is 98.6%. The nitrogen doped composite carbon material with large aperture and high porosity is favorable for loading more active substances under the same mass. In addition, when the active material has a large volume change during charge and discharge, a certain buffer space can be given.
FIG. 3 shows a nitrogen-doped carbon composite material-supported LiFe of the embodiment 0.4 Mn 0.6 PO 4 Is a microscopic topography of the positive electrode material. From fig. 3, it can be seen that the active material LiFe in the form of particles 0.4 Mn 0.6 PO 4 Loaded in the pores of the nitrogen-doped composite carbon material.
Example 3
This is done with reference to example 2Embodiments, except that in the first mixture, the graphene oxide content was 2.0 mg/mL and the carbon nanotubes content was 1.0 mg/mL; in the second mixture, the added raw materials are lithium iron phosphate material and ternary material, wherein the chemical formula of the lithium iron phosphate material is LiFe 0.2 Mn 0.8 PO 4 The average diameter is 0.32 mu m, the content of the lithium iron phosphate material in the second mixture is controlled to be 18 mg/mL, and the chemical general formula of the ternary material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 The content of ternary material in the second mixture was 9 mg/mL, the ternary material was single crystal particles, and the average diameter of the ternary material was 2.3. Mu.m.
The nitrogen doped composite carbon material loaded LiFe is prepared after freeze drying and hydrazine hydrate reduction 0.2 Mn 0.8 PO 4 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 Is a positive electrode material of (a).
Example 4
This example was performed with reference to example 3, except that: in the second mixture, the added raw materials are composite positive electrode materials, the composite positive electrode materials are of a core-shell structure, the inner core is a ternary material, the outer shell is a lithium iron phosphate material, and the chemical formula of the lithium iron phosphate material is LiFe 0.2 Mn 0.8 PO 4 The chemical general formula of the ternary material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 The ternary material is a polycrystalline particle, the average diameter of the ternary material is 15 mu m, and the mass ratio of the ternary material to the lithium iron phosphate material in the composite positive electrode material is 8:2.
The nitrogen doped composite carbon material loaded LiFe is prepared after freeze drying and hydrazine hydrate reduction 0.2 Mn 0.8 PO 4 And LiNi 0.8 Co 0.1 Mn 0.1 O 2 Is a positive electrode material of (a).
Loading LiFe on the prepared nitrogen-doped composite carbon material 0.2 Mn 0.8 PO 4 And Ni 0.8 Co 0.1 Mn 0.1 O 2 After grinding the anode material, respectively weighing the anode material, conductive carbon black and PVDF according to the mass ratio of 85:5:10, and uniformly mixing in N-methylpyrrolidoneCoating the slurry on aluminum foil to prepare a positive plate, assembling the battery in a glove box filled with argon, taking a graphite negative electrode as a counter electrode, taking Celgard 2300 as a diaphragm, and 1mol/L LiPF 6/ DMC (volume ratio 1:1) is electrolyte, and the CR2025 button cell is assembled.
The test voltage window of the assembled button cell is between 2.5 and 4.3V, the first charge specific capacity is 217.78 mAh/g and the first discharge specific capacity is 194.73 mAh/g under the multiplying power of 0.2 and C (the specific capacity calculation in the application is based on the mass of the ternary material with electrochemical activity and the lithium iron phosphate material in the positive electrode material). The specific capacity of discharge of the button cell reaches 183.1mAh/g under the 1C multiplying power, after 800 circles of 1C circulation, the specific capacity retention rate of discharge of the button cell is 84.3%, and the specific capacity retention rate is higher than that of the conventional NCM8 material.
In the present example, a high specific capacity NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) The polycrystalline material is used as the inner core of the composite positive electrode material, the surface of the polycrystalline material is coated with the lithium iron phosphate material, the polycrystalline material can be used for stabilizing the interface of the ternary material, the composite positive electrode material is loaded in the pores of the nitrogen-doped composite carbon material, the three-dimensional porous composite carbon material can be used for absorbing organic electrolyte, increasing ion conducting channels in an electrode, simultaneously, a rapid conductive sub-network can be provided, the problem of low electronic conductivity of the lithium iron phosphate material is solved, and the multiplying power performance and the cycling stability of the material are comprehensively improved.
Example 5
A certain amount of carbon nano tube aqueous dispersion is measured and added into graphene oxide aqueous dispersion, and the mixture is stirred at room temperature for 1.5 and h to obtain a first mixture, wherein the content of graphene oxide in the first mixture is controlled to be 3.0 mg/mL, and the content of carbon nano tubes is controlled to be 1.0 mg/mL. Wherein the average size of the graphene oxide is 18.6 mu m, and the size distribution is varied from 2.3 mu m to 400 mu m; the carbon nanotubes are carboxylated single-walled carbon nanotubes.
Respectively weighing raw materials of lithium hydroxide monohydrate, ferrous oxalate dihydrate, manganous sulfate and ammonium dihydrogen phosphate, adding the raw materials into the first mixture, controlling the molar ratio of Li element, fe element, mn element and phosphate radical in the mixture to be 1:0.4:0.6:1, wherein the concentration of Fe element in the mixture is 0.3 mol/L, the concentration of Mn element is 0.2 mol/L, simultaneously adding urea as a nitrogen doping agent, controlling the mass ratio of graphene oxide to urea in the mixture to be 1:2, introducing protective nitrogen atmosphere, heating to 80 ℃ at the stirring speed of 150 rpm, and keeping for 6 h to obtain a second mixture in gel shape.
Freezing the second mixture with liquid nitrogen, transferring to vacuum freeze dryer, setting vacuum pressure at 40 Pa, and drying at-40deg.C for 48 hr to obtain LiFe-loaded material 0.4 Mn 0.6 PO 4 The three-dimensional graphene oxide of the precursor is yellow in appearance.
Will be loaded with LiFe 0.4 Mn 0.6 PO 4 Transferring the three-dimensional graphene oxide of the precursor into a sagger, placing the sagger into a high-temperature sintering furnace, pre-introducing protective nitrogen 1 h, controlling the temperature in the sintering furnace to rise to 700 ℃ at 4 ℃/min under the nitrogen atmosphere, and keeping the temperature at 700 ℃ for 15 h to obtain the nitrogen-doped composite carbon material loaded LiFe 0.4 Mn 0.6 PO 4 Is a positive electrode material of lithium iron phosphate material LiFe 0.4 Mn 0.6 PO 4 In situ generated in the pores of the composite carbon material, liFe 0.4 Mn 0.6 PO 4 The average particle diameter of (2) was 0.54. Mu.m.
Comparative example 1
Comparative example 1 was conducted with reference to example 5, except that comparative example 1 was conducted without adding a nitrogen dopant to the first mixture, and the reaction conditions in the remaining production steps were identical to those of the starting materials, to produce a positive electrode material of comparative example 1.
Characterization of Performance
The nitrogen-doped composite carbon material prepared in example 5 is loaded with LiFe 0.4 Mn 0.6 PO 4 After grinding the positive electrode material and the comparative positive electrode material prepared in comparative example 1, respectively weighing the positive electrode material, conductive carbon black and PVDF according to the mass ratio of 85:5:10, homogenizing in N-methyl pyrrolidone, coating on aluminum foil to prepare a positive electrode plate, vacuum drying, assembling a battery in a glove box filled with argon, and taking a metal lithium plate as a counter electrode Electrode, celgard 2300 is used as a diaphragm, and 1mol/L LiPF 6 DMC (volume ratio 1:1) as electrolyte, assembled into CR2025 button cell. The positive electrode materials prepared in example 5 and comparative example 1 were assembled into button cells, respectively, under normal temperature conditions, and electrochemical performance tests were performed with a test voltage window of 2.5-4.5V, and test results are shown in table 1.
Table 1: electrochemical performance test results (specific capacities were all calculated based on active content).
| Sample of | Specific charge capacity (mAh/g) of 0.1C | Specific charge capacity (mAh/g) of 0.2C | Specific charge capacity (mAh/g) of 0.5C | 1C specific charging capacity (mAh/g) |
| Example 5 | 160.02 | 157.33 | 149.76 | 140.05 |
| Comparative example 1 | 158.65 | 154.76 | 142.38 | 131.52 |
As can be seen from Table 1, the nitrogen-doped composite carbon material prepared by the method is used for loading the positive electrode material, and has better multiplying power performance compared with the positive electrode material loaded by the carbon material without doping nitrogen element, because the surface of the nitrogen-doped composite carbon material has more active sites, more electrochemical reaction sites can be provided for active substances, more channels are provided for electron transmission, and the conductivity of the material is comprehensively improved.
Example 6
Example 6 was performed with reference to example 5, except that: in the first mixture, ternary material LiNi is also added 0.5 Co 0.2 Mn 0.3 O 2 Such that in the first mixture the ternary material LiNi 0.5 Co 0.2 Mn 0.3 O 2 The ternary material represents 20% of the total weight of the active material in the final synthesized cathode material, at a concentration of 29.5 g/L.
Example 7
A certain amount of carbon nano tube aqueous dispersion is measured and added into graphene oxide aqueous dispersion, and the mixture is stirred at room temperature for 1.5 and h to obtain a first mixture, wherein the content of graphene oxide in the first mixture is controlled to be 3.0 mg/mL, and the content of carbon nano tubes is controlled to be 1.0 mg/mL. Wherein the average size of the graphene oxide is 18.6 mu m, and the size distribution is varied from 2.3 mu m to 400 mu m; the carbon nanotubes are carboxylated multiwall carbon nanotubes.
Respectively weighing lithium iron phosphate precursor lithium hydroxide monohydrate, ferrous sulfate heptahydrate and phosphoric acid, adding the lithium iron phosphate precursor lithium hydroxide monohydrate, ferrous sulfate heptahydrate and phosphoric acid into the first mixture, controlling the molar ratio of Li element, fe element and phosphate radical in the mixture to be 1.02:1:1, wherein the concentration of Fe element in the mixture is 0.8 mol/L, simultaneously adding urea as a nitrogen doping agent, controlling the mass ratio of graphene oxide to urea in the mixture to be 1:1.8, introducing protective argon atmosphere, heating to 70 ℃ at the stirring speed of 150 rpm, and maintaining 5 h to obtain a second mixture.
Freezing the second mixture, transferring to vacuum freeze dryer, setting vacuum pressure at 40 Pa, and drying at-40deg.C for 48 hr to obtain LiFePO loaded 4 The three-dimensional graphene oxide of the precursor,it appears dark brown.
Will be loaded with LiFePO 4 Transferring the three-dimensional graphene oxide of the precursor into a sagger, placing the sagger into a high-temperature sintering furnace, pre-introducing protective nitrogen 1 h, controlling the temperature in the sintering furnace to rise to 600 ℃ at 6 ℃/min under the nitrogen atmosphere, and keeping the temperature at 600 ℃ for 10 h to obtain the nitrogen-doped composite carbon material loaded LiFePO 4 Is a nano lithium iron phosphate material LiFePO 4 In situ generated in the pores of the composite carbon material, wherein LiFePO 4 The average particle diameter of (a) is 270 mu m, and the active material LiFePO in the positive electrode material 4 The mass ratio of the cathode material to the whole cathode material is 90 percent.
Fig. 4 is a morphology diagram of the positive electrode material prepared in this example.
From fig. 4, it can be observed that the nano-sized lithium iron phosphate material LiFePO 4 Is coated by graphene sheets.
Comparative example 2
Reference is made to comparative example 2 which was compared with example 7, except that comparative example 2 was prepared as a cathode material LiFePO of comparative example 2 without adding graphene oxide, carbon nanotubes and nitrogen dopant to the first mixture, and the reaction conditions in the remaining preparation steps were identical to those of the raw materials 4 。
Characterization of Performance
The nitrogen-doped composite carbon material prepared in the embodiment 7 is loaded with LiFePO 4 Is prepared according to comparative example 2 4 After grinding, respectively weighing a positive electrode material, conductive carbon black and PVDF according to the mass ratio of 80:10:10, homogenizing in N-methyl pyrrolidone, coating on aluminum foil to prepare two positive electrode sheets, assembling a battery in a glove box filled with argon, taking a lithium sheet as a counter electrode, taking Celgard 2300 as a diaphragm, and 1mol/L LiPF 6 DMC (volume ratio 1:1) as electrolyte, assembled into CR2025 button cell.
And (3) performing charge and discharge tests and rate performance tests on the test voltage window of the assembled button cell between 2.0 and 4.2V.
Fig. 5 shows charge and discharge curves at 0.1C of a battery including the positive electrode material prepared in example 7 and the positive electrode material prepared in comparative example 2, respectively.
As can be seen from fig. 5, the battery including the positive electrode material prepared in example 7 exhibited a specific discharge capacity of 160.6 mAh/g, while the battery including the positive electrode material prepared in comparative example 2 exhibited a specific discharge capacity of 123.4 mAh/g only. In addition, the polarization between the charge and discharge curve plateau of the battery containing the positive electrode material prepared in example 7 was smaller, which suggests that the nitrogen-doped composite carbon material is advantageous in improving electrochemical kinetics in the positive electrode material.
Fig. 6 shows the rate performance graphs at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, and 10C of the battery respectively including the positive electrode material prepared in example 7 and the positive electrode material prepared in comparative example 2.
As can be seen from fig. 6, the battery including the positive electrode material prepared in example 7 still had a specific discharge capacity of 81.8 mAh/g at 10C, whereas the battery including the positive electrode material prepared in comparative example 2 only exhibited a specific discharge capacity of 30.2 mAh/g, the nitrogen-doped composite carbon material supported LiFePO prepared in example 7 4 The positive electrode material of (2) exhibits excellent rate performance. This is probably because the nitrogen-doped composite carbon material can construct a three-dimensional conductive network in the positive electrode, and the doping of N on the composite carbon material is favorable for enhancing the ion adsorption capacity in the electrochemical reaction and improving the lithium storage performance. Meanwhile, the three-dimensional graphene can absorb organic electrolyte to provide a rapid ion guide channel.
Example 8
A certain amount of carbon nano tube aqueous dispersion is measured and added into graphene oxide aqueous dispersion, and the mixture is stirred at room temperature for 0.5 to h to obtain a first mixture, wherein the content of graphene oxide in the first mixture is controlled to be 2 mg/mL, and the content of carbon nano tubes is controlled to be 0.5 mg/mL. Wherein the average particle diameter of the graphene oxide is 19.7 mu m, and the size distribution is varied from 2.3 mu m to 400 mu m; the carbon nanotubes are carboxylated multiwall carbon nanotubes.
Adding nitrogen doping agent urea into the first mixture, controlling the mass ratio of graphene oxide to urea in the mixture to be 1:3, uniformly mixing the mixture under 200W for 1h, transferring the mixture to a refrigerator for freezing at-10 ℃, transferring the mixture to a vacuum freeze dryer, setting the vacuum pressure to be 40 Pa, and drying the mixture at-40 ℃ for 24h to obtain the three-dimensional graphene oxide compounded with carbon nano tubes and urea, wherein the appearance of the three-dimensional graphene oxide is yellow.
And placing the three-dimensional graphene oxide in an argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, and reacting at 800 ℃ for 5 h, wherein in the step, the nitrogen doping reaction and the reduction reaction are completed in one step by adopting a high-temperature reduction method, so that the nitrogen doped composite carbon material is prepared.
As can be seen from observation by a scanning electron microscope, the average pore size of the obtained nitrogen-doped composite carbon material is about 45 mu m, and the porosity of the nitrogen-doped composite carbon material measured and customized by a mercury intrusion method is 95.38%. The nitrogen doped composite carbon material with large aperture and high porosity is favorable for loading more active substances under the same mass, and can give a certain buffer space when the active substances have larger volume change during charge and discharge.
Fig. 7 shows XPS spectra of the nitrogen-doped composite carbon material prepared in this example.
The content of nitrogen atoms in the prepared nitrogen-doped composite carbon material is 6.5 weight percent as measured by an X-ray photoelectron spectrum at 0-1200 eV.
The foregoing describes only exemplary embodiments or examples of the present application and is not intended to limit the present application. The present application is susceptible to various modifications and changes by those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are within the scope of the following claims.
Claims (10)
1. A positive electrode material for a lithium ion battery, characterized by comprising an active material supported in a nitrogen-doped composite carbon material,
the nitrogen-doped composite carbon material has a three-dimensional porous structure, the average pore diameter of the nitrogen-doped composite carbon material is 15-60 mu m, the porosity is not lower than 90 percent, the nitrogen-doped composite carbon material comprises three-dimensional graphene and carbon nano tubes, the carbon nano tubes are mutually wound on the surface of a sheet layer of the three-dimensional graphene, a hybridization structural unit is formed between the carbon nano tubes and the three-dimensional graphene,
the active material is loaded in the pores of the nitrogen-doped composite carbon material, the mass ratio of the active material in the positive electrode material is not less than 60%,
The active substance comprises a lithium iron phosphate material, wherein the lithium iron phosphate material has a chemical formula of LiFe x M (1-x) PO 4 Wherein 0 is<x is less than or equal to 1, and M is one or more of Mn, co, ti, mg, ca elements.
2. The cathode material according to claim 1, wherein the mass ratio of the carbon nanotubes in the nitrogen-doped composite carbon material is 2-60%, preferably 2-20%, more preferably 5-10%.
3. The cathode material according to claim 1 or 2, wherein the graphene oxide has a size in the range of 2-400 μm and an average size in the range of 15-30 μm.
4. A cathode material according to any one of claims 1 to 3, wherein the nitrogen-doped composite carbon material has an average pore size of 15-30 μm.
5. The positive electrode material according to any one of claims 1 to 4, wherein the porosity of the nitrogen-doped composite carbon material is 95% or more.
6. The cathode material according to any one of claims 1 to 5, wherein the nitrogen-doped composite carbon material has a nitrogen doping amount of 0.1-10 wt%, preferably 0.5-7wt%.
7. The positive electrode material according to any one of claims 1 to 6, which has a chemical formula of LiFe x Mn (1-x) PO 4 Wherein 0.ltoreq.x<1, M is Mn element, preferably, the chemical formula of the lithium iron phosphate material is LiFe 0.4 Mn 0.6 PO 4 。
8. The positive electrode material according to any one of claims 1 to 7, wherein the lithium iron phosphate material has an average particle diameter of 0.03 to 2 μm.
9. The positive electrode material according to any one of claims 1 to 8, wherein the active substance further comprises a ternary material having a chemical formula LiNi y Co z N (1-y-z) O 2 Wherein 0.5.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.0.2, N is one or more of Mn, al, mg, ca, zr, mo, nb, preferably the amount of ternary material is 10-90% relative to the total weight of the active material.
10. The positive electrode material according to claim 9, wherein the lithium iron phosphate material is coated on the surface of the ternary material or the ternary material and the lithium iron phosphate material are in a mixed state.
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