CN111180709A - Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof - Google Patents
Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 75
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- 239000010949 copper Substances 0.000 title claims abstract description 52
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229940062993 ferrous oxalate Drugs 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PPDVIXPISPVIQE-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[Fe+2].[Li+] Chemical compound C(C(=O)[O-])(=O)[O-].[Fe+2].[Li+] PPDVIXPISPVIQE-UHFFFAOYSA-L 0.000 claims 3
- 239000010405 anode material Substances 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 229920000867 polyelectrolyte Polymers 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- -1 transition metal oxalates Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 241000196324 Embryophyta Species 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000707 layer-by-layer assembly Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H—ELECTRICITY
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and a preparation method thereof, belonging to the technical field of lithium ion battery negative electrode materials; the invention relates to a ferrous oxalate complex Fe (C) with positive charges on the surface of a carbon nano tube treated by strong cationic polyelectrolyte and negative charges in the preparation process of ferrous oxalate2O4)2 ‑2Electrostatic attraction and self-assembly to form Fe (C) doped with carbon nanotube2O4)2 ‑2MWCNTs polymer, reaction of the obtained polymer with soluble copper salts to form Fe x Cu 1‑ x C2O4/MWCNTs·yH2O precursor; sintering under the inert atmosphere condition by utilizing the difference of thermodynamic properties among different transition metal oxalates, and decomposing a precursor in situ to obtain a carbon nano tube and metal copper co-doped ferrous oxalate composite material; the invention overcomes the problems of low conductivity, low lithium ion migration rate, high first irreversible capacity, poor cycle performance and the like of the ferrous oxalate negative electrode material in the prior art due to the self reason.
Description
Technical Field
The invention relates to a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and a preparation method thereof, belonging to the technical field of lithium ion battery negative electrode materials.
Background
In recent years, lithium ion batteries have high volumetric energy density and power density, become small portable devices, and are one of the first power sources of large hybrid power machines, and in consideration of the requirements of electric vehicles on the driving mileage and energy density, the lithium ion batteries still face great challenges in performance, cost and safety. Up to now, graphite-based materials still dominate lithium ion battery negative electrode materials. However, its low specific charge-discharge capacity severely limits its further development. Therefore, the development of a novel negative electrode material with high energy density, low cost and safe use has become a hot spot of battery material research in recent years.
At present, the research on the negative electrode material of the lithium ion battery is mainly divided into the following steps according to the lithium storage mechanism of the material: insert type (graphite, TiO)2、Li4Ti5O12) Alloying type (Si, Sn, Al, etc.) and conversion reaction type (Fe)2O3NiO, CoO, etc.). Compared with other alternative materials, the metal oxalate based on the conversion reaction has the advantages of high reversible capacity, excellent cycle performance, abundant resources, environmental friendliness, high safety and the like. However, due to its low electron conductivity, Li+Slow diffusion rates lead to higher first irreversible capacity, poorer rate performance. Thus, the electron conductivity and Li of the material are improved+The diffusion rate becomes a research hotspot of researchers at home and abroad in the aspect of improving the performance of the transition metal oxalate. The following two classes can be roughly classified according to the modification mechanism: (1) and (3) designing a morphology structure: by controlling the grain of the materialThe diversity of particle morphology (cocoon-shaped, rod-shaped, nanowire, three-dimensional sphere, etc.) and structural composition, shortening Li+The insertion/extraction distance of (a) increases a stable diffusion channel; (2) doping modification: in one aspect, the cation sites in the oxalate lattice are doped with metal ions (Co, Mn, Cu, etc.) to improve the material electronic conductivity and Li+A diffusion rate; on the other hand, carbon materials such as graphene are added into oxalate materials to prepare oxalate/graphene (MC)2O4Mg, M = Fe, Mn, Cu, Co, Zn, etc.), which not only improves the electron conductivity of the material as a whole, but also provides sufficient voids for the electrolyte to penetrate into the electrodes. The doping modification research is mainly single doping, so that the problems of unobvious improvement of material performance and the like are easily caused.
Disclosure of Invention
Aiming at the problems of low conductivity, low lithium ion migration rate, high first irreversible capacity, poor cycle performance and the like of the ferrous oxalate negative electrode material caused by the self reason; the invention provides a preparation method of a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite cathode material, which is characterized in that the carbon nano tube, metal copper and rod-shaped ferrous oxalate are compounded by adopting a method of electrostatic self-assembly and in-situ growth, on one hand, the addition of the carbon nano tube provides more and more stable diffusion channels for the migration of lithium ions among material particles, and on the other hand, the introduction of the metal copper can obviously improve the conductivity of an electrode material, thereby improving the electrochemical reaction capability.
The invention is realized by a simple electrostatic self-assembly and in-situ growth method, soluble ferrous salt and oxalic acid are used as raw materials, and a ferrous oxalate complex with negative charges is synthesized at room temperature; then treating the carbon nano tube by strong cationic polyelectrolyte to make the carbon nano tube have positive charges; mixing the two materials with different charges, carrying out electrostatic self-assembly to obtain a carbon nano tube composite ferrous oxalate complex, adding a proper amount of soluble copper salt, moving into a reaction kettle for low-temperature treatment, and further optimizing the morphology structure of a precursor; and washing and drying the precursor treated at low temperature, and finally carrying out low-temperature heat treatment to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1: 5-1: 20, carrying out ultrasonic treatment at normal temperature for 3-5 h, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.2-10 mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1: 5-1: 20, fully stirring and mixing for 1-3 h, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an inert gas atmosphere, and drying at 40-60 ℃ to obtain a carbon nano tube material with positive charges;
(2) sequentially adding soluble ferrous salt, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring for 24-52 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10;
(3) adding the carbon nanotube material with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), stirring for 30min at normal temperature, slowly adding soluble copper salt into the mixed solution, wherein the molar ratio of the soluble copper salt to the soluble ferrous salt is 1: 30-1: 9, continuously stirring and mixing for 1-2 h, transferring into a high-temperature high-pressure reaction kettle, reacting for 6-24 h at 60-150 ℃, filtering, washing and drying after the reaction is finished and natural cooling to obtain Fe x Cu 1-x C2O4/MWCNTs·yH2O precursor (0)<x<1,0<y<2);
(4) Under the atmosphere of argon or nitrogen, Fe obtained in the step (3) x Cu 1-x C2O4/MWCNTs·yH2Placing the O precursor in a vacuum tube furnace, sintering at 200-300 ℃ for 1-6 h to obtain the carbon nano tube and metallic copper co-doped weedA composite cathode material of a lithium iron acid battery.
The mixed solution of the ethanol and the deionized water in the steps (1) and (2) is prepared by mixing the ethanol and the deionized water according to the volume ratio of 1: 1.
In the step (2), the soluble ferrous salt is one or more of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate.
In the step (3), the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetate.
Fe in the step (3) x Cu 1-x C2O4/MWCNTs·yH2The precursor of the oxygen is O,xthe range is 0-1;ythe range is 0 to 2.
The composite cathode material of the lithium ion battery with the co-doped ferrous weed acid of the carbon nano tube and the metal copper is prepared by the method of electrostatic self-assembly and in-situ growth, and more stable diffusion channels are provided for the migration of lithium ions among material particles by utilizing the excellent channel structure of the carbon nano tube; the high conductivity of the metal copper is utilized to improve the conductivity of the material, thereby improving the electrochemical conversion reaction capability. In addition, the stable crystal and structural characteristics of the carbon nano tube also provide a better structural framework for the active material, so that the cycle stability of the composite material is obviously improved.
Drawings
Fig. 1 is a TG thermogravimetric curve of the carbon nanotube and metal copper co-doped ferrous oxalate composite material prepared in example 1 (a) and example 2 (b) of the present invention;
FIG. 2 is an X-ray diffraction diagram of a carbon nanotube and copper metal co-doped ferrous oxalate composite material prepared in example 2 of the present invention;
fig. 3 is a scanning electron microscope (a) and a projection electron microscope (b) of the carbon nanotube and copper-co-doped ferrous oxalate composite material prepared in example 1 of the present invention;
fig. 4 is a graph showing charge and discharge rates and cycles of the carbon nanotube and copper metal co-doped ferrous oxalate composite material prepared in examples 1, 2 and 3 of the present invention, wherein a is the graph of example 1, b is the graph of example 2, and c is the graph of example 3.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:10, performing ultrasonic treatment at normal temperature for 3 hours, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.5mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1:5, fully stirring and mixing for 1 hour, performing centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an argon atmosphere, and drying at 40 ℃ to obtain a carbon nano tube with positive charges;
(2) sequentially adding ferrous chloride, oxalic acid and ascorbic acid into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, and stirring for 48 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous chloride to the oxalic acid is 1:5, and the molar ratio of the ferrous chloride to the ascorbic acid is 10: 1;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1:30, stirring for 30min at normal temperature, slowly adding copper chloride into the mixed solution, wherein the molar ratio of the copper chloride to the ferrous chloride is 1:2, continuously stirring and mixing for 1h, transferring into a high-temperature high-pressure reaction kettle, reacting for 24h at 60 ℃, filtering, washing and drying after the reaction is finished and naturally cooled to obtain Fe 2/ 3 Cu 1/3 C2O4/MWCNTs·yH2O precursor;
(4) under the argon atmosphere, Fe obtained in the step (3) 2/3 Cu 1/3 C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 3h at 300 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The scanning electron microscope and the projection electron microscope of the cathode material of the lithium ion battery with the co-doped ferrous oxalate of the carbon nano tube and the metallic copper are shown in fig. 3, and it can be obviously observed that the nano spherical metallic copper particles are uniformly filled around the rod-shaped ferrous oxalate particles, and the carbon nano tube shuttles to the edge of the rotating particles; the TG thermogravimetric curve of the negative electrode material of this example is shown in fig. 1a, from which it can be seen that the carbon nanotube and metallic copper co-doped ferrous oxalate composite material shows significantly different crystallization water temperatures and oxalate decomposition temperatures.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in fig. 4 (a), wherein the multiplying power cycle result chart is shown in 0.2, 0.5, 1, 2, 3 and 5A g-1Under the current density, the carbon nano tube and metal copper co-doped ferrous oxalate composite material shows excellent rate performance, and the specific discharge capacities of the carbon nano tube and metal copper co-doped ferrous oxalate composite material are 970 mAh g, 830 mAh, 760 mAh, 690 mAh, 640 mAh and 560mAh g respectively-1Specific discharge capacity of (2).
Example 2: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:5, performing ultrasonic treatment at normal temperature for 4 hours, dropwise adding a polydiallyldimethylammonium chloride aqueous solution with the concentration of 1mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethylammonium chloride is 1:10, fully stirring and mixing for 2 hours, performing centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethylammonium chloride, then placing in an inert gas atmosphere, and drying at 50 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding ferrous sulfate, oxalic acid and ascorbic acid into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, and stirring for 30 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous sulfate to the oxalic acid is 1:8, and the molar ratio of the ferrous chloride to the ascorbic acid is 5: 1;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1:20, stirring for 30min at normal temperature, slowly adding copper sulfate into the mixed solution, wherein the molar ratio of the copper sulfate to the ferrous sulfate is 1:5, continuously stirring and mixing for 1.5h, transferring into a high-temperature high-pressure reaction kettle, reacting for 8h at 100 ℃, filtering, washing and drying after the reaction is finished and the natural cooling are carried out, so as to obtain Fe 5/ 6 Cu 1/6 C2O4/MWCNTs·2H2O precursor;
(4) under the argon atmosphere, Fe obtained in the step (3) 5/6 Cu 1/6 C2O4/MWCNTs·2H2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 5h at 200 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The X-ray diffraction pattern of the cathode material of the lithium ion battery with the carbon nano tube and the metal copper co-doped ferrous oxalate prepared by the embodiment is shown in figure 2, and the low diffraction peak intensity of the carbon nano tube can be still seen, which indicates that the ferrous oxalate and the carbon nano tube are effectively compounded; the TG thermogravimetric curve of the negative electrode material of this embodiment is shown in fig. 1b, and it can be seen from the graph that the ferrous oxalate structure of the carbon nanotube and metal copper co-doped ferrous oxalate negative electrode material is not damaged in the heat treatment process.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in figure 4 (b), wherein the multiplying power cycle result chart is shown in figure 1A g-1Under the current density, the carbon nano tube and metal copper co-doped ferrous oxalate composite material shows excellent small current circulation performance, and the discharge specific capacity at the later stage of 100 cycles is 680mAh g-1。
Example 3: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:20, carrying out ultrasonic treatment at normal temperature for 5 hours, dropwise adding a polydiallyldimethylammonium chloride aqueous solution with the concentration of 5mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethylammonium chloride is 1:15, fully stirring and mixing for 3 hours, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethylammonium chloride, then placing in an inert gas atmosphere, and drying at 60 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding ferrous nitrate, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring at normal temperature for 40 hours to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous nitrate to the oxalic acid is 1:10, and the molar ratio of the ferrous chloride to the ascorbic acid is 10: 1;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1:10, stirring for 30min at normal temperature, slowly adding copper nitrate into the mixed solution, wherein the molar ratio of the copper nitrate to the ferrous nitrate is 1:9, continuously stirring and mixing for 2h, transferring into a high-temperature high-pressure reaction kettle, reacting for 6h at 150 ℃, filtering, washing and drying after the reaction is finished and naturally cooled to obtain Fe 9/ 10 Cu 1/10 C2O4/MWCNTs·yH2O precursor;
(4) under nitrogen atmosphere, Fe obtained in the step (3) 9/10 Cu 1/10 C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 4h at 250 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in fig. 4C, wherein the multiplying power cycle result chart is shown in 5A g-1At current density, carbon nanoThe tube and metal copper co-doped ferrous oxalate composite material shows excellent small current circulation performance, and the discharge specific capacity at the later stage of 100 cycles is 580mAh g-1And the cycle performance is excellent.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (5)
1. A preparation method of a carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material is characterized by comprising the following specific steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1: 5-1: 20, carrying out ultrasonic treatment at normal temperature for 3-5 h, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.2-10 mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1: 5-1: 20, fully stirring and mixing for 1-3 h, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an inert gas atmosphere, and drying at 40-60 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding soluble ferrous salt, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring for 24-52 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), stirring the mixture at normal temperature for 30min, slowly adding soluble copper salt into the mixed solution, wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1: 30-1: 10, the molar ratio of the soluble copper salt to the soluble ferrous salt is 1: 1-1: 9, continuously stirring and mixing the mixture for 1-2 h, transferring the mixture into a high-temperature high-pressure reaction kettle, reacting the mixture for 6-24 h at the temperature of 60-150 ℃, and after the reaction is finished and the mixture is naturally cooled, slowly adding the soluble copper salt into the mixed solutionFiltering, washing and drying to obtain Fe x Cu 1-x C2O4/MWCNTs·yH2O precursor;
(4) under the atmosphere of argon or nitrogen, Fe obtained in the step (3) x Cu 1-x C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering at 200-300 ℃ for 1-6 h to obtain the carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material.
2. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the soluble ferrous salt is one or more of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate in any ratio; the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetate.
3. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the mixed liquid of the ethanol and the deionized water is prepared by mixing the ethanol and the deionized water according to the volume ratio of 1: 1.
4. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10, and the molar ratio of the soluble ferrous salt to the ascorbic acid is 5: 1-10: 1.
5. The carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material prepared by the preparation method of the carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material of any one of claims 1 to 4.
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