CN113604904A - Preparation method, product and application of fusiform ternary @ carbon @ stone needle nanofiber material - Google Patents
Preparation method, product and application of fusiform ternary @ carbon @ stone needle nanofiber material Download PDFInfo
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- CN113604904A CN113604904A CN202111025357.1A CN202111025357A CN113604904A CN 113604904 A CN113604904 A CN 113604904A CN 202111025357 A CN202111025357 A CN 202111025357A CN 113604904 A CN113604904 A CN 113604904A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000002121 nanofiber Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000004575 stone Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 55
- 238000010041 electrostatic spinning Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 230000006196 deacetylation Effects 0.000 claims description 7
- 238000003381 deacetylation reaction Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 4
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 244000309464 bull Species 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940071264 lithium citrate Drugs 0.000 claims description 4
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 229940097206 manganese citrate Drugs 0.000 claims description 4
- 235000014872 manganese citrate Nutrition 0.000 claims description 4
- 239000011564 manganese citrate Substances 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000001523 electrospinning Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 7
- 239000002657 fibrous material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002127 nanobelt Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000011573 trace mineral Substances 0.000 description 4
- 235000013619 trace mineral Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012769 bulk production Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/021—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
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
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Abstract
The invention relates to a preparation method of a lithium ion battery anode material, in particular to a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material. It comprises the following steps: 1) dissolving soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid in a dimethylformamide solution to obtain a solution A; 2) transferring the A into a reaction kettle, reacting for 8-15 h at 100-130 ℃, cooling to room temperature, washing, and drying to obtain a precursor B; 3) heating the precursor B at the heating rate of 2-5 ℃/min to 600-750 ℃ for calcination, and keeping the temperature to obtain a fusiform ternary @ carbon nanotube; 4) dispersing, ball-milling, drying and calcining the fusiform ternary @ carbon nanotube and the stone needle powder to obtain the fusiform ternary @ carbon @ stone needle powder; 5) dissolving 30-35 parts by weight of fusiform ternary @ carbon @ stone needle and 25-35 parts by weight of chitosan in a polar solution to prepare a spinning solution; 6) spinning to obtain a fusiform ternary @ carbon @ stone needle nanofiber material; the nanofiber material prepared by the method has good electrochemical performance.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery anode material, in particular to a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material.
Background
Lithium ion secondary batteries have been widely used as high specific energy chemical power sources in the fields of mobile communication, notebook computers, video cameras, portable instruments and meters, and the like, and have rapidly developed into one of the most important secondary batteries at present. Lithium ion batteries, which are the latest generation of green high-energy storage batteries, have been rapidly developed in the early 90 s of the 20 th century, and are favored because of their advantages of high voltage, high energy density, long cycle life, little environmental pollution, and the like.
Due to the ternary material LiNi1-x-yCoxMnyO2(abbreviated as NCM, wherein 0<x<1, 0<y<1) Has the characteristics superior to lithium iron phosphate and lithium cobaltate, and can prepare ternary electrode materials with different properties by adjusting the proportion of nickel, cobalt and manganese. The NCM improves the structural stability of the material, and the charge-discharge cycle stability and high-temperature stability of the material, but the electrochemical properties still need to be improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material.
The second object of the present invention is to: the fusiform ternary @ carbon @ stone needle nanofiber material prepared by the method is provided.
The third object of the present invention is to: applications of the above products are provided.
The first purpose of the invention is realized by the following scheme:
a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material comprises the following steps:
1) dissolving soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium salt to the soluble nickel salt to the soluble cobalt salt to the soluble manganese salt to the terephthalic acid is 1:1-x-y: x: y: 0.4; stirring to be uniform to obtain a solution A;
2) transferring the A into a reaction kettle, reacting for 8-15 h at 100-130 ℃, cooling to room temperature, washing, and drying to obtain a precursor B;
3) heating the precursor B at the heating rate of 2-5 ℃/min to 600-750 ℃ for calcination, and keeping the temperature to obtain a fusiform ternary @ carbon nanotube;
4) dispersing the fusiform ternary @ carbon nano tube and stone needle powder, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is (20-40): 1, ball milling, drying and calcining at 400-500 ℃ to obtain fusiform ternary @ carbon @ stone needle powder;
5) dissolving 30-35 parts by weight of fusiform ternary @ carbon @ stone needle and 25-35 parts by weight of chitosan into 45-55 parts by weight of polar solution, and fully mixing to prepare uniform spinning solution;
6) and spinning the spinning solution by using an electrostatic spinning device to obtain the fusiform ternary @ carbon @ stone needle nanofiber material.
The invention provides a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material, the fusiform ternary material has a large specific surface area and can be fully contacted with an electrolyte, the electrochemical performance of the material is improved, the stone needle powder is rich in trace elements such as magnesium and iron and rare earth elements such as strontium, yttrium, copper and chromium, and a small amount of trace elements and rare earth elements can be doped into a ternary lattice in the calcining process, so that the electrochemical performance of the material is improved. The preparation process is relatively simple and easy to operate.
Preferably, the preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material comprises the following specific steps:
1) dissolving soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium salt to the soluble nickel salt to the soluble cobalt salt to the soluble manganese salt to the terephthalic acid is 1:1-x-y: x: y: 0.4; stirring the mixture for 1 to 2 hours until the mixture is uniform to obtain a solution A;
2) transferring the A into a reaction kettle, reacting for 8-15 h at 100-130 ℃, cooling to room temperature, washing for 3-5 times by using deionized water and an organic solvent, and drying in an oven at 60-80 ℃ overnight to obtain a precursor B;
3) placing the precursor B in a muffle furnace, heating to 600-750 ℃ at a heating rate of 2-5 ℃/min, calcining, and keeping the temperature for 2-4 h to obtain a fusiform ternary @ carbon nanotube;
4) dispersing the fusiform ternary @ carbon nano tube and stone needle powder in ethanol, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is (20-40): 1, ball-milling for 5-8 h, drying in a blast oven for 3-5 h, and calcining at 400-500 ℃ to obtain fusiform ternary @ carbon @ stone needle powder;
5) dissolving 30-35 parts by weight of fusiform ternary @ carbon @ stone needle and 25-35 parts by weight of chitosan into 45-55 parts by weight of polar solution, magnetically stirring at room temperature for 30-60 min, and fully mixing to prepare uniform spinning solution; the concentration of the spinning solution is 2% -60%;
6) and spinning the spinning solution by using an electrostatic spinning device to obtain the fusiform ternary @ carbon @ stone needle nanofiber material.
The selection and selection of each component in the preparation of the solution A, the selection of a washing solvent in the preparation process of the precursor B, the heating rate and the calcination temperature in the preparation process of the fusiform ternary @ carbon nanotube, the raw material proportion and the calcination temperature in the preparation process of the fusiform ternary @ carbon @ stone needle powder and the proportion and the concentration of a spinning solution have synergistic influence on the performance of the fusiform ternary @ carbon @ stone needle nanofiber material, and the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance can be obtained through specific selection and control of the invention.
Preferably, in the step 1), the lithium salt is one or a combination of lithium nitrate, lithium acetate and lithium citrate; the nickel salt is one or the combination of nickel nitrate, nickel acetate or nickel citrate; the cobalt salt is one or the combination of cobalt nitrate, cobalt acetate or cobalt citrate; the manganese salt is one or the combination of manganese nitrate, manganese acetate or manganese citrate.
The selection of lithium salt, nickel salt, cobalt salt and manganese salt influences the performance of the solution A, so that the performance of the precursor B is influenced.
Preferably, in the step 2), the organic solvent is one or a combination of absolute ethyl alcohol and acetone.
Preferably, in the step 5), the polar solvent is one or a combination of formic acid, glacial acetic acid or trifluoroacetic acid; the deacetylation degree of the chitosan is 80-100%.
The selection of the polar solvent and the control of the deacetylation degree of the chitosan influence the performance of the spinning solution, and the specific selection and control of the invention can help obtain the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance in the subsequent spinning process.
Preferably, in the step 6), the electrostatic spinning process parameters are as follows: 1-50 kV, the receiving distance is 1-50 cm, and the solution flow is 0.01-20 mL/h.
The electrostatic spinning process parameter control has influence on the performance of the fusiform ternary @ carbon @ stone needle nanofiber material, and the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance can be obtained through specific selection and control.
Preferably, the electrostatic spinning device comprises an electrostatic spinning machine body, an injection nozzle is fixedly installed at the top of the inner wall of the electrostatic spinning machine body, a fixing frame is fixedly installed at the bottom of the inner wall of the electrostatic spinning machine body through a bolt, a threaded hole is formed in one side of the inner wall of the fixing frame, a roller is contacted with the bottom of the inner wall of the electrostatic spinning machine body, a connecting frame is rotatably sleeved at the top of the outer wall of the roller, a motor is fixedly installed at the top of the connecting frame through a bolt, a rotating rod is welded at the output end of the motor, a positioning thread is formed in the outer wall of one end, close to the motor, of the rotating rod, the positioning thread is sleeved in the threaded hole, a rotating ring is fixedly sleeved at the middle part of the outer wall of the electrostatic spinning machine body, a supporting frame is rotatably sleeved at the outer wall of the rotating ring, a cross rod is rotatably sleeved at one side of the inner wall of the supporting frame, a receiving roller is fixedly sleeved at the outer wall of the cross rod, and the output end of the injection nozzle is opposite to the receiving roller, the support frame is run through to horizontal pole one end, horizontal pole one end outer wall fixed cover has the second gear, the meshing of second gear bottom is connected with first gear, the fixed cover of first gear is in the middle part of bull stick outer wall.
The receiving roller can transversely move and rotate at the same time by controlling the motor, and two motion states of the receiving roller can be completed only by a single motor; through the motor just reversing, under screw hole and location screw are spacing, can drive the receiving roll on the support frame and carry out lateral shifting, make when injection shower nozzle is limited to spinning spray range, through removing the receiving roll, make the spinning gathering area bigger on the receiving roll, suitable bulk production. After the motor of the invention is operated, the receiving roller is driven to rotate by the components such as the rotating rod, the two gears and the like, so that the spinning can be more uniformly distributed on the receiving roller during electrostatic spinning, and the formation of fiber materials is facilitated; therefore, the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance can be obtained.
As a preferred technical scheme of the invention, one end of the rotating rod penetrates through the fixing frame, and the limiting rod is welded in the fixing frame.
As a preferred technical scheme of the invention, the bottom end of the support frame is slidably sleeved on the outer wall of the limiting rod, and the rotating ring and the first gear are both positioned right above the limiting rod.
As a preferable technical scheme of the invention, the bottom of the support frame is contacted with the bottom of the inner wall of the fixed frame, and the rotating ring is positioned between the positioning thread and the first gear.
As a preferred technical solution of the present invention, the receiving roller is located inside the supporting frame, and the second gear is located outside the supporting frame.
As a preferred technical scheme of the invention, the electrostatic spinning machine body and the motor are both electrically connected with an external power supply, the rotating ring is in a circular ring shape, and the fixing frame is in a U-shaped shape.
The second purpose of the invention is realized by the following scheme:
the invention provides a fusiform ternary @ carbon @ stone needle nanofiber material which is prepared according to any one of the methods.
The third purpose of the invention is realized by the following scheme:
the invention provides an application of a fusiform ternary @ carbon @ stone needle nanofiber material in a lithium battery material.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material, the fusiform ternary material has a large specific surface area and can be fully contacted with an electrolyte, the electrochemical performance of the material is improved, the stone needle powder is rich in trace elements such as magnesium and iron and rare earth elements such as strontium, yttrium, copper and chromium, and a small amount of trace elements and rare earth elements can be doped into a ternary lattice in the calcining process, so that the electrochemical performance of the material is improved. The preparation process is relatively simple and easy to operate.
2. The selection of lithium salt, nickel salt, cobalt salt and manganese salt influences the performance of the solution A, so that the performance of the precursor B is influenced, and the specific selection and control of the preparation method can help obtain a fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance in the subsequent spinning process;
3. the selection of a polar solvent and the control of the deacetylation degree of chitosan influence the performance of the spinning solution, and the specific selection and control of the method can help obtain a fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance in the subsequent spinning process;
4. the electrostatic spinning process parameter control has influence on the performance of the fusiform ternary @ carbon @ stone needle nanofiber material, and the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance can be obtained through specific selection and control;
5. the receiving roller can transversely move and rotate at the same time by controlling the motor, and two motion states of the receiving roller can be completed only by a single motor; through the motor just reversing, under screw hole and location screw are spacing, can drive the receiving roll on the support frame and carry out lateral shifting, make when injection shower nozzle is limited to spinning spray range, through removing the receiving roll, make the spinning gathering area bigger on the receiving roll, suitable bulk production. After the motor of the invention is operated, the receiving roller is driven to rotate by the components such as the rotating rod, the two gears and the like, so that the spinning can be more uniformly distributed on the receiving roller during electrostatic spinning, and the formation of fiber materials is facilitated; therefore, the fusiform ternary @ carbon @ stone needle nanofiber material with better electrochemical performance can be obtained.
Drawings
FIG. 1 is an SEM image of a fusiform ternary @ carbon @ stone needle nanofiber material in example 1;
FIG. 2 is an SEM image of a fusiform ternary @ carbon @ stone needle nanofiber material in example 2;
FIG. 3 is a cycle life diagram of the fusiform ternary @ carbon @ stone needle nanofiber material of example 3;
FIG. 4 is a front view showing the overall structure of the electrospinning device of the present invention;
FIG. 5 is a front sectional view showing the overall structure of the electrospinning device of the present invention;
FIG. 6 is an enlarged view of the structure A of FIG. 5 according to the present invention;
FIG. 7 is an enlarged view of the structure B of FIG. 6 according to the present invention;
FIG. 8 is a front view of a swivel of an electrospinning apparatus of the present invention;
in the figure, 1, an electrostatic spinning machine body; 11. an injection nozzle; 2. a fixed mount; 21. a threaded hole; 22. a limiting rod; 3. a roller; 31. a connecting frame; 32. a motor; 33. a rotating rod; 34. positioning the screw thread; 35. rotating the ring; 36. a first gear; 4. a support frame; 41. a cross bar; 42. a receiving roller; 43. a second gear.
Detailed Description
The first embodiment is as follows:
dissolving soluble lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium nitrate to the nickel nitrate to the cobalt nitrate to the manganese nitrate to the terephthalic acid is 1:0.333: 0.333: 0.4; stirring for 1 hour to be uniform by magnetic force to obtain solution A; transferring the A into a reaction kettle, reacting for 15 h at 100 ℃, cooling to room temperature, washing for 3 times by using deionized water and ethanol, and drying in an oven at 60 ℃ overnight to obtain a precursor B; placing the precursor B in a muffle furnace, heating to 750 ℃ at the heating rate of 2 ℃/min, calcining, and keeping the temperature for 2 h to obtain a fusiform ternary @ carbon nanotube; dispersing the fusiform ternary @ carbon nano tube and stone needle powder in ethanol, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is 25: 1, ball-milling for 5 h, drying in a blast oven for 3 h, and calcining at 400 ℃ to obtain fusiform ternary @ carbon @ stone needle powder; dissolving 35 parts by weight of fusiform ternary @ carbon @ stone needle and 35 parts by weight of chitosan in 45 parts by weight of polar solution glacial acetic acid, magnetically stirring for 60 min at room temperature, and fully mixing to prepare a uniform spinning solution; wherein the degree of deacetylation of chitosan is 80%; the concentration of the spinning solution is 2%; spinning the spinning solution by using an electrostatic spinning device, wherein the process parameters of electrostatic spinning are as follows: and (3) 20 kilovolts, the receiving distance is 25 cm, and the solution flow is 5 mL/h, so that the fusiform ternary @ carbon @ stone needle nanofiber material is obtained. FIG. 1 is an SEM image of a fusiform ternary @ carbon @ stone needle nanofiber material. The fiber diameter is 200-260 nm. Through detection, the first discharge specific capacity is 175 mAh/g, and the first discharge specific capacity is 156mAh/g after 50 times of circulation.
Example two:
dissolving soluble lithium acetate, nickel acetate, cobalt acetate, manganese acetate and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium acetate to the nickel acetate to the cobalt acetate to the manganese acetate to the terephthalic acid is 1: 0.5: 0.3: 0.2: 0.4; stirring for 2 hours until the solution is uniform by magnetic force to obtain solution A; transferring the A into a reaction kettle, reacting for 8 h at 130 ℃, cooling to room temperature, washing for 5 times by using deionized water and ethanol, and drying in an oven at 80 ℃ overnight to obtain a precursor B; placing the precursor B in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, calcining, and keeping the temperature for 3 h to obtain a fusiform ternary @ carbon nanotube; dispersing the fusiform ternary @ carbon nano tube and stone needle powder in ethanol, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is 30: 1, ball-milling for 5 h, drying in a blast oven for 3 h, and calcining at 450 ℃ to obtain fusiform ternary @ carbon @ stone needle powder; dissolving 30 parts by weight of fusiform ternary @ carbon @ stone needle and 25 parts by weight of chitosan in 45 parts by weight of polar solution glacial acetic acid, magnetically stirring for 60 min at room temperature, and fully mixing to prepare a uniform spinning solution; wherein the degree of deacetylation of chitosan is 90%; the concentration of the spinning solution is 5%; spinning the spinning solution by using an electrostatic spinning device, wherein the process parameters of electrostatic spinning are as follows: and (3) 30 kilovolts, the receiving distance is 30 centimeters, the solution flow is 10 mL/h, and the fusiform ternary @ carbon @ stone needle nanofiber material is obtained. FIG. 2 is an SEM image of a fusiform ternary @ carbon @ stone needle nanofiber material. The fiber diameter was 200 and 240 nm. Through detection, the first discharge specific capacity is 173 mAh/g, and through 50 times of circulating discharge specific capacity is 153 mAh/g.
Example three:
dissolving soluble lithium citrate, nickel citrate, cobalt citrate, manganese citrate and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium citrate to the nickel citrate to the cobalt citrate to the manganese citrate to the terephthalic acid is 1: 0.8: 0.1: 0.1: 0.4; stirring for 2 hours until the solution is uniform by magnetic force to obtain solution A; transferring the A into a reaction kettle, reacting for 8 h at 130 ℃, cooling to room temperature, washing for 5 times by using deionized water and acetone, and drying in an oven at 80 ℃ overnight to obtain a precursor B; placing the precursor B in a muffle furnace, heating to 700 ℃ at the heating rate of 5 ℃/min, calcining, and keeping the temperature for 3 h to obtain a fusiform ternary @ carbon nanotube; dispersing the fusiform ternary @ carbon nano tube and stone needle powder in ethanol, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is 40: 1, ball-milling for 5 h, drying in a blast oven for 3 h, and calcining at 450 ℃ to obtain fusiform ternary @ carbon @ stone needle powder; dissolving 35 parts by weight of fusiform ternary @ carbon @ stone needle and 35 parts by weight of chitosan in 50 parts by weight of polar solution trifluoroacetic acid, magnetically stirring for 60 min at room temperature, and fully mixing to prepare a uniform spinning solution; wherein the degree of deacetylation of chitosan is 90%; the concentration of the spinning solution is 5%; spinning the spinning solution by using an electrostatic spinning device, wherein the process parameters of electrostatic spinning are as follows: 25 kilovolts, the receiving distance is 25 cm, the solution flow is 10 mL/h, and the fusiform ternary @ carbon @ stone needle nanofiber material is obtained. FIG. 3 is a cycle life diagram of a fusiform ternary @ carbon @ stone needle nanofiber material. The first discharge specific capacity is 178 mAh/g, and after 50 times of circulation, the discharge specific capacity is 157 mAh/g.
Example four:
the same as example 1, except that the electrospinning was carried out using the specific electrospinning apparatus of the present invention: the electrospinning apparatus shown in fig. 4-8: the electrostatic spinning machine comprises an electrostatic spinning machine body 1, wherein the electrostatic spinning machine body 1 is an existing electrostatic spinning machine, internal mechanisms of the electrostatic spinning machine body 1 are disclosed, and redundant description is omitted, an injection nozzle 11 is fixedly installed at the top of the inner wall of the electrostatic spinning machine body 1, so that electrostatic spinning can be conveniently carried out by using the injection nozzle 11, a fixing frame 2 is fixedly installed at the bottom of the inner wall of the electrostatic spinning machine body 1 through bolts, the electrostatic spinning machine body 1 can conveniently fix the fixing frame 2, and a threaded hole 21 is formed in one side of the inner wall of the fixing frame 2;
the bottom of the inner wall of the electrostatic spinning machine body 1 is contacted with the roller 3, the electrostatic spinning machine body 1 can support the roller 3, the top of the outer wall of the roller 3 is rotatably sleeved with the connecting frame 31, the connecting frame 31 can limit the roller 3, the top of the connecting frame 31 is fixedly provided with the motor 32 through bolts, the connecting frame 31 can support the motor 32, when the motor 32 moves transversely, the connecting frame 31 and the roller 3 can improve the stability of the motor 32 when moving, the roller 3 can reduce the resistance of the motor 32 when moving through rolling, the output end of the motor 32 is welded with the rotating rod 33, the motor 32 can drive the rotating rod 33 to rotate after running, and the motor 32 can rotate forwards and backwards, which is the prior art and is not described in more detail herein;
the outer wall of one end of the rotating rod 33 close to the motor 32 is provided with a positioning thread 34, the positioning thread 34 is in threaded sleeve in the threaded hole 21, one end of the rotating rod 33 is in threaded sleeve in the threaded hole 21 through the positioning thread 34, the positioning thread 34 and the threaded hole 21 are convenient for supporting and limiting the rotating rod 33, the middle part of the outer wall of the electrostatic spinning machine body 1 is fixedly sleeved with a rotating ring 35, the outer wall of the rotating ring 35 is rotatably sleeved with a support frame 4, the rotating ring 35 can be used for connecting the rotating rod 33 with the support frame 4, the rotating rod 33 is matched with a limiting rod 22 to limit the support frame 4, the support frame 4 can move transversely along with the rotating rod 33 and cannot rotate along with the rotating rod 33, one side of the inner wall of the support frame 4 is rotatably sleeved with a cross rod 41, the outer wall of the cross rod 41 is fixedly sleeved with a receiving roller 42, the cross rod 41 can support the receiving roller 42, the output end of the injection nozzle 11 is opposite to the receiving roller 42, and is convenient for the injection nozzle 11 to spray spinning on the receiving roller 42, support frame 4 is run through to horizontal pole 41 one end, and the fixed cover of horizontal pole 41 one end outer wall has second gear 43 for second gear 42 can drive horizontal pole 41 after rotating and rotate, and second gear 43 bottom meshing is connected with first gear 36, makes first gear 36 can drive second gear 43 after rotating and rotate, and first gear 36 is fixed to be overlapped in bull stick 33 outer wall middle part, and the bull stick 33 of being convenient for drives first gear 36 after rotating and rotates.
Specifically, referring to fig. 6, one end of the rotating rod 33 penetrates through the fixing frame 2, so that the fixing frame 2 can support the rotating rod 33, and the limiting rod 22 is welded in the fixing frame 2, thereby facilitating the fixing frame 2 to support the limiting rod 22.
Specifically, referring to fig. 6, the bottom end of the supporting frame 4 is slidably sleeved on the outer wall of the limiting rod 22, so that the limiting rod 22 can limit the supporting frame 4, the supporting frame 4 can only move laterally but cannot rotate, and the rotating ring 35 and the first gear 36 are both located right above the limiting rod 22.
Specifically, referring to fig. 6, the bottom of the supporting frame 4 is in contact with the bottom of the inner wall of the fixing frame 2, so that the fixing frame 2 can limit and support the supporting frame 4, and the rotating ring 35 is located between the positioning thread 34 and the first gear 36.
Specifically, referring to fig. 6, the receiving roller 42 is located inside the supporting frame 4, so that the supporting frame 4 can shield and protect the receiving roller 42, the second gear 43 is located outside the supporting frame 4, and the second gear 42 rotates outside the supporting frame 4.
Specifically, referring to fig. 4, 6 and 8, the electrostatic spinning machine body 1 and the motor 32 are electrically connected to an external power supply, the external power supply supplies power, the rotating ring 35 is in a circular ring shape, so that the rotating ring 35 can rotate in the supporting frame 4 conveniently, and the fixing frame 2 is in a U-shape, so that the fixing frame 2 can support the rotating rod 33 conveniently.
The working principle is as follows: when in use, the motor 32 is controlled to rotate positively and negatively, the motor 32 drives the rotating rod 33 to rotate after running, at the moment, under the supporting and limiting of the threaded hole 21 and the positioning thread 34 on the rotating rod 33, the rotating rod 33 rotates and moves transversely (communicated with a rotating bolt principle), so that the motor 32, the support frame 4 and the rotating rod 33 are driven to move transversely as a whole, at the same time, under the limiting of the rotating ring 35 and the limiting rod 22, the support frame 4 can only move transversely but not rotate, because the position of the injection nozzle 11 is fixed and the injection range is fixed, the transverse movement of the support frame 4 and the receiving roller 42 can be used for increasing the spinning gathering area on the receiving roller 42, meanwhile, after the rotating rod 33 rotates, the first gear 36 and the second gear 43 can drive the cross rod 41 to rotate, the cross rod 41 can drive the receiving roller 42 to rotate in the support frame 4, and during electrostatic spinning, the receiving roller 42 is rotated, the spray spinning is more uniformly distributed on the receiving roller 42, and the connecting frame 31 and the roller 3 can support the motor 32, so that the motor 32 is more stable in operation and movement.
Through detection, the first discharge specific capacity is 188 mAh/g, and the first discharge specific capacity is 170mAh/g after 500 times of circulating discharge.
Example five:
the same as example 2 except that electrospinning was carried out using a specific electrospinning apparatus as described in example 4. Through detection, the first discharge specific capacity is 190 mAh/g, and the first discharge specific capacity is 172 mAh/g after 50 times of circulating discharge.
Example six:
the same as example 3 except that electrospinning was carried out using a specific electrospinning apparatus as described in example 4. Through detection, the first discharge specific capacity is 185 mAh/g, and the first discharge specific capacity is 161mAh/g after 50 times of circulation.
Comparative example 1
As in example 1, different step 1) the molar ratio of soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid was 1:0.333: 0.5: 0.5: 0.4; step 4), the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is 50: 1. through detection, the first discharge specific capacity is 145 mAh/g, and the first discharge specific capacity is 126mAh/g after 100 times of circulation discharge.
Comparative example 2
The same as example 1, except that step 2) the solution A was reacted at 160 ℃ for 14 h; step 3) heating the titanium dioxide nanosheets and the stone needle powder to 800 ℃ for calcination; and step 4) calcining the precursor in an inert atmosphere at 600 ℃ to obtain the nano-belt lithium titanate @ stone needle powder. Through detection, the first discharge specific capacity is 150mAh/g, and the first discharge specific capacity is 120 mAh/g after 50 times of circulating discharge.
The above data for examples 1-6 and comparative examples 1-2 illustrate that:
1. compared with the formula or different process of the comparative example 1-2, the nanobelt lithium titanate @ stone needle powder composite fiber material prepared by the formula and process parameters of the embodiments 1-6 of the invention has better electrochemical performance;
2. compared with the nanobelt lithium titanate @ stone needle powder composite fiber material prepared by adopting a conventional electrostatic spinning device in examples 1-3, the nanobelt lithium titanate @ stone needle powder composite fiber material prepared by adopting the specific electrostatic spinning device in examples 4-6 of the invention has better electrochemical performance.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a fusiform ternary @ carbon @ stone needle nanofiber material is characterized by comprising the following steps of:
1) dissolving soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium salt to the soluble nickel salt to the soluble cobalt salt to the soluble manganese salt to the terephthalic acid is 1:1-x-y: x: y: 0.4; stirring to be uniform to obtain a solution A;
2) transferring the A into a reaction kettle, reacting for 8-15 h at 100-130 ℃, cooling to room temperature, washing, and drying to obtain a precursor B;
3) heating the precursor B at the heating rate of 2-5 ℃/min to 600-750 ℃ for calcination, and keeping the temperature to obtain a fusiform ternary @ carbon nanotube;
4) dispersing the fusiform ternary @ carbon nano tube and stone needle powder, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is (20-40): 1, ball milling, drying and calcining at 400-500 ℃ to obtain fusiform ternary @ carbon @ stone needle powder;
5) dissolving 30-35 parts by weight of fusiform ternary @ carbon @ stone needle and 25-35 parts by weight of chitosan into 45-55 parts by weight of polar solution, and fully mixing to prepare uniform spinning solution;
6) and spinning the spinning solution by using an electrostatic spinning device to obtain the fusiform ternary @ carbon @ stone needle nanofiber material.
2. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 1, which is characterized by comprising the following specific steps:
1) dissolving soluble lithium salt, nickel salt, cobalt salt, manganese salt and terephthalic acid in a dimethylformamide solution, wherein the molar ratio of the soluble lithium salt to the soluble nickel salt to the soluble cobalt salt to the soluble manganese salt to the terephthalic acid is 1:1-x-y: x: y: 0.4; stirring the mixture for 1 to 2 hours until the mixture is uniform to obtain a solution A;
2) transferring the A into a reaction kettle, reacting for 8-15 h at 100-130 ℃, cooling to room temperature, washing for 3-5 times by using deionized water and an organic solvent, and drying in an oven at 60-80 ℃ overnight to obtain a precursor B;
3) placing the precursor B in a muffle furnace, heating to 600-750 ℃ at a heating rate of 2-5 ℃/min, calcining, and keeping the temperature for 2-4 h to obtain a fusiform ternary @ carbon nanotube;
4) dispersing the fusiform ternary @ carbon nano tube and stone needle powder in ethanol, wherein the mass ratio of the fusiform ternary @ carbon nano tube to the stone needle powder is (20-40): 1, ball-milling for 5-8 h, drying in a blast oven for 3-5 h, and calcining at 400-500 ℃ to obtain fusiform ternary @ carbon @ stone needle powder;
5) dissolving 30-35 parts by weight of fusiform ternary @ carbon @ stone needle and 25-35 parts by weight of chitosan into 45-55 parts by weight of polar solution, magnetically stirring at room temperature for 30-60 min, and fully mixing to prepare uniform spinning solution; the concentration of the spinning solution is 2% -60%;
6) and spinning the spinning solution by using an electrostatic spinning device to obtain the fusiform ternary @ carbon @ stone needle nanofiber material.
3. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 2, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: in the step 1), the lithium salt is one or a combination of lithium nitrate, lithium acetate and lithium citrate; the nickel salt is one or the combination of nickel nitrate, nickel acetate or nickel citrate; the cobalt salt is one or the combination of cobalt nitrate, cobalt acetate or cobalt citrate; the manganese salt is one or the combination of manganese nitrate, manganese acetate or manganese citrate.
4. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 3, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: in the step 2), the organic solvent is one or a combination of absolute ethyl alcohol and acetone.
5. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 4, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: in the step 5), the polar solvent is one or a combination of formic acid, glacial acetic acid or trifluoroacetic acid; the deacetylation degree of the chitosan is 80-100%.
6. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 5, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: in the step 6), the technological parameters of electrostatic spinning are as follows: 1-50 kV, the receiving distance is 1-50 cm, and the solution flow is 0.01-20 mL/h.
7. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to any one of claims 1-6, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: the electrostatic spinning device comprises an electrostatic spinning machine body (1), an injection nozzle (11) is fixedly mounted at the top of the inner wall of the electrostatic spinning machine body (1), a fixing frame (2) is fixedly mounted at the bottom of the inner wall of the electrostatic spinning machine body (1) through a bolt, a threaded hole (21) is formed in one side of the inner wall of the fixing frame (2), a roller (3) is contacted with the bottom of the inner wall of the electrostatic spinning machine body (1), a connecting frame (31) is rotatably sleeved at the top of the outer wall of the roller (3), a motor (32) is fixedly mounted at the top of the connecting frame (31) through a bolt, a rotating rod (33) is welded at the output end of the motor (32), a positioning thread (34) is formed in the outer wall of one end, close to the motor (32), of the rotating rod (33), the positioning thread (34) is sleeved in the threaded hole (21), a rotating ring (35) is fixedly sleeved at the middle part of the outer wall of the electrostatic spinning machine body (1), the utility model discloses a syringe, including swivel (35) outer wall, support frame (4), horizontal pole (41) outer wall fixed cover, injection shower nozzle (11) output is just to receiving roller (42), support frame (41) one end runs through support frame (4), horizontal pole (41) one end outer wall fixed cover has second gear (43), second gear (43) bottom meshing is connected with first gear (36), first gear (36) fixed cover is in bull stick (33) outer wall middle part.
8. The preparation method of the fusiform ternary @ carbon @ stone needle nanofiber material according to claim 7, wherein the fusiform ternary @ carbon @ stone needle nanofiber material is characterized in that: one end of the rotating rod (33) penetrates through the fixing frame (2), and a limiting rod (22) is welded in the fixing frame (2);
the bottom end of the support frame (4) is slidably sleeved on the outer wall of the limiting rod (22), and the rotating ring (35) and the first gear (36) are both positioned right above the limiting rod (22);
the bottom of the support frame (4) is contacted with the bottom of the inner wall of the fixed frame (2), and the rotating ring (35) is positioned between the positioning thread (34) and the first gear (36).
9. A fusiform ternary @ carbon @ stone needle nanofiber material is prepared according to any one of the methods.
10. The application of the shuttle-shaped ternary @ carbon @ stone needle nanofiber material as claimed in claim 9 in a lithium battery material.
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