CN111525117B - Three-dimensional porous carbon coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof - Google Patents
Three-dimensional porous carbon coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 55
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 28
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004642 Polyimide Substances 0.000 claims abstract description 29
- 229920001721 polyimide Polymers 0.000 claims abstract description 29
- -1 phenylethynyl-p-phenylene Chemical group 0.000 claims abstract description 25
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 24
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 105
- 238000010438 heat treatment Methods 0.000 claims description 85
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 238000005406 washing Methods 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 46
- 239000012298 atmosphere Substances 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 35
- 239000012265 solid product Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 150000001721 carbon Chemical class 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 8
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 239000002077 nanosphere Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000004227 thermal cracking Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of sodium ion batteries and discloses three-dimensional porous carbon-coated Co3O4The negative electrode material of the sodium-ion battery comprises the following formula raw materials and components: co3O4Nanometer microsphere, 4' - (phenylethynyl-p-phenylene) diethanedioic anhydride, 1, 5-naphthalene diamine, isoquinoline and diphenyl sulfone. Co3O4The nano-microsphere has the characteristics of small particle size, porous hollow structure, high specific surface area and the like, and the super-crosslinked porous polyimide coated nano Co is obtained by polymerizing 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride and 1, 5-naphthalene diamine3O4The porous carbon material formed by high-temperature thermal cracking is uniformly coated with nano Co3O4The carbon coating is nano Co3O4The volume expansion of the carbon material provides a buffer layer, the abundant pore structure improves a diffusion channel for sodium ions, the transmission path of the sodium ions is shortened, the abundant nitrogen element can adjust the electronic state of the carbon material, the defect active sites are improved, and the conductivity and the sodium ion adsorption capacity of the cathode material are improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to three-dimensional porous carbon-coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof.
Background
The sodium ion battery is a secondary rechargeable battery, the working principle is similar to that of a lithium ion battery, the storage and the release of electric energy are realized mainly by the movement of sodium ions between a positive electrode and a negative electrode, the cost of the sodium ion battery is much lower than that of the lithium ion battery and the lithium iron phosphate battery due to the rich, cheap and easily-obtained sodium salt raw material and the characteristic of sodium salt that low-concentration electrolyte is allowed to be used, and the sodium ion battery has no overdischarge characteristic and can discharge to zero voltage, so the sodium ion battery is an excellent substitute when the requirement on energy density is not high.
The sodium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, an electrolyte and the like, wherein an active material in the negative electrode has great influence on the electrochemical performance of the sodium ion battery, and the current negative electrode material of the sodium ion battery mainly comprises grapheneIsocarbon material, SnO2、Fe3O4Transition metal oxide, MoS2Isotransition metal oxide sulfides, etc., wherein Co3O4Has higher theoretical specific capacity and is a sodium ion battery cathode active material with great development potential, but Co3O4Of less conductive, ordinary Co3O4The specific surface area of the particles is not high, and the nano Co3O4Easily agglomerate to cause insufficiency of electrochemical active center, and the nano Co3O4The phenomenon of volume expansion is easy to occur in the charging and discharging processes, and the actual capacitance of the sodium ion battery is seriously influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides three-dimensional porous carbon-coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof solve the problem of nano Co3O4Agglomeration and volume expansion are easily generated during the charging and discharging processes.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material comprises the following raw materials and components: co3O4Nano microsphere, 4' - (phenylethynyl-p-phenylene) diethanedioic anhydride, 1, 5-naphthalene diamine, isoquinoline and diphenyl sulfone, wherein Co3O4The mass ratio of the nano microspheres to the 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride to the 1, 5-naphthalenediamine to the isoquinoline is 60-150:100:10-18: 1-2.5.
Preferably, the three-dimensional porous carbon is coated with Co3O4The negative electrode material of the sodium ion battery
(1) Adding distilled water solvent and glucose into a reaction bottle, stirring and dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃ for reaction for 5-10h, filtering and washing the solution, placing the solid product into a sodium hydroxide solution with the mass fraction of 2-6%, heating to 120 ℃ in an atmosphere oil bath kettle, stirring at constant speed for reaction for 2-5h, filtering, washing and drying to prepare the catalystObtaining hydroxylated carbon nano-microspheres, then placing the hydroxylated carbon nano-microspheres in a medium ethanol solvent, adding cobalt nitrate, carrying out aging reaction for 48-96h after uniform ultrasonic dispersion, filtering and drying the solution, placing the solid product in an atmosphere resistance furnace, heating at a rate of 2-5 ℃/min, keeping the temperature in a nitrogen atmosphere for 2-3h, then keeping the temperature in an air atmosphere and calcining for 1-3h to prepare the Co-based nano-microspheres3O4And (4) nano microspheres.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3-4 in an atmosphere oil bath kettle under the nitrogen atmosphere to 110 ℃, uniformly stirring for reaction for 40-60h, adding hydrochloric acid to adjust the pH of the solution to 2-4, uniformly stirring for 2-6h, filtering the solution to remove the solvent, washing a solid product by using a composite washing solvent to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 140 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 5-10h, filtering the solution, washing the product by using the composite washing solvent, and drying, the preparation method obtains 4,4' - (phenylethynyl-p-phenyl) diether dianhydride.
(3) Adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4Uniformly dispersing nano microspheres by ultrasonic, adding 4,4' - (phenylethynyl p-phenylene) diethanedioic anhydride and 1, 5-naphthalenediamine, uniformly stirring for 6-10h, adding isoquinoline serving as a catalyst, heating to 110-3O4。
(4) Placing the super-crosslinked porous polyimide coated nano Co3O4 in an atmosphere resistance furnace, heating at the rate of 2-8 ℃/min to 550-650 ℃ in the nitrogen atmosphere, and carrying out heat preservation and calcination for 2-3h to obtain the three-dimensional porous carbon coated Co3O43O4The negative electrode material of the sodium ion battery.
Preferably, the mass ratio of the hydroxylated carbon nano microspheres to the cobalt nitrate in the step (1) is 0.2-0.5: 1.
Preferably, the atmosphere oil bath pot in the step (1) comprises an oil bath room, a heating sheet is arranged below the oil bath room, a base is arranged above the heating sheet, a reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath room, a first air chamber air inlet tube is movably connected to the left side of the gas exchange tube, the first air chamber air inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a second air chamber air inlet tube is fixedly connected with a connecting rod, the second air chamber air inlet tube is movably connected with a conversion air passage, the conversion air passage is fixedly connected with a first air chamber air passage and a second air chamber air passage respectively, the first air chamber air inlet tube is fixedly connected with a first air chamber, and the second air chamber air inlet tube is fixedly connected with a second air chamber.
Preferably, the composite washing solvent in the step (2) is distilled water and diethyl ether.
Preferably, the mass ratio of the solid mixed product to the diphenyl sulfone in the step (3) is 1: 40-50.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material takes the carbon nano-microsphere as a template, and rich hydroxyl on the surface adsorbs Co3+Preparation of Co3O4The nano-microsphere has the advantages of small particle size, porous hollow structure, high specific surface area and the like, and is favorable for improving the electrochemical performance of the cathode material.
The three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material is prepared by taking 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride with side chain containing alkynyl group as dianhydride monomer and 1, 5-naphthalene diamine containing naphthalene ring as diamine monomer through in-situ polymerization method to obtain super-crosslinked porous polyimide coated nano Co3O4The alkynyl group of the side chain is passed through in the course of thermal imidizationThe alkynyl crosslinking effect is realized, the generated crosslinking structure hinders the conformation transformation of a polyimide molecular chain, the collapse of a polyimide framework and a pore structure is inhibited, and the space between polymer molecular chains is regulated and controlled by alkynyl crosslinking sites, so that the generation of a new microporous structure is promoted, the super-crosslinked polyimide has a large number of pores and microporous structures, the molecular chain has a rigid naphthalene ring structure, the microporous structure can be maintained not to collapse in the high-temperature thermal cracking process, and the porous carbon material is formed to uniformly coat the nano Co3O4。
The three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material has the carbon layer coating function and rich pore structure of nano Co3O4The volume expansion provides a buffer layer, reduces the volume change caused by the deintercalation of sodium ions, and simultaneously, a large number of pore structures can improve the wettability of the cathode material to electrolyte, and improve a diffusion channel for the sodium ions, thereby shortening the transmission path of the sodium ions, and the electronic state of the carbon material can be adjusted by abundant nitrogen elements in the porous carbon, thereby improving the defect active sites, being beneficial to improving the conductivity and the sodium ion adsorption capacity of the cathode material, and leading the three-dimensional porous carbon to coat Co3O4The sodium ion battery negative electrode material shows excellent electrochemical performance and good electric capacity.
Drawings
FIG. 1 is a schematic front view of an atmosphere oil bath pan;
FIG. 2 is an enlarged schematic view of an inlet pipe of the air chamber;
FIG. 3 is a schematic view of a plenum-inlet duct adjustment.
1. An oil bath chamber; 2. a heating plate; 3. a base; 4. a reaction bottle; 5. a gas exchange tube; 6. an air inlet pipe of the air chamber; 7. a connecting rod; 8. a sliding shaft; 9. adjusting the nut; 10. a second air inlet pipe of the air chamber; 11. switching an air passage; 12. an air channel of the air chamber; 13. a gas chamber two-way gas passage; 14. a first air chamber; 15 air chamber II.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material comprises the following raw materials and components: co3O4Nano microsphere, 4' - (phenylethynyl-p-phenylene) diethanedioic anhydride, 1, 5-naphthalene diamine, isoquinoline and diphenyl sulfone, wherein Co3O4The mass ratio of the nano microspheres to the 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride to the 1, 5-naphthalenediamine to the isoquinoline is 60-150:100:10-18: 1-2.5.
Three-dimensional porous carbon coated Co3O4The negative electrode material of the sodium ion battery
(1) Adding distilled water solvent and glucose into a reaction bottle, stirring and dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃ for reaction for 5-10h, filtering and washing the solution, placing a solid product into a sodium hydroxide solution with the mass fraction of 2-6%, heating to 120 ℃ in an atmosphere oil bath kettle, wherein the atmosphere oil bath kettle comprises an oil bath chamber, a heating sheet is arranged below the oil bath chamber, a base is arranged above the heating sheet, the reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath chamber, a gas chamber one air inlet tube is movably connected on the left side of the gas exchange tube, the gas chamber one air inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a gas chamber two air inlet tubes are fixedly connected with the connecting rod, and the gas chamber two air inlet tubes are movably connected with a conversion air passage, the conversion air passage is respectively and fixedly connected with an air passage I of an air chamber and an air passage II of the air chamber, an air inlet pipe of the air chamber is fixedly connected with the air chamber I, an air inlet pipe of the air chamber II is fixedly connected with the air chamber II, the mixture is stirred at a constant speed for reaction for 2-5 hours, filtered, washed and dried to prepare hydroxylated carbon nano microspheres, then the hydroxylated carbon nano microspheres are placed in a medium ethanol solvent and added with cobalt nitrate, the mass ratio of the medium ethanol solvent to the cobalt nitrate is 0.2-0.5:1, the aging reaction is carried out for 48-96 hours after the ultrasonic dispersion is uniform, the solution is filtered and dried, the solid products are placed in an atmosphere resistance furnace, the heating rate is 2-5 ℃/min, the temperature is kept for 2-3 hours in a nitrogen atmosphere, then the temperature is kept and calcined for 1-3 hours in an air atmosphere, and Co is prepared3O4And (4) nano microspheres.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3-4 in an atmosphere oil bath kettle under the nitrogen atmosphere to 110 ℃, uniformly stirring for reaction for 40-60h, adding hydrochloric acid to adjust the pH of the solution to 2-4, uniformly stirring for 2-6h, filtering the solution to remove the solvent, sequentially washing the solid product by using a composite washing solvent, namely distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 120-140 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 5-10h, filtering the solution to remove the solvent, and (3) washing the solid product by using a composite washing solvent of distilled water and diethyl ether in sequence and fully drying to prepare the 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride.
(3) Adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4After the nano microspheres are uniformly dispersed by ultrasonic, adding 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride and 1, 5-naphthylenediamine, uniformly stirring for 6-10h, adding isoquinoline as a catalyst, heating to 110-, heating to 320-350 ℃ in the nitrogen atmosphere, reacting for 20-30h, washing the solid product with acetone to remove diphenyl sulfone, and drying to obtain the super-crosslinked porous polyimide coated nano Co.3O4。
(4) Placing the super-crosslinked porous polyimide coated nano Co3O4 in an atmosphere resistance furnace, heating at the rate of 2-8 ℃/min to 550-650 ℃ in the nitrogen atmosphere, and carrying out heat preservation and calcination for 2-3h to obtain the three-dimensional porous carbon coated Co3O43O4The negative electrode material of the sodium ion battery.
Example 1
(1) Preparation of Co3O4Nano microsphere component 1: adding distilled water solvent and glucose into a reaction bottle, stirring to dissolve, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, reacting for 5h, filtering and washing the solution, placing the solid product into a sodium hydroxide solution with the mass fraction of 2%, and performing oil treatment in an atmosphereHeating to 100 ℃ in a bath kettle, wherein the atmosphere oil bath kettle comprises an oil bath room, a heating sheet is arranged below the oil bath room, a base is arranged above the heating sheet, a reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath room, a gas chamber I gas inlet tube is movably connected on the left side of the gas exchange tube, the gas chamber I gas inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a gas chamber II gas inlet tube is fixedly connected with a conversion gas passage, the conversion gas passage is respectively fixedly connected with a gas chamber I air passage and a gas chamber II air passage, the gas chamber I gas inlet tube is fixedly connected with the gas chamber I, the gas chamber II gas inlet tube is fixedly connected with the gas chamber II, stirring reaction is carried out for 2 hours at a constant speed, filtering, washing and drying are carried out to prepare hydroxylated carbon nano microspheres, then the hydroxylated carbon nano microspheres are placed in a medium ethanol solvent and added with cobalt nitrate, the mass ratio of the two is 0.2:1, aging reaction is carried out for 48h after uniform ultrasonic dispersion, the solution is filtered and dried, the solid product is placed in an atmosphere resistance furnace, the heating rate is 2 ℃/min, the temperature is kept for 2h in a nitrogen atmosphere, and then the heat is kept and calcined for 1h in an air atmosphere to prepare the Co3O4And (3) a nano microsphere component 1.
(2) Preparation of 4,4' - (phenylethynyl-p-phenylene) diether dianhydride component 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3 in an atmosphere oil bath kettle to 100 ℃ under the nitrogen atmosphere, uniformly stirring for 40 hours for reaction, adding hydrochloric acid to adjust the pH of the solution to 4, uniformly stirring for 2 hours, filtering the solution to remove the solvent, sequentially washing a solid product by using a composite washing solvent of distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 120 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 5 hours, filtering the solution to remove the solvent, sequentially washing the solid product by using composite washing solvents of distilled water and diethyl ether, and fully drying to obtain 4,4' - (phenylethynyl-p-phenyl) diethanedioic anhydride component 1.
(3) Preparation of super-crosslinked porous polyimide coated nano Co3O4Component 1: is turned to the reverse directionAdding N-methyl pyrrolidone solvent and Co into a bottle3O4Uniformly dispersing a nano microsphere component 1 by ultrasonic, adding a 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 1 and 1, 5-naphthalenediamine in a mass ratio of 60:100:10:1, uniformly stirring for 6 hours, adding isoquinoline serving as a catalyst, heating to 110 ℃, uniformly stirring for reaction for 4 hours, heating to 180 ℃, reacting for 20 hours, cooling the solution in ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying, uniformly mixing a solid mixed product and diphenyl sulfone in a mass ratio of 1:40, heating to 320 ℃ in nitrogen atmosphere, reacting for 20 hours, washing the solid product by using acetone to remove the diphenyl sulfone, and drying to prepare the super-crosslinked porous polyimide coated nano Co3O4And (3) component 1.
(4) Preparation of three-dimensional porous carbon-coated Co3O4The sodium ion battery negative electrode material 1: coating super-crosslinked porous polyimide with nano Co3O4Placing the component 1 in an atmosphere resistance furnace, heating the temperature to 550 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 2h to prepare the three-dimensional porous carbon-coated Co3O4The negative electrode material 1 for a sodium-ion battery of (1).
Example 2
(1) Preparation of Co3O4Nano microsphere component 2: adding distilled water solvent and glucose into a reaction bottle, stirring and dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 180 ℃, reacting for 5h, filtering and washing the solution, putting a solid product into 3% sodium hydroxide solution, heating to 120 ℃ in an atmosphere oil bath kettle, wherein the atmosphere oil bath kettle comprises an oil bath chamber, a heating sheet is arranged below the oil bath chamber, a base is arranged above the heating sheet, the reaction bottle is arranged above the base, a gas exchange tube is arranged on the left side of the oil bath chamber, a gas chamber I gas inlet tube is movably connected on the left side of the gas exchange tube, the gas chamber I gas inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, the connecting rod is fixedly connected with a gas chamber II gas inlet tube, the gas chamber II gas inlet tube is movably connected with a conversion gas passage, and the conversion gas passage is respectively fixedly connected with a gas chamber I gas passage and a gas chamber II gas passage, qi (Qi)Fixedly connecting a first air inlet pipe of the chamber I with a first air chamber, fixedly connecting a second air inlet pipe of the air chamber with a second air chamber, stirring at a constant speed for 5 hours for reaction, filtering, washing and drying to obtain hydroxylated carbon nano microspheres, then placing the hydroxylated carbon nano microspheres in a medium ethanol solvent and adding cobalt nitrate, wherein the mass ratio of the medium ethanol solvent to the cobalt nitrate is 0.5:1, performing aging reaction for 60 hours after uniform ultrasonic dispersion, filtering and drying the solution, placing the solid product in an atmosphere resistance furnace, heating at a rate of 4 ℃/min, keeping the temperature in a nitrogen atmosphere for 3 hours, then keeping the temperature in the air atmosphere for calcining for 1 hour to obtain Co3O4And (3) a nano microsphere component 2.
(2) Preparation of 4,4' - (phenylethynyl-p-phenylene) diether dianhydride component 2: adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3.2 in an atmosphere oil bath kettle to 110 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 60 hours, adding hydrochloric acid to adjust the pH of the solution to 3, uniformly stirring for 2 hours, filtering the solution to remove the solvent, sequentially washing a solid product by using a composite washing solvent of distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 140 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 10 hours, filtering the solution to remove the solvent, sequentially washing the solid product by using composite washing solvents of distilled water and diethyl ether, and fully drying to prepare 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 2.
(3) Preparation of super-crosslinked porous polyimide coated nano Co3O4And (2) component: adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4Uniformly dispersing a nano microsphere component 2 by ultrasonic, adding a 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 2 and 1, 5-naphthylenediamine, uniformly stirring for 10 hours, adding isoquinoline serving as a catalyst in a mass ratio of 80:100:12:1.4, heating to 110 ℃, uniformly stirring for reaction for 4 hours, heating to 200 ℃, reacting for 28 hours, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying, uniformly mixing a solid mixed product and diphenyl sulfone in a mass ratio of 1:42, heating in a nitrogen atmosphere, andreacting for 30 hours at 340 ℃, washing the solid product by using acetone to remove diphenyl sulfone, and drying to prepare the super-crosslinked porous polyimide coated nano Co3O4And (3) component 2.
(4) Preparation of three-dimensional porous carbon-coated Co3O4Sodium ion battery negative electrode material 2: coating super-crosslinked porous polyimide with nano Co3O4Placing the component 2 in an atmosphere resistance furnace, heating the temperature to 600 ℃ at the heating rate of 8 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 3h to prepare the three-dimensional porous carbon-coated Co3O4The sodium ion battery negative electrode material 2.
Example 3
(1) Preparation of Co3O4Nano microsphere component 3: adding distilled water solvent and glucose into a reaction bottle, stirring and dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 180 ℃, reacting for 8 hours, filtering and washing the solution, placing a solid product into a sodium hydroxide solution with the mass fraction of 4%, heating to 110 ℃ in an atmosphere oil bath pot, wherein the atmosphere oil bath pot comprises an oil bath chamber, a heating sheet is arranged below the oil bath chamber, a base is arranged above the heating sheet, the reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath chamber, a gas chamber I gas inlet tube is movably connected on the left side of the gas exchange tube, the gas chamber I gas inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a gas chamber II gas inlet tube is fixedly connected with the connecting rod, the gas chamber II gas inlet tube is movably connected with a conversion gas passage, and the conversion gas passage is respectively fixedly connected with a gas chamber I gas passage and a gas chamber II gas passage, fixedly connecting an air inlet pipe of the first air chamber with the first air chamber, fixedly connecting an air inlet pipe of the second air chamber with the second air chamber, stirring at a constant speed for reaction for 4 hours, filtering, washing and drying to obtain hydroxylated carbon nano microspheres, then placing the hydroxylated carbon nano microspheres in a medium ethanol solvent and adding cobalt nitrate, wherein the mass ratio of the medium ethanol solvent to the cobalt nitrate is 0.35:1, performing aging reaction for 72 hours after uniform ultrasonic dispersion, filtering and drying the solution, placing the solid product in an atmosphere resistance furnace, heating at a rate of 4 ℃/min, preserving heat for 2.5 hours in a nitrogen atmosphere, then preserving heat and calcining for 2 hours in an air atmosphere to obtain Co3O4And (3) a nano microsphere component.
(2) Preparation of 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 3: adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3.5 in an atmosphere oil bath kettle to 105 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 50 hours, adding hydrochloric acid to adjust the pH of the solution to 3, uniformly stirring for 4 hours, filtering the solution to remove the solvent, sequentially washing a solid product by using a composite washing solvent of distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 130 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 8 hours, filtering the solution to remove the solvent, sequentially washing the solid product by using composite washing solvents of distilled water and diethyl ether, and fully drying to prepare 4,4' - (phenylethynyl-p-phenyl) diethanedioic anhydride component 3.
(3) Preparation of super-crosslinked porous polyimide coated nano Co3O4And (3) component: adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4Uniformly dispersing a nano microsphere component 3 by ultrasonic, adding a 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 3 and 1, 5-naphthylenediamine, uniformly stirring for 8 hours, adding isoquinoline serving as a catalyst in a mass ratio of 100:100:14:1.8, heating to 120 ℃, uniformly stirring for reaction for 5 hours, heating to 190 ℃, reacting for 25 hours, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying, uniformly mixing a solid mixed product and diphenyl sulfone in a mass ratio of 1:45, heating to 330 ℃ in a nitrogen atmosphere, reacting for 25 hours, washing the solid product by using acetone to remove the diphenyl sulfone, and drying to prepare the super-crosslinked polyimide coated nano Co3O4And (3) component.
(4) Preparation of three-dimensional porous carbon-coated Co3O4Sodium ion battery negative electrode material 3: coating super-crosslinked porous polyimide with nano Co3O4Placing the component 3 in an atmosphere resistance furnace, heating to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out heat preservation and calcination for 2.5h to obtain the three-dimensional porous carbon-coated Co3O4Sodium (II) ofAn ion battery negative electrode material 3.
Example 4
(1) Preparation of Co3O4Nano microsphere component 4: adding distilled water solvent and glucose into a reaction bottle, stirring and dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃, reacting for 8h, filtering and washing the solution, placing a solid product into a sodium hydroxide solution with the mass fraction of 5%, heating to 110 ℃ in an atmosphere oil bath pot, wherein the atmosphere oil bath pot comprises an oil bath chamber, a heating sheet is arranged below the oil bath chamber, a base is arranged above the heating sheet, the reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath chamber, a gas chamber I gas inlet tube is movably connected on the left side of the gas exchange tube, the gas chamber I gas inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a gas chamber II gas inlet tube is fixedly connected with the connecting rod, the gas chamber II gas inlet tube is movably connected with a conversion gas passage, and the conversion gas passage is respectively fixedly connected with a gas chamber I gas passage and a gas chamber II gas passage, fixedly connecting an air inlet pipe of the first air chamber with the first air chamber, fixedly connecting an air inlet pipe of the second air chamber with the second air chamber, stirring at a constant speed for 5 hours for reaction, filtering, washing and drying to obtain hydroxylated carbon nano microspheres, then placing the hydroxylated carbon nano microspheres in a medium ethanol solvent and adding cobalt nitrate, wherein the mass ratio of the medium ethanol solvent to the cobalt nitrate is 0.4:1, performing aging reaction for 80 hours after uniform ultrasonic dispersion, filtering and drying the solution, placing the solid product in an atmosphere resistance furnace, heating at a rate of 5 ℃/min, preserving heat for 3 hours in a nitrogen atmosphere, then preserving heat and calcining for 1 hour in an air atmosphere to obtain Co3O4And (4) a nano microsphere component.
(2) Preparation of 4,4' - (phenylethynyl-p-phenylene) diether dianhydride component 4: adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3.8 in an atmosphere oil bath kettle to 110 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 60 hours, adding hydrochloric acid to adjust the pH of the solution to 2, uniformly stirring for 6 hours, filtering the solution to remove the solvent, sequentially washing a solid product by using a composite washing solvent of distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 140 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 5 hours, filtering the solution to remove the solvent, sequentially washing the solid product by using composite washing solvents of distilled water and diethyl ether, and fully drying to prepare 4,4' - (phenylethynyl-p-phenyl) diethanedioic anhydride component 4.
(3) Preparation of super-crosslinked porous polyimide coated nano Co3O4And (4) component: adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4Uniformly dispersing a nano microsphere component 4 by ultrasonic, adding a 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride component 4 and 1, 5-naphthylenediamine, uniformly stirring for 10 hours, adding isoquinoline serving as a catalyst in a mass ratio of 120:100:16:2.2, heating to 140 ℃, uniformly stirring for reaction for 4 hours, heating to 200 ℃, reacting for 25 hours, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying, uniformly mixing a solid mixed product and diphenyl sulfone in a mass ratio of 1:40, heating to 340 ℃ in a nitrogen atmosphere, reacting for 28 hours, washing the solid product by using acetone to remove the diphenyl sulfone, and drying to prepare the super-crosslinked polyimide coated nano Co3O4And (4) component.
(4) Preparation of three-dimensional porous carbon-coated Co3O4Sodium ion battery negative electrode material 4: coating super-crosslinked porous polyimide with nano Co3O4Placing the component 4 in an atmosphere resistance furnace, heating to 650 ℃ at the heating rate of 8 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 3h to prepare the three-dimensional porous carbon-coated Co3O4The negative electrode material 4 for sodium ion batteries.
Example 5
(1) Preparation of Co3O4Nano microsphere component 5: adding distilled water solvent and glucose into a reaction bottle, stirring for dissolving, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃, reacting for 10h, filtering and washing the solution, putting a solid product into a sodium hydroxide solution with the mass fraction of 6%, heating to 120 ℃ in an atmosphere oil bath kettle, wherein the atmosphere oil bath kettle comprises an oil bath chamber, a heating sheet is arranged below the oil bath chamber, a base is arranged above the heating sheet, and a container is arranged above the basePlacing a reaction bottle, arranging a gas exchange tube on the left side of an oil bath room, movably connecting the left side of the gas exchange tube with a first gas chamber gas inlet pipe, fixedly connecting the first gas chamber gas inlet pipe with a connecting rod, fixedly connecting the connecting rod with a sliding shaft, movably connecting the sliding shaft with an adjusting nut, fixedly connecting the connecting rod with a second gas chamber gas inlet pipe, movably connecting the second gas chamber gas inlet pipe with a conversion gas passage, fixedly connecting the conversion gas passage with a first gas chamber gas passage and a second gas chamber gas passage respectively, fixedly connecting the first gas chamber gas inlet pipe with the first gas chamber, fixedly connecting the second gas chamber gas inlet pipe with the second gas chamber, stirring at a constant speed for 5 hours for reaction, filtering, washing and drying to obtain hydroxylated carbon nano microspheres, then placing the hydroxylated carbon nano microspheres in a medium ethanol solvent and adding cobalt nitrate, wherein the mass ratio of the first gas chamber gas inlet pipe to the first gas chamber and the second gas chamber is 0.5:1, performing aging reaction for 96 hours after uniform ultrasonic dispersion, filtering and drying the solution, placing the solid product in an atmosphere resistance furnace, the heating rate is 5 ℃/min, the heat preservation is carried out for 3h in a nitrogen atmosphere, and then the heat preservation calcination is carried out for 3h in an air atmosphere to prepare the Co3O4And (5) a nano microsphere component.
(2) Preparation of 4,4' - (phenylethynyl-p-phenylene) diether dianhydride component 5: adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:4 in an atmosphere oil bath kettle to 110 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 60 hours, adding hydrochloric acid to adjust the pH value of the solution to 2, uniformly stirring for 6 hours, filtering the solution to remove the solvent, sequentially washing a solid product by using a composite washing solvent of distilled water and diethyl ether to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, placing the 4,4' - (phenylethynyl-p-benzene) diphthalic acid into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 140 ℃ under the nitrogen atmosphere, uniformly stirring for reaction for 10 hours, filtering the solution to remove the solvent, sequentially washing the solid product by using composite washing solvents of distilled water and diethyl ether, and fully drying to obtain 4,4' - (phenylethynyl-p-phenyl) diethanedioic anhydride component 5.
(3) Preparation of super-crosslinked porous polyimide coated nano Co3O4And (5) component: adding N-methyl pyrrolidone solvent and Co into a reaction bottle3O4After the nano microsphere component 5 is uniformly dispersed by ultrasonic, adding 4,4' - (phenylethynyl)P-phenylene) diether dianhydride component 5 and 1, 5-naphthalene diamine are stirred at a constant speed for 10 hours, isoquinoline is added as a catalyst, the mass ratio of the four components is 60:100:10:1, the mixture is heated to 140 ℃, stirred at a constant speed for reaction for 6 hours, the temperature is raised to 200 ℃, the reaction is carried out for 30 hours, the solution is cooled in ice water bath, distilled water is added until a large amount of precipitate is separated out, the solution is filtered, washed and dried, the solid mixed product and diphenyl sulfone are uniformly mixed according to the mass ratio of 1:50, then the mixture is heated to 350 ℃ in a nitrogen atmosphere, the reaction is carried out for 30 hours, acetone is used for washing the solid product to remove the diphenyl sulfone, and the mixture is dried to prepare the super-crosslinked porous polyimide coated nano Co coated with nano Co3O4And (5) component.
(4) Preparation of three-dimensional porous carbon-coated Co3O4The sodium ion battery negative electrode material 5: coating super-crosslinked porous polyimide with nano Co3O4Placing the component 5 in an atmosphere resistance furnace, heating to 650 ℃ at the heating rate of 8 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 3h to obtain the three-dimensional porous carbon-coated Co3O4The negative electrode material 5 for sodium ion batteries.
The three-dimensional porous carbon-coated Co in the example was added to N-methylpyrrolidone solvent separately3O4The method comprises the steps of adding acetylene black and polyvinylidene fluoride into the sodium ion battery negative electrode materials 1-5 respectively, coating uniformly dispersed slurry on the surface of copper foil, drying and slicing to obtain sodium ion battery negative electrode working electrodes 1-5, assembling a CR2450 button sodium ion half-cell by taking a sodium sheet as a positive working electrode and glass fiber as a diaphragm, and carrying out electrochemical performance test on a LAND CT2001A battery test system, wherein the electrolyte is a mixed solution of ethylene carbonate and diethyl carbonate of NaPF6 with the concentration of 1 mol/L.
In summary, the three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material takes the carbon nano-microsphere as a template, and rich hydroxyl on the surface adsorbs Co3+Preparation of Co3O4The nano-microsphere has the advantages of small particle size, porous hollow structure, high specific surface area and the like, and is favorable for improving the electrochemical performance of the cathode material.
The super-crosslinked porous polyimide coated nano Co is prepared by using 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride with side chain containing alkynyl group as dianhydride monomer and 1, 5-naphthalene diamine containing naphthalene ring as diamine monomer through in-situ polymerization3O4The alkynyl of the side chain passes through alkynyl crosslinking effect in the thermal imidization process, the generated crosslinking structure hinders the conformational transformation of a polyimide molecular chain, the collapse of a polyimide framework and a pore structure is inhibited, and the space between polymer molecular chains is regulated and controlled through alkynyl crosslinking sites, so that the generation of a new microporous structure is promoted, the super-crosslinked polyimide has a large amount of pores and microporous structures, the molecular chain has a rigid naphthalene ring structure, and the microporous structure can be maintained not to collapse in the high-temperature thermal cracking process, thereby forming a porous carbon material to uniformly coat the nano Co3O4。
The carbon layer coating function and the abundant pore structure are nano Co3O4The volume expansion provides a buffer layer, reduces the volume change caused by the deintercalation of sodium ions, and simultaneously, a large number of pore structures can improve the wettability of the cathode material to electrolyte, and improve a diffusion channel for the sodium ions, thereby shortening the transmission path of the sodium ions, and the electronic state of the carbon material can be adjusted by abundant nitrogen elements in the porous carbon, thereby improving the defect active sites, being beneficial to improving the conductivity and the sodium ion adsorption capacity of the cathode material, and leading the three-dimensional porous carbon to coat Co3O4The sodium ion battery negative electrode material shows excellent electrochemical performance and good electric capacity.
Claims (1)
1. Three-dimensional porous carbon coated Co3O4The sodium ion battery cathode material comprises the following raw materials and components, and is characterized in that: co3O4Nanosphere, 4' - (benzene)Ethynyl p-phenylene) diethanedioic anhydride, 1, 5-naphthalenediamine, isoquinoline, diphenylsulfone, where Co3O4The mass ratio of the nano microspheres to the 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride to the 1, 5-naphthalenediamine to the isoquinoline is 60-150:100:10-18:1-2.5, and the three-dimensional porous carbon is coated with Co3O4The preparation method of the sodium ion battery negative electrode material comprises the following steps:
(1) adding distilled water and glucose into a hydrothermal reaction kettle, heating to 190 ℃ for 170-3O4Nano-microspheres;
(2) adding a mixed solvent of distilled water and ethanol into a reaction bottle, heating 4,4' - (phenylethynyl-p-benzene) phthalonitrile and potassium hydroxide in a mass ratio of 1:3-4 in an atmosphere oil bath kettle under a nitrogen atmosphere to 110 ℃, reacting for 40-60h, adding hydrochloric acid to adjust the pH of the solution to 2-4, stirring for 2-6h, filtering and washing a solid product by using a composite washing solvent to obtain 4,4' - (phenylethynyl-p-benzene) diphthalic acid, then placing the solid product into a mixed solvent of glacial acetic acid and acetic anhydride, heating to 120-140 ℃ under the nitrogen atmosphere, reacting for 5-10h, filtering, washing the product by using the composite washing solvent, and drying to prepare 4,4' - (phenylethynyl-p-benzene) diether dianhydride;
(3) adding Co to N-methylpyrrolidone solvent3O4The method comprises the steps of dispersing nano microspheres uniformly by ultrasonic, adding 4,4' - (phenylethynyl-p-phenylene) diethanedioic anhydride and 1, 5-naphthalenediamine, stirring for 6-10h, adding isoquinoline serving as a catalyst, heating to 140 ℃ for 110-140 ℃, reacting for 4-6h, heating to 200 ℃ for 180-30 h, reacting for 20-30h, precipitating, filtering, washing and drying, uniformly mixing a solid mixed product and diphenyl sulfone, and heating in a nitrogen atmosphereReacting for 20-30h at the temperature of 320-350 ℃, washing and drying to obtain the super-crosslinked porous polyimide coated nano Co3O4；
(4) Placing the super-crosslinked porous polyimide coated nano Co3O4 in an atmosphere resistance furnace, heating at the rate of 2-8 ℃/min to 550-650 ℃ in the nitrogen atmosphere, and carrying out heat preservation and calcination for 2-3h to obtain the three-dimensional porous carbon coated Co3O43O4The sodium ion battery negative electrode material of (1); the mass ratio of the hydroxylated carbon nano-microspheres to the cobalt nitrate in the step (1) is 0.2-0.5: 1; the atmosphere oil bath pot in the step (1) comprises an oil bath room, a heating sheet is arranged below the oil bath room, a base is arranged above the heating sheet, a reaction bottle is placed above the base, a gas exchange tube is arranged on the left side of the oil bath room, a first air chamber air inlet tube is movably connected to the left side of the gas exchange tube, the first air chamber air inlet tube is fixedly connected with a connecting rod, the connecting rod is fixedly connected with a sliding shaft, the sliding shaft is movably connected with an adjusting nut, a second air chamber air inlet tube is fixedly connected with a connecting rod, the second air chamber air inlet tube is movably connected with a conversion air passage, the conversion air passage is respectively fixedly connected with a first air chamber air passage and a second air chamber air passage, the first air chamber air inlet tube is fixedly connected with a first air chamber, and the second air chamber air inlet tube is fixedly connected with a second air chamber; the composite washing solvent in the step (2) is distilled water and diethyl ether; the mass ratio of the solid mixed product in the step (3) to the diphenyl sulfone is 1: 40-50.
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