CN112886016A - Preparation method of internal high-defect carbon nanotube composite material with through cobalt-nickel catalytic tube inner structure - Google Patents
Preparation method of internal high-defect carbon nanotube composite material with through cobalt-nickel catalytic tube inner structure Download PDFInfo
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- CN112886016A CN112886016A CN202110152459.3A CN202110152459A CN112886016A CN 112886016 A CN112886016 A CN 112886016A CN 202110152459 A CN202110152459 A CN 202110152459A CN 112886016 A CN112886016 A CN 112886016A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 title claims description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910002441 CoNi Inorganic materials 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 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 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 239000012300 argon atmosphere Substances 0.000 description 10
- 239000011669 selenium Substances 0.000 description 9
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 6
- 229910014589 Na—Se Inorganic materials 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalyst tube, which comprises the following steps: weighing a cobalt source, a nickel source and a carbon source, fully mixing and grinding; step two, uniformly heating the ground product to 300-700 ℃ at a heating rate of 5-20 ℃/min in an inert gas atmosphere, naturally cooling the product and collecting the product; step three, standing the product obtained in the step two in nitric acid, corroding for 12 hours, separating out residual solid, and drying; and step four, mixing the product obtained in the step three with selenium powder in proportion, placing the mixture in a reaction kettle in a sealed glove box under an inert gas atmosphere, heating the mixture to 260 ℃ in a homogeneous reaction instrument, and preserving the heat for 12 hours to obtain the product CoNi @ Se/C. The material prepared by the invention has excellent sodium ion storage performance, high charge and discharge capacity and good rate capability, and can remarkably improve the conductivity and structural stability of the material in the charge and discharge process.
Description
The technical field is as follows:
the invention belongs to the technical field of composite material synthesis, relates to preparation of carbon nano tube materials, and particularly relates to a preparation method of an internal high-defect carbon nano tube composite material with a through structure in a cobalt-nickel catalytic tube.
Background art:
the application of the electrochemical energy storage technology effectively solves the problems of storage, utilization and conversion of clean energy, and has wide development prospect in the future. At present, lithium ion batteries are widely applied to the field of electrochemical energy storage due to the advantages of excellent performances of the lithium ion batteries, such as high energy density, high energy conversion rate, good safety and the like. However, as research on lithium ion batteries continues, the capacity of lithium ion batteries has been difficult to increase. To meet the demand for ever-evolving large energy storage devices, we are beginning to look at other battery systems. Rechargeable Na-Se batteries are considered to be a promising next generation battery due to their high energy density and low cost. In the Na-Se battery, Se is used as a battery positive electrode, and a sodium sheet is used as a negative electrode. However, the volume expansion of selenium in the charging and discharging process and the shuttle effect of the polyselenide are problems, so that the battery of the system can not reach the theoretical capacity. It is crucial to study a suitable carrier for selenium in Na-Se cells to solve the problems of volume expansion and shuttle effect.
The carbon nano tube is a common soft carbon material, has a good graphitized structure and has excellent conductivity. Meanwhile, the carbon nano tube has good mechanical strength, and the problem of volume expansion and shuttle effect in the charging and discharging reaction process can be effectively inhibited by loading selenium in a one-dimensional network formed by the carbon nano tube. However, the carbon nanotubes themselves have small tube diameters, so that loading selenium in the tubes is difficult, and the carbon nanotubes have few surface defects and are difficult to fix selenium. If the technology can increase the tube diameter of the carbon nano tube by a confinement method, increase the defects and strengthen the fixing capacity of the carbon nano tube to Se element, the application of the material in the field of Na-Se battery electrode materials is expected to be popularized.
The invention content is as follows:
the invention aims to provide a preparation method of an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalytic tube, which realizes the controllable in-situ growth of a carbon nanotube by controlling the process conditions in the reaction process and then coordinating with a CoNi alloy catalyst to catalyze the growth of the carbon nanotube.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalyst tube comprises the following steps:
the method comprises the following steps: weighing a cobalt source, a nickel source and a carbon source according to a proportion, and fully mixing and grinding;
step two: placing the ground product in a crucible, placing the crucible in a reactor, uniformly heating at a heating rate of 5-20 ℃/min in an inert gas atmosphere, controlling the temperature to be 300-700 ℃, immediately cooling after the reaction temperature is reached, and collecting the product after the temperature is reduced to room temperature;
step three: standing the product obtained in the step two in nitric acid, corroding for 12 hours, separating out residual solids, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder, placing the mixture in a reaction kettle in a sealed glove box inert gas atmosphere, heating the mixture to 100-300 ℃ in a homogeneous reactor, and preserving the heat for 6-12 hours to obtain a product CoNi @ Se/C.
Furthermore, the cobalt source and the nickel source are analytically pure cobalt nitrate, cobalt carbonate, cobalt sulfate, nickel nitrate, nickel sulfate and nickel chloride.
Further, the carbon source is urea and melamine.
Further, the weight ratio of the cobalt source, the nickel source and the carbon source is 1: (6-19): (3-40).
Furthermore, the crucible is a quartz crucible or an alumina crucible.
Further, the reactor is a tube furnace.
Further, the inert gas is argon.
Further, the concentration of the nitric acid is 0.5, 1M or 3M.
Further, the weight ratio of the product obtained in the third step to the selenium powder is 1: (1.5-4).
According to the invention, CoNi/C is prepared by adopting a solid phase method, a cobalt source and a nickel source react to generate a CoNi alloy in the reaction process, then carbon around the CoNi alloy is gathered on the surface of the alloy along with the increase of temperature, the carbon grows along a certain direction along with the increase of concentration, and the CoNi alloy is influenced along with the growth of the carbon nano tube in the tube, so that the carbon nano tube which is through in the tube is finally generated. The use of urea and melamine realizes N doping, excessive CoNi alloy is washed away by acid, so that the bond between the alloy and carbon is broken, more active sites are exposed in the tube, the subsequent selenium loading is facilitated, and finally, the CoNi @ Se/C is obtained by solid-phase loading of Se;
the CoNi @ Se/C prepared by the invention has excellent sodium ion storage performance, high charge-discharge capacity and good rate capability, and can remarkably improve the conductivity and structural stability of the material in the charge-discharge process;
the CoNi @ Se/C material prepared by the invention has the advantages of cheap and easily-obtained raw materials and simple preparation method.
Drawings
FIG. 1 is a scanning electron micrograph of a sample of example 1
FIG. 2 is a graph of the cycle performance of the sodium ion battery of example 1
The specific implementation mode is as follows:
example 1:
the method comprises the following steps: fully grinding 0.1g of cobalt nitrate, 0.9g of nickel nitrate and 2g of melamine in a mortar;
step two: placing the ground product in a quartz or alumina crucible, placing the crucible in a tube furnace, heating at a constant speed at a heating rate of 5 ℃/min under the argon atmosphere to 700 ℃, and naturally cooling and collecting the product to obtain the product;
step three: standing the obtained product in nitric acid with the concentration of 3M, corroding for 12 hours, separating out residual solid, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder in a ratio of 2:3, placing the mixture in a reaction kettle in a sealed glove box under an argon atmosphere, heating the mixture to 260 ℃ in a homogeneous reaction instrument, and preserving the heat for 12 hours to obtain CoNi @ Se/C.
Example 2:
the method comprises the following steps: fully grinding 0.05g of cobalt nitrate, 0.95g of nickel nitrate and 2g of urea in a mortar;
step two: placing the ground product in a quartz or alumina crucible, placing the crucible in a tube furnace, heating at a constant speed at a heating rate of 10 ℃/min under the argon atmosphere to 600 ℃, and naturally cooling and collecting the product to obtain the product;
step three: standing the obtained product in nitric acid with the concentration of 1M, corroding for 12 hours, separating out residual solid, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder in a ratio of 1:4, placing the mixture in a reaction kettle in a sealed glove box under an argon atmosphere, heating the mixture to 260 ℃ in a homogeneous reaction instrument, and preserving the heat for 12 hours to obtain CoNi @ Se/C.
Example 3:
the method comprises the following steps: fully grinding 0.6g of cobalt nitrate, 0.4g of nickel nitrate and 2g of urea in a mortar;
step two: placing the ground product in a quartz or alumina crucible, placing the crucible in a tube furnace, heating at a constant speed at a heating rate of 20 ℃/min under the argon atmosphere to 300 ℃, and naturally cooling and collecting the product to obtain the product;
step three: standing the obtained product in nitric acid with the concentration of 0.5M, corroding for 12 hours, separating out residual solid, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder in a ratio of 1:4, placing the mixture in a reaction kettle in a sealed glove box under an argon atmosphere, heating the mixture to 260 ℃ in a homogeneous reaction instrument, and preserving the heat for 12 hours to obtain CoNi @ Se/C.
When the sample of example 1 is observed under a transmission electron microscope, it can be seen from fig. 1 that the product exhibits bamboo-like carbon tubes with through structures. Preparing the obtained product into a button type sodium ion battery, and specifically packaging the button type sodium ion battery by the following steps: uniformly grinding the product, a conductive agent (Super P) and a bonding agent (PVDF) according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours at 80 ℃ in a vacuum drying oven. And then assembling the electrode plates into a Na-Se battery, performing constant-current charge and discharge test on the battery by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01V-3.0V, assembling the obtained material into a button battery, and testing the performance of the sodium-ion battery cathode material, wherein the cycle performance is shown in figure 2.
Example 4:
the method comprises the following steps: fully grinding 1g of cobalt carbonate, 6g of nickel chloride and 3g of urea in a mortar;
step two: placing the ground product in a quartz or alumina crucible, placing the crucible in a tube furnace, heating at a constant speed at a heating rate of 20 ℃/min under the argon atmosphere to 300 ℃, and naturally cooling and collecting the product to obtain the product;
step three: standing the obtained product in nitric acid with the concentration of 0.5M, corroding for 12 hours, separating out residual solid, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder in a ratio of 1:2, placing the mixture in a reaction kettle in a sealed glove box under an argon atmosphere, heating the mixture to 100 ℃ in a homogeneous reaction instrument, and preserving the heat for 10 hours to obtain CoNi @ Se/C.
Example 5:
the method comprises the following steps: fully grinding 1g of cobalt sulfate, 15g of nickel sulfate and 16g of urea in a mortar;
step two: placing the ground product in a quartz or alumina crucible, placing the crucible in a tube furnace, heating at a constant speed at a heating rate of 20 ℃/min under the argon atmosphere to 300 ℃, and naturally cooling and collecting the product to obtain the product;
step three: standing the obtained product in nitric acid with the concentration of 0.5M, corroding for 12 hours, separating out residual solid, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder in a ratio of 1:3, placing the mixture in a reaction kettle in a sealed glove box under an argon atmosphere, heating the mixture to 300 ℃ in a homogeneous reaction instrument, and preserving the heat for 6 hours to obtain CoNi @ Se/C.
Claims (9)
1. A preparation method of an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalyst tube is characterized by comprising the following steps:
the method comprises the following steps: weighing a cobalt source, a nickel source and a carbon source according to a proportion, and fully mixing and grinding;
step two: placing the ground product in a crucible, placing the crucible in a reactor, uniformly heating at a heating rate of 5-20 ℃/min in an inert gas atmosphere, controlling the temperature to be 300-700 ℃, immediately cooling after the reaction temperature is reached, and collecting the product after the temperature is reduced to room temperature;
step three: standing the product obtained in the step two in nitric acid, corroding for 12 hours, separating out residual solids, and drying;
step four: and (3) mixing the product obtained in the step three with selenium powder, placing the mixture in a reaction kettle in a sealed glove box inert gas atmosphere, heating the mixture to 100-300 ℃ in a homogeneous reactor, and preserving the heat for 6-12 hours to obtain a product CoNi @ Se/C.
2. The method for preparing the internally-penetrated high-defect carbon nanotube composite material with a cobalt nickelate catalytic tube as claimed in claim 1, wherein the cobalt source and the nickel source are analytically pure cobalt nitrate, cobalt carbonate, cobalt sulfate, nickel nitrate, nickel sulfate and nickel chloride.
3. The method for preparing the internal high-defect carbon nanotube composite material with a through structure in the cobalt nickelate catalytic tube according to claim 1, wherein the carbon source is urea or melamine.
4. The method for preparing the internally-penetrated high-defect carbon nanotube composite material with the cobalt nickelate catalytic tube as claimed in claim 2, wherein the weight ratio of the cobalt source, the nickel source and the carbon source is 1: (6-19): (3-40).
5. The method for preparing the carbon nanotube composite material with the communicated inner structure of the cobalt nickelate catalytic tube as claimed in claims 2 and 3, wherein the crucible is a quartz crucible or an alumina crucible.
6. The method for preparing the internally-penetrated high-defect carbon nanotube composite material with a cobalt nickelate catalytic tube as claimed in claim 1, wherein the reactor is a tube furnace.
7. The method for preparing the internally-penetrated high-defect carbon nanotube composite material with a cobalt nickelate catalytic tube as claimed in claim 1, wherein the inert gas is argon.
8. The method for preparing the internally highly defective carbon nanotube composite material having a through structure in a cobalt nickelate catalyst tube according to claim 1, wherein the concentration of the nitric acid is 0.5, 1M or 3M.
9. The method for preparing the internally-penetrated high-defect carbon nanotube composite material with the structure in the cobalt nickelate catalytic tube according to claim 1, wherein the weight ratio of the product obtained in the third step to the selenium powder is 1: (1.5-4).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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