CN112886017A - Internal high-defect carbon nanotube composite material with communicated cobalt-nickel catalytic tube inner structure and application thereof - Google Patents
Internal high-defect carbon nanotube composite material with communicated cobalt-nickel catalytic tube inner structure and application thereof Download PDFInfo
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- CN112886017A CN112886017A CN202110152479.0A CN202110152479A CN112886017A CN 112886017 A CN112886017 A CN 112886017A CN 202110152479 A CN202110152479 A CN 202110152479A CN 112886017 A CN112886017 A CN 112886017A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title description 4
- 229910002441 CoNi Inorganic materials 0.000 claims abstract description 23
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011669 selenium Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 14
- 239000002071 nanotube Substances 0.000 claims abstract description 10
- HVAKSLUOHARFLM-UHFFFAOYSA-N selenium;sodium Chemical compound [Se][Na] HVAKSLUOHARFLM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000007547 defect Effects 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 229910014589 Na—Se Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method 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
- 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 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
- 238000003917 TEM image Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 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 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
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an internal high-defect carbon nanotube composite material with a through nickel cobalt catalytic tube structure and application thereof, wherein selenium is loaded on a solid phase at an internal defect part of a CoNi/C nanotube doped with the internal defect; the CoNi @ Se/C nanotube material is a bamboo-like carbon tube with a through structure; a sodium selenium battery positive electrode containing a CoNi @ Se/C nanotube material, and a sodium selenium battery comprising the sodium selenium battery positive electrode; according to the invention, Se is loaded in a solid phase in the CoNi carbon nanotube material, so that CoNi @ Se/C is obtained, the CoNi @ Se/C material has excellent sodium ion storage performance, high charge-discharge capacity and good rate capability, and the conductivity and structural stability of the material in the charge-discharge process can be obviously improved.
Description
The technical field is as follows:
the invention belongs to the technical field of batteries, relates to a battery electrode material, and particularly relates to an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalytic tube and application thereof.
Technical background:
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 an internal high-defect carbon nanotube composite material with a through structure in a cobalt-nickel catalyst tube, so that the structure of a battery is more stable, the load capacity of the battery is increased, and the multiplying power and the cycle performance of the battery are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
an internal high-defect carbon nanotube composite material with a through cobalt nickelate catalytic tube structure is characterized in that selenium is loaded on a solid phase at the internal defect position of a CoNi/C nanotube doped with the internal defect.
The invention also has the following technical characteristics:
the CoNi @ Se/C nanotube material is a bamboo-like carbon tube with a through structure.
Preferably, the mass ratio of the CoNi/C to the selenium is 1:4 or 2: 3.
Further, the invention provides a preparation method of the CoNi @ Se/C nanotube material, which 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 constant speed at a heating rate of 5-20 ℃/min in an inert gas atmosphere, controlling the temperature to be 300-700 ℃, and naturally cooling and collecting the product;
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 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 a product CoNi @ Se/C.
Preferably, the cobalt source and the nickel source are analytically pure cobalt nitrate and nickel nitrate.
Preferably, the carbon source is urea, melamine or glucose.
Preferably, the weight ratio of the cobalt source, the nickel source and the carbon source is as follows: 0.5: 9.5: 20. 1: 9: 20 or 3: 2: :10.
The crucible is a quartz crucible or an alumina crucible.
The reactor is a tubular furnace.
Preferably, the inert gas is argon.
The concentration of the nitric acid is 0.5, 1M or 3M.
Preferably, the weight ratio of the product 2 to the selenium powder is 1:4 or 2: 3.
The invention also discloses a sodium-selenium battery anode containing the CoNi @ Se/C nanotube material.
The invention also provides a sodium-selenium battery comprising the sodium-selenium battery anode.
According to the invention, Se is loaded in the CoNi carbon nanotube material in a solid phase manner, so that CoNi @ Se/C is obtained, and the CoNi carbon nanotube is a highly graphitized carbon nanotube, so that the material loaded with the selenium has the advantages of good electron transmission path and high mechanical strength when being used in the charging and discharging processes of the sodium selenium battery, and can improve the conductivity and relieve the influence caused by volume expansion in the charging and discharging processes. The communicated tube structure increases the internal storage space, improves the selenium loading capacity, enhances the adsorption capacity of the selenium by the exposed active sites inside, and reduces the influence caused by the shuttle effect. Therefore, the obtained CoNi @ Se/C material 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.
Drawings
FIG. 1 is a transmission electron micrograph of a sample according to the present invention
FIG. 2 is a diagram of the cycle performance of the sodium ion battery of the present invention
Detailed Description
The preparation method of the material comprises the following steps:
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: 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 the argon atmosphere, heating the mixture to 260 ℃ in a homogeneous reaction instrument, and preserving the heat for 12 hours to obtain the selenium-enriched selenium-
CoNi@Se/C。
Example 3:
the method comprises the following steps: fully grinding 3g of cobalt nitrate, 2g of nickel nitrate and 10g 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. 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, and assembling the obtained material into a button battery to test the performance of the sodium ion battery cathode material; the cycling performance is shown in figure 2.
Claims (5)
1. The composite material is characterized in that selenium is loaded on the internal defect position of a CoNi/C nanotube doped with the internal defect in a solid phase mode.
2. The cobalt-nickelate catalyst tube structurally-through internal high-defect carbon nanotube composite material as claimed in claim 1, wherein the CoNi @ Se/C nanotube material is a bamboo-like carbon tube structurally-through.
3. The cobalt-nickelate catalyst tube inner structure-through internal high-defect carbon nanotube composite material as claimed in claim 1, wherein the mass ratio of CoNi/C and selenium is 1:4 or 2: 3.
4. A sodium selenium battery positive electrode comprising the CoNi @ Se/C nanotube material of any one of claims 1 to 3.
5. A sodium selenium battery comprising the sodium selenium battery positive electrode according to claim 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110152479.0A CN112886017A (en) | 2021-02-04 | 2021-02-04 | Internal high-defect carbon nanotube composite material with communicated cobalt-nickel catalytic tube inner structure and application thereof |
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| CN202110152479.0A CN112886017A (en) | 2021-02-04 | 2021-02-04 | Internal high-defect carbon nanotube composite material with communicated cobalt-nickel catalytic tube inner structure and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113964323A (en) * | 2021-10-22 | 2022-01-21 | 陕西科技大学 | Copper-nickel alloy in-situ autocatalytic growth carbon nanotube composite material and preparation method thereof |
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