CN113003564A - Carbon nanotube composite iron-carbon diimine material and preparation method and application thereof - Google Patents
Carbon nanotube composite iron-carbon diimine material and preparation method and application thereof Download PDFInfo
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- CN113003564A CN113003564A CN202110210233.4A CN202110210233A CN113003564A CN 113003564 A CN113003564 A CN 113003564A CN 202110210233 A CN202110210233 A CN 202110210233A CN 113003564 A CN113003564 A CN 113003564A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 76
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 21
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 25
- JNTHZXXKFZZCFA-UHFFFAOYSA-N [Fe].N=C=N Chemical compound [Fe].N=C=N JNTHZXXKFZZCFA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 10
- -1 organic acid iron salt Chemical class 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940080818 propionamide Drugs 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- PQQAOTNUALRVTE-UHFFFAOYSA-L iron(2+);diformate Chemical compound [Fe+2].[O-]C=O.[O-]C=O PQQAOTNUALRVTE-UHFFFAOYSA-L 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 3
- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- QCQJPUZAVFHPMN-UHFFFAOYSA-N iron(2+);propan-2-olate Chemical compound [Fe+2].CC(C)[O-].CC(C)[O-] QCQJPUZAVFHPMN-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 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 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 18
- 238000004108 freeze drying Methods 0.000 description 14
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- AKLSSKNRPSKJBO-UHFFFAOYSA-K 2-aminoacetate;iron(3+) Chemical compound [Fe+3].NCC([O-])=O.NCC([O-])=O.NCC([O-])=O AKLSSKNRPSKJBO-UHFFFAOYSA-K 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
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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
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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Abstract
The invention discloses a carbon nano tube composite iron-carbon diimine material and a preparation method and application thereof. In the prepared composite structure, the existence of the network skeleton interwoven by the carbon nano tubes is beneficial to relieving the volume expansion of the material in the charge and discharge processes; in addition, the staggered carbon nano tube conductive network is beneficial to the transmission of ions and electrons, and the conductivity of the material is improved, so that the electrochemical performance of the iron-carbon diimine material is effectively improved. The prepared carbon nano tube composite iron carbodiimide material is applied to a sodium ion battery cathode material, and shows excellent sodium storage performance and rate capability.
Description
Technical Field
The invention belongs to the field of composite material synthesis, and particularly relates to a carbon nano tube composite iron-carbon diimine material, and a preparation method and application thereof.
Background
In recent years, due to the restriction of lithium resources, finding energy storage devices capable of replacing lithium batteries becomes a research hotspot in the field of energy storage. The sodium ion battery has the advantages of rich sodium content in the earth crust, low price, high safety and the like, which are similar to the working principle of the lithium ion battery, so the sodium ion battery is concerned by broad scholars. However, the large ionic radius of sodium ions causes problems of slow kinetics of electrochemical reaction of the electrode, large volume change of materials and the like, so that development of an electrode material which is beneficial to intercalation/deintercalation of sodium ions, strong in stability and high in capacity is very important.
The iron-carbon diimine material is considered as a very potential sodium ion battery cathode material due to the characteristics of low and flat charge-discharge potential platform, high reversible reaction characteristic, large capacity and the like, but the iron-carbon diimine material has complex synthesis steps and high synthesis cost, and the phenomenon of volume expansion exists in the charge-discharge process. If a material can be found to be compounded with the material, the structural stability of the material is improved, the volume expansion generated when sodium ions are embedded and removed is relieved, and the composite material can be prepared by a simpler method, the application of the material in the field of battery electrode materials is expected to be popularized.
Disclosure of Invention
Aiming at the problems of complex synthesis steps, high synthesis cost and easy volume expansion in the charging and discharging processes of the iron carbodiimide material in the related technology, the invention relieves the volume expansion problem of the iron carbodiimide material in the charging and discharging processes by synchronous compounding with the carbon nano tube and enhances the conductivity of the iron carbodiimide material, thereby improving the cycle and rate capability of the battery.
In order to achieve the above object, the present invention provides a method for preparing a carbon nanotube composite iron-carbon diimine material, comprising the following steps:
1) adding carbon nanotubes into 40-60 ml of distilled water and dispersing to obtain a solution A;
2) adding an organic acid iron salt and a carbon-nitrogen-containing organic compound into the solution A, stirring, and adding 0.1-0.25 g of hexadecyl trimethyl ammonium bromide in the stirring process to obtain a solution B, wherein the mass ratio of the organic acid iron salt to the carbon nano tube in the solution B is (60:1) - (15:1), and the mass ratio of the organic acid iron salt to the carbon-nitrogen-containing organic compound is (3:1) - (1: 6);
3) heating the solution B under the action of microwaves for reaction, wherein the microwave power is 500-800W, the reaction temperature is 60-100 ℃, the reaction time is 5-15 min, and collecting a product after the reaction is finished;
4) and calcining the product at the temperature of 400-700 ℃, and keeping the temperature for 30 min-5 h to obtain the carbon nano tube composite iron carbodiimide material.
Preferably, ultrasonic dispersion is adopted for dispersion in the step 1) for 3-10 hours.
Preferably, the organic acid iron salt in step 2) comprises iron formate, iron glycinate or iron isopropoxide.
Preferably, the carbon-nitrogen containing organic compound in step 2) comprises ethylenediamine or propionamide.
Preferably, the rotating speed of stirring in the step 2) is 300-700 r/min, and the stirring time is 5-15 min.
Preferably, the solution B in the step 3) is reacted in a microwave synthesizer, and after the reaction is finished, the product is centrifugally washed and is freeze-dried.
Preferably, the product in step 4) is placed in a quartz or alumina crucible, and the crucible is placed in a tube furnace for calcination.
Preferably, the calcination in the step 4) is carried out in an argon atmosphere, and the temperature is uniformly increased at a temperature increasing rate of 5-35 ℃/min.
The invention also provides a carbon nano tube composite iron-carbon diimine material prepared by the preparation method of the carbon nano tube composite iron-carbon diimine material.
The invention also provides an application of the carbon nano tube composite iron-carbon diimine material as a negative electrode material of a sodium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention takes the carbon nitrogen-containing organic compound, the organic acid ferric salt and the carbon nano tube as raw materials to prepare the carbon nano tube composite iron carbodiimide material, and has the advantages of easily obtained raw materials, low cost, simple preparation method and strong repeatability.
2) The invention adopts the microwave synthesis method to prepare the precursor of the carbon nano tube composite iron carbodiimide material, has high heating speed, greatly shortens the synthesis time, has high heat energy utilization rate, saves energy and is pollution-free.
3) In the invention, the iron-carbon diimine material and the carbon nanotube material are synchronously compounded, so that the electrochemical performance of the iron-carbon diimine is effectively improved. In the composite structure, the existence of the network skeleton interwoven by the carbon nano tubes is beneficial to relieving the volume expansion of the material in the charge and discharge processes; in addition, the staggered carbon nano tube conductive network is beneficial to the transmission of ions and electrons, and the conductivity of the material is improved. The prepared composite material is applied to a sodium ion battery cathode material, and shows excellent sodium storage performance and rate capability.
Drawings
FIG. 1 is an XRD pattern of a carbon nanotube composite iron carbodiimide material prepared by the invention;
FIG. 2 is an SEM image of a carbon nanotube composite iron carbodiimide material prepared by the invention;
FIG. 3 is a diagram of the electrochemical performance of the carbon nanotube composite iron carbodiimide material prepared by the invention.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a preparation method of a carbon nano tube composite iron-carbon diimine material, which specifically comprises the following steps:
1) weighing a certain mass of carbon nanotubes, adding the carbon nanotubes into a beaker filled with 40-60 ml of distilled water, and carrying out ultrasonic treatment for 3-10 hours to uniformly disperse the carbon nanotubes into the solution;
2) adding certain mass of analytically pure organic acid ferric salt and carbon-nitrogen-containing organic compounds into the solution, wherein the organic acid ferric salt comprises ferric formate, ferric glycinate, ferric isopropoxide and the like, the carbon-nitrogen-containing organic compounds comprise ethylenediamine, propionamide and the like, the mass ratio of the organic acid ferric salt to the carbon nano tubes in the mixed solution is (60:1) - (15:1), the mass ratio of the organic acid ferric salt to the carbon-nitrogen-containing organic compounds is (3:1) - (1:6), stirring the mixed solution on a stirrer at the rotating speed of 300-700 r/min for 5-15 min, and adding 0.1-0.25 g of Cetyl Trimethyl Ammonium Bromide (CTAB) in the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to be 500-800W, adjusting the reaction temperature to be 60-100 ℃, heating and reacting for 5-15 min under the action of the microwave, after the reaction is finished, centrifugally washing the product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, uniformly heating to 400-700 ℃ at a heating rate of 5-35 ℃/min under the argon atmosphere, and preserving heat for 30 min-5 h to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
The invention also provides the carbon nano tube composite iron carbodiimide material prepared by the preparation method, and the iron carbodiimide material and the carbon nano tube material are synchronously compounded, so that the electrochemical performance of the iron carbodiimide is effectively improved. In the composite structure, the existence of the network skeleton interwoven by the carbon nano tubes is beneficial to relieving the volume expansion of the material in the charge and discharge processes; in addition, the staggered carbon nano tube conductive network is beneficial to the transmission of ions and electrons, and the conductivity of the material is improved. The carbon nanotube composite iron carbodiimide material is applied to the negative electrode material of the sodium ion battery, and shows excellent sodium storage performance and rate capability.
The present invention will be described with reference to specific examples.
Example 1:
1) weighing 0.12g of carbon nano tube, adding the carbon nano tube into a beaker filled with 60ml of distilled water, and carrying out ultrasonic treatment for 8 hours to uniformly disperse the carbon nano tube into the solution;
2) adding 3.0g of ferric glycinate and 2.0g of ethylenediamine into the solution, stirring the mixed solution on a stirrer for 10min at the rotating speed of 500r/min, and adding 0.15g of CTAB during the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to 600W, controlling the reaction temperature to 80 ℃, heating and reacting for 10min under the action of microwave, after the reaction is finished, centrifugally washing the product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, heating to 550 ℃ at a constant speed at a heating rate of 5 ℃/min under the argon atmosphere, and preserving heat for 1h to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
The product obtained in example 1 was analyzed by means of a Japanese science D/max2000 PCX-ray diffractometer, and FIG. 1 is an XRD pattern of the obtained product, which confirmed that the obtained product was FeNCN.
Observing the obtained product under a scanning electron microscope, wherein the SEM atlas of the product is shown in figure 2, and the product is in a shell-shaped structure, the surface of the structure has more polyhedral structures, and carbon nanotubes are interwoven inside a carbon layer.
Preparing the obtained product into a button type sodium ion battery, and specifically packaging the button type sodium ion battery by the following steps: grinding active powder, a conductive agent (Super P) and an adhesive (carboxymethyl cellulose CMC) uniformly 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 sodium ion half-cell, performing constant-current charge-discharge test on the cell by adopting a Xinwei electrochemical workstation, testing the voltage at 0.01V-3.0V, assembling the obtained material into a button cell, and testing the performance of the sodium ion cell cathode material of the button cell, wherein the cell shows the capacity of 530mAh/g under the current density of 100mA/g as shown in figure 3, so that the material has excellent sodium storage performance and the cycle and rate performance of the cell.
Example 2:
1) weighing 0.1g of carbon nano tube, adding the carbon nano tube into a beaker filled with 50ml of distilled water, and carrying out ultrasonic treatment for 6 hours to uniformly disperse the carbon nano tube into the solution;
2) adding 3.0g of ferric formate and 1.0g of propionamide into the solution, stirring the mixed solution on a stirrer for 8min at the rotation speed of 700r/min, and adding 0.12g of CTAB during the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to 800W, controlling the reaction temperature to 90 ℃, heating and reacting for 15min under the action of microwave, after the reaction is finished, centrifugally washing the product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, heating to 650 ℃ at a constant speed at a heating rate of 10 ℃/min under the argon atmosphere, and preserving heat for 2h to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
Example 3:
1) weighing 0.05g of carbon nano tube, adding the carbon nano tube into a beaker filled with 45ml of distilled water, and carrying out ultrasonic treatment for 4 hours to uniformly disperse the carbon nano tube into the solution;
2) adding 2.0g of ferric isopropoxide and 2.0g of ethylenediamine into the solution, stirring the mixed solution on a stirrer for 12min at the rotating speed of 400r/min, and adding 0.1g of CTAB in the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to 500W, controlling the reaction temperature to 70 ℃, heating and reacting for 8min under the action of microwave, after the reaction is finished, centrifugally washing the product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, heating to 400 ℃ at a constant speed at a heating rate of 20 ℃/min under the argon atmosphere, and preserving heat for 4 hours to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
Example 4:
1) weighing a certain mass of carbon nanotubes, adding the carbon nanotubes into a beaker filled with 40ml of distilled water, and carrying out ultrasonic treatment for 3 hours to uniformly disperse the carbon nanotubes into the solution;
2) adding a certain mass of analytically pure iron formate and propionamide into the solution, wherein the mass ratio of the iron formate to the carbon nano tubes in the mixed solution is 60:1, the mass ratio of the iron formate to the propionamide is 3:1, stirring the mixed solution on a stirrer for 15min at the rotating speed of 300r/min, and adding 0.1g of Cetyl Trimethyl Ammonium Bromide (CTAB) in the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to 500W, controlling the reaction temperature to be 60 ℃, heating and reacting for 5min under the action of microwave, after the reaction is finished, centrifugally washing a product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, uniformly heating to 400 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, and preserving heat for 30min to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
Example 5:
1) weighing a certain mass of carbon nanotubes, adding the carbon nanotubes into a beaker filled with 60ml of distilled water, and carrying out ultrasonic treatment for 10 hours to uniformly disperse the carbon nanotubes into the solution;
2) adding a certain mass of analytically pure ferric oxide and propionamide into the solution, wherein the mass ratio of the ferric oxide to the carbon nano tubes in the mixed solution is 15:1, the mass ratio of the ferric oxide to the propionamide is 1:6, stirring the mixed solution on a stirrer for 5min at the rotation speed of 700r/min, and adding 0.25g of Cetyl Trimethyl Ammonium Bromide (CTAB) in the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwave to 800W, controlling the reaction temperature to be 100 ℃, heating and reacting for 15min under the action of microwave, after the reaction is finished, centrifugally washing a product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, heating to 700 ℃ at a constant speed at a heating rate of 35 ℃/min under the argon atmosphere, and preserving heat for 5 hours to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
Example 6:
1) weighing a certain mass of carbon nanotubes, adding the carbon nanotubes into a beaker filled with 50ml of distilled water, and carrying out ultrasonic treatment for 6 hours to uniformly disperse the carbon nanotubes into the solution;
2) adding a certain mass of analytically pure ferric glycinate and ethylenediamine into the solution, wherein the mass ratio of the ferric glycinate to the carbon nano tubes in the mixed solution is 40:1, the mass ratio of the ferric glycinate to the ethylenediamine is 1:2, stirring the mixed solution on a stirrer for 10min at the rotation speed of 500r/min, and adding 0.2g of Cetyl Trimethyl Ammonium Bromide (CTAB) in the stirring process;
3) transferring the uniformly mixed solution into a three-neck flask, putting the three-neck flask into a microwave synthesizer, adjusting the power of microwaves to 650W, controlling the reaction temperature to 85 ℃, heating and reacting for 10min under the action of microwaves, after the reaction is finished, centrifugally washing a product, and freeze-drying the product;
4) and (3) placing the sample after freeze drying in a quartz or alumina crucible, placing the crucible in a tube furnace, uniformly heating to 600 ℃ at a heating rate of 20 ℃/min in an argon atmosphere, and preserving heat for 3h to obtain the product, namely the carbon nano tube composite iron carbodiimide material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a carbon nano tube composite iron-carbon diimine material is characterized by comprising the following steps:
1) adding carbon nanotubes into 40-60 ml of distilled water and dispersing to obtain a solution A;
2) adding an organic acid iron salt and a carbon-nitrogen-containing organic compound into the solution A, stirring, and adding 0.1-0.25 g of hexadecyl trimethyl ammonium bromide in the stirring process to obtain a solution B, wherein the mass ratio of the organic acid iron salt to the carbon nano tube in the solution B is (60:1) - (15:1), and the mass ratio of the organic acid iron salt to the carbon-nitrogen-containing organic compound is (3:1) - (1: 6);
3) heating the solution B under the action of microwaves for reaction, wherein the microwave power is 500-800W, the reaction temperature is 60-100 ℃, the reaction time is 5-15 min, and collecting a product after the reaction is finished;
4) and calcining the product at the temperature of 400-700 ℃, and keeping the temperature for 30 min-5 h to obtain the carbon nano tube composite iron carbodiimide material.
2. The method for preparing the carbon nanotube composite iron-carbon diimine material of claim 1, wherein the dispersion in the step 1) is carried out by ultrasonic dispersion for 3-10 hours.
3. The method of claim 1, wherein the organic acid iron salt in step 2) comprises iron formate, iron glycinate or iron isopropoxide.
4. The method for preparing a carbon nanotube composite iron-carbon diimine material of claim 1, wherein the carbon-nitrogen containing organic compound in step 2) comprises ethylenediamine or propionamide.
5. The method for preparing the carbon nanotube composite iron-carbon diimine material of claim 1, wherein the stirring speed in the step 2) is 300-700 r/min, and the stirring time is 5-15 min.
6. The method for preparing the carbon nanotube composite iron-carbon diimine material of claim 1, wherein the solution B in the step 3) is reacted in a microwave synthesizer, and after the reaction is finished, the product is centrifugally washed and freeze-dried.
7. The method for preparing the carbon nano tube composite iron-carbon diimine material of claim 1, wherein the product of the step 4) is placed in a quartz or alumina crucible, and the crucible is placed in a tube furnace for calcination.
8. The method for preparing the carbon nanotube composite iron-carbon diimine material of claim 7, wherein in the step 4), the calcination is carried out in an argon atmosphere, and the temperature is raised at a constant speed at a rate of 5-35 ℃/min.
9. A carbon nanotube composite iron-carbon carbodiimide material, which is prepared by the method for preparing the carbon nanotube composite iron-carbon carbodiimide material according to any one of claims 1 to 8.
10. Use of the carbon nanotube composite iron carbodiimide material as defined in claim 9 as a negative electrode material for sodium ion batteries.
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