CN114229832A - Preparation method of carbon-nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material and lithium ion battery cathode material thereof - Google Patents
Preparation method of carbon-nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material and lithium ion battery cathode material thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 7
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- 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
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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
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Abstract
The invention relates to a preparation method of a carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide nano cube material and a lithium ion battery cathode material thereof in the technical field of lithium ion battery materials, wherein cobalt nitrate hexahydrate is used as a cobalt source, 2-methylimidazole is used as a carbon source and a nitrogen source, deionized water is used as a solvent, the reaction is carried out at room temperature, after the reaction is finished, the reaction is centrifugally washed and dried in a vacuum drying box to obtain a ZIF-67 cube, then the high-temperature calcination is carried out under the protection of argon to prepare a Co @ NC-CNT nano material cube precursor, and finally, sodium hypophosphite is used as a phosphorus source, and the phosphorization is carried out under the protection of argon to prepare the carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP @ NC-CNT) nano cube material. The prepared (CoP @ NC-CNT) nano cubic material is used as the lithium ion battery cathode material, and has the cycling stability and the rate capability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material and a method for manufacturing a lithium ion battery by using the same.
Background
Lithium ion batteries have now found widespread use in human production as an extremely important energy storage year. The development of electrode materials for lithium ion batteries has attracted a great deal of attention from researchers. In the traditional lithium ion battery, graphite with low cost and high conductivity is generally adopted as a negative electrode material, and the specific capacity can reach 372 mAh.g-1. However, the development of carbon negative electrode materials is limited by their own low lithium storage capacity, and therefore, research on negative electrode materials with higher specific capacities is receiving great attention from researchers.
In recent years, the widespread use of metal organic framework Materials (MOFs) in various fields has attracted the attention of battery researchers. The material is obtained by self-assembly of metal ions and organic ligands, and becomes a lithium ion battery cathode material with great development prospect by virtue of the advantages of a three-dimensional porous structure, flexibly adjustable pore channel size, larger specific surface area and the like. The larger specific surface area can effectively increase the contact area with the electrolyte, and the controllable porous structure also enables Li+Is easier to be embedded and extracted in the electrode material, thereby improving the electrochemical performance of the electrode material. However, MOFs have the defects of poor conductivity, low electron transfer rate in the charging and discharging process, low coulombic efficiency of the first charging and discharging due to high specific surface area, reduced volume energy density of the material and the like, and the large-scale application of MOFs as LIBs negative electrode materials is seriously hindered. To address these deficiencies, researchers have made extensive research efforts on MOF material modification. For example, MOFs can be converted into carbon materials, metal composite materials, carbon/metal composite materials, and other MOF-derived materials by heat treatment using the MOFs as sacrificial templates. At the same time, metal phosphides are subject to considerable disadvantages due to their higher theoretical capacity and low polarizationHowever, the conductivity is low, and the volume expansion is easy to cause the rapid capacity decay during the charge and discharge of the lithium ion battery. Are generally not considered interesting and less studied in the application of MOF derived materials.
Disclosure of Invention
The invention provides a preparation method of a carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material aiming at the requirement that the electrochemical performance of a lithium ion battery cathode material in the prior art needs to be further improved, and the prepared material is used as the cycling stability and the rate capability of the lithium ion battery cathode material.
The invention aims to realize the purpose, and provides a preparation method of a carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material, which comprises the steps of taking cobalt nitrate hexahydrate as a cobalt source, 2-methylimidazole as a carbon source and a nitrogen source, taking deionized water as a solvent, reacting at room temperature, centrifugally washing after the reaction is finished, drying in a vacuum drying box to obtain a ZIF-67 cube, calcining at high temperature under the protection of argon gas to prepare a Co @ NC-CNT nano material cube precursor, and finally carrying out phosphorization under the protection of argon gas by taking sodium hypophosphite as a phosphorus source to prepare the carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP @ NC-CNT) nanocube material.
Further, the mass ratio of the cobalt nitrate hexahydrate, the 2-methylimidazole and the deionized water is as follows: 1, (15-16) and 34.
Further, the ZIF-67 cube was prepared by the following steps: firstly, dispersing cobalt nitrate hexahydrate and Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water to form a solution A with the concentration of 0.1mg/ml, then dispersing 2-methylimidazole in the deionized water to form a solution B with the concentration of 0.8mg/ml, mixing and stirring A, B solutions according to the volume ratio of 1 (6-8) for 20 min, centrifuging, washing, drying and collecting a product after the reaction is finished, and thus obtaining a ZIF-67 cube.
Further, the Co @ NC-CNT nanocube precursor was prepared by the following steps: and (3) placing the prepared ZIF-67 cube in a porcelain boat, heating to 500-600 ℃ at a heating rate of 2 ℃/min in a vacuum tube furnace under the protection of argon, preserving heat for 2-5 h, and naturally cooling to room temperature in the furnace.
Further, the specific preparation steps of the CoP @ NC-CNT nanocube material are as follows: placing the Co @ NC-CNT nanocube precursor into a ceramic boat, weighing sodium hypophosphite with the mass ratio of (4-6): 1 to the Co @ NC-CNT nanocube precursor into another ceramic boat, and then carrying out phosphorization under the protection of argon to prepare the carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP @ NC-CNT) nanocube material.
Compared with the prior art, the CoP @ NC-CNT nanocube material used as the lithium ion battery cathode material has the following advantages:
(1) the porous structure of the CoP @ NC-CNT nanocube material prepared by taking the ZIF-67 cube as a precursor not only relieves the volume effect of the electrode material in the charging and discharging process, but also shortens the transmission path of electrons and ions, greatly accelerates the migration rate of lithium ions, and enhances the electrode reaction kinetics process;
(2) the nitrogen-doped carbon material prepared by using 2-methylimidazole as a nitrogen source can further reduce volume change and form a favorable conductive framework, so that the overall structural stability of the composite material is improved;
(3) in the process of high-temperature carbonization of a CoP @ NC-CNT nanocube material prepared by using cobalt nitrate as a cobalt source, under the catalytic action of cobalt element, carbon element grows outwards to form a carbon nanotube structure, the derived carbon nanotubes have superconductivity, three-dimensional uneven pores among the mutually connected carbon nanotubes can shorten an ion diffusion path, provide huge free space and facilitate the transmission of electrolyte and charges;
(4) sodium hypophosphite is used as a phosphorus source to prepare the CoP @ NC-CNT nano cubic material, and the metal phosphide and the carbon material are compounded to enhance the conductivity and buffer the volume expansion in the charge-discharge process, so that the electrochemical performance is improved.
The invention also aims to provide a lithium ion battery cathode material prepared from the CoP @ NC-CNT nanocube material, which comprises the CoP @ NC-CNT nanocube material prepared by the method with the mass ratio of 7:2:1, an acetylene black conductive agent and a PVDF binder.
Drawings
FIG. 1 is a scanning electron micrograph of a ZIF-67 cube (FIG. 1 a), CoP @ NC-CNT nanocube material (FIG. 1b) prepared in example 1.
FIG. 2 is a transmission electron micrograph of a ZIF-67 cube (FIG. 2 a), CoP @ NC-CNT nanocube material (FIG. 2b) prepared in example 1.
FIG. 3 is the EDS mapping (FIGS. 3 a-e) and selected area electron diffraction patterns (FIG. 3 f) of the CoP @ NC-CNT nanocube material prepared in example 1.
FIG. 4 is a graph comparing the rate performance of the battery negative electrode of example 2 with ZIF-67 cubic and CoP @ NC-CNT nanocubes as materials at different current densities.
FIG. 5 shows the negative electrode of the battery in example 2 made of the ZIF-67 cubic and CoP @ NC-CNT nanocubes-1Graph comparing the cycling performance of 100 cycles at current density.
Detailed Description
In order to better illustrate the technical process and the object of the present invention, the experimental process of the present invention is further described below with reference to specific examples.
Example 1
ZIF-67 cube, Co @ NC-CNT nanocube, and CoP @ NC-CNT nanocube materials were prepared.
(1) Preparation of ZIF-67 cubes:
firstly, weighing 58 mg of cobalt nitrate hexahydrate and 1mg of cetyltrimethylammonium bromide (CTAB) and dissolving the cobalt nitrate hexahydrate and the 1mg of cetyltrimethylammonium bromide (CTAB) in 2 mL of deionized water to form a solution A; and then weighing 908 mg of 2-methylimidazole, dissolving in 14 mL of deionized water to form a solution B, quickly adding the solution A into the solution B at room temperature, magnetically stirring for 20 min, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol and deionized water, and drying the purple sample in a vacuum oven at 60 ℃ overnight to obtain the ZIF-67 cube.
(2) Preparation of Co @ NC-CNT nanocubes:
and (3) placing the prepared ZIF-67 cube in a porcelain boat, placing the porcelain boat in a vacuum tube furnace, calcining the porcelain boat under the protection of argon, heating to 550 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain the Co @ NC-CNT nanocube material.
(3) Preparation of carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP) @ NC-CNT nanocube material:
placing the prepared Co @ NC-CNT nanocube material into a ceramic boat, weighing sodium hypophosphite in a mass ratio of 1:5 into another ceramic boat, placing the two ceramic boats into a vacuum tube furnace, heating to 350 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 h to prepare the carbon-nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP) @ NC-CNT nanocube material.
FIG. 1 is a scanning electron micrograph of a ZIF-67 cube (FIG. 1 a) and a CoP @ NC-CNT nanocube material (FIG. 1b) prepared in this example. As is clear from FIG. 1(a), the ZIF-67 precursor is a cubic structure, uniformly dispersed and smooth on the surface, and has a particle size of about 400 nm. FIG. 1(b) is an SEM image of a CoP @ NC-CNT nanocube material, the SEM result shows that the CoP @ NC-CNT nanocube material obtained through calcination and phosphating retains the form of a ZIF-67 cube and has a rough surface, and the carbon element grows outwards to form a carbon nanotube under the catalytic action of the cobalt element in the high-temperature carbonization process of the CoP @ NC-CNT nanocube material.
FIG. 2(a) Transmission Electron microscopy of ZIF-67 cubes prepared in this example. The morphology of the ZIF-67 cube is clearly observed in FIG. 2(a), which has a smooth surface with an average size of about 400 nm. FIG. 2(b) is a CoP @ NC-CNT nanocube material, and the CoP @ NC-CNT nanocube material obtained after phosphorization still retains the original size and cubic structure of the ZIF-67 precursor, except that Co particles in the CoP @ NC-CNT nanocube material can be seen to be well confined in the carbon skeleton.
FIG. 3 is an EDS mapping chart and a selected area electron diffraction chart of the CoP @ NC-CNT nanocube material prepared in this example. The distribution of elements in the CoP @ NC-CNT nanocubes was determined by energy dispersive X-ray spectroscopy (EDS) mapping measurements. The electron diffraction patterns of the selected region of fig. 3(b-e) r are green, red, orange and yellow respectively representing four elements of Co, C, P and N, and the distribution of the four elements of Co, C, P and N can be seen to be uniform in the region distribution shown in each picture. FIG. 3(f) shows a Selected Area Electron Diffraction (SAED) plot of CoP @ NC-CNT nanocubes.
Example 2
In the embodiment, the CoP @ NC-CNT nanocube material prepared in the embodiment 1 is used as a negative electrode of a lithium ion battery to assemble the lithium ion battery.
NMP (N-methyl pyrrolidone) is used as a solvent, the prepared CoP @ NC-CNT nanocube material is used as an active substance, acetylene black is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, the mass ratio of the three substances is 7:2:1, slurry is prepared by magnetic stirring for 8 hours, the prepared slurry is uniformly coated on a copper foil by a coating machine, and the temperature is kept at 80 ℃ for 10 hours. After drying, the sheet was cut into electrode pieces by a slicer, and then dried in vacuum at 120 ℃ for 12 hours to remove a small amount of moisture. The electrode slice directly carries out 2032 type button cell assembly as the lithium ion battery negative pole in the glove box that is full of argon gas after weighing, and the assembly order of battery is from last to down respectively: and the obtained button cell is further tested on a charge and discharge tester. The charge and discharge current is calculated according to the mass of the CoP @ NC-CNT nanocubes and 100 mA g-1、200 mA g-1、400 mA g-1、800 mA g-1、1000 mA g-1、2000 mA g-1And 100 mA g-1The prepared button cell is subjected to charge and discharge tests at the current density of 0.01-3V and passing 100 mA g-1Current density of CoP @ NC-CNT nanocubes were tested for 100 cycles to investigate their cycling stability.
Meanwhile, the battery is assembled by using the ZIF-67 cube as a negative electrode material by the same method, and comparative tests of cycle performance and rate performance are carried out under the same test conditions.
FIG. 4 is a multiplying power performance test chart of a battery cathode with cubic ZIF-67 and CoP @ NC-CNT nanocube materials as different current densities, and the voltage interval is 0.01-3.0V. When charging and discharging, the current density is 100 mA g-1、200 mA g-1、400 mA g-1、800 mA g-1、1000 mA g-1、2000 mA g-1Then, its discharge capacity was maintained at 583.66 mAh g, respectively, substantially smoothly-1、460.64 mAh g-1、387.00 mAh g-1334.70 mAh g-1, 314.02 mAh g-1 and 255.27 mAh g-1. When the current density returns to 100 mA g-1Its discharge capacity can smoothly return to 421.76 mAh g-1The CoP @ NC-CNT nanocube material prepared by the method has excellent rate performance and good reversibility.
FIG. 5 is a cycle performance test chart showing that the negative electrodes of the lithium ion battery in this embodiment respectively use ZIF-67 cubic materials and CoP @ NC-CNT nanocubes as materials, and the cycle performance test chart shows that the current density is 100 mA g-1, and the voltage interval is 0.01-3V. As is obvious from FIG. 5, the CoP @ NC-CNT nanocube material has higher specific capacity of the ZIF-67 cube, the capacity is still maintained at 494.68 mAhg < -1 > after 100 cycles, and the capacity of the ZIF-67 cube electrode is only 84.98 mAhg < -1 >. Thus, the CoP @ NC-CNT nanocube material has good cycling stability.
Claims (6)
1. A preparation method of a carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material comprises the steps of taking cobalt nitrate hexahydrate as a cobalt source, 2-methylimidazole as a carbon source and a nitrogen source, taking deionized water as a solvent, reacting at room temperature, centrifugally washing after the reaction is finished, drying in a vacuum drying oven to obtain a ZIF-67 cube, then calcining at high temperature under the protection of argon gas to prepare a Co @ NC-CNT nano material cube precursor, and finally phosphorizing under the protection of argon gas by taking sodium hypophosphite as a phosphorus source to prepare the carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP @ NC-CNT) nanocube material.
2. The method for preparing the carbon nanotube-containing nitrogen-carbon doped cobalt phosphide nanocube material according to claim 1, wherein the mass ratio of the cobalt nitrate hexahydrate, the 2-methylimidazole and the deionized water is as follows: 1, (15-16) and 34.
3. The method for preparing carbon nanotube-containing nitrogen-carbon doped cobalt phosphide nanocube material according to claim 1, wherein the ZIF-67 cube is prepared by the following steps: firstly, dispersing cobalt nitrate hexahydrate and Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water to form a solution A with the concentration of 0.1mg/ml, then dispersing 2-methylimidazole in the deionized water to form a solution B with the concentration of 0.8mg/ml, mixing and stirring A, B solutions according to the volume ratio of 1 (6-8) for 20 min, centrifuging, washing, drying and collecting a product after the reaction is finished, and thus obtaining a ZIF-67 cube.
4. The method of making carbon nanotube-containing nitrogen-carbon doped cobalt phosphide nanocube material of claim 3, wherein the Co @ NC-CNT nanocube precursor is prepared by: and (3) placing the prepared ZIF-67 cube in a porcelain boat, heating to 500-600 ℃ at a heating rate of 2 ℃/min in a vacuum tube furnace under the protection of argon, preserving heat for 2-5 h, and naturally cooling to room temperature in the furnace.
5. The method for preparing the carbon nanotube-containing nitrogen-carbon doped cobalt phosphide nanocube material according to claim 3, wherein the specific preparation steps of the CoP @ NC-CNT nanocube material are as follows: placing the Co @ NC-CNT nanocube precursor into a ceramic boat, weighing sodium hypophosphite with the mass ratio of (4-6): 1 to the Co @ NC-CNT nanocube precursor into another ceramic boat, and then carrying out phosphorization under the protection of argon to prepare the carbon nanotube-containing nitrogen-carbon-doped cobalt phosphide (CoP @ NC-CNT) nanocube material.
6. The lithium ion battery negative electrode material is characterized by comprising the CoP @ NC-CNT nanocube material prepared according to any one of claims 1 to 5 and having a mass ratio of 7:2:1, an acetylene black conductive agent and a PVDF binder.
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