CN111952570A - Cobalt-nitrogen-carbon composite material containing single-atom active site and preparation method and application thereof - Google Patents
Cobalt-nitrogen-carbon composite material containing single-atom active site and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a cobalt nitrogen carbon composite material containing a single atom active site, which comprises the steps of firstly preparing a ZIF-8 crystal; obtaining ZIF-8@ ZIF67 crystal, namely MOFs precursor; then calcining the MOFs precursor at high temperature in an inert atmosphere, and naturally cooling to room temperature; and (3) carrying out acid washing treatment on the cooled substance, then washing the substance to be neutral for multiple times, and finally drying the substance. The preparation method utilizes the advantages of the metal organic framework compound precursor, and obtains the target product only by three steps of preparation, calcination and acid washing of the precursor, and the prepared material has high yield, good stability and strong repeatability, meets the requirements of green chemistry, has short preparation period and low requirements on equipment, and has great application potential. The cobalt nitrogen carbon composite material prepared by the method improves the lithium affinity of the material, shortens the diffusion distance of lithium ions and electrons, buffers the volume change in the circulating process, and further effectively improves the electrochemical performance of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and relates to a cobalt nitrogen carbon composite material containing a single atom active site, and a preparation method and application thereof.
Background
Electrochemical energy storage is widely applied to chargeable and dischargeable electronic equipment, and lithium ion batteries have the characteristics of high energy density, light weight, small volume, long service life and the like and become the current mainstream technology, and meanwhile, the lithium ion batteries with high specific energy tend to be in the field of electric automobiles from electronic terminal equipment, play an important role in intermittent renewable novel energy (such as wind energy, solar energy and the like) storage, and meet the higher requirements on the performance of each aspect of the lithium ion batteries. And the performance improvement of the negative electrode material can obviously improve the capacity, the multiplying power and the cycle performance of the lithium ion battery. The current commercialized lithium ion battery cathode material is graphite, and is limited by low theoretical specific capacity (375mAh/g) and the safety problem caused by lithium dendrite easily generated during heavy current discharge, so that the development requirement of the market on the lithium ion battery with high specific energy and high safety is difficult to meet.
By introducing heteroatom doping such as N, B, S, P, O or the like in the carbon-based material, the lithium storage performance can be improved by providing more active sites and adjusting the electronic structure of the carbon material. Meanwhile, theoretical calculation results show that metal doping, particularly single atom metal doping, is considered to be an effective way for further improving the performance of the carbon-based material, and a metal nitrogen carbon composite material with metal and nitrogen doped simultaneously can be further obtained by adopting a metal organic framework compound (MOFs) precursor with excellent performance, so that the electronic structure of the carbon matrix and the surface interface property of the material can be further adjusted, a hollow framework structure can be formed, the mass transfer process of battery reaction is facilitated, and the volume expansion problem of a cathode material generally can be improved. Most of the lithium ion battery cathode materials prepared by adopting MOFs precursors currently utilize the advantages of a hollow framework structure and nitrogen-doped carbon, the further regulation effect of surface metal doping on a carbon matrix is not considered, and the lithium ion battery cathode materials are less in metal nitrogen-carbon materials containing single-atom active sites. Most MOF derived nitrogen doped carbon based materials require further conversion of the metal to its oxide, sulfide or phosphide for utilization.
Based on the method, the MOFs precursor is adopted, the single-atom cobalt-nitrogen-doped carbon-based lithium ion battery cathode material is prepared by a one-step calcination and acid washing method, the structure and the property of the carbon-based material are adjusted through an atomic-level CoNx active site, and the lithium storage performance of the nitrogen-doped carbon cathode material is improved.
Disclosure of Invention
The invention improves and improves the structure and performance of the nitrogen-doped carbon material by constructing the cobalt-nitrogen-carbon composite material containing the single-atom active site, thereby improving the electrochemical performance of the carbon-based negative electrode material, including the lithium affinity, the conductivity and the mass transfer performance of the material, and the specific capacity, the cycling stability and the rate capability of the lithium ion battery.
The invention adopts the following technical scheme:
a preparation method of a cobalt nitrogen carbon composite material containing a single-atom active site comprises the following specific steps:
the method comprises the following steps: dissolving metal nitrate hydrate in methanol to prepare a solution A, dissolving dimethyl imidazole in methanol to prepare a solution B, pouring the solution A into the solution B, stirring at room temperature for reaction, performing centrifugal separation on a product obtained by the reaction, washing with methanol for multiple times to remove residual reactants, and drying to obtain a ZIF-8 crystal;
in the step, the concentration of the metal nitrate is 0.02-0.10M, and the molar ratio of the metal nitrate to the dimethyl imidazole (namely the metal ions and the ligands) is 1:4-1: 8; stirring and reacting for 4-24 h; the rotation speed of centrifugal separation is 8000-10000 rpm; the drying temperature is 60-80 ℃;
step two: dissolving the ZIF-8 crystal obtained in the step one in methanol to prepare a solution C, dissolving a cobalt nitrate hydrate in methanol to prepare a solution D, dissolving dimethyl imidazole in methanol to prepare a solution E, quickly pouring the solution D into the solution C, mixing, adding the solution D into the solution E together, stirring at room temperature for reaction, performing centrifugal separation on a product obtained by the reaction, washing with methanol for multiple times to remove residual reactants, and drying to obtain a ZIF-8@ ZIF67 crystal, namely an MOFs precursor;
in the step, the concentration of the cobalt nitrate is 0.02-0.10M, and the molar ratio of the cobalt nitrate to the dimethyl imidazole (namely the metal ions and the ligands) is 1:4-1: 8; stirring and reacting for 4-24 h; the rotation speed of centrifugal separation is 8000-10000 rpm; the drying temperature is 60-80 ℃;
step three: calcining the MOFs precursor obtained in the step two at high temperature in an inert atmosphere, and naturally cooling to room temperature; performing acid washing treatment on the cooled substance, then washing the substance to be neutral for multiple times, and finally drying the substance to obtain the cobalt-nitrogen-carbon composite material containing the monoatomic active site;
in the step, the calcination temperature is 800-; the drying temperature is 60-80 ℃.
Further, in the third step, the cooled substance is subjected to acid washing treatment by adopting a hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 2-4M, and the acid washing time is 12-48 h.
Further, in the third step, deionized water is adopted for washing.
The preparation method provided by the invention utilizes the advantages of the metal organic framework compound precursor, and obtains the target product only by three steps of preparation, calcination and acid washing of the precursor, and the prepared material has high yield, good stability and strong repeatability, and provides a choice for exploring a lithium ion battery cathode material with high rate characteristic and excellent large-scale synthesis performance. The invention only adopts a simple epitaxial growth method and a calcining and pickling method, has simple process, meets the requirements of green chemistry, has short manufacturing period and low requirements on equipment, and has great application potential.
The invention provides the cobalt-nitrogen-carbon composite material containing more active sites by adopting the preparation method, improves the lithium affinity of the material, shortens the diffusion distance of lithium ions and electrons, buffers the volume change in the circulating process, and further effectively improves the electrochemical performance of the material.
When the cobalt-nitrogen-carbon composite material containing the monoatomic active site prepared by the method is used as a lithium ion battery cathode material, the test is carried out under the current density of 500mA/g, the first discharge specific capacity can reach 602mAh/g, the discharge specific capacity can still reach 443.4mAh/g after the cycle of 463 times, and the excellent cycle performance is shown; the result of constant current discharge test under the large current density of 2000mA/g shows that the first discharge specific capacity can reach 555.3mAh/g, the discharge specific capacity can still be kept at 177.7mAh/g after 500 times of circulation, and the high-power-density high-power-consumption high-power-; in the rate performance test of different current densities from small to large, the material has good capacity retention rate under different current densities in a circulating manner, and the test result shows that the cobalt-nitrogen-carbon composite material containing the single-atom active sites has excellent high capacity and high rate characteristics and is a potential application material of a lithium ion battery with high energy density and high power density.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understandable, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
Fig. 1 is an SEM image of a cobalt nitrogen carbon composite containing a single atom active site.
Figure 2 is an XRD pattern of a cobalt nitrogen carbon composite containing monatomic active sites.
Fig. 3 is a TEM image of a cobalt nitrogen carbon composite containing a single atom active site.
Fig. 4 is an AC-STEM diagram of a cobalt nitrogen carbon composite containing a single atom active site.
Figure 5 is an XPS spectrum of a cobalt nitrogen carbon composite containing a single atom active site.
FIG. 6 is a cycle performance curve of a lithium ion battery with a cobalt nitrogen carbon composite material containing a single atom active site as a negative electrode at a low current density of 0.5A/g.
FIG. 7 is a cycle performance curve of a lithium ion battery with a cobalt nitrogen carbon composite material containing a single atom active site as a negative electrode under a large current density of 2A/g.
Fig. 8 is a rate performance curve of a lithium ion battery using a cobalt nitrogen carbon composite material containing a single atom active site as a negative electrode.
Fig. 9 is a cycle performance curve of a lithium ion battery with the nitrogen-doped carbon composite material as the negative electrode under a large current density of 2A/g.
Fig. 10 is a rate performance curve of a lithium ion battery with a nitrogen-doped carbon composite as the negative electrode.
Detailed Description
Example 1
The preparation method of the cobalt nitrogen carbon composite material containing the monatomic active site comprises the following steps:
1) 5.95g of Zn (NO)3)2·6H2Dissolving O in 150mL of methanol to prepare a solution A, and dissolving 6.16g of 2-methylimidazole in 150mL of methanol to prepare a solution B; mixing the solution A and the solution B at room temperature, stirring and reacting for 24h, centrifuging the product obtained by the reaction at 8000rpm for 5min, washing with methanol for 5 times, and then vacuum-drying at 70 ℃;
2) fully dissolving the ZIF-8 nanocrystal (0.747g) obtained in the step 1) in 150mL of methanol, and carrying out ultrasonic treatment for 5min to mark the solution as solution C; then 8.75g Co (NO)3)2·6H2Dissolving O in 200mL of methanol, and performing ultrasonic treatment for 5min to mark as a solution D; dissolving 9.23g of 2-methylimidazole in 50mL of methanol, and marking as a solution E; then quickly pouring the solution D into the solution C, adding the obtained mixed solution into the solution E, and stirring and reacting for 24 hours at room temperature; the mixture obtained by the reaction was centrifuged at 8000rpm for 5min and washed with methanol several times,drying at 70 ℃, and collecting the obtained ZIF-8@ ZIF-67 crystal, namely an MOFs precursor;
3) putting the MOFs precursor obtained in the step 2) into a tube furnace, heating to 850 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment on the precursor in flowing N2Keeping for 2h, and naturally cooling to room temperature; washing the black powder obtained from cooling in 2M HCl solution at room temperature for 24h to remove excess Co species and nanoparticles; and finally, washing the product to be neutral by using deionized water, and drying at 70 ℃ to obtain the cobalt-nitrogen-carbon composite material containing the monoatomic active sites.
SEM test was performed using a FEI Quanta FEG model 250 scanning electron microscope from Philips, Netherlands. A powdery or massive material sample is coated on a black conductive adhesive and then subjected to gold spraying treatment, and an SEM can be used for representing the surface appearance and the size of the sample. XRD test was performed using X-ray diffractometer model D/max-gamma. beta. manufactured by Japan science and electric machines corporation to analyze the composition and structure of the sample. Referring to fig. 1, SEM analysis shows that: the cobalt-nitrogen-carbon composite material keeps the polyhedral structure of MOFs, is beneficial to the mass transfer process of battery reaction, and can improve the electron transmission on the surface of the material due to the winding of the short carbon nano tube on the surface. Referring to fig. 2, XRD analysis shows that: cobalt nanoparticles and graphitized carbon exist in the material as main components. Referring to fig. 3, TEM analysis shows: the material is in a hollow structure, the cobalt nanoparticles are uniformly distributed on the surfaces of multiple surfaces and in the cavity, the hollow structure is favorable for relieving the volume expansion problem commonly existing in the negative electrode of the lithium battery, and the uniform distribution of the nanoparticles is favorable for charge transmission and substance transmission of the battery material. Referring to FIG. 4, AC-STEM analysis shows that: the thin carbon layer of the material contains an atomic level distribution of active sites, and referring to fig. 5, XPS analysis further confirmed that: the active site is CoNx, and the active site of the single atom is proved to have strong catalytic action and lithium affinity, can participate and adjust the lithium storage process of the cathode material, and improves the capacity and rate capability of the battery by adjusting the electronic structure and surface interface property of the carbon-based material.
Grinding the prepared cobalt nitrogen carbon composite material containing the monoatomic active site into powderFinally, the cell performance of the lithium ion cell negative electrode was measured using a CR2025 coin cell test material. A working electrode was first prepared by mixing 70 wt% of active material, 5 wt% of polymer binder (CMC, 3%) and 25 wt% of conductive material (super-P-Li), and then the slurry was coated on a copper foil and dried at 60 ℃ for 24 h. The cells were assembled in a glove box using a Cellgard2300 microporous polypropylene member separator and a Li wafer counter electrode, using a 1:1(w/w) mixture of EC and DMC containing 1M LiPF6 as the electrolyte, and a voltage window of 0.01-3V (vs. Li in Wuhan, CT 2001A) on a LANHE cell test system (CT2001A, China)+/Li) battery charge/discharge tests were performed. FIG. 6 shows that when the cobalt-nitrogen-carbon composite material is used as a lithium ion battery cathode material and is tested under a low current density of 500mA/g, the first discharge specific capacity can reach 602mAh/g, and the discharge specific capacity can still reach 443.4mAh/g after 463 cycles, so that excellent cycle performance is shown. FIG. 7 shows that when the cobalt-nitrogen-carbon composite material is used as a lithium ion battery cathode material and is subjected to constant current discharge test at a large current density of 2000mA/g, the first discharge specific capacity can reach 555.3mAh/g, the discharge specific capacity can still be kept at 177.7mAh/g after 500 times of circulation, and the cobalt-nitrogen-carbon composite material has stable circulation performance at the large current density. FIG. 8 shows that in the rate performance test under different current densities from small to large, the cobalt-nitrogen-carbon composite material has good capacity retention rate under different current densities in circulation. The result shows that the cobalt-nitrogen-carbon composite material containing the single-atom active site has excellent high-capacity and high-rate characteristics, and is a potential application material of a lithium ion battery with high energy density and high power density.
Example 2
The preparation method of the nitrogen-doped carbon composite lithium ion battery cathode material comprises the following steps:
1) 5.95g of Zn (NO)3)2·6H2Dissolving O in 150mL of methanol, pouring the prepared solution into 150mL of methanol solution containing 6.16g of 2-methylimidazole, mixing and stirring at room temperature for reaction for 24h, centrifuging the product obtained by the reaction for 5min at 8000rpm, washing with methanol for 5 times, and then vacuum-drying at 70 ℃;
2) step 1) The resulting product was placed in a tube furnace and heated to 850 ℃ at a ramp rate of 2 ℃/min and under flowing N2And keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain a product, namely the nitrogen-doped carbon composite lithium ion battery cathode material (serving as a comparison material).
The electrochemical performance test method consistent with example 1 was used. As is clear from fig. 9 and 10, the material in this example has significantly poorer rate capability and long cycle stability at different current densities than the material in example 1.
The above description is only for the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the scope of the present invention, which is disclosed by the present invention, and the equivalent or change thereof belongs to the protection scope of the present invention.
Claims (5)
1. A preparation method of a cobalt nitrogen carbon composite material containing a single-atom active site is characterized by comprising the following specific steps:
the method comprises the following steps: dissolving metal nitrate hydrate in methanol to prepare a solution A, dissolving dimethyl imidazole in methanol to prepare a solution B, pouring the solution A into the solution B, stirring at room temperature for reaction, performing centrifugal separation on a product obtained by the reaction, washing with methanol for multiple times, and drying to obtain a ZIF-8 crystal;
in the step, the concentration of the metal nitrate is 0.02-0.10M, and the molar ratio of the metal nitrate to the dimethyl imidazole is 1:4-1: 8; stirring and reacting for 4-24 h; the rotation speed of centrifugal separation is 8000-10000 rpm; the drying temperature is 60-80 ℃;
step two: dissolving the ZIF-8 crystal obtained in the step one in methanol to prepare a solution C, dissolving a cobalt nitrate hydrate in methanol to prepare a solution D, dissolving dimethyl imidazole in methanol to prepare a solution E, quickly pouring the solution D into the solution C, mixing, adding the solution D into the solution E together, stirring at room temperature for reaction, performing centrifugal separation on a product obtained by the reaction, washing with methanol for multiple times, and drying to obtain a ZIF-8@ ZIF67 crystal, namely an MOFs precursor;
in the step, the concentration of the cobalt nitrate is 0.02-0.10M, and the molar ratio of the cobalt nitrate to the dimethyl imidazole is 1:4-1: 8; stirring and reacting for 4-24 h; the rotation speed of centrifugal separation is 8000-10000 rpm; the drying temperature is 60-80 ℃;
step three: calcining the MOFs precursor obtained in the step two at high temperature in an inert atmosphere, and naturally cooling to room temperature; performing acid washing treatment on the cooled substance, then washing the substance to be neutral for multiple times, and finally drying the substance to obtain the cobalt-nitrogen-carbon composite material containing the monoatomic active site;
in the step, the calcination temperature is 800-; the drying temperature is 60-80 ℃.
2. The method for preparing the cobalt nitrogen carbon composite material containing the monoatomic active site according to claim 1, wherein in the third step, the cooled substance is subjected to acid washing treatment by using a hydrochloric acid solution, the concentration of the hydrochloric acid solution is 2-4M, and the acid washing time is 12-48 h.
3. The method for preparing the cobalt nitrogen carbon composite material containing the monoatomic active site according to claim 1, wherein in the third step, deionized water is used for washing.
4. The cobalt nitrogen carbon composite material containing the single atom active site prepared by the method of any one of claims 1 to 3.
5. Use of the monatomic active site-containing cobalt nitrogen carbon composite material of claim 4 as a negative electrode material for lithium ion batteries.
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| CN113184922A (en) * | 2021-04-23 | 2021-07-30 | 浙江晨阳新材料有限公司 | Sodium ion battery positive electrode material, preparation method and application |
| CN113437305A (en) * | 2021-05-10 | 2021-09-24 | 宁波工程学院 | 2D-Co @ NC composite material and preparation method and application thereof |
| CN113548699A (en) * | 2021-07-20 | 2021-10-26 | 安徽昊源化工集团有限公司 | Cobalt oxide/carbon nanotube composite material, preparation method thereof and application thereof in lithium air battery |
| CN114768848A (en) * | 2022-04-12 | 2022-07-22 | 齐鲁工业大学 | Preparation method of high-load monatomic catalyst based on zeolite imidazolate framework-67/yeast composite structure |
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