CN114005973B - Preparation method and application of heteroatom modified composite anode material - Google Patents
Preparation method and application of heteroatom modified composite anode material Download PDFInfo
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Abstract
The invention belongs to the field of high-power lithium ion capacitors, and particularly relates to a preparation method and application of a heteroatom modified composite negative electrode material.
Description
Technical Field
The invention belongs to the field of high-power lithium ion capacitors, and particularly relates to a preparation method and application of a heteroatom modified composite anode material.
Background
The lithium ion capacitor as a novel energy storage device has the advantages of high power density, high electrostatic capacity and long cycle life, and is expected to be widely applied to the fields of new energy automobiles, solar energy, wind energy and the like.
Because the lithium ion capacitor has the characteristics of high power density and high energy density, the lithium ion capacitor has higher requirements on the large-current discharge capacity of the cathode material. The traditional graphite cathode material has a highly oriented lamellar structure because of high graphitization degree, but the compatibility of graphite and electrolyte is poor, and the phenomenon of solvent ion co-intercalation easily occurs in the charge and discharge process, so that graphite interlayer peeling, electrode pulverization and low cycle performance are caused in the process of heavy current discharge, and potential safety hazards are caused. Graphite is not the best choice for the negative electrode material of high power lithium ion capacitors. Hard carbon is carbon which is difficult to graphitize, has a highly disordered isotropic stable structure and a larger interlayer spacing, and can allow lithium ions to rapidly diffuse. In addition, the hard carbon has better compatibility with electrolyte, has higher lithium ion diffusion coefficient and wider lithium intercalation potential interval, is favorable for rapid intercalation of lithium ions, prevents precipitation of dendrite lithium, and is suitable for heavy current discharge. Compared with graphite cathode, the hard carbon has high capacity, good multiplying power performance, long cycle life, high safety and good low temperature performance. At present, hard carbon becomes the most potential negative electrode material of a lithium ion power battery for a high-power vehicle, an energy storage device of an ultrahigh-power lithium ion capacitor and a sodium ion battery, and becomes a research hot spot. The hard carbon has higher capacity, but has voltage hysteresis, the first irreversible capacity is larger, the highest first charge and discharge efficiency is only about 80 percent, and the larger irreversible capacity reduces the energy density of the energy storage device and increases the manufacturing cost. It has been found that doping of heteroatoms in hard carbon materials can be surface modified and have a great effect on their properties.
At present, the heteroatoms commonly used for doping microporous carbon materials include nitrogen, sulfur, chlorine, fluorine and the like, and the heteroatoms can be doped in the hard carbon material singly or a plurality of heteroatoms can be doped together. Single element doped hard carbon materials can increase their specific surface and pore volume. However, the heteroatom content after activation is reduced to a certain extent, so that the effective inhibition of the heteroatom loss is a key problem for expanding the research on the pore structure of the carbon material in the future. Compared with single-atom doping, the multi-atom co-doping can further improve the overall performance of the carbon material due to the synergistic effect, and the microporous carbon material subjected to multi-atom co-doping generally has good physicochemical properties and has important application values in the fields of energy storage, batteries, capacitors and the like. However, the current literature report for synthesizing the co-doped microporous carbon material is less, most of the synthesis steps are complex, and therefore, a simpler and more effective preparation method needs to be further explored.
It was found that fluorine doping can regulate electron cloud structures of carbon atoms as far as several bonds away, thereby increasing the number of active sites of the carbon material. Meanwhile, fluorine atoms and carbon atoms form bonds, nitrogen separation can be promoted, doping amount of fluorine atoms and nitrogen atoms is increased, more extra electrons are provided, and electronic conductivity of the composite material is improved.
In addition, the soft carbon anode material has the advantages of low and stable charge and discharge potential platform, large charge and discharge quantity, high initial efficiency and good cycle performance. After the soft carbon and the hard carbon are compounded, the first effect and the high-current discharge capacity of the composite material can be greatly improved.
Therefore, the method has great research significance on the surface modification and the composite technology of the hard carbon material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a heteroatom modified composite anode material.
The method is realized by the following technical scheme:
a preparation method of a heteroatom modified composite anode material comprises the following steps:
1) Precursor preparation: ball milling soft carbon, hard carbon and heteroatom modifier at high temperature until the mixture is uniform, cooling and pulverizing into particles to obtain a precursor;
2) Chemical Vapor Deposition (CVD): placing a precursor in a temperature zone of the CVD tube furnace close to a gas outlet, placing a nitrogen source in a temperature zone of the CVD tube furnace close to a gas inlet, vacuumizing the CVD quartz tube after the placement is finished, slowly introducing carrier gas after the pressure reaches below 5Pa, heating the precursor temperature zone, and starting to heat the nitrogen source temperature zone after the process temperature of the precursor temperature zone is close to that of the precursor temperature zone; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure in the quartz tube to be 950-1000 Pa; and (5) timing for 100 minutes after the nitrogen source temperature zone and the precursor temperature zone reach the process temperature, so as to obtain the heteroatom modified composite anode material.
Heteroatom modifiers as described in step 1): soft carbon: the weight ratio of hard carbon is 1: (3-4): (5-6).
The heteroatom modifier of step 1) is Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF).
The soft carbon and the hard carbon are all commercially available anode materials.
The temperature of the high-temperature ball milling in the step 1) is 300-600 ℃.
The nitrogen source in the step 2) is urea or melamine.
The process temperature of the precursor body temperature region in the step 2) is 300-350 ℃.
The process temperature of the nitrogen source temperature zone in the step 2) is 300-400 ℃.
The carrier gas flow rate in the step 2) is 145sccm/min.
The carrier gas is argon.
The heteroatom modified composite anode material is used for manufacturing anode sheets of lithium ion capacitors or lithium ion batteries.
The heteroatom modified composite negative electrode material is used for manufacturing a negative electrode plate of a high-power lithium ion capacitor.
The heteroatom modified composite anode material is used as an anode active material of a lithium ion capacitor or a lithium ion battery.
The heteroatom modified composite anode material is used as an anode active material of an ultra-high power lithium ion capacitor.
The beneficial effects are that:
the heteroatom modified composite anode material prepared by the method has high first charge and discharge efficiency and excellent power performance.
The method of the invention ensures that the composite material has larger interlayer spacing, is favorable for the diffusion of lithium ions, has higher first charge and discharge efficiency and high current discharge capacity, and the lithium ion capacitor assembled based on the negative electrode material has the characteristics of double high of high energy density and high power density.
According to the method, the first charge and discharge efficiency and the power performance of the composite material are improved through high-temperature compounding of soft carbon and hard carbon.
The method carries out co-doping modification of fluorine atoms and nitrogen atoms on the surface of the composite material, increases the catalytic activity defect sites on the surface of the composite material, and improves the capacity of the composite material.
Drawings
FIG. 1 is a scanning electron microscope image of a heteroatom-modified composite anode material prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction chart of the heteroatom-modified composite anode material prepared in example 1 of the present invention;
FIG. 3 is a 0.2C rate charge-discharge curve of a half cell assembled from the heteroatom-modified composite anode material prepared in example 1 of the present invention;
fig. 4 is a graph showing the discharge curves of the full cell assembled by the heteroatom modified composite anode material prepared in example 2 of the present invention at a high current pulse.
Detailed Description
The following detailed description of the invention is provided in further detail, but the invention is not limited to these embodiments, any modifications or substitutions in the basic spirit of the present examples, which still fall within the scope of the invention as claimed.
Example 1
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 8.3g of polytetrafluoroethylene, 24.9g of soft carbon and 49.8g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing urea in a temperature zone of the CVD tube furnace, which is close to a gas inlet, vacuumizing the CVD quartz tube after placing, introducing carrier gas argon at a flow rate of 145sccm/min after reaching below 5Pa, heating the precursor temperature zone, and starting heating the nitrogen source temperature zone after approaching 300 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 300 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Example 2
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: 9.1g of polytetrafluoroethylene, 31.85g of soft carbon and 50.05g of hard carbon are weighed, fully melted and stirred for 2 hours at 300 ℃, cooled at normal temperature, and crushed into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing urea in a temperature zone of the CVD tube furnace, which is close to a gas inlet, performing vacuumizing treatment in a CVD quartz tube after placing, introducing carrier gas argon at a flow rate of 145sccm/min after reaching 5Pa or less, heating the precursor temperature zone, and starting heating a nitrogen source temperature zone after approaching 300 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 300 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Example 3
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: 8.3g of polyvinylidene fluoride, 33.2g of soft carbon and 41.5g of hard carbon are weighed and mixed, the mixture is fully melted and stirred for 2 hours at 300 ℃, cooled at normal temperature, and then crushed into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace close to a gas outlet, placing urea in a temperature zone of the CVD tube furnace close to a gas inlet, vacuumizing the CVD quartz tube after placing, introducing carrier gas argon at a flow rate of 145sccm/min after reaching below 5Pa, heating the precursor temperature zone, starting heating a nitrogen source temperature zone after approaching 350 ℃, turning off a mechanical pump when the temperature of one side of the nitrogen source temperature zone is approaching 150 ℃, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 350 ℃, timing for 100min, and completing the preparation of the heteroatom co-doped composite anode material to obtain the heteroatom modified composite anode material.
Example 4
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 8.3g of polytetrafluoroethylene, 24.9g of soft carbon and 49.8g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing melamine in a temperature zone of the CVD tube furnace, which is close to a gas inlet, firstly vacuumizing the CVD quartz tube after the placement is finished, introducing carrier gas argon at a flow rate of 145sccm/min after the pressure reaches below 5Pa, then heating the precursor temperature zone, and starting to heat a nitrogen source temperature zone after the temperature is close to 300 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 300 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Example 5
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 8.3g of vinylidene fluoride, 33.2g of soft carbon and 41.5g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing melamine in a temperature zone of the CVD tube furnace, which is close to a gas inlet, firstly vacuumizing the CVD quartz tube after the placement is finished, introducing carrier gas argon at a flow rate of 145sccm/min after the pressure reaches below 5Pa, then heating the precursor temperature zone, and starting to heat a nitrogen source temperature zone after the temperature is close to 350 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 350 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Comparative example 1
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 8.3g of polytetrafluoroethylene, mixing 49.8g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace close to a gas outlet, placing urea in a temperature zone of the CVD tube furnace close to a gas inlet, vacuumizing the CVD quartz tube after the placement, introducing carrier gas argon at a flow rate of 145sccm/min after the pressure is below 5Pa, heating the precursor temperature zone, starting heating a nitrogen source temperature zone after the temperature is close to 300 ℃, turning off a mechanical pump when the temperature at one side of the nitrogen source temperature zone is close to 150 ℃, observing the pressure in the quartz tube and controlling the pressure to be about 1000Pa, and timing for 100min after the temperature of the nitrogen source temperature zone reaches 350 ℃ and the temperature of the precursor temperature zone reaches 300 ℃ to finish the preparation of the heteroatom modified composite anode material to obtain the heteroatom modified composite anode material.
Comparative example 2
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 24.9g of soft carbon and 49.8g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing urea in a temperature zone of the CVD tube furnace, which is close to a gas inlet, vacuumizing the CVD quartz tube after placing, introducing carrier gas argon at a flow rate of 145sccm/min after reaching below 5Pa, heating the precursor temperature zone, and starting heating the nitrogen source temperature zone after approaching 300 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 300 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Comparative example 3
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: mixing 33.2g of soft carbon and 49.8g of hard carbon, fully melting and stirring the mixture at 350 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing melamine in a temperature zone of the CVD tube furnace, which is close to a gas inlet, firstly vacuumizing the CVD quartz tube, introducing carrier gas argon at a flow rate of 145sccm/min after the temperature of the precursor is below 5Pa, heating the precursor temperature zone, starting heating a nitrogen source temperature zone after the temperature of the precursor temperature zone is close to 350 ℃, turning off a mechanical pump when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 350 ℃, timing for 100min, and thus completing the preparation of the nitrogen doped composite anode material.
Comparative example 4
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 24.9g of soft carbon and 49.8g of hard carbon, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing melamine in a temperature zone of the CVD tube furnace, which is close to a gas inlet, firstly vacuumizing the CVD quartz tube after the placement is finished, introducing carrier gas argon at a flow rate of 145sccm/min after the pressure reaches below 5Pa, then heating the precursor temperature zone, and starting to heat a nitrogen source temperature zone after the temperature is close to 300 ℃; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 350 ℃ and the precursor temperature zone reaches 300 ℃, timing for 100min, and completing the preparation of the heteroatom-modified composite anode material to obtain the heteroatom-modified composite anode material.
Comparative example 5
The preparation method of the heteroatom modified composite anode material specifically comprises the following steps:
1) Precursor preparation: weighing 33.2g of soft carbon and 41.5g of hard carbon, mixing, fully melting and stirring the mixture at 300 ℃ for 2 hours, cooling at normal temperature, and then crushing into particles in an air flow mill to obtain a precursor with the particle size of about 4 mu m;
2) Chemical vapor deposition: placing a precursor in a temperature zone of a CVD tube furnace, which is close to a gas outlet, placing melamine in a temperature zone of the CVD tube furnace, which is close to a gas inlet, firstly vacuumizing the CVD quartz tube after the placement is finished, introducing carrier gas argon at a flow rate of 145sccm/min after the pressure is below 5Pa, then heating the precursor temperature zone, starting to heat a nitrogen source temperature zone after the temperature is close to 350 ℃, turning off a mechanical pump when the temperature at one side of the nitrogen source temperature zone is close to 150 ℃, observing the pressure in the quartz tube, and controlling the pressure to be about 1000Pa; and (3) after the nitrogen source temperature zone reaches 400 ℃ and the precursor temperature zone reaches 350 ℃, timing for 100min, and completing the preparation of the heteroatom doped composite anode material to obtain the heteroatom modified composite anode material.
Experimental example 1 electrochemical Performance test
To test the performance of the heteroatom modified composite of the present invention, the negative electrode materials of the above examples or comparative examples were used in half cell and full cell test modes: conductive agent (Super-P): binder (PVDF) =92: 3:3 (weight ratio), adding a proper amount of NMP solvent to blend into paste, coating the paste on copper foil, and drying the paste in a vacuum oven at 120 ℃ for 12 hours to prepare a negative plate; the full battery uses lithium cobaltate as an anode active material, is mixed with a conductive agent and a binder according to the weight ratio of 90:5:5, is added with a proper amount of NMP solvent to prepare slurry, is coated on an aluminum foil, and is dried in a vacuum oven at 120 ℃ to form an anode plate; the electrolyte is electrolyte for a high-power lithium ion battery, and the diaphragm is a ceramic diaphragm; the half cell adopts a lithium belt as a counter electrode, and other conditions are the same; performing capacity test on half batteries by adopting 0.2C multiplying power, and performing power performance test on full batteries by 1000A discharging equipment; the charge and discharge voltage is limited to 2.2-4.4V; the results were as follows:
as can be seen from table 1, the first effect and the power performance of the composite material can be improved under the proper preparation conditions of the composite material after fluorine and nitrogen atom co-doping modification;
FIG. 1 is a scanning electron microscope image of the composite material prepared in example 1, the particle size of the composite material prepared is in the range of 2-5 μm;
FIG. 2 is a XRD pattern comparison of the composite material prepared in example 1 and a hard carbon material, and it can be seen that the characteristic peak of the composite material is more sharp, which indicates that the composite material has a higher graphitization degree, and the characteristic peak is shifted to a large angle, which indicates that the layer spacing of the prepared composite material is larger than that of a common hard carbon material, so that the composite material is more favorable for lithium ion transmission and has a better high-current discharge capacity;
FIG. 3 is a 0.2C charge-discharge curve of a half cell assembled by using the composite material prepared in example 1 as a negative electrode, wherein the specific capacity of the composite material reaches 379.9mAh/g, and the initial effect reaches 82.2%;
fig. 4 shows the pulse discharge performance at 250A current of a soft pack battery assembled using the composite material prepared in example 1 as a negative electrode, with a power density of 19.2kW/kg and a specific energy of 124.3Wh/kg.
Claims (6)
1. The preparation method of the heteroatom modified composite anode material is characterized by comprising the following steps of:
1) Precursor preparation: ball milling soft carbon, hard carbon and heteroatom modifier at high temperature until the mixture is uniform, cooling and pulverizing into particles to obtain a precursor;
2) Chemical vapor deposition: placing a precursor in a temperature zone of the CVD tube furnace close to a gas outlet, placing a nitrogen source in a temperature zone of the CVD tube furnace close to a gas inlet, vacuumizing the CVD quartz tube after the placement is finished, slowly introducing carrier gas after the pressure reaches below 5Pa, heating the precursor temperature zone, and starting to heat the nitrogen source temperature zone after the process temperature of the precursor temperature zone is close to that of the precursor temperature zone; when the temperature of one side of the nitrogen source temperature zone is close to 150 ℃, turning off the mechanical pump, observing the pressure in the quartz tube, and controlling the pressure in the quartz tube to be 950-1000 Pa; after the nitrogen source temperature zone and the precursor temperature zone reach the process temperature, timing for 100min to obtain the heteroatom modified composite anode material;
the heteroatom modifier in the step 1) is polytetrafluoroethylene or polyvinylidene fluoride;
the temperature of the high-temperature ball milling in the step 1) is 300-600 ℃;
the nitrogen source in the step 2) is urea or melamine;
the heteroatom modified composite negative electrode material is used for manufacturing a negative electrode plate of a lithium ion capacitor.
2. The method for preparing a heteroatom-modified composite anode material according to claim 1, wherein the heteroatom modifier in step 1) is as follows: soft carbon: the weight ratio of hard carbon is 1: (3-4): (5-6).
3. The method for preparing a heteroatom-modified composite anode material as claimed in claim 1, wherein the process temperature of the precursor body temperature region in step 2) is 300-350 ℃.
4. The method for preparing a heteroatom-modified composite anode material as claimed in claim 1, wherein the process temperature of the nitrogen source temperature zone is 300-400 ℃.
5. The method for preparing a heteroatom-modified composite anode material as claimed in claim 1, wherein the carrier gas flow in step 2) is 145sccm/min.
6. The heteroatom-modified composite negative electrode material prepared by the preparation method of claim 1 is used for preparing a negative electrode plate of a lithium ion capacitor.
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