CN114497510A - Nitrogen-phosphorus doped carbon material with ultrahigh specific surface area and application thereof - Google Patents
Nitrogen-phosphorus doped carbon material with ultrahigh specific surface area and application thereof Download PDFInfo
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- CN114497510A CN114497510A CN202210122750.0A CN202210122750A CN114497510A CN 114497510 A CN114497510 A CN 114497510A CN 202210122750 A CN202210122750 A CN 202210122750A CN 114497510 A CN114497510 A CN 114497510A
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- H01M4/00—Electrodes
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
Abstract
A nitrogen-phosphorus doped carbon material with ultrahigh specific surface area and application thereof. The preparation method of the doped carbon material comprises the following steps: mixing the nitrogen source, the phosphorus source and an optional reaction solvent and then carrying out polymerization reaction; and carrying out heat treatment on the obtained reaction product under a protective atmosphere to obtain the electrode material. The electrode material prepared according to the invention has ultrahigh specific surface area (the specific surface area is up to 2195.9 m)2The nitrogen-phosphorus doped carbon material has excellent electrochemical performance and is suitable for being applied to lithium batteries.
Description
Technical Field
The present invention generally relates to a secondary battery electrode material.
Background
In order to construct a clean, low-carbon, safe and efficient energy system, the development of secondary batteries, particularly lithium ion batteries, is promoted to a great extent. The lithium ion battery, as the most successful battery system for commercialization at present, has the advantages of high energy density, wide working temperature range, long service life and the like, and is widely applied to aspects such as 3C electronic equipment and power automobiles. Lithium batteries will have much broader and more efficient development.
The carbon material with low cost, rich and various structures and environmental friendliness is the most widely applied negative electrode material of the lithium battery at present. Researches find that the capacity and rate capability of the lithium battery can be well improved by combining the high-specific-surface-area carbon material with rich pore channel structures. Meanwhile, heteroatom doping also provides additional active sites to further improve the capacity of the carbon material. However, the preparation method of the carbon material with high specific surface area usually requires a pore-forming activating agent and a template agent, and the subsequent treatment uses corrosive reagents such as hydrochloric acid and hydrofluoric acid, so that the preparation process has the defects of complex process, complex operation, environmental pollution, high cost, harsh equipment requirement and the like.
Disclosure of Invention
It is an object of the present invention to provide a secondary battery electrode material having a high specific surface area which overcomes at least some or all of the above-mentioned disadvantages.
According to a first aspect of the present invention, there is provided a method of preparing an electrode material for a secondary battery, comprising:
providing a nitrogen source selected from at least one of the group consisting of aniline, tri-n-propylamine, tri-n-butylamine, isoquinoline, and quinoline;
providing a phosphorus source selected from at least one of the group consisting of hexachlorocyclotriphosphazene, phosphorus trichloride, phosphorus pentachloride and phosphoric acid;
optionally providing a reaction solvent;
mixing the nitrogen source, the phosphorus source and an optional reaction solvent, and then carrying out polymerization reaction, wherein the molar ratio of nitrogen contained in the nitrogen source to phosphorus contained in the phosphorus source is (23-4): 1, the polymerization reaction temperature is 140-220 ℃, the reaction time is 4-8 h, and the reaction pressure is 0.5-3.5 MPa;
cooling the reaction solution to obtain a solid reaction product;
and carrying out heat treatment on the obtained solid reaction product in a protective atmosphere to obtain the electrode material, wherein the heat treatment temperature is 800-1600 ℃, and the time is 1-3 hours.
According to the process of the present invention, the nitrogen source and the reaction solvent are preferably provided by the same species, for example aniline.
According to the process of the invention, the phosphorus source is preferably hexachlorocyclotriphosphazene.
According to the process of the invention, the nitrogen to phosphorus molar ratio is preferably 5.5: 1.
according to the method, the polymerization reaction temperature is preferably 140-180 ℃, and most preferably about 160 ℃; the reaction pressure is preferably 1 to 2MPa, for example, 1.5 MPa.
According to the method, the ultrasonic mixing mode is preferably adopted for mixing, and the time can be 1-4 h, preferably 1.5-2.5 h, and most preferably 2 h.
According to the method of the invention, the heat treatment temperature is preferably 1100-1300 ℃, and most preferably about 1200 ℃. The heating rate in the heat treatment process is preferably 0.5-10 ℃/min, and most preferably about 3 ℃/min.
According to another aspect of the present invention, there is provided a secondary battery electrode, which is manufactured by coating the electrode material prepared by the above-described method on a metal substrate such as copper foil and drying.
The coating agent can be prepared by mixing the electrode material, small-particle conductive carbon black (super P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1: 1.
The electrode material prepared according to the invention has ultrahigh specific surface area (the specific surface area is up to 2195.9 m)2The nitrogen-phosphorus doped carbon material has excellent electrochemical performance and is suitable for being applied to lithium batteries. The electrode plate made of the nitrogen-phosphorus doped carbon material with the ultrahigh specific surface area can obtain a lithium ion battery with high specific discharge capacity and good rate performance, and can realize reversible charge and discharge with high specific capacity.
Drawings
Fig. 1 is a nitrogen adsorption and desorption graph of nitrogen-phosphorus doped carbon material Y1 prepared according to example 1 of the present invention.
Fig. 2 is a pore size distribution diagram of nitrogen and phosphorus doped carbon material Y1 prepared according to example 1 of the present invention.
Fig. 3 is a lithium battery charge and discharge performance graph of the nitrogen and phosphorus doped carbon material Y1 prepared according to example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, comparative examples and the accompanying drawings. It is to be understood that these are for purposes of illustration and explanation only and are not limiting of the invention.
In the following examples/comparative examples, the lithium ion battery was subjected to charge-discharge and cycle performance tests using a LANDCT2001A tester (blue electronics, Inc., Wuhan City).
Example 1
S1, adding aniline and hexachlorocyclotriphosphazene into a 50mL polytetrafluoroethylene reaction kettle, mixing, performing ultrasonic treatment at 25 ℃ for 2h to form a uniform and stable solution, and then putting the reaction kettle into a stainless steel outer container to react for 6h at 160 ℃ in an air drying machine;
wherein, aniline 24ml, hexachlorocyclotriphosphazene 6g (molar ratio 16: 1);
s2: after the reaction is finished, cooling to room temperature to obtain a crude product, and storing in a vacuum seal manner;
s3: and (3) carrying out heat treatment on the crude product in a vacuum tube furnace at 1200 ℃ for 2h under the argon atmosphere to obtain the nitrogen-phosphorus doped carbon material Y1 with the high surface area.
Examples 2 to 6
Except that the molar ratio of the reactants in step S1 was replaced with 12: 1,14: 1,18: 1, 20: 1 and 22: 1, examples 2 to 6 were carried out in the same manner as in example 1; the obtained nitrogen-phosphorus doped carbon material with the ultrahigh specific surface area is sequentially named as Y2, Y3, Y4, Y5 and Y6.
Examples 7 to 10
Examples 7 to 10 were sequentially carried out in the same manner as in example 1 except that the reaction temperatures in step S2 were changed to 140 ℃, 180 ℃, 200 ℃ and 220 ℃, respectively; the obtained nitrogen-phosphorus doped carbon materials are sequentially named as Y7, Y8, Y9 and Y10.
Comparative examples 1 to 4
Comparative examples 1 to 4 were sequentially carried out as in example 1 except that aniline in step S1 was replaced with tri-n-propylamine, tri-n-butylamine, isoquinoline and quinoline, respectively; the obtained nitrogen-phosphorus doped carbon materials are sequentially named as D1, D2, D3 and D4.
Comparative examples 5 to 7
Comparative examples 5 to 7 were conducted in the same manner as in example 1 except that hexachlorocyclotriphosphazene in step S1 was replaced with phosphorus trichloride, phosphorus pentachloride and phosphoric acid, respectively; the obtained nitrogen-phosphorus doped carbon materials are sequentially named as D5, D6 and D7.
Preparation of Battery electrodes
(A) According to the following steps of 8:1, weighing nitrogen-phosphorus doped carbon material Y1 and Super P, grinding uniformly, adding polyvinylidene fluoride with the same amount as that of Super P(PVDF), adding a proper amount of N-methyl pyrrolidone (NMP), continuously grinding into viscous slurry, uniformly coating the slurry on a copper foil by a scraper, wherein the coating amount is 1.0-1.5 mg/cm2。
(B) And drying the copper foil coated with the nitrogen-phosphorus doped carbon material with the high surface area at room temperature for 0.5 h, and then putting the copper foil into an oven for drying and cutting the copper foil into pieces to obtain the battery electrode.
Fig. 1-2 are microscopic representations of the nitrogen-phosphorus doped carbon material Y1 obtained in example 1 by a plurality of different means, and the results are as follows:
from the isothermal nitrogen adsorption and desorption curves and the pore size distribution diagram of fig. 1 and 2, the specific surface area of Y1 is up to 2195.9m2The material contains abundant pore structure, and the pore volume reaches 1.4cm3The main pore diameters are intensively distributed around 0.4, 1.5 and 2.5 nm.
Characterization of the specific surface areas of the samples D1-D7 obtained in comparative examples 1-7
Different battery electrodes were obtained by following D1-D7 in the same manner as described above for "preparation of battery electrodes" (i.e., replacing only Y1 with D1-D7, respectively).
According to the same test method as that of fig. 3, the nitrogen adsorption and desorption curves obtained from D1 to D7 were calculated, and the specific surface areas of the respective materials were found to be different from each other, and as shown in table 1 below, the specific surface areas of Y1 are listed together for comparison.
Table 1: specific surface area of each sample material
Electrochemical performance test
Fig. 3 is a graph showing the charge and discharge curves of the electrode manufactured using Y1 at different current densities in a lithium battery. In FIG. 3, the current densities of the discharge curves from left to right are 50mA/g, 100mA/g, 500mA/g, 1000mA/g, and 2000mA/g, respectively. As can be seen from FIG. 3, the material was charged and discharged at a current density of 50mA/g, and the calculated lithium battery capacity was 84.7 mAh/g, and the battery capacity was maintained at 422.8 mAh/g at a current density of 2000 mA/g. This indicates that material Y1 was able to charge and discharge at high current density, exhibiting excellent capacity and high rate charge and discharge performance.
Therefore, the nitrogen-phosphorus doped carbon material obtained by the method has excellent electrochemical performance, can be used as a battery cathode material, particularly an electrode material of a lithium battery, and has good application prospect and industrial production potential in the field of electrochemical energy storage.
Electrical characterization of samples Y2-Y10 from examples 2-10
Different battery electrodes were obtained by following Y2-Y10 in the same manner as described above for "preparing battery electrodes" (i.e., simply replacing Y1 with Y2-Y10, respectively).
The respective battery electrodes obtained from Y2 to Y10 were tested in the same test method as that of FIG. 3, and it was found by calculation that the respective materials had capacities at current densities of 50mA/g and 2000mA/g in a lithium ion battery as shown in Table 2 below, respectively. For comparison, Y1 is also listed in lithium batteries.
Table 2: capacity value of each sample material in lithium battery under different current densities
As can be seen from table 2, the reaction ratio in step S1 and the reaction temperature in step S2 have a significant effect on the final surface area. Among them, as can be seen from comparative examples 1 to 6, in step S1, the optimum reaction ratio was 16:1, if the ratio deviates from this range, the specific surface area decreases to various degrees, and the electrical properties decrease significantly. It can be found by comparing examples 1 and 7 to 10 that the optimum reaction temperature is 160 ℃ at step S2, and the specific surface area is decreased to a different extent and the electrical properties are remarkably decreased. It can be seen from comparative examples 1 to 4 that in step S1, when aniline is the most preferable nitrogen-containing reactant and other nitrogen sources are selected, the specific surface area is reduced and the electrical properties are remarkably reduced. It can be seen from comparative examples 5 to 7 that in step S1, the optimum phosphorus-containing reactant is hexachlorocyclotriphosphazene, and other phosphorus sources are selected, so that the specific surface area is reduced and the electrical properties are obviously reduced.
Claims (5)
1. A method for preparing an electrode material for a secondary battery, comprising:
providing a nitrogen source selected from at least one of the group consisting of aniline, tri-n-propylamine, tri-n-butylamine, isoquinoline, and quinoline;
providing a phosphorus source selected from at least one of the group consisting of hexachlorocyclotriphosphazene, phosphorus trichloride, phosphorus pentachloride and phosphoric acid;
optionally providing a reaction solvent;
mixing the nitrogen source, the phosphorus source and an optional reaction solvent, and then carrying out polymerization reaction, wherein the molar ratio of nitrogen contained in the nitrogen source to phosphorus contained in the phosphorus source is (23-4): 1, the polymerization reaction temperature is 140-220 ℃, the reaction time is 4-8 h, and the reaction pressure is 0.5-3.5 MPa;
cooling the reaction solution to obtain a solid reaction product;
and carrying out heat treatment on the obtained solid reaction product in a protective atmosphere to obtain the electrode material, wherein the heat treatment temperature is 800-1600 ℃, and the time is 1-3 hours.
2. The method of claim 1, wherein the nitrogen source and the reaction solvent are provided by the same species.
3. The method of claim 2, wherein the nitrogen source and the reaction solvent are both provided by aniline.
4. The method of claim 1, wherein the phosphorus source is hexachlorocyclotriphosphazene.
5. A secondary battery electrode prepared by coating the electrode material prepared by the method according to any one of claims 1 to 4 on a metal substrate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744794A (en) * | 2016-12-07 | 2017-05-31 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| CN108231425A (en) * | 2017-12-28 | 2018-06-29 | 盐城工学院 | It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof |
| CN109970043A (en) * | 2019-04-08 | 2019-07-05 | 中国石油大学(华东) | Nitrogen-phosphor codoping carbon nanosheet and preparation method thereof, alkali metal-ion battery electrode, alkali metal-ion battery and electric device |
| WO2021104055A1 (en) * | 2019-11-27 | 2021-06-03 | 深圳先进技术研究院 | Nanomaterial and preparation method therefor, electrode, and secondary battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744794A (en) * | 2016-12-07 | 2017-05-31 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| CN108231425A (en) * | 2017-12-28 | 2018-06-29 | 盐城工学院 | It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof |
| CN109970043A (en) * | 2019-04-08 | 2019-07-05 | 中国石油大学(华东) | Nitrogen-phosphor codoping carbon nanosheet and preparation method thereof, alkali metal-ion battery electrode, alkali metal-ion battery and electric device |
| WO2021104055A1 (en) * | 2019-11-27 | 2021-06-03 | 深圳先进技术研究院 | Nanomaterial and preparation method therefor, electrode, and secondary battery |
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