CN116216693A - Ammonium phosphate salt doped modified asphalt-based hard carbon anode material and preparation method thereof - Google Patents
Ammonium phosphate salt doped modified asphalt-based hard carbon anode material and preparation method thereof Download PDFInfo
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- CN116216693A CN116216693A CN202310260081.8A CN202310260081A CN116216693A CN 116216693 A CN116216693 A CN 116216693A CN 202310260081 A CN202310260081 A CN 202310260081A CN 116216693 A CN116216693 A CN 116216693A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an ammonium phosphate salt doped modified asphalt-based hard carbon anode material and a preparation method thereof, wherein the method comprises the following steps: firstly, crushing and grinding petroleum asphalt with a softening point of 250-270 ℃ into fine particles, placing the fine particles in a muffle furnace, and performing oxidation crosslinking reaction by taking air as an oxygen source; secondly, ball-milling and mixing ammonium phosphate salt and oxidized asphalt particles; and thirdly, placing the mixed material into a high-temperature carbonization furnace, and carbonizing under an inert atmosphere to obtain the ammonium phosphate salt doped modified asphalt-based hard carbon anode material. The asphalt-based hard carbon anode material modified by ammonium phosphate doping is obtained by carrying out oxidation crosslinking reaction on petroleum asphalt and combining ammonium phosphate-assisted high-temperature solid phase reaction. The sodium ion half-cell prepared from the material has specific capacity exceeding 300mAh/g, the initial coulomb efficiency reaches about 85%, and the sodium storage performance is excellent, thus the material has potential commercial application value.
Description
Technical Field
The invention relates to an ammonium phosphate salt doped modified asphalt-based hard carbon anode material and a preparation method thereof, belonging to the technical field of new energy material development.
Background
Along with the progress and development of society, the demand of human beings for energy is more and more increased, but traditional fossil energy, such as coal, petroleum, natural gas and the like, are difficult to meet the demands of the progress and development of society, and the use of traditional fossil energy is extremely easy to cause environmental pollution, endanger human health and destroy the home where human beings depend on to live, so the development of sustainable pollution-free new energy industry is a requisite path for the progress and development of human beings. New energy batteries represented by lithium ion batteries gradually enter daily life of people in the last 80 th century, are widely applied to various electronic products, and power batteries begin to be applied to the field of automobiles in the 21 st century, so that the industrial scale of the power batteries is gradually enlarged, the social demands are growing increasingly, and carbon materials such as artificial graphite and the like are widely used as negative electrode materials of the lithium ion batteries. However, the development of lithium ion batteries is limited by the limitation of lithium resources, and compared with the lithium ion batteries, sodium resources are widely distributed in the crust, so that the lithium ion batteries are easy to exploit and low in price, and the sodium ion batteries are gradually favored by researchers. Compared with the artificial graphite anode material, the interlayer spacing of the hard carbon anode material is obviously increased, the larger interlayer spacing can accommodate more sodium ions, the hard carbon has more defects and micropores, and the defect positions and the micropores of the hard carbon anode material can also accommodate part of sodium ions, so that the development of the advanced hard carbon anode material has important significance for promoting the development of new energy industry.
Disclosure of Invention
In order to solve the technical problems, the asphalt-based hard carbon anode material with higher reversible capacity is prepared by co-carbonizing ammonium phosphate salt and petroleum asphalt particles to dope P, N, O three hetero atoms. Because asphalt is easy to change into more ordered graphite structure at high temperature, the asphalt is a material which is extremely easy to graphitize, after oxidation crosslinking reaction, a plurality of aromatic hydrocarbon molecules in the asphalt are crosslinked together through oxygen atoms, the molecular weight is gradually increased, and the asphalt is changed from thermoplastic to thermosetting. And the radius diameter of the phosphorus atom is larger than that of the carbon atom and the oxygen atom, when the ammonium phosphate salt and the oxidized petroleum asphalt particles are carbonized after high-temperature solid phase reaction, the interlayer spacing of the hard carbon material is obviously increased compared with that of single-atom O doping, and the interlayer lithium intercalation capability is greatly improved. The P, N diatomic existence increases interlayer defect sites, enlarges interlayer distance, increases disorder degree of the material, prevents graphitization trend of asphalt at high temperature, and obtains the material of the invention, ammonium phosphate salt doped modified asphalt-based hard carbon anode material, which has larger specific capacity and higher reversible capacity. The preparation technical scheme of the ammonium phosphate salt doped modified asphalt-based hard carbon anode material comprises the following steps:
step 1: grinding
Taking petroleum asphalt with the softening point of 250-270 ℃, crushing and grinding the petroleum asphalt into fine particles,
step 2: oxidation
The petroleum asphalt fine particles obtained after grinding in the step 1 are oxidized and crosslinked by taking air as an oxygen source to form asphalt particles,
step 3: mixing
Taking ammonium phosphate, grinding and mixing the ammonium phosphate and asphalt particles obtained after the oxidation crosslinking reaction in the step 2 into a mixed material,
step 4: carbonization
And (3) carbonizing the mixed material ground in the step (3) in inert atmosphere to obtain a finished product, namely the ammonium phosphate salt doped modified asphalt-based hard carbon anode material.
Further, the oxidation crosslinking reaction device in the step 2 is a muffle furnace, and the temperature in the muffle furnace is controlled as follows:
when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min;
heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than or equal to 320 ℃;
when the furnace temperature is more than 320 ℃, the heat preservation and oxidation are carried out for 12 hours, and then the furnace is naturally cooled to room temperature.
Further, the grinding in the step 3 is specifically ball milling for 1h in a star ball mill at 200 r/min.
Further, in the step 3, the ammonium phosphate salt is one or more of monoammonium phosphate, diamine phosphate and ammonium polyphosphate.
Further, in the step 4, the carbonization treatment equipment is a high-temperature carbonization furnace, and in the carbonization process, the temperature in the high-temperature carbonization furnace is set as follows:
when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min;
heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than 350 ℃;
heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 350 ℃ and less than 550 ℃;
heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 550 ℃ and less than 850 ℃;
when the furnace temperature is more than or equal to 850 ℃ and less than or equal to 1100 ℃, the temperature is raised at the speed of 2 ℃/min, after the carbonization process is finished, the hard carbon is naturally cooled to the room temperature, and then is taken out and screened by a 200-mesh sieve.
The invention also comprises the ammonium phosphate salt doped modified asphalt-based hard carbon anode material prepared by any method.
The beneficial effects are that: according to the invention, a mode of combining an air oxidation method and a high-temperature solid phase method is adopted, and low-cost petroleum asphalt is used as a raw material to prepare a hard carbon anode material with excellent performance; obtaining thermosetting asphalt particles by oxidative crosslinking of asphalt under simple conditions; the modifier ammonium phosphate salt and asphalt particles are uniformly mixed by a mechanical ball milling mode; the ball milling time is controlled to obtain the particle size meeting the requirements; and obtaining the ammonium phosphate doped modified hard carbon anode material through solid-solid high-temperature reaction in the asphalt particle pyrolysis process. The whole production process does not involve complicated procedures, is energy-saving, environment-friendly and safe, and is suitable for large-scale preparation and popularization of new materials.
Drawings
FIG. 1 is an XRD pattern of monoammonium phosphate doped petroleum pitch hard carbon material prepared in the examples of the invention;
FIG. 2 is a graph showing pore size distribution of monoammonium phosphate doped petroleum pitch hard carbon material prepared in the example of the invention;
FIG. 3 is a graph showing charge and discharge curves of monoammonium phosphate doped with petroleum pitch hard carbon materials prepared in the example of the invention;
fig. 4 is an SEM image of monoammonium phosphate doped petroleum pitch hard carbon material prepared in the example of the present invention.
Detailed Description
The present invention is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the invention and not limiting of its scope, and various modifications of the invention, which are equivalent to those skilled in the art upon reading the invention, will fall within the scope of the invention as defined in the appended claims.
Examples
The preparation method of the ammonium phosphate salt doped modified asphalt-based hard carbon anode material comprises the following steps:
step 1: grinding
Taking petroleum asphalt with the softening point of 250-270 ℃, crushing and grinding the petroleum asphalt into fine particles,
step 2: oxidation
Taking 100g of petroleum asphalt fine particles (D50 which is less than or equal to 20 um) obtained in the step 1 and taking air as an oxygen source to perform an oxidation crosslinking reaction to obtain asphalt particles, wherein the oxidation crosslinking reaction equipment is a muffle furnace, and the temperature in the muffle furnace is controlled as follows: when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min; heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than or equal to 320 ℃; when the furnace temperature is more than 320 ℃, the heat preservation and oxidation are carried out for 12 hours, the furnace is naturally cooled to room temperature,
step 3: mixing
Placing oxidized petroleum asphalt particles and monoammonium phosphate in a planetary ball mill according to the mass ratio of 100:0, 94:6, 88:12 and 82:18, ball milling for 1h at 200r/min, performing mechanical ball milling and mixing,
step 4: carbonization
The mixed material ground in the step 3 is placed in inert atmosphere for carbonization treatment, carbonization treatment equipment is a high-temperature carbonization furnace, and in the carbonization process, the temperature in the high-temperature carbonization furnace is set as follows: when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min; heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than 350 ℃; heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 350 ℃ and less than 550 ℃; heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 550 ℃ and less than 850 ℃; and when the furnace temperature is more than or equal to 850 ℃ and less than or equal to 1100 ℃, heating at the speed of 2 ℃/min, naturally cooling the hard carbon to room temperature after the carbonization process is finished, taking out the hard carbon, sieving the hard carbon with a 200-mesh sieve to obtain a finished product, namely the ammonium phosphate salt doped modified asphalt-based hard carbon anode material, and physically observing the obtained material to prepare the battery.
Material observations
As shown in FIG. 1, these materials all exhibited characteristic peaks of typical amorphous carbon, with layer spacing greater than 0.37nm, characteristic peaks of typical hard carbon, as measured by XRD.
As shown in fig. 2, the modified hard carbon has more micro-mesoporous characteristics than the unmodified material, and can add more micro-mesopores Kong Chuna.
As shown in fig. 3, the reversible capacity gradually increases with the change of the dopant addition amount during the first charge and discharge, but the coulombic efficiency is not significantly reduced, which indicates that the element doping can effectively improve the performance of the hard carbon sodium storage.
As shown in fig. 4, the hard carbon exhibits an irregular morphology with a particle size below 15um, which is a feature due to the irregular ball milling of the pre-pitch particles.
Battery assembly
The anode active material is the hard carbon material obtained in the embodiment of the invention, the anode is used in a half cell, the conductive agent is conductive carbon black, the binder is carboxymethyl cellulose, and the hard carbon is prepared from styrene-butadiene latex by the following steps: conductive carbon black: carboxymethyl cellulose: styrene-butadiene latex=90: and (3) dissolving the materials in deionized water according to the mass ratio of 4:3:3 to prepare slurry, coating the slurry on a copper foil, drying, rolling and punching the slurry to prepare an electrode slice, controlling the active substances on the surface of the electrode to be 7-9 mg/cm < 2 >, then preparing a button cell in a glove box filled with argon, wherein the negative electrode is a sodium slice, the glass fiber membrane is a diaphragm, and 1mol/L NaClO4/EC: PC (volume ratio of 1:1) is electrolyte to assemble the button cell of LIR 2430.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. The preparation method of the ammonium phosphate salt doped modified asphalt-based hard carbon anode material is characterized by comprising the following steps of:
step 1: grinding
Taking petroleum asphalt with the softening point of 250-270 ℃, crushing and grinding the petroleum asphalt into fine particles,
step 2: oxidation
The petroleum asphalt fine particles obtained after grinding in the step 1 are oxidized and crosslinked by taking air as an oxygen source to form asphalt particles,
step 3: mixing
Taking ammonium phosphate, grinding and mixing the ammonium phosphate and asphalt particles obtained after the oxidation crosslinking reaction in the step 2 into a mixed material,
step 4: carbonization
And (3) carbonizing the mixed material ground in the step (3) in inert atmosphere to obtain a finished product, namely the ammonium phosphate salt doped modified asphalt-based hard carbon anode material.
2. The preparation method of the ammonium phosphate salt doped modified asphalt-based hard carbon anode material according to claim 1, wherein the oxidation crosslinking reaction equipment in the step 2 is a muffle furnace, and the temperature in the muffle furnace is controlled as follows:
when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min;
heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than or equal to 320 ℃;
when the furnace temperature is more than 320 ℃, the heat preservation and oxidation are carried out for 12 hours, and then the furnace is naturally cooled to room temperature.
3. The method for preparing the ammonium phosphate salt doped modified asphalt-based hard carbon anode material according to claim 1, which is characterized in that: the grinding in the step 3 is specifically ball milling for 1h in a star ball mill at 200 r/min.
4. The method for preparing a phosphate doped modified asphalt-based hard carbon anode material according to claim 4, wherein the method comprises the following steps: the ammonium phosphate salt in the step 3 is one or more of monoammonium phosphate, diamine phosphate and ammonium polyphosphate.
5. The method for preparing the ammonium phosphate salt doped modified asphalt-based hard carbon anode material according to claim 1, which is characterized in that: in the step 4, the carbonization treatment equipment is a high-temperature carbonization furnace, and in the carbonization process, the temperature in the high-temperature carbonization furnace is set as follows:
when the room temperature is less than or equal to the furnace temperature less than 200 ℃, heating at a speed of 5 ℃/min;
heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 200 ℃ and less than 350 ℃;
heating at a speed of 1 ℃/min when the furnace temperature is more than or equal to 350 ℃ and less than 550 ℃;
heating at a speed of 3 ℃/min when the furnace temperature is more than or equal to 550 ℃ and less than 850 ℃;
when the furnace temperature is more than or equal to 850 ℃ and less than or equal to 1100 ℃, the temperature is raised at the speed of 2 ℃/min, after the carbonization process is finished, the hard carbon is naturally cooled to the room temperature, and then is taken out and screened by a 200-mesh sieve.
6. An ammonium phosphate salt doped modified asphalt-based hard carbon anode material is characterized in that: a process according to any one of claims 1 to 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
| CN116812913B (en) * | 2023-08-30 | 2023-11-21 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
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