CN114678505A - Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof - Google Patents
Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114678505A CN114678505A CN202210339329.5A CN202210339329A CN114678505A CN 114678505 A CN114678505 A CN 114678505A CN 202210339329 A CN202210339329 A CN 202210339329A CN 114678505 A CN114678505 A CN 114678505A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- sulfur
- phosphorus
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 a sulfur-phosphorus co-doped hard carbon composite material and a preparation method thereof, wherein the composite material is of a core-shell structure, a shell is nitrogen-containing amorphous carbon, and the mass percentage of the shell is 1-10% of the mass of the composite material. The mass ratio of sulfur atoms in the inner core is 1.11-1.88%, the mass ratio of phosphorus atoms in the inner core is 1.88-2.23%, and the balance is hard carbon. The preparation method comprises the following steps: adding hydrocarbon, sulfur-phosphorus organic matter and nitrogen-containing polymer into an organic solvent to prepare an organic solution, adding the organic solution into a high-pressure reaction kettle for reaction, filtering, and freeze-drying the filtered powder to obtain a porous hard carbon precursor; and (2) adding a dilute hydrochloric acid solution and a porous hard carbon precursor into the oxidant solution in sequence, performing ultrasonic dispersion uniformly, reacting at the temperature of 0-4 ℃ for 12-72 hours, cleaning with 10% dilute hydrochloric acid, performing vacuum drying, grinding, transferring to a tubular furnace, and carbonizing in an argon inert atmosphere to obtain the porous hard carbon precursor. The invention can improve the specific capacity, give consideration to the power performance and the first efficiency and reduce the impedance.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a sulfur-phosphorus co-doped hard carbon composite material and a preparation method of the sulfur-phosphorus co-doped hard carbon composite material.
Background
The hard carbon is non-graphitizable amorphous carbon, has large interlayer spacing, good rapid charge and discharge performance, and especially excellent low-temperature charge and discharge performance. At present, hard carbon is mainly prepared from high-molecular polymer materials, such as coconut shells, starch, resin and the like, the high-molecular polymer generates air holes in the pyrolysis process, so that the specific surface area of the hard carbon is higher, moisture and oxygen are easily absorbed, side reactions are more, the first coulombic efficiency is lower, the effective specific capacity is lower (about 300 mAh/g), the electronic conductivity deviation (lower than that of graphite by one order of magnitude) is caused by a porous structure, and in order to further improve the electronic conductivity of the hard carbon material, a material with high conductivity needs to be doped and coated. For example, phosphorus doping improves the specific capacity of the material, nitrogen doping improves the electronic conductivity of the material, boron doping improves the interlayer spacing of the material, sulfur doping improves the rate capability of the material, but the existence of single element or compound doping only improves one performance of the material, while other performances are not improved. For example, chinese patent publication No. CN202110908449.8 discloses "a phosphorus-nitrogen doped biomass hard carbon material, and a preparation method and an application thereof" at 8/9/2021, in a composite material prepared by using the material, phosphorus atoms are doped between carbon layers, the carbon layer spacing is increased, and surface active sites are increased, the specific capacity of a negative electrode material is higher, the conductivity is good, the polarization is small, the first coulomb efficiency is lower, the cycle performance is good, but there is a problem that the first efficiency and the specific capacity cannot be considered at the same time.
Disclosure of Invention
The invention aims to overcome the defects and provide the sulfur-phosphorus co-doped hard carbon composite material which can improve the specific capacity, give consideration to the power performance and the first efficiency and reduce the resistance.
The invention also aims to provide a preparation method of the sulfur-phosphorus co-doped hard carbon composite material.
The invention relates to a sulfur-phosphorus co-doped hard carbon composite material, which comprises the following components in part by weight: the composite material is of a core-shell structure, the inner core is hard carbon containing sulfur and phosphorus, the outer shell is amorphous carbon containing nitrogen, and the mass of the outer shell accounts for 1-10% of the mass of the composite material.
The sulfur-phosphorus co-doped hard carbon composite material comprises the following components in parts by weight: the mass ratio of sulfur atoms in the inner core is 1.11-1.88%, the mass ratio of phosphorus atoms in the inner core is 1.88-2.23%, and the balance is hard carbon.
The invention relates to a preparation method of a sulfur-phosphorus co-doped hard carbon composite material, which comprises the following steps:
(1) according to the mass ratio of 100: 1-20: weighing hydrocarbon, sulfur and phosphorus organic matters and nitrogen-containing polymers 1-10, adding the weighed hydrocarbon, sulfur and phosphorus organic matters and nitrogen-containing polymers into an organic solvent to prepare an organic solution, then adding the organic solution into a high-pressure reaction kettle, reacting for 1-6 hours at the temperature of 100-200 ℃ and the pressure of 1-5 Mpa, filtering, and freeze-drying powder obtained after filtering for 24 hours at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) preparing 0.5-5 wt% of oxidant solution, sequentially adding 10% of dilute hydrochloric acid solution (the volume of the dilute hydrochloric acid solution is 5% of the oxidant solution), porous hard carbon precursor, the mass ratio of the oxidant solution to the porous hard carbon precursor is 1-10: 100, reacting at 0-4 ℃ for 12-72 hours after uniform ultrasonic dispersion, cleaning with 10% of dilute hydrochloric acid, vacuum drying at 80 ℃ for 24 hours, grinding until the particle size D50 is 5-20 micrometers, transferring to a tubular furnace, and carbonizing at 700-1000 ℃ for 1-6 hours under the inert atmosphere of argon to obtain the hard carbon composite material.
The preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the hydrocarbon in the step (1) is one of phenolic resin, furfural resin, epoxy resin, coconut shell, starch, glucose or sucrose;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the sulfur-phosphorus organic matter in the step (1) is one of methamidophos, acephate or fosthiazate;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the nitrogen-containing polymer in the step (1) is one of aniline, thiophene, pyrrole or urea;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the organic solvent in the step (1) is carbon tetrachloride or cyclohexane.
As described aboveThe preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the oxidant in the step (2) is (NH)4)2S2O8、H2O2、K2Cr2O7Or KIO3One kind of (1).
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can show that: according to the invention, the phosphorus atoms are doped in the hard carbon of the inner core, the lithium storage active points of the material are improved by utilizing the hole formed by the catalytic action of the sulfur-phosphorus compound in the preparation process, the energy density is improved by utilizing the high specific capacity of the phosphorus, the sulfur atoms are doped between carbon layers, the carbon layer spacing is increased, the surface active sites are increased, the lithium ion migration rate can be greatly increased, and the power performance is improved. Meanwhile, the sulfur atom forms a crosslinking effect between carbon-carbon chemical bonds, namely the carbon-sulfur-carbon chemical bonds improve the structural stability of the material and improve the cycle performance.
The shell is firstly coated with organic compounds such as aniline and the like, then the organic compounds such as polyaniline and the like are formed by polymerization and carbonized to obtain nitrogen-containing amorphous carbon which has the characteristics of high electronic conductivity and stable and strong structure, low impedance and the like of-C-N-chemical bond, and the cycle performance and the power performance are improved; meanwhile, the surface of the inner core is coated with an amorphous lifting material, so that the first efficiency is further improved.
Drawings
Fig. 1 is an SEM image of a hard carbon composite prepared in example 1.
Detailed Description
Example 1
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) weighing 100g of phenolic resin, 10g of methamidophos and 5g of aniline, adding the materials into 500ml of carbon tetrachloride, carrying out ultrasonic dispersion uniformly, transferring the mixture into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 150 ℃ and the pressure of 3Mpa, filtering, and freeze-drying the obtained powder for 24 hours at the temperature of minus 40 ℃ to obtain a porous hard carbon precursor;
(2) adding 5g (NH4)2S2O8 into 500ml deionized water to prepare a 1% solution, sequentially adding 10ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, performing ultrasonic dispersion uniformly, reacting at 0-4 ℃ for 48h, cleaning with dilute hydrochloric acid (10 wt%), performing vacuum drying at 80 ℃ for 24h, grinding to 10 micrometers, transferring to a tubular furnace, and carbonizing at 800 ℃ for 3h under an argon inert atmosphere to obtain the hard carbon composite material.
Example 2
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) weighing 100g of furfural resin, 1g of acephate and 1g of thiophene, adding the materials into 500ml of cyclohexane, performing ultrasonic dispersion uniformly, transferring the materials into a high-pressure reaction kettle, reacting for 6 hours at the temperature of 100 ℃ and the pressure of 5Mpa, filtering, and performing freeze drying on the obtained powder for 24 hours at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) adding 1g K2Cr2O7 into 200ml of deionized water to prepare a 0.5% solution, sequentially adding 1ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, performing ultrasonic dispersion uniformly, reacting at the temperature of 0-4 ℃ for 12 hours, cleaning with dilute hydrochloric acid (10 wt%), performing vacuum drying at the temperature of 80 ℃ for 24 hours, grinding to 5 micrometers, transferring to a tubular furnace, and carbonizing at the temperature of 700 ℃ for 6 hours under the inert atmosphere of argon to obtain the hard carbon composite material.
Example 3
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) weighing 100g of coconut shell, 20g of fosthiazate and 10g of pyrrole, adding into 500ml of cyclohexane organic solvent, carrying out ultrasonic dispersion uniformly, transferring into a high-pressure reaction kettle, reacting for 1h at the temperature of 200 ℃ and the pressure of 1Mpa, filtering, and freeze-drying the obtained powder for 24h at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) adding 10g of H2O2 into 200ml of deionized water to prepare a 5wt% solution, sequentially adding 10ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, performing ultrasonic dispersion uniformly, reacting at 0-4 ℃ for 72h, cleaning with dilute hydrochloric acid (10 wt%), performing vacuum drying at 80 ℃ for 24h, grinding to 20 micrometers, transferring to a tubular furnace, and carbonizing at 1000 ℃ for 1h under an argon inert atmosphere to obtain the hard carbon composite material.
Comparative example:
weighing 100g of phenolic resin, adding the phenolic resin into 500ml of carbon tetrachloride organic solvent, uniformly dispersing by ultrasonic, transferring the mixture into a high-pressure reaction kettle, reacting at the temperature of 150 ℃ and the pressure of 3Mpa for 3h, filtering, drying at the temperature of 80 ℃ in vacuum for 24h to obtain a hard carbon precursor, grinding the hard carbon precursor to 10 micrometers, transferring the hard carbon precursor into a tubular furnace, and carbonizing the hard carbon precursor at the temperature of 800 ℃ for 3h in an argon inert atmosphere to obtain the hard carbon composite material.
Test example 1: SEM test
Fig. 1 is an SEM image of the hard carbon composite material prepared in example 1, and it can be seen from fig. 1 that the material has a granular structure, a reasonable size distribution, and a particle size of 3 to 8 μm.
Test example 2: physicochemical Properties and button cell test thereof
The hard carbon composite materials prepared in examples 1 to 3 and comparative example were subjected to particle size, tap density, specific surface area, interlayer distance, powder resistivity and specific capacity thereof.
The test method comprises the following steps: GB/T-24332019 graphite cathode material for lithium ion batteries:
the hard carbon composite materials obtained in the examples 1-3 and the comparative example are respectively used as negative electrode materials of lithium ion batteries to be assembled into button batteries A1, A2, A3 and B1; the preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The binder used was LA132 binder, conductive agent SP, negative electrode materials prepared in examples 1 to 3 and comparative example, respectively, and the solvent was redistilled water in the following proportions: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220mL, and preparing a negative pole piece; the electrolyte is LiPF6/EC + DEC (volume ratio is 1:1, concentration is 1.3mol/L), the metal lithium sheet is a counter electrode, the diaphragm is made of Polyethylene (PE), the simulated battery is assembled in an argon-filled glove box, the electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.00V-2.0V, and the charging and discharging rate is 0.1C. The multiplying power (2C, 0.1C) and the cycle performance (0.2C/0.2C, 200 times) of the button cell battery are tested at the same time. The test data are detailed in table 1.
As can be seen from table 1, the materials prepared in examples 1 to 3 have high specific capacity and first efficiency, because the material is doped with phosphorus to increase the specific capacity of the material, nitrogen atoms reduce the electronic impedance of the material and increase the rate and cycle performance, and sulfur atoms increase the interlayer spacing of the material to increase the rate; meanwhile, the porous precursor prepared by the hydrothermal method has a porous structure, and the specific surface area of the porous precursor is improved. The materials of the examples and comparative examples were also tested for sulfur and phosphorus content by a carbon sulfur analyzer and ICP, respectively.
TABLE 1 comparison of physicochemical parameters of examples 1-3 with comparative examples
Test example 3: soft package battery
The composite materials prepared in examples 1-3 and comparative example were used as negative electrode materials, and a negative electrode sheet was prepared using a ternary material (LiNi)1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/l) is used as electrolyte, the celegard2400 is used as a diaphragm to prepare 2Ah soft package batteries C1, C2, C3 and D, and the ternary lithium battery is obtained, and the test results are detailed in tables 2-5.
TABLE 2 imbibition Capacity of negative plate
The liquid absorption capacity of the pole piece is shown in table 2, and as can be seen from table 2, the liquid absorption and retention capacities of the negative electrode in examples 1 to 3 are obviously superior to those of the comparative example, and the analysis reason is that: the hard carbon cathode electrode prepared by a hydrothermal method is of a porous structure and a high specific surface area, and the liquid absorption and retention capacity of the cathode electrode is improved.
TABLE 3 comparison of the magnifications of examples 1-3 with comparative examples
Rate capability
The rate performance of the soft package battery is tested, the charging and discharging voltage range is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, the soft package battery is charged at 1.0C, 3.0C, 5.0C, 10.0C and 20.C, the soft package battery is discharged at 1.0C, and the test results are shown in table 3. As can be seen from table 3, the rate charge performance of the pouch cells in examples 1-3 is significantly better than the comparative example, i.e., the charge time is shorter, the analytical reason is that: the migration of lithium ions is required in the charging process of the battery, the surface of the cathode material in the embodiment is coated with nitrogen atoms with high electronic conductivity to reduce impedance, and the prepared material is of a porous structure, so that the diffusion rate of the lithium ions in the charging and discharging process is improved, and the rate capability of the lithium ions is improved.
Table 4 comparison of cycle performance of lithium ion batteries of examples 1-3 and comparative examples
And (3) testing the cycle performance:
the cycle performance test method comprises the following steps: the charging and discharging current is 3C/3C, the voltage range is 2.5-4.2V, the cycle number is 500 times, and the test result is shown in table 4. As can be seen from table 4, the cycle performance of the lithium ion battery prepared by using the hard carbon composite negative electrode material obtained in examples 1 to 3 is significantly better than that of the comparative example at each stage, because the nitrogen atoms promote the electronic conductivity and structural stability of the material in the structure of the nitrogen-phosphorus-sulfur doped hard carbon composite material by a hydrothermal method, and the porous material prepared by the hydrothermal method has liquid absorption and retention properties, thereby promoting the cycle performance of the material, and meanwhile, sufficient electrolyte improves the diffusion channel of lithium ions, reduces the diffusion resistance of lithium ions, improves the conductivity of the material, and improves the cycle performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications, equivalent variations and modifications made on the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the technical solution of the present invention.
Claims (8)
1. A sulfur and phosphorus co-doped hard carbon composite material is characterized in that: the composite material is of a core-shell structure, the inner core is hard carbon containing sulfur and phosphorus, the outer shell is amorphous carbon containing nitrogen, and the mass of the outer shell accounts for 1-10% of the mass of the composite material.
2. The sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 1, wherein: the mass ratio of sulfur atoms in the inner core is 1.11-1.88%, the mass ratio of phosphorus atoms in the inner core is 1.88-2.23%, and the balance is hard carbon.
3. A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) according to the mass ratio of 100: 1-20: weighing hydrocarbon, sulfur and phosphorus organic matters and nitrogen-containing polymers 1-10, adding the weighed hydrocarbon, sulfur and phosphorus organic matters and nitrogen-containing polymers into an organic solvent to prepare an organic solution, then adding the organic solution into a high-pressure reaction kettle, reacting for 1-6 hours at the temperature of 100-200 ℃ and the pressure of 1-5 Mpa, filtering, and freeze-drying powder obtained after filtering for 24 hours at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) preparing 0.5-5 wt% of oxidant solution, sequentially adding 10% of dilute hydrochloric acid solution (the volume of the dilute hydrochloric acid solution is 5% of that of the oxidant solution), porous hard carbon precursor, wherein the mass ratio of the oxidant solution to the porous hard carbon precursor is 1-10: 100, performing ultrasonic dispersion uniformly, reacting at the temperature of 0-4 ℃ for 12-72 hours, cleaning with 10% of dilute hydrochloric acid, performing vacuum drying at the temperature of 80 ℃ for 24 hours, grinding until the granularity D50 is 5-20 micrometers, transferring to a tubular furnace, and carbonizing at the temperature of 700-1000 ℃ for 1-6 hours under the inert atmosphere of argon gas to obtain the hard carbon composite material.
4. The preparation method of the sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the hydrocarbon in the step (1) is one of phenolic resin, furfural resin, epoxy resin, coconut shell, starch, glucose or sucrose.
5. The preparation method of the sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the sulfur-phosphorus organic matter in the step (1) is one of methamidophos, acephate or fosthiazate.
6. The preparation method of the sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the nitrogen-containing polymer in the step (1) is one of aniline, thiophene, pyrrole or urea.
7. The preparation method of the sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the organic solvent in the step (1) is carbon tetrachloride or cyclohexane.
8. The preparation method of the sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 3, wherein the preparation method comprises the following steps: the oxidant in the step (2) is (NH)4）2S2O8、H2O2、K2Cr2O7Or KIO3One kind of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210339329.5A CN114678505B (en) | 2022-04-01 | 2022-04-01 | Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210339329.5A CN114678505B (en) | 2022-04-01 | 2022-04-01 | Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114678505A true CN114678505A (en) | 2022-06-28 |
| CN114678505B CN114678505B (en) | 2022-11-29 |
Family
ID=82076621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210339329.5A Active CN114678505B (en) | 2022-04-01 | 2022-04-01 | Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114678505B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064686A (en) * | 2022-08-01 | 2022-09-16 | 晖阳(贵州)新能源材料有限公司 | Preparation method of copper phosphide/phosphorus/carbon nanotube co-doped hard carbon composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150280227A1 (en) * | 2014-03-27 | 2015-10-01 | Imra America, Inc. | Predoping method for an electrode active material in an energy storage device, and energy storage devices |
| CN106848258A (en) * | 2017-03-27 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of graphitized carbon cathode material preparation method |
| CN110416517A (en) * | 2019-07-29 | 2019-11-05 | 卢昌琴 | A kind of negative electrode material and preparation method thereof of lithium-ion-power cell double-coating structure |
| CN113428855A (en) * | 2021-06-18 | 2021-09-24 | 浙江大学 | Sulfur and phosphorus doped biomass porous carbon material and preparation method thereof |
| CN114044506A (en) * | 2021-11-16 | 2022-02-15 | 长沙矿冶研究院有限责任公司 | Polyatomic co-doped porous carbon material, preparation method thereof and application thereof in super capacitor |
| CN114188511A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Nitrogen-doped carbon-coated graphite composite material and preparation method and application thereof |
-
2022
- 2022-04-01 CN CN202210339329.5A patent/CN114678505B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150280227A1 (en) * | 2014-03-27 | 2015-10-01 | Imra America, Inc. | Predoping method for an electrode active material in an energy storage device, and energy storage devices |
| CN106848258A (en) * | 2017-03-27 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of graphitized carbon cathode material preparation method |
| CN110416517A (en) * | 2019-07-29 | 2019-11-05 | 卢昌琴 | A kind of negative electrode material and preparation method thereof of lithium-ion-power cell double-coating structure |
| CN114188511A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Nitrogen-doped carbon-coated graphite composite material and preparation method and application thereof |
| CN113428855A (en) * | 2021-06-18 | 2021-09-24 | 浙江大学 | Sulfur and phosphorus doped biomass porous carbon material and preparation method thereof |
| CN114044506A (en) * | 2021-11-16 | 2022-02-15 | 长沙矿冶研究院有限责任公司 | Polyatomic co-doped porous carbon material, preparation method thereof and application thereof in super capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064686A (en) * | 2022-08-01 | 2022-09-16 | 晖阳(贵州)新能源材料有限公司 | Preparation method of copper phosphide/phosphorus/carbon nanotube co-doped hard carbon composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114678505B (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111384381B (en) | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof | |
| CN114142011B (en) | Hard carbon composite material and preparation method and application thereof | |
| CN114420939B (en) | High-rate spherical hard carbon composite material and preparation method and application thereof | |
| CN113764644B (en) | Quick-filling composite graphite material and preparation method thereof | |
| CN113889593B (en) | Preparation method of hard carbon-coated soft carbon composite material | |
| CN114613974B (en) | Long-life quick-charging type lithium ion battery cathode material and preparation method thereof | |
| CN115101741B (en) | Nitrogen-doped graphene-coated silicon-carbon composite material and preparation method and application thereof | |
| CN114583093A (en) | Preparation method and application of high-energy-density hard carbon composite negative electrode material | |
| CN114497506A (en) | Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof | |
| CN105845886A (en) | Negative electrode material for ion battery and preparation method of negative electrode material | |
| CN114678505B (en) | Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof | |
| CN114094070A (en) | Titanium niobate-coated hard carbon composite material and preparation method thereof | |
| CN113889595A (en) | Preparation method of solid electrolyte coated graphite composite material | |
| CN115663157A (en) | Hard carbon composite material for lithium ion battery and preparation method thereof | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN114852989A (en) | Preparation method of soft carbon-hard carbon composite material with high first efficiency | |
| CN114975918A (en) | Graphite composite material coated with fast ion conductor and preparation method thereof | |
| CN111211311B (en) | Preparation method of porous nano lithium iron phosphate composite material | |
| CN109686981B (en) | Composite binder applied to lithium-sulfur battery and preparation method thereof | |
| CN114162814A (en) | Modification method of graphite | |
| CN115520851B (en) | Preparation method of hard carbon-soft carbon-fast ion conductor composite material | |
| CN115849366B (en) | High-energy quick-charging graphite material for power battery and preparation method thereof | |
| CN115312739A (en) | Silver-doped hard carbon composite material and preparation method thereof | |
| CN105576214A (en) | Modification method based on carbon-nitrogen conducting layer modified lithium titanate material | |
| CN115513453A (en) | Silver-doped hard carbon composite material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |