CN117894969B - Graphene-containing negative electrode material - Google Patents
Graphene-containing negative electrode material Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 20
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- 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
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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Abstract
The invention relates to the technical field of negative electrode materials, in particular to a negative electrode material containing graphene, which comprises the following components in parts by mass: 3-8 parts of porous graphene, 20-30 parts of modified graphene and 1-2 parts of silicon boride. The preparation method comprises the step of uniformly mixing the porous graphene, the modified graphene and the silicon boride to obtain the negative electrode material. The negative electrode material provided by the invention has the advantages of simple and efficient preparation method, low cost, better cycle performance and coulombic efficiency of the prepared lithium ion battery and wide application prospect.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a negative electrode material containing graphene.
Background
Graphene, which is used as a carbon nanomaterial, has a great application potential in the field of energy storage due to its unique physicochemical properties, and particularly in the technical field of Lithium Ion Batteries (LIBs). Graphene has an ultra-large specific surface area, excellent conductivity and extremely high mechanical strength, so that the graphene can be used as a high-performance electrode material or electrode additive in a lithium battery.
In the modification of the lithium battery anode material, the graphene can obviously improve the contact area between an active substance and electrolyte and improve an electron transmission path, so that the charge and discharge efficiency and the cycling stability of the battery are improved. Through compounding graphene with other active materials with high energy density, such as lithium cobalt oxide (LiCoO 2) and lithium nickel manganese cobalt ternary material (NMC), the volume change problem in the charge and discharge process can be effectively relieved, the structural stability is enhanced, and the energy density and the service life of the battery are further improved.
On the other hand, the graphene can also be used for the optimal design of the lithium battery anode material. The traditional graphite negative electrode often faces the problems of interlayer spacing expansion and stripping caused by lithium ion intercalation during deep charging, and the graphene can greatly reduce the impedance of lithium ion intercalation/deintercalation due to the thickness of a monoatomic layer and an unlimited lithium ion diffusion channel, so that the coulomb efficiency and the cycle durability of the battery can be improved while rapid charging and discharging are realized.
In addition, the graphene is utilized to construct a three-dimensional porous network structure, and the three-dimensional porous network structure is used as a current collector or a conductive framework, so that active substances can be effectively dispersed, and a good conductive network is provided, which is particularly important for the development of all-solid-state lithium batteries, and is helpful for solving the key problems of poor contact between a solid electrolyte and an inter-electrode interface and low conductivity, and promoting the development of lithium ion batteries to the directions of higher safety and longer service life.
The research and application of graphene in the field of lithium batteries provide a brand-new solution and a wide application prospect for improving the overall performance of batteries, and the graphene becomes one of core hot spots of current energy storage science and technology research. However, despite the advantages that graphene exhibits, how to implement a large-scale, low-cost and environmentally friendly graphene preparation process, and explore its optimal application strategy in complex battery systems, is still an important topic of future scientific research.
CN 117199331B provides a silicon/graphene/carbon fiber composite negative electrode material and a preparation method thereof, which belong to the technical field of batteries and comprise the following steps: (1) Weighing raw materials of Al, si and composite elements according to the mass ratio, smelting, continuously adding a refining agent, and uniformly stirring to obtain an alloy melt; after solidification treatment, putting the mixture into a dilute hydrochloric acid solution for stirring, and then washing and drying the mixture to obtain nano silicon powder; (2) Adding the nano silicon powder and the modifier into water, and stirring by ultrasonic to obtain modified nano silicon powder dispersion; (3) Slowly dripping the graphene dispersion liquid into the modified nano silicon powder dispersion liquid, stirring, centrifuging, washing, and freeze-drying to obtain a silicon/graphene composite material; (4) And placing the carbon fiber and the silicon/graphene composite material in acetone, performing ultrasonic dispersion and drying to obtain the silicon/graphene/carbon fiber composite material. The composite anode material provided by the invention improves the charge and discharge efficiency and prolongs the service life of the lithium ion battery. But the preparation conditions are severe.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a graphene-containing anode material which comprises the following components in parts by mass: 3-8 parts of porous graphene, 20-30 parts of modified graphene and 1-2 parts of silicon boride. The addition of the silicon boride can improve the performance of the battery and enhance the capacity retention rate of the battery due to the combination of the excellent performances of the boron atoms and the silicon atoms.
Further, the preparation method of the porous graphene comprises the following steps:
S1, uniformly mixing graphene and ferric oxide powder to obtain a mixture of the graphene and the ferric oxide powder, wherein the mass ratio of the graphene to the ferric oxide powder is (10-100) to 1;
s2, adding the mixture obtained in the step S1 into pure water with the mass 5 times of that of the mixture, uniformly mixing, and then adjusting the pH value of the solution to be 2-3 by adopting inorganic acid to obtain a mixed solution;
s3, dropwise adding a hydrogen peroxide solution into the mixed solution obtained in the step S2, and performing oxidation reaction, wherein the reaction temperature is kept at 30-50 ℃ and the reaction time is 2-3 hours, so that graphene is converted into graphene oxide; after hydrogen peroxide is added dropwise, under the catalysis of ferric oxide powder, the pH value of the reaction solution is strictly controlled, and the solid phase catalysis Fenton oxidation is adopted to prepare graphene oxide, so that the effect is good, and the prepared graphene has excellent performance and is obviously better than the effect of pure hydrogen peroxide oxidation;
S4, filtering, acid washing, water washing and drying the reaction liquid obtained in the step S3 to obtain graphene oxide; the acid washing is adopted, so that impurities such as ferric oxide powder and the like remained in the solid can be removed, the quality of graphene oxide is improved, and the acid used for acid washing is dilute sulfuric acid;
and S5, carrying out microwave treatment on the graphene oxide obtained in the step S4 to obtain the porous graphene. The porous graphene prepared by the method has the advantages of low density, good conductivity, compressibility, high porosity, large specific surface area and the like.
Further, the inorganic acid in the step S2 is at least one of hydrofluoric acid and perchloric acid. The inorganic acid adopts hydrofluoric acid, so that insoluble impurities such as silicon dioxide in graphene can be removed additionally, and the perchloric acid is adopted, so that the pH value is regulated, and meanwhile, the inorganic acid has strong oxidizing property and is favorable for oxidation reaction.
Further, the hydrogen peroxide concentration in the step S3 is 27.5wt%, and the addition amount of the hydrogen peroxide solution is 50-80% of the mass of the graphene in the step S1.
Further, in the step S5, the microwave power is 1kW, the frequency is 2450MHz, and the treatment time is 8-12 hours.
Further, the preparation method of the modified graphene comprises the following steps:
S21, uniformly mixing the graphene oxide obtained by the method in the step S4 with inorganic salt, and then adding the mixture into pure water with the mass 5 times that of the graphene oxide to obtain a mixed solution;
s22, placing the mixed solution obtained in the step S21 into a hydrothermal reaction kettle, and reacting for 3-5 hours at the temperature of 120-220 ℃;
And S23, cooling the reaction liquid obtained in the step S22, filtering, washing and drying to obtain the modified graphene.
Further, in the step S21, the mass ratio of the graphene oxide to the inorganic salt is 50:1.
Further, the inorganic salt in the step S21 is at least one of sodium sulfite, magnesium nitrate and sodium bisulfite. The inorganic salt contains sodium sulfite, sodium bisulphite and other reducing salts, and can react with oxygen-containing groups of graphite oxide to further improve the performance of the modified graphene.
The invention also provides a preparation method of the negative electrode material, which comprises the specific process of uniformly mixing the porous graphene, the modified graphene and the silicon boride to obtain the negative electrode material.
Further, the mixing is to uniformly mix the components by adopting a ball mill.
The invention provides a novel negative electrode material, which has the advantages of simple and efficient preparation method and low cost, and further has better cycle performance and coulomb efficiency of the prepared lithium ion battery and wide application prospect.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The negative electrode material containing graphene comprises 3g of porous graphene, 20g of modified graphene and 1g of silicon boride.
The preparation method of the porous graphene comprises the following steps:
s1, uniformly mixing 40g of graphene and 4g of ferric oxide powder to obtain a mixture of the graphene and the ferric oxide powder;
S2, uniformly mixing the mixture obtained in the step S1 with 220g of pure water, and then adjusting the pH value of the solution to be 2-3 by using perchloric acid to obtain a mixed solution;
S3, dropwise adding 20g of 27.5wt% hydrogen peroxide solution into the mixed solution obtained in the step S2, and performing oxidation reaction, wherein the reaction temperature is kept at 30-40 ℃ and the reaction time is 2 hours, so that graphene is converted into graphene oxide;
s4, filtering, dilute sulfuric acid washing, water washing and drying the reaction liquid obtained in the step S3 to obtain graphene oxide;
And S5, carrying out microwave treatment on the graphene oxide obtained in the step S4 to obtain porous graphene, wherein the specific surface area is 1921m 2/g, the microwave power is 1kW, the frequency is 2450MHz, and the treatment time is 9h.
The preparation method of the modified graphene comprises the following steps:
S21, mixing 21g of graphene oxide obtained by the method in the step S4 with 0.42g of sodium sulfite, and then adding the mixture into 105g of pure water to obtain a mixed solution;
s22, placing the mixed solution obtained in the step S21 into a hydrothermal reaction kettle, and reacting for 3 hours at the temperature of 180-220 ℃;
and S23, cooling the reaction liquid obtained in the step S22, filtering, washing and drying to obtain 20g of modified graphene.
And uniformly mixing the porous graphene, the modified graphene and the silicon boride obtained in the steps by adopting a ball mill according to the mass ratio to obtain the anode material.
Embodiment 2, a negative electrode material containing graphene comprises 8g of porous graphene, 30g of modified graphene and 2g of silicon boride.
The preparation method of the porous graphene comprises the following steps:
S1, uniformly mixing 40g of graphene and 2g of ferric oxide powder to obtain a mixture of the graphene and the ferric oxide powder;
s2, uniformly mixing the mixture obtained in the step S1 with 210g of pure water, and then adjusting the pH value of the solution to be 2-3 by adopting hydrofluoric acid to obtain a mixed solution;
s3, dropwise adding 30g of 27.5wt% hydrogen peroxide solution into the mixed solution obtained in the step S2, and performing oxidation reaction, wherein the reaction temperature is kept at 40-50 ℃ and the reaction time is 3 hours, so that graphene is converted into graphene oxide;
s4, filtering, dilute sulfuric acid washing, water washing and drying the reaction liquid obtained in the step S3 to obtain graphene oxide;
S5, carrying out microwave treatment on the graphene oxide obtained in the step S4 to obtain porous graphene, wherein the specific surface area is 1898m 2/g, the microwave power is 1kW, the frequency is 2450MHz, and the treatment time is 12 hours.
The preparation method of the modified graphene comprises the following steps:
s21, mixing 31g of graphene oxide, 0.31g of sodium bisulphite and 0.31g of magnesium nitrate obtained by the method in the step S4, and then adding the mixture into 155g of pure water to obtain a mixed solution;
S22, placing the mixed solution obtained in the step S21 into a hydrothermal reaction kettle, and reacting for 5 hours at the temperature of 130-170 ℃;
s23, cooling the reaction liquid obtained in the step S22, filtering, washing and drying to obtain 30g of modified graphene.
And uniformly mixing the porous graphene, the modified graphene and the silicon boride obtained in the steps by adopting a ball mill according to the mass ratio to obtain the anode material.
Embodiment 3, a negative electrode material containing graphene comprises 3g of porous graphene, 20g of modified graphene and 1g of silicon boride.
The preparation method of the porous graphene comprises the following steps:
s1, uniformly mixing 40g of graphene and 3g of ferric oxide powder to obtain a mixture of the graphene and the ferric oxide powder;
S2, uniformly mixing the mixture obtained in the step S1 with 215g of pure water, and then adjusting the pH value of the solution to be 2-3 by using perchloric acid to obtain a mixed solution;
s3, dropwise adding 25g of 27.5wt% hydrogen peroxide solution into the mixed solution obtained in the step S2, and performing oxidation reaction, wherein the reaction temperature is kept at 30-40 ℃ and the reaction time is 3 hours, so that graphene is converted into graphene oxide;
s4, filtering, dilute sulfuric acid washing, water washing and drying the reaction liquid obtained in the step S3 to obtain graphene oxide;
And S5, carrying out microwave treatment on the graphene oxide obtained in the step S4 to obtain porous graphene, wherein the specific surface area is 1913m 2/g, the microwave power is 1kW, the frequency is 2450MHz, and the treatment time is 10 hours.
The preparation method of the modified graphene comprises the following steps:
S21, mixing 21g of graphene oxide obtained by the method in the step S4 with 0.42g of sodium sulfite, and then adding the mixture into 105g of pure water to obtain a mixed solution;
S22, placing the mixed solution obtained in the step S21 into a hydrothermal reaction kettle, and reacting for 4 hours at the temperature of 180-200 ℃;
and S23, cooling the reaction liquid obtained in the step S22, filtering, washing and drying to obtain 20g of modified graphene.
And uniformly mixing the porous graphene, the modified graphene and the silicon boride obtained in the steps by adopting a ball mill according to the mass ratio to obtain the anode material.
Comparative example 1 the iron oxide powder component of step S1 of example 1 was removed and the details thereof were not repeated in the same manner as in example 1.
Comparative example 2 the perchloric acid in step S2 of example 1 was replaced with hydrochloric acid, and the other steps are the same as in example 1, and will not be repeated.
Comparative example 3 sodium sulfite in step S21 of example 1 was replaced with sodium sulfate, and the other steps are the same as example 1, and will not be repeated.
Comparative example 4 the silicon boride component of example 1 was removed and the details of the procedure of example 1 were omitted.
The anode materials prepared in the examples and comparative examples of the present invention were used as anode active materials, respectively, according to the anode active materials: CMC (sodium carboxymethyl cellulose): SP (superconducting carbon black): SBR (styrene butadiene rubber) =3.85: 0.055:0.070: and after being uniformly mixed in a mass ratio of 0.07, the mixture is coated on a copper foil current collector, and a negative electrode plate is obtained for standby after drying. The lithium sheet is used as a positive electrode, copper foil and aluminum foil are used as current collectors of the negative electrode and the positive electrode respectively, a polyethylene/propylene composite microporous membrane is used as a diaphragm, LD-LP03 type electrolyte manufactured by Kodado company is used as electrolyte, and the button cell is assembled in an argon glove drying box (the moisture is controlled below 15 ppm). The battery manufactured by using the basic conditions is tested by using a computer-controlled tester, the charging current is 0.5C, the discharging current is 1C, and the charging and discharging voltage range is 0-3V.
The battery samples prepared in the above examples and comparative examples were subjected to performance test, and the results are shown in table 1.
TABLE 1
| Sequence number | First coulombic efficiency% | Specific capacity of first discharge, mAh/g | Maximum number of charge-discharge cycles, circle |
| Example 1 | 95.38 | 468 | 3900 |
| Example 2 | 95.01 | 451 | 3700 |
| Example 3 | 95.11 | 456 | 3800 |
| Comparative example 1 | 83.14 | 332 | 2600 |
| Comparative example 2 | 92.41 | 421 | 3300 |
| Comparative example 3 | 90.18 | 401 | 3000 |
| Comparative example 4 | 93.11 | 431 | 3500 |
As can be seen from the data in the table, the test data of the examples 1-3 are all good, the first discharge specific capacity of the prepared battery is more than 450 mAh/g, the first coulomb efficiency is more than 95%, and the maximum number of normal-temperature charge and discharge cycles of the finished battery prepared from the prepared negative electrode material reaches more than 3700 circles. The data of comparative example 1 shows that removal of the iron oxide powder component has the greatest effect on cell performance, as graphene oxide prepared by simple hydrogen peroxide oxidation has poor quality, affecting the final cell performance; the data of comparative example 2 show that the strong oxidizing acid has better effect of adjusting the pH value; the data of comparative example 3 shows that salts with reducing properties are more advantageous for process preparation; the data of comparative example 4 shows that silicon boride can enhance the performance of the anode material.
Claims (5)
1. The graphene-containing anode material is characterized by comprising the following components in parts by mass: 3-8 parts of porous graphene, 20-30 parts of modified graphene and 1-2 parts of silicon boride;
The preparation method of the porous graphene comprises the following steps:
S1, uniformly mixing graphene and ferric oxide powder to obtain a mixture of the graphene and the ferric oxide powder, wherein the mass ratio of the graphene to the ferric oxide powder is (10-100) to 1;
s2, adding the mixture obtained in the step S1 into pure water with the mass 5 times of that of the mixture, uniformly mixing, and then adjusting the pH value of the solution to be 2-3 by adopting inorganic acid to obtain a mixed solution;
s3, dropwise adding a hydrogen peroxide solution into the mixed solution obtained in the step S2, and performing oxidation reaction, wherein the reaction temperature is kept at 30-50 ℃ and the reaction time is 2-3 hours, so that graphene is converted into graphene oxide;
s4, filtering, acid washing, water washing and drying the reaction liquid obtained in the step S3 to obtain graphene oxide;
s5, carrying out microwave treatment on the graphene oxide obtained in the step S4 to obtain porous graphene;
The preparation method of the modified graphene comprises the following steps:
S21, uniformly mixing graphene oxide obtained by the method in the step S4 with inorganic salt, and then adding the mixture into pure water with the mass 5 times that of the graphene oxide to obtain a mixed solution, wherein the inorganic salt is at least one of sodium sulfite, magnesium nitrate and sodium bisulphite, and the mass ratio of the graphene oxide to the inorganic salt is 50:1;
s22, placing the mixed solution obtained in the step S21 into a hydrothermal reaction kettle, and reacting for 3-5 hours at the temperature of 120-220 ℃;
And S23, cooling the reaction liquid obtained in the step S22, filtering, washing and drying to obtain the modified graphene.
2. The negative electrode material according to claim 1, wherein the inorganic acid in step S2 is at least one of hydrofluoric acid and perchloric acid.
3. The negative electrode material according to claim 1, wherein the hydrogen peroxide concentration in the step S3 is 27.5wt%, and the hydrogen peroxide solution is added in an amount of 50-80% of the mass of the graphene in the step S1.
4. The anode material according to claim 1, wherein the microwave power in step S5 is 1kW, the frequency is 2450MHz, and the treatment time is 8 to 12 hours.
5. The negative electrode material according to any one of claims 1 to 4, wherein the battery prepared by using the negative electrode material has a specific capacity of 451 to 468 mAh/g for initial discharge, a coulombic efficiency of 95.01 to 95.38% for initial discharge, and a maximum number of charge-discharge cycles at normal temperature of 3700 to 3900 cycles.
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| CN111821982A (en) * | 2020-04-26 | 2020-10-27 | 闽南师范大学 | Graphene oxide-cerium oxide-iron oxide composite material, synthesis method and application of graphene oxide-cerium oxide-iron oxide composite material in catalytic degradability |
| CN113699787A (en) * | 2021-08-18 | 2021-11-26 | 徐州蒙之禾塑料科技有限公司 | Antibacterial anti-static fiber coating and preparation method thereof |
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| CN102718209A (en) * | 2012-06-11 | 2012-10-10 | 电子科技大学 | Method for preparing graphene based on reduction of divalent iron ion |
| CN111821982A (en) * | 2020-04-26 | 2020-10-27 | 闽南师范大学 | Graphene oxide-cerium oxide-iron oxide composite material, synthesis method and application of graphene oxide-cerium oxide-iron oxide composite material in catalytic degradability |
| CN113699787A (en) * | 2021-08-18 | 2021-11-26 | 徐州蒙之禾塑料科技有限公司 | Antibacterial anti-static fiber coating and preparation method thereof |
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