CN111446447A - Method for preparing sulfur stannide/carbon composite material by supercritical carbon dioxide fluid and application - Google Patents
Method for preparing sulfur stannide/carbon composite material by supercritical carbon dioxide fluid and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a tin sulfide/carbon composite material by using supercritical carbon dioxide fluid and application thereof, belonging to the technical field of preparation of tin sulfide/carbon composite materials. A method for preparing a sulfur stannide/carbon composite material by using supercritical carbon dioxide fluid and an application thereof are provided, wherein a mixture obtained by uniformly mixing a sulfur source, a tin source, a solvent and a carbon source according to a certain proportion is placed into a high-pressure ball milling tank, ball milling is carried out under a certain condition, a sample obtained after ball milling is respectively washed for 2-4 times by absolute ethyl alcohol and deionized water, annealing is carried out in a protective atmosphere furnace after freeze drying, grinding is carried out after cooling to obtain a sulfur stannide/carbon composite material sample, and the sulfur stannide/carbon composite material can be prepared by using the strong dispersity of the supercritical carbon dioxide under a supercritical state and the reaction conditions provided by the supercritical carbon dioxide under high pressure and low temperature.
Description
Technical Field
The invention relates to the technical field of preparation of tin sulfide/carbon composite materials, in particular to a method for preparing a tin sulfide/carbon composite material by using supercritical carbon dioxide fluid and application of the tin sulfide/carbon composite material.
Background
With the large-scale development and utilization of lithium ion batteries, the shortage of resources such as lithium on the earth and cobalt necessary for commercial lithium ion batteries, and the like, it is urgent to develop a commercial power battery with lower cost, wherein, the sodium ion battery is due to the lower costThe cost and the richness of the raw materials of the lithium ion battery pack become important roles for replacing the lithium ion battery. Among them, since the ion radius of sodium ions is larger than that of lithium ions, the commercial graphite negative electrode has a low theoretical capacity in a sodium ion battery and cannot function as a battery negative electrode. Compared with the traditional carbon cathode, the sulfur-tin compound, including tin sulfide and stannous sulfide, has theoretical capacity of 1028mAhg as the sulfur-tin compound has alloying reaction in the reaction of the sodium ion battery-1(stannous sulfide) and 1141mAhg-1(tin sulfide), but its poor conductivity and the extremely large volume expansion in the charge-discharge process, are 242% (stannous sulfide) and 324% (tin sulfide), respectively, greatly limit its application in the field of sodium ion battery negative electrode materials.
The most common method in the prior art is to construct a composite material of the sulfur-tin compound and carbon to solve the problems of poor conductivity and volume expansion of the composite material, the method for compounding the sulfur-tin compound and the carbon material is single, and the sulfur-tin compound/carbon composite material is mostly prepared by compounding a tin source, a sulfur source and a carbon source through a hydrothermal method during material compounding.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a sulfur tin compound/carbon composite material by using a supercritical carbon dioxide fluid as a solvent and a reaction medium, and the method is a production method which is low in reaction temperature, environment-friendly and easy to industrialize and is prepared by using the strong dispersity of the supercritical carbon dioxide in a supercritical state and the reaction conditions provided by the supercritical carbon dioxide at high pressure and low temperature.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A method of preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, comprising the steps of:
s1, uniformly mixing a sulfur source, a tin source, a solvent and a carbon source according to a certain proportion to obtain a mixture, putting the mixture into a high-pressure ball milling tank, vacuumizing the high-pressure ball milling tank, filling CO2 gas into the high-pressure ball milling tank, and ball milling the mixture for 0.5-48 hours under the conditions that the pressure is 65-200 bar, the temperature is 20-80 ℃ and the ball milling rotating speed is 100-700 r/min;
s2, after the ball milling reaction in the S1 is finished, quickly releasing CO2 gas in a high-pressure ball milling tank, collecting the obtained reaction liquid, performing suction filtration, washing the obtained sample with absolute ethyl alcohol and deionized water for 2-4 times respectively, and performing freeze drying;
s3, annealing the sample obtained in the S2 in a protective atmosphere furnace at the temperature of 300-600 ℃ for 0.5-12h, wherein the heating rate is 0.5-5 ℃, and grinding after cooling to obtain the sulfur stannide/carbon composite material sample.
Further, the sulfur source in the S1 is thiourea or thioacetamide, and the purity of the sulfur source is not lower than chemical purity.
Further, the tin source in the S1 is anhydrous stannous sulfide, anhydrous stannic sulfide or crystallized stannic sulfide, and the purity of the tin source is not lower than the chemical purity.
Further, the solvent in the S1 is ethanol or ethylene glycol, and the purity of the solvent is not lower than chemical purity.
Further, the carbon source in S1 includes carbon materials or carbonaceous materials such as graphene, graphene oxide, electrolytic carbon, and the like, and the purity of the carbon source is not lower than chemical purity.
Further, the mass ratio of the tin source to the carbon source or the sulfur source to the carbon source is 0.1-10: 1, the mass ratio of the mixture to the solvent is 1: 10-80.
Further, in the S1, when the pressure in the high-pressure ball milling tank is 75-100bar, the temperature is 25-45 ℃, and the ball milling speed is 200-.
Further, in the step S3, when the temperature of the protective atmosphere furnace is 450-550 ℃, the annealing time is 2-8h, and the heating rate is 2-5 ℃.
Further, in the step S3, the atmosphere in the protective atmosphere furnace is argon, which is an inert gas.
An application of a supercritical carbon dioxide fluid in preparation of a tin sulfide/carbon composite material is to use a tin sulfide/carbon composite material sample obtained in S3 as a negative electrode material of a sodium-ion battery, and the preparation method is to use 70:15:15, respectively weighing the tin sulfide/carbon composite material, super-P and sodium carboxymethyl cellulose, grinding uniformly to prepare an electrode, and obtaining the sodium ion battery cathode material.
Drawings
FIG. 1 is a block flow diagram of the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD pattern) of a stannous sulfide/electrolytic carbon composite prepared according to example 1 of the present invention;
fig. 3 is a graph of the cycling performance of a sodium ion battery assembled from a stannous sulfide/electrolytic carbon composite prepared in example 1 of the present invention.
Detailed Description
Example (b):
referring to fig. 1-3, a method for preparing a tin sulfide/carbon composite material with supercritical carbon dioxide fluid comprises the following steps:
s1, uniformly mixing a sulfur source, a tin source, a solvent and a carbon source according to a certain proportion to obtain a mixture, putting the mixture into a high-pressure ball milling tank, vacuumizing the high-pressure ball milling tank, filling CO2 gas into the high-pressure ball milling tank, and ball milling the mixture for 0.5-48 hours under the conditions that the pressure is 65-200 bar, the temperature is 20-80 ℃ and the ball milling rotating speed is 100-700 r/min;
s2, after the ball milling reaction in the S1 is finished, quickly releasing CO2 gas in a high-pressure ball milling tank, collecting the obtained reaction liquid, performing suction filtration, washing the obtained sample with absolute ethyl alcohol and deionized water for 2-4 times respectively, and performing freeze drying;
s3, annealing the sample obtained in the S2 in a protective atmosphere furnace at the temperature of 300-600 ℃ for 0.5-12h, wherein the heating rate is 0.5-5 ℃, and grinding after cooling to obtain the sulfur stannide/carbon composite material sample.
The sulfur source in S1 is thiourea or thioacetamide, and the purity of the sulfur source is not lower than chemical purity.
The tin source in the S1 is anhydrous stannous sulfide, anhydrous stannic sulfide or crystallized stannic sulfide, and the purity of the tin source is not lower than the chemical purity.
The solvent in the S1 is ethanol or ethylene glycol, and the purity of the solvent is not lower than chemical purity.
The carbon source in the S1 comprises carbon materials or carbon-containing materials such as graphene, graphene oxide, electrolytic carbon and the like, and the purity of the carbon source is not lower than the chemical purity.
The mass ratio of the tin source to the carbon source or the sulfur source to the carbon source is 0.1-10: 1, the mass ratio of the mixture to the solvent is 1: 10-80.
In S1, ball milling is carried out on the mixture for 12-24h under the conditions that the pressure in the high-pressure ball milling tank is 75-100bar, the temperature is 25-45 ℃ and the ball milling rotation speed is 200-400 r/min.
In S3, when the temperature of the protective atmosphere furnace is 450-550 ℃, the annealing time is 2-8h, and the heating rate is 2-5 ℃.
In S3, the atmosphere in the protective atmosphere furnace is inert gas argon.
An application of a sulfur stannide/carbon composite material prepared by supercritical carbon dioxide fluid is to use a sulfur stannide/carbon composite material sample obtained in S3 as a negative electrode material of a sodium-ion battery, and the preparation method is to use 70:15:15, respectively weighing the tin sulfide/carbon composite material, super-P and sodium carboxymethyl cellulose, grinding uniformly to prepare an electrode, and obtaining the sodium ion battery cathode material.
Example 1:
0.6g thioacetamide, 0.9g anhydrous stannous chloride, 0.06g electrolytic carbon and 40ml ethylene glycol are put into a high-pressure ball milling tank, vacuum pumping is carried out, then carbon dioxide gas is introduced to ensure that the air pressure in the ball milling tank reaches 80bar, and the stirring reaction is carried out for 15 hours at the temperature of 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product for 3 times by using absolute ethyl alcohol and washing the product for 3 times by using deionized water, then carrying out suction filtration, freezing and drying, and annealing at 550 ℃ for 3 hours to obtain the stannous chloride/electrolytic carbon composite material. The X-ray diffraction (XRD) pattern of the prepared stannous sulfide/electrolytic carbon composite material is shown in figure 2, and the diffraction peaks of the X-ray diffraction (XRD) pattern correspond to the standard PDF card of stannous sulfide (PDF #32-0354) and the steamed bun peaks of amorphous carbon at the temperature of 20 ℃, so that the stannous sulfide/electrolytic carbon composite material is proved to be the stannous sulfide/carbon composite material.
An electrode was prepared using the stannous sulfide/carbon composite material prepared in example 1 as follows.
Respectively weighing stannous sulfide/carbon composite material, super-P and sodium carboxymethylcellulose in a mass ratio of 70:15:15, grinding uniformly to prepare an electrode, taking a metal sodium sheet as a counter electrode, taking electrolyte as 1 mol/L NaClO4/EC-PC (1:1), taking glass fiber as a diaphragm, and assembling into a simulated sodium ion battery, wherein the mass ratio of the stannous sulfide/carbon composite material to the super-P to the sodium carboxymethylcellulose is 0.2Ag for the corresponding battery shown in figure 3-1And the cycle performance curve in the voltage range of 0.01-2.5V shows that the measured battery is 0.2Ag-1The high-capacity lithium ion battery has good cycle performance, capacity retention rate and coulombic efficiency close to 99%, and the cycle performance is excellent.
Example 2:
0.6g thioacetamide, 0.9g crystallized tin tetrachloride, 0.06g graphene and 40ml ethanol are put into a high-pressure ball milling tank, vacuumizing is carried out, then carbon dioxide gas is introduced to ensure that the air pressure in the ball milling tank reaches 80bar, and stirring reaction is carried out for 15h at 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product with absolute ethyl alcohol for 3 times, washing the product with deionized water for 3 times, performing suction filtration, freeze-drying, and annealing at 350 ℃ for 3 hours to obtain the tin chloride/graphene composite material.
An electrode was prepared from the tin sulfide/carbon composite material obtained in example 2 in the following manner.
Weighing a tin sulfide/carbon composite material, super-P and sodium carboxymethylcellulose according to a mass ratio of 70:15:15, grinding uniformly to prepare an electrode, taking a metal sodium sheet as a counter electrode, and taking an electrolyte as 1 mol/L NaClO4the/EC-PC (1:1) and the glass fiber are taken as the diaphragm to assemble the simulated sodium ion battery.
Example 3:
0.6g of thiourea, 0.9g of crystalline tin tetrachloride, 0.06g of electrolytic carbon and 40ml of ethylene glycol are placed in a high-pressure ball milling tank, vacuum pumping is carried out, then carbon dioxide gas is introduced to ensure that the air pressure in the ball milling tank reaches 80bar, and the stirring reaction is carried out for 15 hours at the temperature of 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product for 3 times by using absolute ethyl alcohol and 3 times by using deionized water, performing suction filtration, freeze-drying, and annealing at 350 ℃ for 3 hours to obtain the stannous chloride/electrolytic carbon composite material.
An electrode was prepared from the tin sulfide/carbon composite material obtained in example 3 in the following manner.
The simulated sodium ion battery is assembled by respectively weighing a tin sulfide/carbon composite material, super-P and sodium carboxymethylcellulose in a mass ratio of 70:15:15, uniformly grinding the materials to prepare an electrode, taking a metal sodium sheet as a counter electrode, taking electrolyte as 1 mol/L NaClO4/EC-PC (1:1) and taking glass fiber as a diaphragm.
Example 4:
0.6g of thioacetamide, 0.9g of anhydrous stannous chloride, 0.06g of graphene and 40ml of ethylene glycol are placed in a high-pressure ball milling tank, the high-pressure ball milling tank is vacuumized, then carbon dioxide gas is introduced to enable the air pressure in the ball milling tank to reach 80bar, and the high-pressure ball milling tank is stirred and reacted for 15 hours at the temperature of 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product for 3 times by using absolute ethyl alcohol and washing the product for 3 times by using deionized water, then carrying out suction filtration, freezing and drying, and annealing at 550 ℃ for 3 hours to obtain the stannous chloride/electrolytic carbon composite material.
An electrode was prepared using the stannous sulfide/carbon composite material prepared in example 4 as follows.
The simulated sodium ion battery is assembled by respectively weighing a stannous sulfide/carbon composite material, super-P and sodium carboxymethylcellulose in a mass ratio of 70:15:15, uniformly grinding the materials to prepare an electrode, taking a metal sodium sheet as a counter electrode, taking electrolyte as 1 mol/L NaClO4/EC-PC (1:1) and taking glass fiber as a diaphragm.
Example 5:
0.6g thioacetamide, 0.9g anhydrous stannous chloride, 0.06g electrolytic carbon and 40ml ethylene glycol are put into a high-pressure ball milling tank, vacuum pumping is carried out, then carbon dioxide gas is introduced to ensure that the air pressure in the ball milling tank reaches 80bar, and the stirring reaction is carried out for 15 hours at the temperature of 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product for 3 times by using absolute ethyl alcohol and washing the product for 3 times by using deionized water, then carrying out suction filtration, freezing and drying, and annealing at 550 ℃ for 3 hours to obtain the stannous chloride/electrolytic carbon composite material.
An electrode was prepared using the stannous sulfide/carbon composite material prepared in example 5 as follows.
The simulated sodium ion battery is assembled by respectively weighing a stannous sulfide/carbon composite material, super-P and sodium carboxymethylcellulose in a mass ratio of 70:15:15, uniformly grinding the materials to prepare an electrode, taking a metal sodium sheet as a counter electrode, taking electrolyte as 1 mol/L NaClO4/EC-PC (1:1) and taking glass fiber as a diaphragm.
Example 6:
0.3g thioacetamide, 0.45g anhydrous stannous chloride, 0.06g electrolytic carbon and 40ml ethylene glycol are put into a high-pressure ball milling tank, vacuum pumping is carried out, then carbon dioxide gas is introduced to ensure that the air pressure in the ball milling tank reaches 80bar, and the stirring reaction is carried out for 15 hours at the temperature of 35 ℃.
And after cooling to room temperature, taking out the product in the reactor, washing the product for 3 times by using absolute ethyl alcohol and washing the product for 3 times by using deionized water, then carrying out suction filtration, freezing and drying, and annealing at 550 ℃ for 3 hours to obtain the stannous chloride/electrolytic carbon composite material.
An electrode was prepared using the stannous sulfide/carbon composite material prepared in example 6 as follows.
The simulated sodium ion battery is assembled by respectively weighing a stannous sulfide/carbon composite material, super-P and sodium carboxymethylcellulose in a mass ratio of 70:15:15, uniformly grinding the materials to prepare an electrode, taking a metal sodium sheet as a counter electrode, taking electrolyte as 1 mol/L NaClO4/EC-PC (1:1) and taking glass fiber as a diaphragm.
The method for preparing the sulfur-tin compound/carbon composite material at low temperature by directly providing reaction through the supercritical carbon dioxide fluid and reacting the sulfur source with the tin source can react at 35 ℃, so that the high-temperature condition of hydrothermal reaction is effectively avoided, meanwhile, the sulfur-tin compound is more uniformly compounded on the carbon material by utilizing the characteristic of the supercritical carbon dioxide fluid, the sulfur-tin compound is attached to the carbon material, and the obtained sulfur-tin compound/carbon composite material has good consistency, so that the sulfur-tin compound/carbon composite material has excellent sodium storage characteristic and electrochemical performance, and has the advantages of high sodium storage performance and high electrochemical performance when the temperature is 0.2Ag-1The discharge capacity after 100 times of charge-discharge circulation under the current density is slowly attenuated, the coulombic efficiency is close to 99 percent, the sodium ion electrode negative electrode material has wide application prospect, the reaction condition is reduced, and the large-scale commercialization potential is realized.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; any person skilled in the art is within the technical scope of the present disclosure; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.
Claims (10)
1. A method for preparing a sulfur stannide/carbon composite material by using supercritical carbon dioxide fluid is characterized by comprising the following steps: the method comprises the following steps:
s1, uniformly mixing a sulfur source, a tin source, a solvent and a carbon source according to a certain proportion to obtain a mixture, putting the mixture into a high-pressure ball milling tank, vacuumizing the high-pressure ball milling tank, filling CO2 gas into the high-pressure ball milling tank, and ball milling the mixture for 0.5-48 hours under the conditions that the pressure is 65-200 bar, the temperature is 20-80 ℃ and the ball milling rotating speed is 100-700 r/min;
s2, after the ball milling reaction in the S1 is finished, quickly releasing CO2 gas in a high-pressure ball milling tank, collecting the obtained reaction liquid, performing suction filtration, washing the obtained sample with absolute ethyl alcohol and deionized water for 2-4 times respectively, and performing freeze drying;
s3, annealing the sample obtained in the S2 in a protective atmosphere furnace at the temperature of 300-600 ℃ for 0.5-12h, wherein the heating rate is 0.5-5 ℃, and grinding after cooling to obtain the sulfur stannide/carbon composite material sample.
2. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: the sulfur source in the S1 is thiourea or thioacetamide, and the purity of the sulfur source is not lower than chemical purity.
3. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: and the tin source in the S1 is anhydrous stannous sulfide, anhydrous stannic sulfide or crystallized stannic sulfide, and the purity of the tin source is not lower than the chemical purity.
4. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: the solvent in the S1 is ethanol or ethylene glycol, and the purity of the solvent is not lower than chemical purity.
5. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: the carbon source in the S1 comprises carbon materials or carbon-containing materials such as graphene, graphene oxide, electrolytic carbon and the like, and the purity of the carbon source is not lower than the chemical purity.
6. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: the mass ratio of the tin source to the carbon source or the sulfur source to the carbon source is 0.1-10: 1, the mass ratio of the mixture to the solvent is 1: 10-80.
7. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: in the S1, when the pressure in the high-pressure ball milling tank is 75-100bar, the temperature is 25-45 ℃, and the ball milling speed is 200-.
8. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: in the S3, when the temperature of the protective atmosphere furnace is 450-550 ℃, the annealing time is 2-8h, and the heating rate is 2-5 ℃.
9. The method of claim 1 for preparing a tin sulfide/carbon composite material from a supercritical carbon dioxide fluid, wherein: and in the step S3, the gas in the protective atmosphere furnace is inert gas argon.
10. Use of a supercritical carbon dioxide fluid to produce a tin sulfide/carbon composite material according to claim 1, wherein: taking the sulfur stannide/carbon composite material sample obtained in the step S3 as a negative electrode material of a sodium-ion battery, wherein the preparation method comprises the following steps of: 15:15, respectively weighing the tin sulfide/carbon composite material, super-P and sodium carboxymethyl cellulose, grinding uniformly to prepare an electrode, and obtaining the sodium ion battery cathode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101388454A (en) * | 2008-10-23 | 2009-03-18 | 天津斯特兰能源科技有限公司 | Method for preparing carbon coated phosphates positive pole material by super critical fluid |
| CN106099069A (en) * | 2016-08-15 | 2016-11-09 | 华南理工大学 | A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof |
| KR101702742B1 (en) * | 2015-02-10 | 2017-02-03 | 고려대학교 산학협력단 | Method of coating lithium-containing phosphate particles with carbon |
| CN106654192A (en) * | 2016-08-13 | 2017-05-10 | 华南理工大学 | Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof |
| CN106887578A (en) * | 2017-04-01 | 2017-06-23 | 中南大学 | A kind of artificial gold/CNT composite Nano negative material and preparation method thereof |
| CN108258211A (en) * | 2017-12-29 | 2018-07-06 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of titanium dioxide/graphene composite material |
-
2020
- 2020-04-03 CN CN202010258363.0A patent/CN111446447A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101388454A (en) * | 2008-10-23 | 2009-03-18 | 天津斯特兰能源科技有限公司 | Method for preparing carbon coated phosphates positive pole material by super critical fluid |
| KR101702742B1 (en) * | 2015-02-10 | 2017-02-03 | 고려대학교 산학협력단 | Method of coating lithium-containing phosphate particles with carbon |
| CN106654192A (en) * | 2016-08-13 | 2017-05-10 | 华南理工大学 | Tin sulfide/graphene sodium ion battery composite cathode material and preparation method thereof |
| CN106099069A (en) * | 2016-08-15 | 2016-11-09 | 华南理工大学 | A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof |
| CN106887578A (en) * | 2017-04-01 | 2017-06-23 | 中南大学 | A kind of artificial gold/CNT composite Nano negative material and preparation method thereof |
| CN108258211A (en) * | 2017-12-29 | 2018-07-06 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of titanium dioxide/graphene composite material |
Non-Patent Citations (1)
| Title |
|---|
| LI, KEYU等: "Preparation and lithium ion batteries properties of SnS2 nanoparticle/reduced graphene oxide nanosheet nanocomposites using supercritical carbon dioxide", 《SYNTHETIC METALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
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