CN110980795A - Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material - Google Patents
Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material Download PDFInfo
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Abstract
The invention belongs to the technical field of nano material preparation, and relates to a hydrothermal method for preparing Cu2‑xA method of S nanoflower, comprising: adding a copper salt into deionized water, stirring until the copper salt is completely dissolved, sequentially stirring a sulfur source and a surfactant to obtain a clear solution, wherein the volume molar ratio of the deionized water to the copper salt to the sulfur source to the surfactant is 20-40 mL: 0.15-4 mmol: 0.75-10 mmol: 2.5-300 mmol; and transferring the clear solution to a reaction kettle, carrying out hydrothermal reaction at 110-180 ℃ for 12-36 h, naturally cooling to room temperature, centrifuging, repeatedly and alternately cleaning with ethanol and deionized water in sequence, and carrying out vacuum drying to obtain the product. The invention regulates and controls Cu2‑xThe Cu content, reaction temperature and the like in S to prepare Cu with high specific surface area and more defects2‑xThe S nanoflower is a good photocatalyst and photo-thermal material, and can effectively improve the photo-thermal conversion efficiency of converting solar energy into heat energy. Mild, controllable and controllable reaction conditionsSimple operation, strong practicability and the prepared Cu2‑xThe S nanoflower near-infrared photothermal material has the advantages of long service life, good stability and the like, and is convenient for large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to a hydrothermal method for preparing Cu2-xS nanometer flower method and its application in near infrared photothermal material.
Background
Since the 21 st century, with the development and recovery of global economy, the energy demand of all countries in the world is rapidly increased, so that the contradiction between energy supply and demand is increasingly obvious, particularly the competition on fossil energy is prominent, and the energy mainly comprises petroleum, coal and natural gas. The widespread use of fossil energy leads to prominent environmental problems, such as severe air pollution, global temperature rise, loss of biodiversity and increasingly significant land desertification, and the disordered development and utilization of fossil energy leads to increasingly depleted traditional energy reserves. In order to meet the energy demand, the development and use of clean energy, the optimization and adjustment of energy structures, and the reduction of environmental pollution are necessary requirements for realizing the sustainable development of energy, society, and environment.
Solar energy is abundant in nature, is an ideal pollution-free renewable energy source, and the photothermal material is more and more concerned by students as a material capable of effectively absorbing sunlight in a full spectrum range and then converting the sunlight into heat energy. The solar energy-saving device overcomes the defects of high energy consumption and large pollution of the traditional fossil fuel, realizes the effective utilization of solar energy, and plays an important role in the fields of aviation, automobiles, energy-saving buildings, waste treatment, seawater purification, cancer treatment, energy-saving devices and the like.
In photothermal materials, cuprous sulfide (Cu)2S) shows wide application prospect. Cuprous sulfide has the advantages of narrow band gap, high utilization rate of solar energy, good photocatalytic performance and thermal stability, and huge application potential in the field of solar photo-thermal conversion, and becomes a hotspot of research in the field of current photo-thermal conversion nano materials due to the advantages of simple preparation process, low cost, excellent absorption function and the like. Compared with mercury, lead and other nano materials, cuprous sulfide has less pollution to the environment, and the method conforms to the concept of green environmental protection. The research utilizes a hydrothermal synthesis method to prepare a series of Cu2-xS nanometer flower near infrared photothermal material, by adjusting Cu2-xThe Cu content in S further improves the photo-thermal performance of the material. On the premise of keeping the morphology and phase of a substance, Cu2-xThe change of Cu content in S is favorable for the change of coordination environment around Cu atoms and S atoms in the crystal structure, thereby causing the micro-change of the crystal structure and changing the materialThe optical property of the material improves the photo-thermal conversion efficiency.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrothermal method for preparing Cu2-xS nanometer flower method and its application in near infrared photothermal material.
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
(1) adding a copper salt into deionized water, stirring until the copper salt is completely dissolved, sequentially stirring a sulfur source and a surfactant to obtain a clear solution, wherein the volume molar ratio of the deionized water to the copper salt to the sulfur source to the surfactant is 20-40 mL: 0.15-4 mmol: 0.75-10 mmol: 2.5-300 mmol;
(2) transferring the clear solution to a reaction kettle, carrying out hydrothermal reaction at 110-180 ℃ for 12-36 h, preferably at 120 ℃ for 24h, naturally cooling to room temperature, centrifuging the product, repeatedly and alternately cleaning with ethanol and deionized water in sequence, carrying out vacuum drying at 60 ℃, and collecting a black product, namely Cu2-xAnd (4) S nanoflower.
In the preferred embodiment of the invention, the copper salt in step (1) is copper nitrate trihydrate, copper chloride or copper sulfate, preferably copper nitrate trihydrate.
In the preferred embodiment of the invention, the sulfur source in the step (1) is glutathione, thiourea or sulfur powder, preferably glutathione.
In the preferred embodiment of the present invention, the surfactant in step (1) is cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, triethylene glycol, preferably cetyl trimethyl ammonium bromide.
In a preferred embodiment of the present invention, when the copper salt in step (1) is copper nitrate trihydrate, the sulfur source is glutathione, and the surfactant is cetyltrimethylammonium bromide, the molar volume ratio of the copper salt, the sulfur source, the surfactant, and the deionized water is 0.828mmol, 0.824mmol, 0.807mmol, or 0.786 mmol: 1 mmol: 2.744 mmol: 30 mL.
Cu prepared according to the method of the invention2-xS nanometer flower with flower shape and size assembled by nanometer sheetsApproximately 200nm to 700 nm.
The inventor finds that: glutathione can be used as a sulfur source and a reducing agent for reducing Cu in a hydrothermal process2+Reduction to Cu+Thiourea, sulfur powder and the like can replace glutathione and have similar effects. Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a synthetic water-soluble polymer compound and plays a role of a cationic surfactant in the synthesis process of the nano material. In the hydrothermal growth process of the crystal, CTAB is adsorbed on the surface of the crystal, and the nanometer flower structure is finally formed by controlling the anisotropic growth of the crystal, thereby playing an important role in the morphological construction process of the nanometer flower. Polyvinylpyrrolidone and triethylene glycol can replace hexadecyl trimethyl ammonium bromide to be used as a surfactant, and Cu is benefited2S forms ultra-thin nanostructures. It has been reported that when synthesizing inorganic metal compound crystal structure, by fine-tuning the amount of reactants, ion vacancies can be introduced into crystal lattice without causing phase change, which can effectively adjust the electronic structure of the material, thereby further affecting the physical and chemical properties thereof. Cu2The Cu element in S has a plurality of chemical states, and if the dosage of the Cu element participating in the synthesis reaction is finely adjusted, the electronic structure of the material can be adjusted and controlled under the condition of no phase change, so that the Cu is realized2And (3) improvement of the performance of the S material.
It is a further object of the present invention to provide Cu prepared by the hydrothermal method described above2-xThe S nanoflower can be applied to near infrared photothermal materials.
Photothermal Property test parameters, measurement of synthesized Cu2-xThe operation steps of temperature change caused by photothermal conversion of the S material are as follows: mixing different Cu2-xDispersing S material in solvent (water/H)2O, N, N-dimethylformamide solution/DMF), preparing turbid liquids with different concentrations (3, 1.5, 0.75, 0.38, 0.19 and 0 mg/ml), and placing 0.5ml into a quartz cuvette; a980 nm near-infrared laser is selected as a light source, and the temperature of the system is measured every 10 seconds by using an infrared thermal imager of NEC on a water dispersion perpendicular to the laser path. Analyzing the solvent by comparing the temperature change of different samples under near infrared light irradiationConcentration and Cu2-xThe influence of factors such as the Cu content in S on the conversion of the light energy of the material into the heat energy is realized, so that the optimal photo-thermal performance is obtained.
Advantageous effects
The invention adopts a hydrothermal synthesis method and regulates and controls Cu2-xThe Cu content, reaction temperature and the like in S to prepare Cu with high specific surface area and more defects2-xThe product of the S nanoflower is a good photocatalyst and a good photo-thermal material, can effectively improve the photo-thermal conversion efficiency of converting solar energy into heat energy, provides a new thought for the design and synthesis of a novel functional photo-thermal material, explores a new way for the reasonable utilization and development of solar energy, and is beneficial to solving the problems of energy shortage and environmental pollution in the world at present. The method has the advantages of mild and controllable reaction conditions, simple operation, strong practicability and capability of preparing the Cu2-xThe S nanoflower near-infrared photothermal material has the advantages of high efficiency, long service life, good stability and the like, and is convenient for large-scale popularization.
Drawings
FIG. 1 Cu obtained in example 12-xAn X-ray powder diffraction analysis pattern (XRD) of the S nanoflower near infrared photothermal material;
FIG. 2 Cu obtained in example 12-xA low power field emission Transmission (TEM) of the S nanoflower near infrared photothermal material;
FIG. 3 Cu obtained in example 12-xS ultraviolet visible absorption spectrum of the nanoflower near-infrared photothermal material;
FIG. 4 Cu obtained in example 12-xThe near infrared photothermal property test of the S nanometer flower near infrared photothermal material in different solvents is carried out, wherein (a) DMF solvent and (b) H2O；
FIG. 5 Cu obtained in example 12-xThe near infrared photothermal property of the S nanoflower near infrared photothermal material in DMF changes with the concentration;
FIG. 6 Cu obtained in example 12-xThe near infrared photothermal property of the S nanoflower near infrared photothermal material in water changes with concentration.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.20-x g (x = 0, 0.01, 0.05, 0.1) of copper nitrate trihydrate powder was weighed, added to 30ml of deionized water, followed by 0.307g of glutathione and 1.0g of cetyltrimethylammonium bromide, respectively, and stirred for 30min at room temperature to form a clear solution. Putting the solution into a 50 mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
The crystal structure and phase of the product were investigated by X-ray diffraction (XRD), and as shown in FIG. 1, the diffraction peaks of all samples were indexed to Cu in cubic phase2S (unit cell parameters: a = 5.561 ANG., JCPDS number 02-1284) means that although the experiment changed the ratio of reactants, it did not cause macroscopic changes in the phase and crystal structure. The appearance and size of the sample are characterized by a Transmission Electron Microscope (TEM), as shown in FIG. 2, it can be observed from the TEM image of the sample that the appearance of the four products is flower-like assembled by nanosheets, and the size is about 200nm to 700 nm. It can be seen that despite the varying proportions of reactants, the flower-like morphology of the resulting product is maintained. The structure of the nanometer flower isThe reflection of incident light among the nano sheets is facilitated, and the absorption of the material to the incident light is improved.
The invention analyzes the ultraviolet visible absorption spectrum of the sample. As shown in FIG. 3, Cu2S as a semiconductor has absorption in both the visible and near infrared regions. The light absorption intensity of the material in the visible light region and the near infrared light region varies with the copper content, and in the four samples, when the molar ratio of copper to sulfur is 1.9:1, the absorption intensity of the material in the two light regions is the highest.
The invention researches the near infrared photothermal property of the prepared material. As shown in fig. 4a, the order of temperature change for the four samples in DMF solvent under the same lighting conditions is: cu2-0.1S>Cu2S>Cu2-0.05S>Cu2-0.01S, the photo-thermal property of the material can be effectively adjusted by adjusting the content of copper in the cuprous sulfide. As can be seen from the results of the photothermal properties tested, Cu was contained therein2-0.1The photothermal properties of S are best, and the temperature of the DMF solution rises by 28 ℃ within 10 min. Under the same experimental conditions, the solvent is changed into water, and the temperature change of the four samples also accords with the Cu2-0.1S>Cu2S>Cu2-0.05S>Cu2-0.01The trend of S shows that the photo-thermal performance of the material is less influenced by the solvent. Continuing with Cu investigation2-xThe photothermal properties of S vary with material concentration, and the results show that the photothermal properties of the material, whether in water or DMF, increase with increasing material concentration. As can be seen from the above experimental results, Cu2-xThe photothermal property of S is related to the material itself, and is not greatly related to the solvent. As can be seen from the results of combining the uv-vis absorption spectra of the samples, the tendency of the photothermal properties of the four samples was consistent with their uv-vis absorption spectra, which was primarily presumed to be due to the difference in the absorption capacity of the samples for 980nm incident light. Sample Cu from the design of the Material2-xAlthough the change of the Cu content in S does not cause the phase change of the material, the electronic structure of the material can be changed due to the local Cu deficiency in the crystal, so that the light absorption capacity in a near infrared region is improved, and the photo-thermal property of the material is facilitatedAnd the conversion improves the photo-thermal performance of the material.
Example 2
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.10-x g (x = 0, 0.005, 0.025, 0.05) of copper nitrate trihydrate powder was weighed into 15ml of deionized water, followed by 0.154g of glutathione and 0.5g of cetyltrimethylammonium bromide, respectively, and stirred for 30min at room temperature to form a clear solution. Putting the solution into a 25 mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 3
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.40-x g (x = 0, 0.02, 0.1, 0.2) of copper nitrate trihydrate powder was weighed, added to 60ml of deionized water, followed by 0.614g of glutathione and 2.0g of cetyltrimethylammonium bromide, respectively, and stirred for 30min at room temperature to form a clear solution. Putting the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 4
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.207-x g (x = 0, 0.01, 0.05, 0.1) of copper sulfate pentahydrate powder was weighed, added to 30ml of deionized water, followed by 0.307g of glutathione and 1.0g of cetyltrimethylammonium bromide, respectively, and stirred at room temperature for 30min to form a clear solution. Putting the solution into a 50 mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 5
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.20 to x g (x = 0, 0.01, 0.05, 0.1) of copper nitrate trihydrate powder was weighed, added to 30ml of deionized water, followed by 0.076g of thiourea and 1.0g of cetyltrimethylammonium bromide, respectively, and stirred for 30min at room temperature to form a clear solution. Putting the solution into a 50 mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 6
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.20-x g (x = 0, 0.01, 0.05, 0.1) of copper nitrate trihydrate powder was weighed out and added to 30ml of deionized water, followed by 0.307g of glutathione and 0.412g of triethylene glycol, respectively, and stirring was continued at room temperature for 30min to form a clear solution. Putting the solution into a 50 mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 7
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.40-x g (x = 0, 0.02, 0.1, 0.2) of copper nitrate trihydrate powder was weighed out and added to 60ml of deionized water, followed by 0.152g of thiourea and 2.0g of cetyltrimethylammonium bromide, respectively, and stirring was continued for 30min at room temperature to form a clear solution. Putting the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
Example 8
Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower comprises the following steps:
0.40-x g (x = 0, 0.02, 0.1, 0.2) of copper nitrate trihydrate powder was weighed out and added to 60ml of deionized water, followed by 0.614g of glutathione and 0.824g of triethylene glycol, respectively, and stirring was continued at room temperature for 30min to form a clear solution. Putting the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into an oven, heating for 24 hours at 120 ℃, opening the reaction kettle after naturally cooling to room temperature, taking out a sample, centrifuging the sample for 3 minutes at the rotation speed of 10000 r/min by using a centrifuge, repeatedly and alternately washing the collected four black substances by using deionized water and absolute ethyl alcohol for multiple times, and then drying the four black substances in a vacuum oven at 60 ℃.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. Hydrothermal method for preparing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps of:
adding a copper salt into deionized water, stirring until the copper salt is completely dissolved, sequentially stirring a sulfur source and a surfactant to obtain a clear solution, wherein the volume molar ratio of the deionized water to the copper salt to the sulfur source to the surfactant is 20-40 mL: 0.15-4 mmol: 0.75-10 mmol: 2.5-300 mmol;
transferring the clear solution to a reaction kettle, carrying out hydrothermal reaction at 110-180 ℃ for 12-36 h, naturally cooling to room temperature, centrifuging the product, repeatedly and alternately cleaning with ethanol and deionized water in sequence, carrying out vacuum drying at 60 ℃, and collecting a black product, namely Cu2-xAnd (4) S nanoflower.
2. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: the copper salt in the step (1) is copper nitrate trihydrate, copper chloride and copper sulfate.
3. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: in the step (1), the copper salt is copper nitrate trihydrate.
4. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: the sulfur source in the step (1) is glutathione, thiourea or sulfur powder.
5. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: the sulfur source in the step (1) is glutathione.
6. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: the surfactant in the step (1) is cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and triethylene glycol.
7. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: the surfactant in the step (1) is cetyl trimethyl ammonium bromide.
8. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: when the copper salt in the step (1) is copper nitrate trihydrate, the sulfur source is glutathione, and the surfactant is cetyl trimethyl ammonium bromide, the molar volume ratio of the copper salt, the sulfur source, the surfactant and the deionized water is 0.828mmol, 0.824mmol, 0.807mmol or 0.786 mmol: 1 mmol: 2.744 mmol: 30 mL.
9. The hydrothermal process of claim 1, producing Cu2-xThe method for preparing the S nanoflower is characterized by comprising the following steps: and (3) transferring the clear solution to a reaction kettle in the step (2), and carrying out hydrothermal reaction at 120 ℃ for 24 hours.
10. Cu obtainable by a process according to any one of claims 1 to 92-xThe application of the S nanoflower is characterized in that: it is applied to near infrared photothermal materials.
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| CN111883642A (en) * | 2020-08-06 | 2020-11-03 | 重庆大学 | Cu 2-xS-based thermoelectric material and solvothermal preparation method |
| CN112536022A (en) * | 2020-11-22 | 2021-03-23 | 重庆交通大学 | CQDS/Cu2Preparation method of S nanoflower |
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| CN115491074A (en) * | 2022-09-26 | 2022-12-20 | 中国海洋大学 | Cuprous sulfide quantum dot-loaded reduced graphene oxide nano particle and composite coating |
| CN115888628A (en) * | 2022-11-30 | 2023-04-04 | 南京信息工程大学 | Cu 2-x Preparation method and application of S adsorption material |
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| CN116393171B (en) * | 2023-03-24 | 2024-05-14 | 哈尔滨工业大学（深圳） | Cu (copper) alloy9S5Base composite photocatalysis nano material, preparation method and application |
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| CN113611833A (en) * | 2021-07-30 | 2021-11-05 | 广东工业大学 | Application of cation intercalation modified CuS @ CTAB electrode material in zinc ion battery |
| CN113788493A (en) * | 2021-09-18 | 2021-12-14 | 安徽师范大学 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
| CN113788493B (en) * | 2021-09-18 | 2023-09-01 | 乌海瑞森新能源材料有限公司 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
| CN115491074A (en) * | 2022-09-26 | 2022-12-20 | 中国海洋大学 | Cuprous sulfide quantum dot-loaded reduced graphene oxide nano particle and composite coating |
| CN115491074B (en) * | 2022-09-26 | 2023-12-05 | 中国海洋大学 | Cuprous sulfide quantum dot loaded reduced graphene oxide nanoparticle and composite coating |
| CN115888628A (en) * | 2022-11-30 | 2023-04-04 | 南京信息工程大学 | Cu 2-x Preparation method and application of S adsorption material |
| CN116393171A (en) * | 2023-03-24 | 2023-07-07 | 哈尔滨工业大学（深圳） | Cu (copper) alloy 9 S 5 Base composite photocatalysis nano material, preparation method and application |
| CN116393171B (en) * | 2023-03-24 | 2024-05-14 | 哈尔滨工业大学（深圳） | Cu (copper) alloy9S5Base composite photocatalysis nano material, preparation method and application |
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