CN113198398A - Preparation method of CuS-graphene composite aerogel - Google Patents

Preparation method of CuS-graphene composite aerogel Download PDF

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CN113198398A
CN113198398A CN202110596535.XA CN202110596535A CN113198398A CN 113198398 A CN113198398 A CN 113198398A CN 202110596535 A CN202110596535 A CN 202110596535A CN 113198398 A CN113198398 A CN 113198398A
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copper
cus
graphene
sulfur
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沈晓冬
李砚涵
夏雨
崔升
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Nanjing Tech University
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    • 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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Abstract

The patent belongs to the field of preparation processes of nano porous materials, and relates to a preparation method of CuS-graphene composite aerogel. The method is firstly toMixing a copper source and a sulfur source in a solvent, introducing graphene and a catalyst, aging, and finally drying. The CuS-graphene composite aerogel prepared by the sol-gel method has the characteristics of high CuS specific capacity, low price, environmental friendliness, strong graphene conductivity and high cycle stability, has the advantages of many active sites, short charge transmission path and high mass transfer performance, and is a good electrode material of the ion battery. The density of the prepared CuS-graphene aerogel is 0.08-0.36 g/cm3The specific surface area is 98-324 m2The specific reversible capacity of the sodium-electricity cathode is 420-1400 mAh/g under the current density of 5A/g. The preparation method has the advantages of simple process, short reaction period and mass production prospect.

Description

Preparation method of CuS-graphene composite aerogel
Technical Field
The invention belongs to the field of preparation processes of nano-porous materials, and relates to a preparation method of a CuS-graphene composite aerogel.
Background
With the rapid development of high and new technologies and the continuous deepening of urbanization processes, energy and environmental problems become important challenges for human beings, and with the rapid development of mobile internet and communication technologies, portable electronic devices, artificial intelligent equipment and the like are rapidly moving into thousands of households and changing the life styles of people, and the rapid development of high-energy density and high-safety ion battery technologies is also promoted. The development of new technology for storing energy by ion batteries is related to the sustainable development of human beings and the change of production life style. The sodium ion battery is expected to be a substitute of the lithium ion battery in the field of energy storage due to the advantages of abundant sodium resources, low cost and the like. However, the common commercialized negative electrode material has the problems of potential safety hazard, low theoretical capacity and the like, and the development of the sodium-electricity negative electrode material with excellent performance has important significance in the fields of energy storage, catalysis and the like by virtue of the advantages of high specific capacity, low price, environmental friendliness and the like of the copper sulfide material, and shows unique advantages relative to oxides. The performance of the material can be further improved by increasing the specific surface area of the material and optimizing the pore structure in the material. Graphene is one of durable hot door materials in the field of electrochemistry, has excellent conductivity and mechanical properties, can form an effective conductive network when being introduced into an electrode material, can effectively improve the circulation stability of the graphene, and accelerates the electron transfer rate. The aerogel, as a material structure which is intrinsically provided with a large specific surface area and a developed pore structure, is combined with copper sulfide and graphene, so that on one hand, the contact area with reactants can be enlarged, active sites of electrocatalytic reaction are increased, a charge transmission path is shortened, the mass transfer performance of an electrode is improved, on the other hand, agglomeration among electrode material particles can be inhibited, and the utilization rate of active substances is improved.
Currently, most of aerogels containing a CuS-graphene system are graphene as a carrier to load CuS nano-particles, so that the electrochemical performance of the system is greatly limited, and CuS nanosphere modified graphene aerogel composite materials (Bano Z, Saeed R, Zhu S, et al. mesoporous CuS nanoparticles purified rGO aeogel for high cationic activity devices Cr (VI) and organic polutants [ J ]. Chemosphere,2020:125846.) prepared by Bano Zahira et al have excellent degradation performance on tetravalent chromium and cationic dyes and do not show good electrochemical storage performance. As a conductive material, graphene has a small contribution to the energy storage effect of the material, and the addition amount of graphene should be controlled to maintain the balance between the electrochemical performance and the conductivity. Therefore, the preparation of the CuS-graphene composite aerogel has great research value.
Disclosure of Invention
The invention aims to provide a method for preparing a blocky CuS-graphene composite aerogel by a sol-gel method.
The technical scheme of the invention is as follows: a preparation method of CuS-graphene composite aerogel comprises the following specific steps: (1) pouring the solvent into a container, adding the copper source and the sulfur source according to the proportion, and stirring until the copper source and the sulfur source are completely dissolved to form a copper-sulfur solution;
(2) measuring a certain amount of graphene oxide aqueous solution, adding the graphene oxide aqueous solution into the copper-sulfur solution prepared in the step (1), and continuously stirring for 1-5 hours to obtain a copper-sulfur-graphene oxide mixed solution;
(3) measuring a certain amount of catalyst, adding the catalyst into the copper-sulfur-graphene oxide mixed solution prepared in the step (2), continuously stirring for 10-60 min, transferring the mixed solution to an oven after stirring, and standing to obtain CuS-graphene wet gel;
(4) and (4) adding ethanol into the CuS-graphene wet gel prepared in the step (3) for aging, and then drying to obtain the CuS-graphene composite aerogel.
Preferably, the solvent in step (1) is one or a mixture of two of methanol, ethanol or isopropanol.
Preferably, the copper source in step (1) is one of copper nitrate trihydrate, copper chloride dihydrate or copper sulfate pentahydrate. The sulfur source is one of thioglycolic acid, mercaptopropionic acid, mercaptosuccinic acid or 6-mercaptohexanoic acid.
Preferably, the concentration of the copper source in the solvent in the step (1) is 0.1-3.1M. The molar ratio of the copper source to the sulfur source in the step (1) is 1 (1-10). The stirring time in the step (1) is 30-180 min.
Preferably, the concentration of the graphene oxide aqueous solution in the step (2) is 1 mg/mL-30 mg/mL; the mass ratio of the graphene oxide in the used graphene oxide aqueous solution to the copper source is 0.0039-0.01.
Preferably, the catalyst in the step (3) is one of formamide or propylene oxide; the volume ratio of the catalyst to the solvent used in the step (1) is 1 (10-50).
Preferably, the standing temperature of the copper-sulfur-graphene oxide mixed solution in the oven in the step (3) is 30-100 ℃, and the standing time is 12-72 hours.
Preferably, the aging process time in the step (4) is 72-168 hours, and ethanol is replaced every 12-48 hours; the drying method comprises freeze drying and CO2Supercritical drying or ethanol supercritical drying.
The density of the CuS-graphene aerogel prepared by the method is 0.08-0.36 g/cm3The specific surface area is 98-324 m2The specific reversible capacity of the sodium-electricity cathode is 420-1400 mAh/g under the current density of 5A/g.
Has the advantages that:
(1) compared with the existing sulfide aerogel preparation technology, the preparation method can utilize the sulfur source to provide sulfur element in the gelling process, form the CuS gel framework in one step, is simple and convenient to operate, and the produced sample has good stability, and is expected to realize batch production.
(2) The CuS-graphene composite aerogel prepared by the invention is blocky and is convenient for subsequent processing and transportation.
(3) The CuS-graphene composite aerogel prepared by the invention has the characteristics of high specific surface area, large porosity and uniform holes, the hole structure is adjustable, the structural stability is high, the specific capacity is high, and the CuS-graphene composite aerogel is a good sodium ion battery cathode material.
Drawings
Fig. 1 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of the CuS-graphene composite aerogel prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of protection.
Example 1
100mL of ethanol, 2.42g of copper nitrate trihydrate and 1.50g of mercaptosuccinic acid (molar ratio of copper to sulfur is 1:1, concentration of copper nitrate and trihydrate is 0.1M in ethanol) are added to a beaker and stirred for 30min to form a copper-sulfur solution. Adding 24.2mL of 1mg/mL graphene oxide aqueous solution into the copper-sulfur solution, stirring for 1h to obtain a copper-sulfur-graphene oxide mixed solution, then adding 2mL formamide, continuing stirring for 10min, transferring the mixture to a 100 ℃ oven, and standing for 12h to obtain the CuS-graphene wet gel. And then, adding ethanol into the CuS-graphene wet gel in an oven at 100 ℃ for aging, wherein the ethanol is added in an amount which is based on that the wet gel is not soaked, and the aging time is 72 hours, and during the aging time, the ethanol is replaced every 12 hours. And (2) placing the CuS-graphene wet gel into a reaction kettle for ethanol supercritical drying, setting the drying temperature to be 265 ℃, keeping the pressure at 8MPa after the temperature rises, keeping the pressure for 3 hours under the constant temperature and the constant pressure, then keeping the constant speed, releasing gas within 30min, and taking out the container after the temperature of the reaction kettle drops to obtain the CuS-graphene aerogel. The prepared material has the density of 0.08g/cm3, the specific surface area of 324m2/g and the average pore diameter of 21nm, and has the reversible specific capacity of 420mAh/g when being used as a sodium electric cathode under the current density of 5A/g.
Fig. 1 is a nitrogen adsorption-desorption curve and a pore diameter distribution diagram of the prepared CuS-graphene composite aerogel, wherein the curve is an iv-type isotherm, the pore diameter is distributed in the range of 1-100 nm, and the average pore diameter is 21nm, which indicates that the CuS-graphene composite aerogel is successfully prepared.
Example 2
72mL of methanol, 36.83g of copper chloride dihydrate and 198.98g of thioglycolic acid (copper to sulfur molar ratio 1:10, copper chloride dihydrate concentration 3M in methanol) were added to a beaker and stirred for 65min to form a copper-sulfur solution. Adding 4.91mL of 30mg/mL graphene oxide aqueous solution into the copper-sulfur solution, stirring for 2h to obtain a copper-sulfur-graphene oxide mixed solution, then adding 7.2mL formamide, continuing stirring for 25min, transferring the mixture to a 30 ℃ oven, and standing for 72h to obtain the CuS-graphene wet gel. And then, adding ethanol into the CuS-graphene wet gel in an oven at 30 ℃ for aging, wherein the ethanol is added in an amount which is based on that the wet gel is not soaked, and the aging time is 168h, and during the aging time, the ethanol is replaced every 48 h. And (3) placing the CuS-graphene wet gel into a reaction kettle for CO2 supercritical drying, setting the drying temperature at 48 ℃, keeping the drying temperature for 10 hours at a constant pressure of 10MPa at a certain air outlet rate, closing air inlet, and releasing the pressure in the reaction kettle to obtain the CuS-graphene aerogel. The prepared material has the density of 0.13g/cm3, the specific surface area of 215m2/g and the average pore diameter of 10nm, and has the reversible specific capacity of 610mAh/g when being used as a sodium electric cathode under the current density of 5A/g.
Example 3
300mL of isopropanol, 149.81g of copper sulfate pentahydrate and 318.42g of mercaptopropionic acid (copper to sulfur molar ratio 1:5, copper sulfate pentahydrate concentration 2M in isopropanol) were added to a beaker and stirred for 100min to form a copper-sulfur solution. Adding 149.81mL of 5mg/mL graphene oxide aqueous solution into the copper-sulfur solution, stirring for 3h to obtain a copper-sulfur-graphene oxide mixed solution, then adding 15mL of propylene oxide, continuing stirring for 40min, transferring the mixture to a 65 ℃ oven, and standing for 42h to obtain the CuS-graphene wet gel. And then, adding ethanol into the CuS-graphene wet gel in an oven at 65 ℃ for aging, wherein the amount of the ethanol is based on the fact that the wet gel is not soaked, and the aging time is 96 hours, and during the aging time, the ethanol is replaced every 21 hours. And (2) placing the CuS-graphene wet gel into a reaction kettle for ethanol supercritical drying, setting the drying temperature to be 260 ℃, raising the temperature, maintaining the pressure at 7MPa and the constant temperature and pressure for 2 hours, then keeping the constant speed, releasing gas within 30min, and taking out the container after the temperature of the reaction kettle is reduced to obtain the CuS-graphene aerogel. The prepared material has the density of 0.36g/cm3, the specific surface area of 98m2/g and the average pore diameter of 35nm, and the reversible specific capacity of 1400mAh/g when the material is used as a sodium electric cathode under the current density of 5A/g.
Example 4
75mL of methanol, 85mL of ethanol, 27.28g of copper chloride dihydrate and 189.73g of 6-mercaptohexanoic acid (the molar ratio of copper to sulfur is 1:8, and the concentration of the copper chloride dihydrate in the mixed solution of the methanol and the ethanol is 1M) are added into a beaker and stirred for 140min to form a copper-sulfur solution. Adding 9.55mL of 20mg/mL graphene oxide aqueous solution into the copper-sulfur solution, stirring for 4h to obtain a copper-sulfur-graphene oxide mixed solution, then adding 4mL of formamide, continuing stirring for 50min, transferring the mixture to a 50 ℃ oven, and standing for 30h to obtain the CuS-graphene wet gel. And then, adding ethanol into the CuS-graphene wet gel in an oven at 50 ℃ for aging, wherein the amount of the ethanol is based on the fact that the wet gel is not soaked, and the aging time is 120h, and during the aging time, the ethanol is replaced every 38 h. Quenching the CuS-graphene wet gel by using liquid nitrogen, and then drying for 24 hours in a freeze dryer with 50Pa to obtain the CuS-graphene aerogel. The prepared material has the density of 0.27g/cm3, the specific surface area of 149m2/g and the average pore diameter of 19nm, and has the reversible specific capacity of 780mAh/g when being used as a sodium electric negative electrode under the current density of 5A/g.
Example 5
200mL of ethanol, 340mL of isopropanol, 65.23g of copper nitrate trihydrate and 74.62g of thioglycolic acid (molar ratio of copper to sulfur is 1:3, concentration of the copper nitrate and the water in the mixed solution of ethanol and isopropanol is 0.5M) are added into a beaker and stirred for 180min to form a copper-sulfur solution. Adding 52.19mL of 10mg/mL graphene oxide aqueous solution into the copper-sulfur solution, stirring for 5h to obtain a copper-sulfur-graphene oxide mixed solution, then adding 18mL of formamide, continuing stirring for 10min, transferring the mixture to an oven at 85 ℃, and standing for 60h to obtain CuS-graphene wet gel. And then, adding ethanol into the CuS-graphene wet gel in an oven at 85 ℃ for aging, wherein the amount of the ethanol is based on the fact that the wet gel is not soaked, and the aging time is 144h, and during the aging time, the ethanol is replaced every 30 h. And (3) placing the CuS-graphene wet gel into a reaction kettle for CO2 supercritical drying, setting the drying temperature to be 52 ℃, maintaining the drying temperature for 7 hours at a constant pressure of 9MPa at a certain air outlet rate, closing air inlet, and releasing the pressure in the reaction kettle to obtain the CuS-graphene aerogel. The prepared material has the density of 0.19g/cm3, the specific surface area of 216m2/g and the average pore diameter of 28nm, and has the reversible specific capacity of 1050mAh/g when being used as a sodium electric cathode under the current density of 5A/g.

Claims (10)

1. A preparation method of CuS-graphene composite aerogel comprises the following specific steps:
(1) pouring the solvent into a container, adding the copper source and the sulfur source according to the proportion, and stirring until the copper source and the sulfur source are completely dissolved to form a copper-sulfur solution;
(2) measuring a certain amount of graphene oxide aqueous solution, adding the graphene oxide aqueous solution into the copper-sulfur solution prepared in the step (1), and continuously stirring for 1-5 hours to obtain a copper-sulfur-graphene oxide mixed solution;
(3) measuring a certain amount of catalyst, adding the catalyst into the copper-sulfur-graphene oxide mixed solution prepared in the step (2), continuously stirring for 10-60 min, transferring the mixed solution to an oven after stirring, and standing to obtain CuS-graphene wet gel;
(4) and (4) adding ethanol into the CuS-graphene wet gel prepared in the step (3) for aging, and then drying to obtain the CuS-graphene composite aerogel.
2. The method according to claim 1, wherein the solvent in step (1) is one or a mixture of methanol, ethanol or isopropanol.
3. The method according to claim 1, wherein the copper source in the step (1) is one of copper nitrate trihydrate, copper chloride dihydrate or copper sulfate pentahydrate; the sulfur source is one of thioglycolic acid, mercaptopropionic acid, mercaptosuccinic acid or 6-mercaptohexanoic acid.
4. The method according to claim 1, wherein the stirring time in the step (1) is 30 to 180 min.
5. The method according to claim 1, wherein the concentration of the copper source in the solvent in the step (1) is 0.1 to 3.1M.
6. The method according to claim 1, wherein the molar ratio of the copper source to the sulfur source in step (1) is 1 (1 to 10).
7. The method according to claim 1, wherein the concentration of the aqueous solution of graphene oxide in step (2) is 1mg/mL to 30 mg/mL; the mass ratio of the graphene oxide in the used graphene oxide aqueous solution to the copper source is 0.0039-0.01.
8. The process according to claim 1, wherein the catalyst in the step (3) is one of formamide or propylene oxide; the volume ratio of the catalyst to the solvent used in the step (1) is 1 (10-50).
9. The method according to claim 1, wherein the temperature of the step (3) is 30 to 100 ℃ and the time of the step (3) is 12 to 72 hours.
10. The preparation method according to claim 1, wherein the aging process time in the step (4) is 72-168 hours, during which ethanol is changed every 12-48 hours; the drying method comprises freeze drying and CO2Supercritical drying or ethanol supercritical drying.
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CN114156447A (en) * 2021-11-17 2022-03-08 南京来璋新材料科技有限公司 Sandwich structure composite material for magnesium ion battery anode and preparation method thereof
CN115010191A (en) * 2022-07-05 2022-09-06 浙江帕瓦新能源股份有限公司 Battery material precursor and preparation method and application thereof
CN115487850A (en) * 2022-10-28 2022-12-20 南京工程学院 Photo-thermal catalytic composite material and preparation method and application thereof

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CN114156447A (en) * 2021-11-17 2022-03-08 南京来璋新材料科技有限公司 Sandwich structure composite material for magnesium ion battery anode and preparation method thereof
CN115010191A (en) * 2022-07-05 2022-09-06 浙江帕瓦新能源股份有限公司 Battery material precursor and preparation method and application thereof
CN115487850A (en) * 2022-10-28 2022-12-20 南京工程学院 Photo-thermal catalytic composite material and preparation method and application thereof
CN115487850B (en) * 2022-10-28 2023-10-24 南京工程学院 Photo-thermal catalytic composite material and preparation method and application thereof

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Application publication date: 20210803