CN111243869B - Composite material, preparation method and application thereof - Google Patents

Composite material, preparation method and application thereof Download PDF

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CN111243869B
CN111243869B CN201910247708.XA CN201910247708A CN111243869B CN 111243869 B CN111243869 B CN 111243869B CN 201910247708 A CN201910247708 A CN 201910247708A CN 111243869 B CN111243869 B CN 111243869B
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composite material
sodium ion
ion hybrid
template
hybrid supercapacitor
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CN111243869A (en
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胡翔
温珍海
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Fujian Institute of Research on the Structure of Matter of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The application discloses the composite material, the composite material is a carbon/FeS quantum dot composite material, and has a three-dimensional ordered porous structure. The composite material has higher energy density and power density. And a preparation method of the composite material and application of the composite material in a sodium ion supercapacitor.

Description

Composite material, preparation method and application thereof
Technical Field
The application relates to a sodium ion hybrid supercapacitor and a preparation method of the sodium ion hybrid supercapacitor based on a three-dimensional ordered porous carbon/FeS quantum dot composite electrode, and belongs to the field of chemical materials.
Background
With the rapid development of the current global economy, the traditional non-renewable energy is consumed in a large amount, thereby causing a serious problem of environmental pollution, and thus the research and development of renewable energy technology are greatly promoted. Among the numerous energy storage devices, lithium ion batteries are most widely used, however, the problem of shortage of lithium resources due to the use of large-scale energy storage devices is becoming more serious. Therefore, scientists have conducted extensive research on sodium ion batteries with similar physicochemical properties to lithium, abundant resources and low price, but the power density of the sodium ion batteries is low, and the cycle performance is still not commercially used.
The super capacitor has longer cycle life, shorter charging time and higher power density than the lithium ion battery and the sodium ion battery, which are widely used, however, the working principle of the super capacitor is that electrolyte ions are absorbed between electrodes to store energy, so the obtained energy density is still low. The sodium ion hybrid super capacitor combines the respective advantages of a sodium ion battery and a super capacitor, the positive electrode of the super capacitor is made of an electrode material of a double electric layer capacitor, such as activated carbon, and the negative electrode of the super capacitor is made of a sodium ion battery negative electrode material through electrochemical oxidation-reduction reaction, so that high energy density and power density are obtained, and the super capacitor is one of the best choices of large power sources. At present, the research on the sodium ion hybrid super capacitor is less, and the working voltage interval is smaller, so that the energy storage density is not greatly improved, and the application of the sodium ion hybrid super capacitor is limited. In recent years, iron sulfide has the characteristics of low price, wide and easily available property, no toxicity, no harm, high specific capacity and the like, and is widely concerned. However, the iron sulfide material generates severe volume expansion in the process of intercalation and deintercalation with sodium ions, so that the circulation stability is poor, and the iron sulfide material is modified and assembled into the sodium ion capacitor, so that the sodium ion capacitor has a wide application prospect.
Disclosure of Invention
According to one aspect of the application, the composite material is a three-dimensional ordered porous carbon/FeS quantum dot composite material, and is used as a sodium ion mixed supercapacitor negative electrode material, a three-dimensional porous structure is obtained by compounding FeS with quantum dot size and a three-dimensional ordered porous carbon material, the three-dimensional porous structure formed by the FeS improves the conductivity of FeS, and volume expansion caused by electrochemical reaction due to FeS and sodium ion intercalation and deintercalation is effectively prevented, so that excellent circulation stability is obtained. On the other hand, the quantum dot sized FeS active material can provide a shorter sodium ion transmission path, and the three-dimensional porous structure is beneficial to the permeation of electrolyte, so that more FeS and sodium ions participate in the reaction, and higher energy density and power density are obtained.
The composite material is characterized in that the composite material is a carbon/FeS quantum dot composite material and has a three-dimensional ordered porous structure.
Optionally, the composite material comprises a framework material and an active substance; the framework material is three-dimensional ordered porous carbon; the active material is FeS quantum dots.
Optionally, the pore diameter of the three-dimensional ordered porous carbon is 150-180 nm;
the particle size of the FeS quantum dots is 1-5 nm.
Optionally, the FeS quantum dots are crystals; the exposed surface of the FeS quantum dot is selected from at least one of a (102) surface, a (110) surface and a (100) surface.
According to another aspect of the application, a preparation method of the composite material is provided, and the method has the advantages of simple production process, environmental friendliness, high product yield, easy industrial scale-up and realization of commercialization. The preparation method of the composite material comprises the steps of taking an iron oleate precursor as an iron source, thiourea as a sulfur source and silicon dioxide as a template, vulcanizing the iron oleate into an FeS active material in the high-temperature heat treatment process, and simultaneously carbonizing and graphitizing the carbon substrate with an organic oleic acid matched chain to be attached to SiO2The surface of the template is finally etched with SiO2Complex of three-dimensional ordered porous carbon/FeS quantum dot obtained by templateAnd (5) synthesizing the materials.
The preparation method of the composite material is characterized by comprising the following steps:
and calcining the mixture containing the template agent, the iron source and the sulfur source in an inactive atmosphere, and removing the template agent to obtain the composite material.
Optionally, the particle size of the template agent is 150-180 nm;
the sulfur source comprises at least one of thiourea and sulfur powder.
Optionally, the template agent is monodisperse spherical SiO2。
Optionally, the iron source is iron oleate.
Optionally, the preparation method of the template comprises the following steps:
adding a silicon source into a mixed solution I containing ethanol, water and ammonia water at 30 ℃, stirring for 5-7 hours, separating, and drying to obtain the microsphere template.
Optionally, the volume ratio of the silicon source to the ethanol to the water to the ammonia water is 6-8: 70-80: 8-12: 2 to 4.
Optionally, the preparation method of the iron source comprises the following steps:
adding inorganic ferric salt and organic acid sodium into a mixed solution II containing ethanol, water and hexane, and refluxing the mixed solution II for 4-6 hours at the temperature of 60-80 ℃ to obtain an iron source.
Optionally, the volume ratio of the inorganic iron salt to the organic acid sodium salt to the ethanol to the water to the hexane is 10-15: 30-40: 35-45: 25-35: 60-80.
Optionally, the molar ratio of the template agent to the iron source to the sulfur source is 2-5: 2-1: 2 to 1.
Optionally, the inert gas is selected from at least one of nitrogen and inert gas;
the calcining temperature is 600-800 ℃, and the calcining time is 1-3 hours;
and heating to the calcining temperature at a heating rate of 1-3 ℃/min.
Alternatively, the temperature of the calcination is 700 ℃ and the time of the calcination is 2 hours;
the temperature is raised to the calcination temperature by a temperature rise rate of 2 ℃/min.
Optionally, the template is removed by etching.
Optionally, the template agent is spherical SiO2And removing by alkali etching.
Optionally, the iron source is iron oleate.
Optionally, the method comprises the steps of:
(1) adding tetraethyl orthosilicate into a mixed solution of ethanol, deionized water and ammonia water at the temperature of 30 ℃, stirring for 2 hours, and centrifugally drying to obtain monodisperse SiO2A template ball;
(2) dissolving ferric chloride hexahydrate and sodium oleate in a mixed solution of ethanol, water and hexane, and refluxing at 70 ℃ for 5 hours to obtain ferric oleate serving as an iron source;
(2) mixing the obtained iron oleate with thiourea and SiO2Uniformly mixing the template balls to obtain a viscous mixture, and calcining the viscous mixture in a tubular furnace to obtain SiO2Intermediate product of/FeS/C;
(4) mixing SiO2Etching SiO by intermediate product of/FeS/C in sodium hydroxide solution2And (4) template to obtain the three-dimensional ordered porous carbon/FeS quantum dot composite material.
As an embodiment, the method for using the three-dimensional ordered porous carbon/FeS quantum dot composite material as the cathode material of the sodium-ion mixed supercapacitor comprises the following steps:
1. mixing ethanol and deionized water at a volume of 7:1 at 30 ℃, then dripping 6ml of ammonia water and stirring for 30min, then adding 5.6ml of tetraethyl orthosilicate, continuously stirring for 2h at 30 ℃, and then centrifugally drying to obtain monodisperse SiO2A template ball;
2. dissolving 40 millimole ferric chloride hexahydrate and 120 millimole sodium oleate in a mixed solution of 80ml ethanol, 60ml water and 140ml hexane, refluxing the mixed solution obtained by ultrasonic stirring in an oil bath kettle at 70 ℃ for 5 hours, and separating out a ferric oleate precursor after the reaction is finished;
3. 1g of iron oleate, 500mg of dioxideUniformly mixing the silicon template ball and 2g of thiourea, finally placing the obtained viscous mixture in a tubular furnace in argon atmosphere, heating to 700 ℃ at the heating rate of 2 ℃/min, calcining for 2h, and cooling to room temperature after complete reaction to obtain SiO2A complex of/FeS/C;
4. etching the intermediate product naturally cooled to room temperature in 1 mol/L sodium hydroxide solution to obtain the three-dimensional ordered porous carbon/FeS quantum dot composite material;
5. the prepared composite material is assembled into a sodium ion hybrid supercapacitor, and the performance of the sodium ion hybrid supercapacitor is tested in an electrochemical workstation and a blue battery testing system.
According to another aspect of the application, a negative electrode material is provided, which comprises at least one of the composite material and the composite material prepared by the method.
According to another aspect of the application, a sodium ion hybrid supercapacitor comprises the negative electrode material. The capacitor material has the advantages of high energy density and power density.
The beneficial effects that this application can produce include:
1) the composite material provided by the application is a composite material of three-dimensional ordered porous carbon/FeS quantum dots, the conductivity of the material can be greatly improved due to the three-dimensional ordered porous structure, the transmission dynamics among electrode materials can be improved, the volume expansion of FeS can be inhibited, and excellent energy density and power density can be obtained.
2) The preparation method of the composite material provided by the application has the advantages of simple production process, environmental friendliness, high product yield, easiness in industrial amplification and realization of commercialization.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product of a manufacturing process embodying the present invention.
FIG. 2 is a field emission scanning electron microscope image of a product obtained by the preparation process of the present invention.
FIG. 3 is a transmission electron microscope image of the product obtained by the preparation process of the present invention.
FIG. 4 is a high resolution transmission electron microscope image of the product of the present invention embodied in the preparation process.
Fig. 5 and 6 are constant current charge and discharge curves of the electrode material prepared by the preparation process of the invention under different current densities.
FIG. 7 is a graph of energy density of electrode materials prepared by the process of the present invention at different power densities.
FIG. 8 is a test chart of the long-cycle stability of the electrode material prepared by the preparation process of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
XRD analysis was performed using a Miniflex 600 powder X-ray diffractometer.
SEM analysis was performed using a Hitachi SU-8020 model field emission scanning electron microscope.
TEM and HRTEM analyses were performed using a field emission transmission electron microscope model Tecnai F20.
Electrical performance analysis was performed using CHI760E electrochemical workstation from shanghai chenhua corporation and wuhan LAND CT2001 battery test system.
Example 1 sample 1#Preparation of (2)
1. Preparing a template;
mixing ethanol and deionized water at a volume of 7:1 at 30 ℃, wherein the volume of ethanol is 70mL and the volume of deionized water is 10mL, then dripping 6mL ammonia water, stirring for 30min, then adding 5.6mL tetraethyl orthosilicate, continuously stirring for 2h at 30 ℃, and centrifugally drying to obtain monodisperse SiO2And (4) template balls.
2. Preparing a precursor;
40 mmole of ferric chloride hexahydrate and 120 mmole of sodium oleate were dissolved in ethanol: water: and in 280mL of a mixed solution with the hexane volume ratio of 4:3:7, refluxing the mixed solution obtained by ultrasonic stirring in an oil bath kettle at 70 ℃ for 5 hours, and separating out an iron oleate precursor after the reaction is finished.
3. A calcination process;
uniformly mixing 1g of iron oleate, 500mg of silica template balls and 2g of thiourea, finally placing the obtained viscous mixture in a tubular furnace in argon atmosphere, heating to 700 ℃ at the heating rate of 2 ℃/min, calcining for 2h, cooling to room temperature after complete reaction to obtain SiO2Complex of/FeS/C.
4. Etching process;
mixing SiO2And etching the silicon dioxide template by the/FeS/C compound in 1 mol/L sodium hydroxide solution to obtain the three-dimensional ordered porous carbon/FeS quantum dot composite material. The composite material thus prepared was sample 1#。
Example 2 sample 2#～6#Preparation of (2)
The preparation method is the same as that of example 1, except that the silicon source tetraethyl orthosilicate is replaced by 7ml, and the prepared composite material is sample 2#。
The preparation method is the same as that of example 1, except that the calcination temperature is 800 ℃, and the prepared composite material is sample 3#。
The preparation method is the same as that of example 1, except that the calcination time is 3 hours, and the prepared composite material is sample 4#。
The preparation method is the same as that of example 1, except that the thiourea as the sulfur source is replaced by sulfur powder, and the prepared composite material is sample 5#。
The preparation method is the same as example 1, except that the heating rate is replaced by 1 ℃/min, and the prepared composite material is sample 6#。
Example 3 sample 1#～6#Structural characterization of
Sample 1#～6#The preparation of (A) is carried out by XRD analysis test, and the test conditions are as follows: the scanning interval is 10-80 degrees, and the scanning speed is 5 degrees/min. Typical test results are shown in FIG. 1, corresponding to sample 1 prepared in example 1#. FIG. 1 shows that the sample is FeS pure phase and has no other impurity peaksThe corresponding standard PDF card is JCPDS NO. 65-9124.
Sample 2#～6#The XRD pattern of fig. 1 is similar.
Example 4 sample 1#～6#Topography characterization of
Sample No. 1#～6#The preparation of (2) was subjected to a topography analysis test. Typical SEM test results are shown in FIG. 2, corresponding to sample 1 prepared in example 1#. Typical TEM test results are shown in FIG. 3, corresponding to sample 1 prepared in example 1#. Typical HRTEM test results are shown in FIG. 4, corresponding to sample 1 prepared in example 1#. Fig. 2-4 show that the prepared FeS active material is a three-dimensional ordered porous structure, and FeS quantum dots are uniformly embedded in a porous carbon frame, so that the unique structural advantage is beneficial to electrolyte permeation in a circulation process, volume expansion is reduced, and the electron conduction capability of the whole electrode material is improved.
Sample 2#～6#Morphology of (1) and sample#Similarly.
Example 5 sample 1#～6#Characterization of the Electrical Properties
Preparing an electrode slice: mixing porous activated carbon, a conductive agent (Super P) and a binder (sodium carboxymethylcellulose (CMC)) according to a mass ratio of 8:1:1, adding 1ml of deionized water to prepare slurry, coating the slurry on an aluminum foil, keeping the temperature of a vacuum drying oven at 100 ℃ for 24 hours, and rolling and slicing the slurry into a positive electrode plate with the diameter of 12 mm; preparing a negative plate: mixing the obtained carbon/FeS composite material, a conductive agent (Super P) and a binder (sodium carboxymethyl cellulose (CMC)) according to a mass ratio of 8:1:1, repeating the preparation process of the positive plate to obtain the negative plate, and finally dissolving 1 mol/L of sodium perchlorate in a volume ratio of 1: and 1, assembling the positive and negative electrode plates into the sodium ion hybrid supercapacitor in a glove box by taking the mixed solution of ethylene carbonate and propylene carbonate as electrolyte.
Performance testing typical test structures are shown in FIGS. 5 to 8, corresponding to sample 1#. FIGS. 5 and 6 show sample 1#Constant current charge and discharge curve diagrams under different current densities; FIG. 7 shows sample 1#At a different placeAn energy density map at power density; FIG. 8 shows sample 1#Stability performance test pattern in long cycle. The test conditions were: under the condition of room temperature, the voltage window is 0.01-4.0V, and the current density is 0.1A/g, 0.2A/g, 0.4A/g, 0.8A/g, 1.6A/g, 3.2A/g and 6.4A/g respectively. Fig. 5 to 8 show: the working voltage of the sodium ion hybrid super capacitor can reach 3.4V after a cyclic voltammetry test is carried out on an electrochemical workstation, the assembled sodium ion hybrid super capacitor is subjected to cyclic and multiplying power tests in a blue battery test system, the specific volume reaches 62-129F/g, the energy density reaches 72.2-151.8 Wh/kg, the power density reaches 145-9280W/kg, the charge and discharge cycle is carried out for 5000 cycles at the rate of 1A/g, and the capacity retention rate reaches 91% of the initial state.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A sodium ion hybrid supercapacitor is characterized by comprising a negative electrode material; the anode material comprises a composite material;
the composite material is a carbon/FeS quantum dot composite material and has a three-dimensional ordered porous structure;
the aperture of the three-dimensional ordered porous carbon is 150-180 nm;
the particle size of the FeS quantum dots is 1-5 nm.
2. The sodium ion hybrid supercapacitor according to claim 1, wherein the method for preparing the composite material comprises the following steps:
and calcining the mixture containing the template agent, the iron source and the sulfur source in an inactive atmosphere, and removing the template agent to obtain the composite material.
3. The sodium ion hybrid supercapacitor according to claim 2,
the particle size of the template agent is 150-180 nm;
the sulfur source comprises at least one of thiourea and sulfur powder.
4. The sodium ion hybrid supercapacitor according to claim 2, wherein the templating agent is monodisperse spherical SiO2。
5. The sodium ion hybrid supercapacitor of claim 2, wherein the iron source is iron oleate.
6. The sodium ion hybrid supercapacitor according to claim 2, wherein the molar ratio of the template to the iron source to the sulfur source is 2-5: 2-1: 2 to 1.
7. The sodium ion hybrid supercapacitor according to claim 2, wherein the inert atmosphere is selected from at least one of nitrogen, an inert atmosphere;
the calcining temperature is 600-800 ℃, and the calcining time is 1-3 hours;
and heating to the calcining temperature at a heating rate of 1-3 ℃/min.
8. The sodium ion hybrid supercapacitor according to claim 2, wherein the template agent is removed by etching.
9. The sodium ion hybrid supercapacitor of claim 8, wherein the templating agent is spherical SiO2And removing by alkali etching.
10. The sodium ion hybrid supercapacitor according to claim 2, comprising the steps of:
(1) at 30 deg.CAdding tetraethyl orthosilicate into a mixed solution of ethanol, deionized water and ammonia water, and stirring to obtain monodisperse SiO2A template ball;
(2) dissolving ferric chloride hexahydrate and sodium oleate in a mixed solution of ethanol, water and hexane, and refluxing for 4-6 hours at 60-80 ℃ to obtain ferric oleate serving as an iron source;
(3) mixing the obtained iron oleate with thiourea and SiO2Uniformly mixing the template spheres to obtain a viscous mixture, calcining to obtain SiO2A complex of/FeS/C;
(4) etching to remove SiO2And (5) template ball to obtain the composite material.
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