CN110571063B - Sn2O3Nano-sheet/functional carbon nano-sheet composite material and preparation method thereof - Google Patents

Sn2O3Nano-sheet/functional carbon nano-sheet composite material and preparation method thereof Download PDF

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CN110571063B
CN110571063B CN201910781021.4A CN201910781021A CN110571063B CN 110571063 B CN110571063 B CN 110571063B CN 201910781021 A CN201910781021 A CN 201910781021A CN 110571063 B CN110571063 B CN 110571063B
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严学华
袁小雪
蒋辉
朱逸涵
程晓农
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00Compounds of tin
    • C01G19/02Oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
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    • H01G11/46Metal oxides
    • YGENERAL 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/13Energy storage using capacitors

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Abstract

The invention relates to a pseudo-capacitance electrode material, in particular to Sn2O3A nano-sheet/functionalized carbon nano-sheet composite material and a preparation method thereof. Firstly preparing functional carbon nano-sheets, and then carrying out hydrothermal reaction to generate Sn2O3The nano-sheet/functionalized carbon nano-sheet composite material has excellent electrochemical performance when being used as a super capacitor electrode material, is simple in preparation process, and has great application in the field of super capacitor energy storage.

Description

Sn2O3Nano-sheet/functional carbon nano-sheet composite material and preparation method thereof
Technical Field
The invention relates to a pseudo-capacitance electrode material, in particular to Sn2O3A nano-sheet/functionalized carbon nano-sheet composite material and a preparation method thereof. Firstly preparing functional carbon nano-sheets, and then carrying out hydrothermal reaction to generate Sn2O3The nano-sheet/functionalized carbon nano-sheet composite material has excellent electrochemical performance when being used as a super capacitor electrode material, is simple in preparation process, and has great application in the field of super capacitor energy storage.
Background
The energy crisis and the increasingly serious environmental problems prompt researchers to carry out deep research on sustainable and efficient energy storage devices, and the super capacitor is used as a novel energy storage element, and the development of the super capacitor plays a vital role in promoting the efficient and sustainable utilization of energy. Electrode materials may be classified into Electric Double Layer Capacitor (EDLC) electrode materials and pseudocapacitive electrode materials according to a charge storage mechanism. Pseudocapacitive electrode materials have a higher specific capacitance than EDLC electrode materials due to faradaic reactions that occur at the electrode/electrolyte surface.
Generally, transition metal oxides, as typical pseudocapacitive materials, have higher specific capacitance and energy density than double-layer capacitive materials. How to adopt proper materials and structures to improve the conductivity of metal oxides is one of the main challenges facing today. At present, there are two basic strategies for improving the electrochemical performance of supercapacitor electrode materials. The rational strategy is to increase the availability of active sites and promote the smooth progress of redox reactions. Another straightforward approach is to increase electron conductivity, providing an efficient way to accelerate the rapid diffusion of electrons.
The preparation method of the carbon nano material mainly comprises a laser graphite evaporation method, a plasma jet deposition method, a condensed phase electrolysis generation method, a graphite arc method and a chemical vapor deposition method, but the preparation and the wide application of the carbon nano material are limited by conditions of instrument and equipment, process parameters, production cost, yield and the like. The chemical activation mode can enable the surface of the carbon nanosheet to generate abundant functional groups, the surface wettability of the electrode can be obviously enhanced, other materials can be more easily grown on the surface of the carbon material, and an oxidation-reduction reaction can be generated in the charging and discharging process, so that additional pseudo-capacitance is provided. The calcination, activation and hydrothermal method involved in the invention is simple and convenient, and can realize carbon nano-sheets and Sn2O3Large-scale preparation of the nano-sheet/functionalized carbon nano-sheet composite material. Second, structurally, the present invention is prepared by mixing Sn2O3The nano sheets and the carbon nano sheets are compounded to construct the 2D/2D nano composite material, and the heterogeneous structure between the two-dimensional nano sheets of the composite material can promote the rapid transmission of charges in the electrochemical reaction process. In addition, in performance, the invention adopts pseudo-capacitive Sn2O3The combination of the nano-sheet and the carbon material with double electric layer capacitance makes full use of the synergistic effect of the nano-sheet and the carbon material with double electric layers capacitance in the charging and discharging process, and the functionalized carbon nano-sheet can improve the conductivity of the electrode material, so that the composite material solves the problem of Sn2O3Nano meterThe sheet has low conductivity and specific capacitance, and exhibits excellent electrochemical performance.
Disclosure of Invention
The invention aims to provide a stable 2D/2D composite morphology and can solve the problem of Sn2O3Sn with nanosheet monomer conductivity and low specific capacitance and full utilization of electric double layer capacitance and pseudocapacitance2O3A nanosheet/functionalized carbon nanosheet composite. The obtained product is a nano composite material with stable structure and good electrochemical performance.
Sn in the invention2O3The nano-sheet/functionalized carbon nano-sheet composite material has a stable structure. Sn (tin)2O3The thickness of the nano-sheet is 25nm, and the thickness of the carbon nano-sheet is 50nm, as shown in figure 1.
Sn in the invention2O3The nano-sheet/functionalized carbon nano-sheet composite material is compared with Sn2O3The electrochemical performance of the nanosheet monomer is remarkably improved. The specific capacity reached 126F/g at a scan rate of 10mV/s, as measured by a CV cycling test with a voltage ranging from-1 to 0.2V and a scan rate of 10mV/s to 50 mV/s. As shown in fig. 2. The technical scheme adopted for realizing the invention is as follows:
Sn2O3the method has the characteristics of simple process, low cost and the like, and the obtained two-dimensional Sn2O3The nano-sheets are uniformly dispersed on the surface of the functionalized carbon nano-sheet, and show excellent electrochemical performance in a super capacitor, and the preparation steps are as follows:
(1) weighing C6H5K3O7·H2And (3) loading the powder in a porcelain boat, putting the porcelain boat into a tubular furnace, heating the porcelain boat to a set temperature b at a certain heating rate a under the atmosphere of nitrogen, preserving the heat, then heating the porcelain boat to a set temperature d at a certain heating rate c, preserving the heat, naturally cooling, collecting a sample, cleaning the obtained powder with a dilute hydrochloric acid solution, washing the powder with deionized water and ethanol respectively, centrifuging the washed powder for three times, drying the washed powder in a vacuum drying box, and drying the dried powder for later use.
Said C6H5K3O7·H2The mass of O was 5 g.
The heating rate a is 2 ℃/min, the temperature b is set to be 450 ℃, and the heat preservation time is 1 h.
The heating rate c is 5 ℃/min, the temperature d is set to be 850 ℃, and the heat preservation time is 1 h.
The concentration of the hydrochloric acid solution is 1 mol/L.
The drying refers to drying for 24 hours in a vacuum drying oven at the temperature of 65 ℃.
(2) And (2) putting the powder obtained in the step (1) into a mixed solution of concentrated nitric acid and concentrated sulfuric acid, stirring in a water bath environment, standing after stirring for a certain time, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven to obtain the functionalized carbon nanosheet.
The volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 3: 1.
The water bath temperature is 85 ℃, and the stirring time is 12 h.
The standing time is 12 h.
The drying refers to drying for 24 hours in a vacuum drying oven at the temperature of 65 ℃.
(3) Preparing the functionalized carbon nanosheet prepared in the step (2) into a suspension, and adding SnCl2·2H2O and Na3C6H5O7·2H2O, continuously stirring and then carrying out ultrasonic treatment, adding NaOH solution, continuously stirring for a period of time, then transferring to a reaction kettle, and reacting at a certain temperature to enable the functionalized carbon nanosheets to better react with Sn2O3Compounding the nano sheets, naturally cooling to room temperature after the reaction is finished, washing and centrifuging for three times by using deionized water and ethanol respectively, and drying in a vacuum drying oven.
The concentration of the functionalized carbon nanosheet suspension is 4 g/L; the functional carbon nano sheet and SnCl2·2H2O and Na3C6H5O7·2H2The mass ratio of O is 0.08: 1.13: 2.94 of; the concentration of the NaOH solution is 0.4M; the volume ratio of the functionalized carbon nanosheet suspension to the NaOH solution is 2: 1.
The continuous stirring time is 30min, and the ultrasonic time is 30 min; continuously stirring for 10 min; the reaction temperature is 180 ℃, the reaction time is 12h, the drying temperature is 60 ℃, and the drying time is 10 h.
The invention is a preparation method with simple process and relatively low cost, firstly preparing carbon nano-sheets by a high-temperature method, then obtaining functional carbon nano-sheets by chemical activation, and finally synthesizing Sn by a hydrothermal method2O3The nano-sheet/functionalized carbon nano-sheet composite material has simple and convenient calcining, activating and hydrothermal methods, and can realize the carbon nano-sheet and Sn2O3Large-scale preparation of the nano-sheet/functionalized carbon nano-sheet composite material. Second, structurally, the present invention is prepared by mixing Sn2O3The nano sheets and the carbon nano sheets are compounded to construct the 2D/2D nano composite material, and the heterogeneous structure between the two-dimensional nano sheets of the composite material can promote the rapid transmission of charges in the electrochemical reaction process. In addition, in performance, the invention adopts pseudo-capacitive Sn2O3The combination of the nano-sheet and the carbon material with double electric layer capacitance makes full use of the synergistic effect of the nano-sheet and the carbon material with double electric layers capacitance in the charging and discharging process, and the functionalized carbon nano-sheet can improve the conductivity of the electrode material, so that the composite material solves the problem of Sn2O3The nano sheet monomer has low conductivity and specific capacitance, and shows excellent electrochemical performance.
Drawings
FIG. 1 shows Sn2O3Scanning electron microscope images of the nanosheet/functionalized carbon nanosheet composite.
FIG. 2 shows Sn2O3CV curve graphs of the nano-sheet/functionalized carbon nano-sheet composite material at different scanning rates.
Detailed Description
The present invention relates to Sn of excellent electrochemical performance2O3The preparation method of the nano-sheet/functionalized carbon nano-sheet composite material comprises the following steps:
(1) weighing 5g C6H5K3O7·H2The O is loaded by a porcelain boat and put into a tubeIn the furnace, the temperature is raised to 450 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, and the heat preservation time is 1 h. Then the temperature is raised to 850 ℃ at the heating rate of 5 ℃/min, and the heat preservation time is 1 h. After natural cooling, the sample was collected, and the obtained powder was washed with a dilute hydrochloric acid solution, then washed with deionized water and ethanol three times each, and dried in a vacuum drying oven at a temperature of 65 ℃ for 24 hours.
(2) Putting the powder obtained in the step (1) into a mixed solution of concentrated nitric acid and concentrated sulfuric acid (the volume ratio is 3:1), stirring for 12 hours in a water bath environment at 85 ℃, standing for 12 hours, washing with deionized water and absolute ethyl alcohol to be neutral, and drying for 24 hours in a vacuum drying oven at the temperature of 65 ℃.
(3) Preparing the functionalized carbon nanosheet prepared in the step (2) into a suspension with the volume of 4g/L being 20ml, and adding 1.13g of SnCl2·2H2O and 2.94g Na3C6H5O7·2H2Continuously stirring for 30min, performing ultrasonic treatment for 30min, adding 10ml of 0.4M NaOH solution, continuously stirring for 10min, transferring to a reaction kettle, and reacting at 180 ℃ for 12h to better react the functionalized carbon nanosheets with Sn2O3Compounding the nano sheets, naturally cooling to room temperature after the reaction is finished, washing and centrifuging for three times by using deionized water and ethanol respectively, and drying for 10 hours in a vacuum drying oven at 60 ℃.

Claims (4)

1.Sn2O3A nanosheet/functionalized carbon nanosheet composite, characterized by: the composite material is composed of surface functionalized carbon nanosheets and two-dimensional flaky Sn2O3Two materials are compounded, have 2D/2D appearance characteristics and are two-dimensional Sn2O3The nano-sheet uniformly grows on the surface of the two-dimensional functionalized carbon nano-sheet in 1M Na2SO4Electrolyte, test voltage range-1V to 0.2V, and scan rate of 10mV/s to 50mV/s in CV cycle test, Sn2O3The nano-sheet/functional carbon nano-sheet composite material has excellent specific capacitance, and the specific capacity reaches 126F/g at the scanning rate of 10 mV/s; sn (tin)2O3Nanosheet/functionalizationThe carbon nano-sheet composite material has uniform size and Sn2O3The thickness of the nano-sheet is 25nm, and the thickness of the carbon nano-sheet is 50 nm.
2. Sn according to claim 12O3The preparation method of the nano-sheet/functionalized carbon nano-sheet composite material is characterized by comprising the following preparation steps: adding SnCl into functionalized carbon nanosheet suspension2·2H2O and Na3C6H5O7·2H2O, continuously stirring and then carrying out ultrasonic treatment, adding NaOH solution, continuously stirring for a period of time, then transferring to a reaction kettle, and reacting at a certain temperature to enable the functionalized carbon nanosheets to better react with Sn2O3Compounding the nano sheets, naturally cooling to room temperature after the reaction is finished, washing and centrifuging for three times by using deionized water and ethanol respectively, and drying in a vacuum drying oven; the preparation method of the functionalized carbon nanosheet comprises the following steps:
(1) weighing C6H5K3O7·H2O is loaded by a porcelain boat, put into a tube furnace, heated to a set temperature b at a certain heating rate a under the atmosphere of nitrogen, and then kept warm, heated to a set temperature d at a certain heating rate c, kept warm, naturally cooled, collected, cleaned by a dilute hydrochloric acid solution, washed by deionized water and ethanol for three times respectively, and dried in a vacuum drying box, and the dried powder is reserved; said C6H5K3O7·H2The mass of O is 5g, the heating rate a is 2 ℃/min, the set temperature b is 450 ℃, the heat preservation time is 1h, the heating rate c is 5 ℃/min, the set temperature d is 850 ℃, the heat preservation time is 1h, the concentration of the hydrochloric acid solution is 1mol/L, and the drying means drying for 24h in a vacuum drying oven at the temperature of 65 ℃;
(2) putting the powder obtained in the step (1) into a mixed solution of concentrated nitric acid and concentrated sulfuric acid, stirring in a water bath environment, standing after stirring for a certain time, washing with deionized water and absolute ethyl alcohol to be neutral, and drying in a vacuum drying oven to obtain a functionalized carbon nanosheet; the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 3:1, the water bath temperature is 85 ℃, the stirring time is 12 hours, the standing time is 12 hours, and the drying refers to drying for 24 hours in a vacuum drying oven at the temperature of 65 ℃.
3. Sn according to claim 22O3The preparation method of the nano-sheet/functionalized carbon nano-sheet composite material is characterized in that the concentration of the functionalized carbon nano-sheet suspension is 4 g/L; the functional carbon nano sheet and SnCl2·2H2O and Na3C6H5O7·2H2The mass ratio of O is 0.08: 1.13: 2.94 of; the concentration of the NaOH solution is 0.4M; the volume ratio of the functionalized carbon nanosheet suspension to the NaOH solution is 2: 1.
4. Sn according to claim 22O3The preparation method of the nano-sheet/functionalized carbon nano-sheet composite material is characterized in that the continuous stirring time is 30min, and the ultrasonic time is 30 min; continuously stirring for 10 min; the reaction temperature is 180 ℃, the reaction time is 12h, the drying temperature is 60 ℃, and the drying time is 10 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718250A (en) * 2012-07-03 2012-10-10 重庆大学 Method for preparing carbon-material-carrying tin dioxide nanosheet composite material
JP2014019607A (en) * 2012-07-18 2014-02-03 Kawamura Institute Of Chemical Research Carbon, metal tin and/or tin oxide composite nano sheet and method for manufacturing the same
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CN104577064B (en) * 2014-12-18 2016-12-07 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of carbon-coated nano lamellar stannic oxide materials
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CN102718250A (en) * 2012-07-03 2012-10-10 重庆大学 Method for preparing carbon-material-carrying tin dioxide nanosheet composite material
JP2014019607A (en) * 2012-07-18 2014-02-03 Kawamura Institute Of Chemical Research Carbon, metal tin and/or tin oxide composite nano sheet and method for manufacturing the same
CN109360740A (en) * 2018-12-17 2019-02-19 华进半导体封装先导技术研发中心有限公司 Porous carbon nanosheet of a kind of two dimension N doping and preparation method thereof

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