CN112951616A - Nitrogen-sulfur co-doped carbon aerogel and preparation method and application thereof - Google Patents

Nitrogen-sulfur co-doped carbon aerogel and preparation method and application thereof Download PDF

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CN112951616A
CN112951616A CN202110131030.6A CN202110131030A CN112951616A CN 112951616 A CN112951616 A CN 112951616A CN 202110131030 A CN202110131030 A CN 202110131030A CN 112951616 A CN112951616 A CN 112951616A
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nitrogen
sulfur
drying
doped carbon
carbon aerogel
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晏金灿
杨洋
王云云
李梦琰
李欣
袁铭霞
陈哲
严春阳
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Shanghai Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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    • 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, LIGHT-SENSITIVE OR TEMPERATURE-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
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    • H01—ELECTRIC ELEMENTS
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    • 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
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Abstract

The invention relates to nitrogen and sulfur co-doped carbon aerogel and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a NaOH/urea/LA ternary solution, precooling the ternary solution, adding cellulose powder at a low temperature, and violently stirring; (2) centrifuging the mixture to obtain cellulose precipitate, and freeze-drying and pulverizing; (3) carrying out temperature programming carbonization on the sample subjected to freeze drying and crushing; (4) and uniformly mixing the carbonized sample with KOH and deionized water, drying, continuously calcining at high temperature in a nitrogen atmosphere, washing with hydrochloric acid and deionized water to be neutral, and drying to obtain the nitrogen-sulfur co-doped carbon aerogel which is used for preparing the electrode material of the supercapacitor. Compared with the prior art, the invention has the advantages of adopting cellulose as the raw material, good pore structure in the material, uniform distribution of nitrogen and phosphorus, good electrochemical performance and the like.

Description

Nitrogen-sulfur co-doped carbon aerogel and preparation method and application thereof
Technical Field
The invention relates to the field of electrode materials of a super capacitor, in particular to nitrogen and sulfur co-doped carbon aerogel and a preparation method and application thereof.
Background
With the development of human society, the attention on energy is higher and higher, and the energy industry is gradually becoming more and more important industry. With the increase of population and the increase of human demand, the demand of society for various energy sources will be greatly increased, and more demands on energy storage and transportation are brought. At present, it is of great significance to reduce the loss of electric energy in transmission and storage, especially to develop an energy storage device with high electric energy storage and small volume and mass.
The super capacitor can be divided into a double electric layer super capacitor and a Faraday capacitor according to an energy storage mechanism, and the two types of super capacitors have respective distinct characteristics. The electrode materials forming the super capacitor can be divided into various types such as one-dimensional linear, two-dimensional sheet and three-dimensional framework according to the structure.
The application of the super capacitor in an energy storage system is widely accepted, the electrochemical performance of the super capacitor makes up the gap between the traditional capacitor and a battery, and the power density and the energy density span several orders of magnitude, so that the super capacitor is suitable for being applied to electric energy in portable or remote equipment, the electrochemical performance of the storage super capacitor mainly depends on an electrode material, and a porous carbon material is tried to be applied to the field of the super capacitor by extensive researchers due to the characteristics of large specific surface area, excellent chemical stability, good conductivity and the like.
Disclosure of Invention
The invention aims to overcome the research blank in the prior art and provide a nitrogen and sulfur co-doped carbon aerogel which adopts cellulose as a raw material, has a good pore structure in the material, uniform distribution of nitrogen and phosphorus and good electrochemical performance, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the inventor knows that most biomass charcoal materials belong to waste utilization, have the advantages of wide raw material source, low cost, small pollution and the like, and have unique advantages and prospects in the application of electrochemical materials due to the fact that most materials or later-modified multi-level pore structures and inherent stability of carbon materials. Cellulose is biomass which is widely stored in nature, particularly in the aspect of electrode materials of a super capacitor, the cellulose-based biomass carbon has certain commercial value in the field of super capacitors due to low cost, super large specific surface area and simple preparation process, and the specific scheme is as follows:
a preparation method of nitrogen and sulfur co-doped carbon aerogel comprises the following steps:
(1) preparing a NaOH/urea/LA ternary solution, precooling the ternary solution to-13 ℃, adding cellulose powder at a low temperature, and violently stirring;
(2) centrifuging the mixture to obtain cellulose precipitate, and freeze-drying and pulverizing;
(3) carrying out temperature programming carbonization on the sample subjected to freeze drying and crushing;
(4) and uniformly mixing the carbonized sample with KOH and deionized water, drying, continuously calcining at high temperature in a nitrogen atmosphere, washing with hydrochloric acid and deionized water to be neutral, and drying to obtain the nitrogen-sulfur co-doped carbon aerogel.
Further, the mass ratio of the cellulose to the NaOH to the urea to the LA to the deionized water in the step (1) is 4:7:12 (5-7) to (70-72).
Further, the rotational speed of the centrifugal separation is 8000-10000r/min, the time is 1-10min, and liquid nitrogen precooling treatment is carried out before freeze-drying.
Further, the carbonization procedure comprises heating to 400-500 deg.C for 2-4h, and then heating to 600-800 deg.C at a temperature rate of 5-10 deg.C/min for 2-5 h.
Further, the mass ratio of the carbonized sample to KOH is 1 (1-2).
Further, the calcining temperature is 600-800 ℃, and the time is 8-16 h.
Further, the drying temperature is 60-80 ℃, and the drying time is 8-16 h.
A nitrogen and sulfur co-doped carbon aerogel prepared by the method.
The application of the nitrogen and sulfur co-doped carbon aerogel is used for preparing an electrode material of a supercapacitor, and the specific method comprises the following steps: and grinding the nitrogen-sulfur co-doped carbon aerogel, mixing the ground carbon-sulfur co-doped carbon aerogel with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain the nitrogen-sulfur co-doped electrode material for the supercapacitor.
Further, the mass ratio of the nitrogen and sulfur co-doped carbon aerogel to the carbon black to the PTFE is 8 (0.8-1.2) to 0.8-1.2.
In the invention, LA (alpha-lipoic acid) is used for doping N, S elements in the carbon material, so that the surface wettability and the conductivity of the carbon material are improved, more chemical active sites are provided, pseudo capacitance is generated in the carbon material, the electrochemical stability of the carbon material is improved, and the specific capacitance is improved;
KOH is used as an activator, the activator reacts with the carbon material at high temperature to consume a part of carbon elements, and generated gases such as carbon monoxide and carbon dioxide escape from the surface of the carbon material to form pores. When the addition amount of KOH or the activation temperature is too low, the aperture ratio of the activated carbon material is reduced, and when the addition amount of KOH or the activation temperature is too high, the pore channels of the activated carbon material are collapsed, the specific surface area of the activated carbon material is reduced, and the specific capacitance of the carbon material is reduced.
Compared with the prior art, the method has the advantages that the natural waste cellulose is used as the carbon precursor, the cost is saved, the price is low, the environment is protected, the carbon precursor is doped with N and S elements, the electrochemical performance of the material is effectively improved, and the prepared porous carbon material has high specific surface area and enhanced electrode material electricity storage capacity.
Drawings
FIG. 1 shows that the nitrogen and sulfur co-doped carbon material for the supercapacitor prepared in example 1 has a current density of 0.5A g-1Gcd.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
(1) Preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:5: 72;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 4 hours, and then performing high-temperature carbonization in the nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 600 ℃ for 5 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 2.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1.2:0.8, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Testing the electrochemical performance of the nitrogen-sulfur co-doped carbon material:
and (3) performing electrochemical performance test on the prepared nitrogen and sulfur co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is a nitrogen and sulfur co-doped porous carbon electrode, the counter electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The CV curve and the GCD curve were tested using 6M KOH solution as the electrolyte.
FIG. 1 shows a novel synthetic route of a cellulose-based nitrogen-sulfur co-doped carbon material, and the electrochemical performance of the carbon material can be seen from the figure, so that a new way for preparing heteroatom-doped carbon electrode materials, especially carbon electrode materials based on renewable low-cost cellulose, is opened up.
The parameter change can be known by comparing the doped substance in the embodiment with that in other embodiments without doping a substance, such as doped urea/LA with electrochemical properties, and undoped without electrochemical properties that can be applied.
Example 2:
(1) preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:6: 71;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 3 hours, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 600 ℃ for 2 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 2.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1.2:0.8, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Example 3:
(1) preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:5: 72;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 2 hours, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 700 ℃ for 5 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 1.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Example 4:
(1) preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:7: 70;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 2 hours, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 800 ℃ for 4 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 2.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Example 5:
(1) preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:5: 72;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 2 hours, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 800 ℃ for 4 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 2.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Example 6:
(1) preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:5: 72;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 3h, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 800 ℃ for 3 h;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, then continuously calcining at 600 ℃ for 12 hours under nitrogen at high temperature, then washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 1.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:0.8:1.2, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
Example 7
(1) Preparing a ternary low-temperature solution of NaOH/urea/LA solution, precooling the solution to-13 ℃, adding cellulose powder under a low-temperature state, and violently stirring, wherein the cellulose/NaOH/urea/LA/deionized water solution is prepared according to the mass ratio: 4:7:12:5: 72;
(2) performing centrifugal separation to obtain cellulose precipitate, freeze-drying, pulverizing at 8000r/min for 5min, and pre-cooling with liquid nitrogen before freeze-drying;
(3) placing the sample in the step (2) in a tubular furnace for pre-carbonization at the temperature of 500 ℃ for 4 hours, and performing high-temperature carbonization in a nitrogen atmosphere at the temperature rise rate of 5-10 ℃/min at the temperature of 700 ℃ for 5 hours;
(4) and (3) uniformly mixing the carbonized sample in the step (3) with KOH and deionized water, drying, calcining at high temperature under nitrogen, washing with hydrochloric acid and deionized water to be neutral, and drying at 60 ℃ for 12 hours to obtain the target product, namely the nitrogen and sulfur co-doped carbon material, wherein the mass ratio of the calcined sample to the KOH is 1: 2.
(5) And (3) grinding the carbon material obtained in the step (4), mixing the carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, and drying the mixture at 60 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped electrode material for the supercapacitor.
In the preparation process of the nitrogen-sulfur co-doped carbon material for the supercapacitor, the process conditions can be adjusted at will within the following process ranges according to requirements (namely, the middle point value or the end value is selected at will):
in the step (1), cellulose/NaOH/urea/LA/deionized water solution is prepared by the following steps of: 4:7:12 (5-7) and (70-72); in the step (2), the rotational speed of centrifugal separation is 8000r/min, the time is 5min, precooling treatment is carried out by liquid nitrogen before freeze-drying; in the step (3), the process conditions of high-temperature calcination are as follows: the pre-carbonization temperature is 500 ℃, the time is 2-4h, the high-temperature carbonization is carried out in the nitrogen atmosphere, the heating rate is 5-10 ℃/min, the temperature is 600-800 ℃, the time is 2-5h, and the mass ratio of the calcined sample to KOH is 1 (1-2); in the step (4), the drying temperature is 60 ℃, and the time is 12 hours; the mass ratio of the nitrogen-sulfur co-doped carbon material to the carbon black to the PTFE is 8 (0.8-1.2) to (0.8-1.2).
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (10)

1. The preparation method of the nitrogen and sulfur co-doped carbon aerogel is characterized by comprising the following steps of:
(1) preparing a NaOH/urea/LA ternary solution, precooling the ternary solution, adding cellulose powder at a low temperature, and violently stirring;
(2) centrifuging the mixture to obtain cellulose precipitate, and freeze-drying and pulverizing;
(3) carrying out temperature programming carbonization on the sample subjected to freeze drying and crushing;
(4) and uniformly mixing the carbonized sample with KOH and deionized water, drying, continuously calcining at high temperature in a nitrogen atmosphere, washing with hydrochloric acid and deionized water to be neutral, and drying to obtain the nitrogen-sulfur co-doped carbon aerogel.
2. The preparation method of the nitrogen-sulfur co-doped carbon aerogel according to claim 1, wherein the mass ratio of the cellulose to the NaOH to the urea to the LA to the deionized water in the step (1) is 4:7:12 (5-7) to (70-72).
3. The preparation method of the nitrogen-sulfur co-doped carbon aerogel according to claim 1, wherein the rotation speed of the centrifugal separation is 8000-10000r/min, the time is 1-10min, and the pre-cooling treatment is performed by using liquid nitrogen before the freeze-drying.
4. The method as claimed in claim 1, wherein the carbonization procedure comprises heating to 400-500 ℃ for 2-4h, and then heating to 600-800 ℃ at a temperature increase rate of 5-10 ℃/min for 2-5 h.
5. The preparation method of the nitrogen-sulfur co-doped carbon aerogel according to claim 1, wherein the mass ratio of the carbonized sample to KOH is 1 (1-2).
6. The method for preparing nitrogen and sulfur co-doped carbon aerogel according to claim 1, wherein the calcination temperature is 600-800 ℃ and the calcination time is 8-16 h.
7. The preparation method of the nitrogen-sulfur co-doped carbon aerogel according to claim 1, wherein the drying temperature is 60-80 ℃ and the drying time is 8-16 h.
8. A nitrogen and sulfur co-doped carbon aerogel prepared according to the method of claims 1-7.
9. The application of the nitrogen and sulfur co-doped carbon aerogel according to claim 8, wherein the aerogel is used for preparing an electrode material of a supercapacitor, and the specific method comprises the following steps: and grinding the nitrogen-sulfur co-doped carbon aerogel, mixing the ground carbon-sulfur co-doped carbon aerogel with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain the nitrogen-sulfur co-doped electrode material for the supercapacitor.
10. The use of the nitrogen and sulfur co-doped carbon aerogel according to claim 9, wherein the mass ratio of the nitrogen and sulfur co-doped carbon aerogel, the carbon black and the PTFE is 8 (0.8-1.2) to (0.8-1.2).
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN114804108A (en) * 2022-02-25 2022-07-29 西安理工大学 N, S preparation method of co-doped MXene/cellulose derived carbon aerogel

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