CN112185709B - High-rate mesoporous RuO 2 Preparation method of/C composite electrode material - Google Patents

High-rate mesoporous RuO 2 Preparation method of/C composite electrode material Download PDF

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CN112185709B
CN112185709B CN202011110933.8A CN202011110933A CN112185709B CN 112185709 B CN112185709 B CN 112185709B CN 202011110933 A CN202011110933 A CN 202011110933A CN 112185709 B CN112185709 B CN 112185709B
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sodium alginate
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CN112185709A (en
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刘庆雷
李明明
赵斌元
张荻
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Maanshan Economic And Technological Development Zone Construction Investment Co ltd
Shanghai Jiaotong University
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Shanghai Jiaotong University
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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
    • 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, 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
    • 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, 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
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • 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, 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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

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Abstract

The invention discloses a high-rate mesoporous RuO 2 The preparation method of the/C composite electrode material mainly comprises the following steps: firstly, sodium alginate and Ru are mixed 3+ Cross-linking, filtering the cross-linked product, freeze drying, carbonizing in inert atmosphere, and air oxidizing to obtain RuO rich in mesopores 2 a/C composite material. The invention is prepared by reacting Ru 3+ The sodium alginate matrix is introduced, and the graphitized carbon-coated RuO is obtained by high-temperature catalysis 2 And (3) nanoparticles. Meanwhile, sodium alginate forms a good mesoporous structure in the high-temperature treatment process, so that the prepared composite material has RuO function 2 The electrochemical performance is excellent, the graphitized porous carbon has good conductivity and a developed pore structure, and when the graphitized porous carbon is used for a super capacitor, the energy storage and release capacity is good even under high current density.

Description

High-rate mesoporous RuO 2 Preparation method of/C composite electrode material
Technical Field
The invention belongs to the technical field of material preparation and super capacitor cathode application, and mainly relates to high-rate mesoporous RuO 2 A preparation method of the/C composite electrode material.
Background
With the continuous consumption of fossil fuels, the demand of human society for renewable clean energy, such as wind energy, solar energy, etc., is continuously expanding. However, the utilization of the new energy sources depends on the external environment to a great extent, so that in order to utilize the energy sources more reasonably and maximally, the energy storage device is adopted to store the energy sources, and the energy sources are used for subsequent use. Commonly used energy storage devices fall into two categories: a capacitor and a battery. The capacitor only usually has a physical electrostatic adsorption process in the energy storage process and is not limited by ion diffusion, so the power density is very high, but the energy density is low; the power density of the battery is low but the energy density is high because the reaction speed is limited by ion diffusion because the battery is subjected to chemical reaction. The super capacitor is a novel energy storage device between a traditional capacitor and a battery, has the rapid charge and discharge characteristics of the capacitor and the energy storage characteristics of the battery, namely has high power density and energy density, and has huge development space in the future energy storage field.
The electrode material is one of the key parameters determining the electrochemical performance of the super capacitor, and the reasonable design of the composition and the structure of the electrode material can effectively improve the power density and the energy density of the electrode material. RuO 2 The conductive polymer has been widely used in super capacitors due to its high conductivity, good electrochemical reversibility, high specific capacitance and high cycle efficiency. But amorphous RuO 2 The oxide network structure is not continuous, which causes great reduction of conductivity, and furthermore, because the price is high, the application is greatly limited, therefore, RuO is needed 2 The composite material is compounded with a cheap matrix with excellent conductivity, so that the composite material can be widely applied to actual production and life.
Current RuO 2 The preparation method of the composite material mainly comprises an electrochemical deposition method [ M.T.Brumbach; alam t.m.; kotula p.g.; McKenzie b.b.; bunker B.C., Acs Applied Materials&Interfaces,2010,2(3), 778-787.]And sol-gel method [1.k. — h.chang; hu c. -c.; chou c. -y., Electrochimica Acta,2009, 54(3),978-983.2. q.jiang; kurra n.; alhabeb m.; gogotsi y.; alshareef h.n., Advanced Energy Materials,2018,8(13)]However, the preparation conditions are severe and the process is complicated because of Ru 3+ Easy hydrolysis, resulting in poor reproducibility of the preparation. The invention is realized by directly reacting Ru 3+ Crosslinking with sodium alginate to inhibit Ru 3+ The hydrolysis forms an egg box structure, so that RuO is generated in the subsequent carbonization and oxidation processes 2 Can be completely wrapped by the carbon layer to form nano particles which are uniformly distributed in the carbon matrix; in addition, sodium alginate can be pyrolyzed at high temperature to form rich mesoporous channels, which is beneficial to the continuous transmission of ions. The method has simple and controllable preparation process and low cost, and is very suitable for producing the electrode material for the supercapacitor in a large scale.
Disclosure of Invention
The object of the present invention is to solve the existing RuO 2 The deficiency of the preparation technology provides a high-rate mesoporous RuO 2 A preparation method of a/C composite electrode material, in particular to RuO with a large number of mesoporous structures 2 The preparation method of the/C composite material has the advantages of simple and controllable preparation process and low cost, and is suitable for being used as an electrode material of a high-rate super capacitor.
The object of the present invention can be achieved by the following processes:
the invention provides a high-rate mesoporous RuO 2 The preparation method of the/C composite electrode material comprises the following steps:
A. sodium alginate and Ru are crosslinked by utilizing the crosslinking characteristic of sodium alginate and polyvalent metal ions 3+ Crosslinking to form gel balls, filtering, freezing and drying to obtain freeze-dried products.
B. Calcining and carbonizing the freeze-dried pellets in inert atmosphere, and oxidizing in air atmosphere to obtain RuO rich in mesopores 2 a/C composite material.
Preferably, in the step A, the mass concentration of the sodium alginate sol is 1.5 percent, and RuCl is adopted 3 The concentration of the solution is 0.1-0.2mol/L, and the sodium alginate sol and RuCl are added 3 The solution is subjected to crosslinking reaction according to the volume ratio of 2:5, and the reaction time is 24-48 h.
Preferably, in the step A, sodium alginate and Ru are mixed 3+ Washing the crosslinked product with deionized water for 3 times, filtering, freezing in liquid nitrogen for 20min, and drying at-65 deg.C for 24-72 hr.
Preferably, in the step B, the carbonization method specifically comprises: in N 2 Under protection, the temperature is raised at a rate of 5 ℃/minCarbonizing, heating to 600 deg.C, holding for 4 hr, and naturally cooling to room temperature, N 2 The flow rate is 0.6-0.8L/min.
Preferably, in the step B, the specific method of oxidation is: oxidizing at the heating rate of 5 ℃/min in the air atmosphere, heating to the temperature of 300-500 ℃, then preserving the heat for 3h, and finally naturally cooling to the room temperature.
Preferably, in the step B, the oxidized composite product is washed 3 times by using deionized water and absolute ethyl alcohol respectively, and then is dried for 24 hours in vacuum at 60 ℃.
Preferably, in the step B, the metallic Ru crosslinked with sodium alginate meets oxygen in the air to generate RuO at a proper temperature 2 The nano particles are uniformly distributed in the carbon matrix, and meanwhile, rich mesoporous channels are formed by pyrolysis of the sodium alginate.
Compared with the prior art, the invention has the following advantages:
1. mesoporous RuO prepared by the invention 2 the/C composite material makes full use of sodium alginate and Ru 3+ The special egg box structure is formed, so that RuO obtained after carbonization and oxidation is obtained 2 The nanoparticles may be completely encapsulated by the conductive carbon layer and uniformly distributed in the carbon matrix.
2. Mesoporous RuO prepared by the invention 2 the/C composite material takes sodium alginate as a precursor of carbon, and forms a graphitized carbon layer after high-temperature calcination, so that the conductivity is greatly improved. Meanwhile, sodium alginate is pyrolyzed at high temperature to form rich mesoporous channels, which is beneficial to the continuous transmission of ions, so that the multiplying power performance is excellent.
3. The preparation method has the advantages of easily available raw materials, simple preparation method, easily controlled process and low cost, and has good application prospect in the field of super capacitors.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows mesoporous RuO prepared in examples 1, 2 and 3 2 XRD pattern of the/C composite material;
FIG. 2(a), FIG. 2(b), and FIG. 2(c) are respectively the mesoporous RuOs prepared in examples 1, 2, and 3 2 SEM image of/C composite material;
FIG. 3 shows mesoporous RuO prepared in examples 1, 2 and 3 2 The rate performance graph of the/C composite material as the cathode material of the super capacitor is that the test solution is 1M H 2 SO 4 And (3) solution.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present invention will be described in detail with reference to the following specific examples:
example 1
High-rate mesoporous RuO 2 The preparation method of the/C composite electrode material comprises the following steps:
step one, dissolving 15g of sodium alginate in 985ml of deionized water, and stirring for 24 hours at room temperature at the rotating speed of 600 r/min.
Step two, 19.6g RuCl 3 ·3H 2 O is dissolved in 480.4ml deionized water and stirred for 6h at the rotating speed of 600 r/min.
Step three, taking 200ml of sodium alginate sol and dropwise adding RuCl 3 Stirring and reacting for 24 hours in the water solution at the rotating speed of 400 r/min.
And step four, repeatedly washing the cross-linked product with deionized water for 3 times, then putting the cross-linked product into liquid nitrogen for freezing for 20min, and drying for 72h at the temperature of-65 ℃.
And step five, putting the freeze-dried precursor in the step four into a tube furnace for carbonization, calcining in a nitrogen atmosphere with the flow rate of 0.6-0.8L/min, heating up to 600 ℃, preserving heat for 4h, and finally naturally cooling to room temperature.
And sixthly, putting the carbonized product into a tubular furnace for oxidation, calcining in air atmosphere at the heating rate of 5 ℃/min, heating to 400 ℃, then preserving heat for 3h, and finally naturally cooling to room temperature.
And step seven, washing the oxidized composite product in the step six by using deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying for 24 hours at the temperature of 60 ℃.
In FIG. 1, B is the mesoporous RuO obtained in this example 2 XRD pattern of the/C composite material; from the three characteristic crystal planes of (110), (101) and (211) in B of FIG. 1, the synthesized product is RuO 2 The broadening of the peak indicates the formation of RuO 2 The grain size is small.
FIG. 2(a) shows the mesoporous RuO obtained in this example 2 SEM image of/C composite material; as shown in FIG. 2(a), the porous carbon matrix formed by the method has a large number of three-dimensional mesoporous channels of 30-50nm, and the synthesized RuO 2 The nano-particles are uniformly distributed on the carbon substrate.
The curve a in FIG. 3 is the mesoporous RuO obtained in this example 2 Rate capability of the/C composite material; as can be seen from the curve a in FIG. 3, the composite material has a mass specific capacitance of 302F/g at a low current density of 0.1A/g, and the performance is still excellent although the specific capacity is gradually reduced with the increase of the current density.
Sample a in Table 1 is the mesoporous RuO obtained in this example 2 the/C composite material is used as the electrochemical performance of the cathode material of the super capacitor; as can be seen, the composite material can maintain 246F/g and 8217mF/cm even at a large current density of 1A/g -2 High capacitance and excellent rate performance.
Example 2
High-rate mesoporous RuO 2 The preparation method of the/C composite electrode material comprises the following steps:
step one, dissolving 15g of sodium alginate in 985ml of deionized water, and stirring for 24h at room temperature and the rotating speed of 600 r/min.
Step two, 13g RuCl 3 ·3H 2 Dissolving O in 487ml deionized water, and stirring for 6h at the rotation speed of 600 r/min.
Step three, taking 200ml of sodium alginate sol and dropwise adding RuCl 3 Stirring and reacting for 24 hours in the water solution at the rotating speed of 400 r/min.
And step four, repeatedly washing the cross-linked product with deionized water for 3 times, then putting the cross-linked product into liquid nitrogen for freezing for 20min, and drying for 72h at the temperature of-65 ℃.
And step five, putting the freeze-dried precursor in the step four into a tube furnace for carbonization, calcining in a nitrogen atmosphere with the flow rate of 0.6-0.8L/min, heating up to 600 ℃, preserving heat for 4h, and finally naturally cooling to room temperature.
And sixthly, putting the carbonized product into a tubular furnace for oxidation, calcining in air atmosphere at the heating rate of 5 ℃/min, heating to 500 ℃, preserving heat for 3h, and finally naturally cooling to room temperature.
And step seven, washing the composite product oxidized in the step six by using deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying for 24 hours at the temperature of 60 ℃.
In FIG. 1, A is the mesoporous RuO obtained in this example 2 XRD pattern of the/C composite material; from the three characteristic crystal planes of (110), (101) and (211) in A of FIG. 1, the synthesized product is RuO 2 The sharp peak indicates the formation of RuO 2 The grain size is larger.
FIG. 2(b) shows the mesoporous RuO obtained in this example 2 SEM image of/C composite material; the RuO synthesized by this method can be seen from FIG. 2(b) 2 The particles are uniformly distributed on the carbon matrix, but the grain size is obviously increased, and the grains are directly connected with each other, so that part of the porous carbon structure is damaged, and part of mesoporous channels are reserved.
The curve b in FIG. 3 is the mesoporous RuO obtained in this example 2 Rate capability of the/C composite material; as can be seen from the curve b in FIG. 3, at a low current density of 0.1A/g, the specific capacitance of the composite material is 168F/g, and although the specific capacitance gradually decreases with the increase of the current density, the performance is still better.
Sample b in Table 1 is the mesoporous RuO obtained in this example 2 the/C composite material is used as the electrochemical performance of the cathode material of the super capacitor; as can be seen from the table, the composite material can maintain 115F/g and 4824mF/cm even at a large current density of 1A/g -2 High capacitance and good multiplying power performance.
Example 3
High-rate mesoporous RuO 2 The preparation method of the/C composite electrode material comprises the following steps:
step one, dissolving 15g of sodium alginate in 985ml of deionized water, and stirring for 24h at room temperature and the rotating speed of 600 r/min.
Step two, 26.1g RuCl 3 ·3H 2 O is dissolved in 473.9ml deionized water and stirred for 6h at the rotating speed of 600 r/min.
Step three, taking 200ml of sodium alginate sol and dropwise adding RuCl 3 Stirring and reacting for 24 hours in the water solution at the rotating speed of 400 r/min.
And step four, repeatedly washing the cross-linked product with deionized water for 3 times, then putting the cross-linked product into liquid nitrogen for freezing for 20min, and drying for 72h at the temperature of-65 ℃.
And step five, putting the freeze-dried precursor in the step four into a tube furnace for carbonization, calcining in a nitrogen atmosphere with the flow rate of 0.6-0.8L/min, heating up to 600 ℃, preserving heat for 4h, and finally naturally cooling to room temperature.
And sixthly, putting the carbonized product into a tubular furnace for oxidation, calcining in air atmosphere at the heating rate of 5 ℃/min, heating to 300 ℃, then preserving heat for 3h, and finally naturally cooling to room temperature.
And step seven, washing the oxidized composite product in the step six by using deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying for 24 hours at the temperature of 60 ℃.
In FIG. 1, C is the mesoporous RuO obtained in this example 2 XRD pattern of the/C composite material; from the three characteristic crystal planes of (110), (101) and (211) in C of FIG. 1, the synthesized product is RuO 2 The broadening of the peak indicates the formation of RuO 2 The grain size is smaller.
FIG. 2(c) shows the mesoporous RuO obtained in this example 2 SEM image of/C composite material; as shown in FIG. 2(c), the porous carbon substrate formed by the method has a large number of mesoporous channels of 50nm, and the synthesized RuO 2 The nano-particles are uniformly distributed on the porous carbon matrix.
The curve c in FIG. 3 is the mesoporous RuO obtained in this example 2 Rate capability of the/C composite material; as can be seen from the curve c in FIG. 3, the specific capacitance of the composite material at a low current density of 0.1A/g was 254F/g, and the specific capacitance gradually decreased with increasing current density, but the specific capacitance gradually decreased with increasing current densityThe performance is still good.
Sample c in Table 1 is the mesoporous RuO obtained in this example 2 the/C composite material is used as the electrochemical performance of the cathode material of the super capacitor; as can be seen from the table, the composite material can maintain 183F/g and 6931mF/cm even at a large current density of 1A/g -2 High capacitance and good multiplying power performance.
TABLE 1 mesoporous RuO prepared in examples 1, 2, 3 2 Multiplying power performance of/C composite material as super capacitor cathode material
Sample (I) Specific capacity of mass (F/g) Surface capacitance (mF/cm) -2 ) Electrolyte solution
a 302(0.1A/g),246(1A/g) 8217(1A/g) 1M H 2 SO 4
b 168(0.1A/g),115(1A/g) 4824(1A/g) 1M H 2 SO 4
c 254(0.1A/g),183(1A/g) 6931(1A/g) 1M H 2 SO 4
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (4)

1. High-rate mesoporous RuO 2 The preparation method of the/C composite electrode material is characterized by comprising the following steps:
A. sodium alginate and Ru are crosslinked by utilizing the crosslinking characteristic of sodium alginate and polyvalent metal ions 3+ Crosslinking to form gel balls, and filtering, freezing and drying to obtain a freeze-dried product;
B. calcining and carbonizing the freeze-dried pellets in inert atmosphere, and oxidizing in air atmosphere to obtain RuO rich in mesopores 2 a/C composite material;
in the step A, the mass concentration of the sodium alginate sol is 1.5 percent, and RuCl is adopted 3 The concentration of the solution is 0.1-0.2mol/L, and the sodium alginate sol and RuCl are added 3 Carrying out crosslinking reaction on the solution according to the volume ratio of 2:5, wherein the reaction time is 24-48 h;
in the step B, the specific method of oxidation is as follows: oxidizing at a heating rate of 5 ℃/min in an air atmosphere, heating to 400 ℃, preserving heat for 3h, and finally naturally cooling to room temperature;
in the step B, the carbonization method specifically comprises the following steps: in N 2 Under protection, carbonizing at a heating rate of 5 ℃/min, heating to 600 ℃, keeping the temperature for 4h, and finally naturally cooling to room temperature, wherein N is 2 The flow rate is 0.6-0.8L/min.
2. The high-rate mesoporous RuO according to claim 1 2 The preparation method of the/C composite electrode material is characterized in that in the step A, sodium alginate and Ru are mixed 3+ Washing the crosslinked product with deionized water for 3 times, filtering, freezing in liquid nitrogen for 20min, and drying at-65 deg.C for 24-72 hr.
3. The high-rate mesoporous RuO according to claim 1 2 The preparation method of the/C composite electrode material is characterized in that in the step B, the oxidized composite product is washed 3 times by using deionized water and absolute ethyl alcohol respectively, and then is dried in vacuum for 24 hours at the temperature of 60 ℃.
4. The high-rate mesoporous RuO according to claim 1 2 The preparation method of the/C composite electrode material is characterized in that in the step B, RuO 2 The structure of the/C composite material is specifically as follows: RuO of 3-5nm 2 The particles are uniformly distributed in the porous carbon matrix, and the conductive carbon layer is wrapped by the outer layer of the nano particles.
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