CN110707335B - Three-dimensional self-supporting composite structure electrode, preparation method thereof and lithium-air battery - Google Patents
Three-dimensional self-supporting composite structure electrode, preparation method thereof and lithium-air battery Download PDFInfo
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- CN110707335B CN110707335B CN201911121198.8A CN201911121198A CN110707335B CN 110707335 B CN110707335 B CN 110707335B CN 201911121198 A CN201911121198 A CN 201911121198A CN 110707335 B CN110707335 B CN 110707335B
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 10
- 239000011230 binding agent Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a three-dimensional self-supporting composite structure electrode, a preparation method thereof and a lithium-air battery. The preparation method of the three-dimensional self-supporting composite structure electrode comprises the following steps: firstly, cutting a polyurethane sponge material into a required shape, and then carbonizing; immersing the carbonized polyurethane sponge into a graphene oxide solution, taking out and drying; and soaking the dried material in a catalyst solution, taking out and airing, and reducing at low temperature to obtain the three-dimensional self-supporting composite structure electrode. The composite structure electrode takes fibers of carbonized polyurethane sponge as a framework and is used as an integral conductive network, and reduced graphene oxide and a catalyst are wrapped and filled on the outer surface and the gaps of the carbonized polyurethane sponge fibers so as to increase the conductivity and the specific surface area of the electrode and provide a large number of active sites for reaction. The electrode does not contain a binder, and can effectively prevent side reactions from occurring in the charging and discharging processes of the battery, thereby improving the energy density of the battery.
Description
Technical Field
The invention relates to the technical field of battery electrodes, in particular to a positive electrode used as a component of a lithium air battery and the like, a preparation method thereof and the lithium air battery with the positive electrode.
Background
With the development of science and technology, lithium air batteries have received attention from people. Because the lithium-air battery has high theoretical energy density and high specific capacity, compared with the common lithium-ion battery anode material, the lithium-air battery anode active material, namely oxygen, can be provided by the external environment, namely air, is environment-friendly and has low cost, thereby having great development and application prospects. Therefore, it is necessary to prepare a porous anode material with high catalytic performance. The negative electrode of the lithium-air battery is lithium metal, and the positive electrode is a porous carbon material containing a catalyst. The positive electrode and the negative electrode are separated by a diaphragm, and electrolyte is added to form a complete battery structure. The positive electrode serves as an air electrode, which mainly contributes to the energy density of the battery and directly affects the output voltage and output power of the battery. During discharge, lithium ions are transported from the negative electrode through the electrolyteLi is transferred to the positive electrode of the structure and combined with oxygen to generate2O2Staying on the positive electrode. At the same time, the electron current is transferred from the negative electrode to the positive electrode of the battery through an external circuit.
In order to increase the integrity of the electrode and prevent the deterioration of the battery performance caused by the falling of the electrode during the cycling, a binder is generally added to the electrode, but the binder, which is an inactive material in the battery, not only reduces the energy density of the battery but also causes a series of unnecessary side reactions after the addition. If an electrode without a binder can be designed, the energy density of the battery can be improved, and the positive effect on the development of future batteries can be achieved. However, the traditional three-dimensional self-supporting electrode is made by a hydrothermal method, and high temperature and long-time energy consumption are needed; the material is prepared by a sol-gel method or a template method, and has the disadvantages of complicated process, time and labor consumption and high cost.
Therefore, how to overcome the defects of large energy consumption, low efficiency and high cost in the preparation of the conventional three-dimensional self-supporting electrode is an urgent problem to be solved in the industry.
Disclosure of Invention
The invention provides an energy-saving, environment-friendly, simple-to-manufacture and low-cost three-dimensional self-supporting composite structure electrode, a preparation method thereof and a lithium-air battery with the electrode, aiming at solving the problems of high energy consumption, low efficiency and high cost in the preparation of the conventional three-dimensional self-supporting electrode.
The invention provides a preparation method of a three-dimensional self-supporting composite structure electrode, which comprises the following steps:
step 1: firstly, cutting a polyurethane sponge material into a required shape, and then carrying out carbonization treatment;
step 2: immersing the carbonized polyurethane sponge into a graphene oxide solution, taking out and drying;
and step 3: and soaking the dried material in a catalyst solution, taking out the material, airing the material at room temperature, and reducing the material at low temperature to obtain the three-dimensional self-supporting composite structure electrode.
Preferably, the polyurethane sponge is cut into a columnar body, and then ultrasonic cleaning and drying are respectively carried out by using deionized water and absolute ethyl alcohol.
Preferably, the carbonization temperature of the carbonization treatment is 600-900 ℃, the time is 2.0-4.0 h, and the atmosphere is Ar or N2。
Preferably, the concentration of the graphene oxide solution is 1-5 mg/ml, the graphene oxide solution is uniformly dispersed by ultrasonic and then used for soaking the carbonized polyurethane sponge, and the carbonized polyurethane sponge is taken out and then subjected to vacuum freeze drying.
Preferably, the catalyst solution is a chloride solution, and the concentration is 0.45-0.55M.
Preferably, the chloride in the chloride solution is one of Ru, Co, Pt or Fe.
Preferably, the temperature of the low-temperature reduction is 190-210 ℃, and the time is 3.5-4.5 h; the atmosphere is Ar/H2Atmosphere in which H25-10 percent.
The invention also provides a three-dimensional self-supporting composite structure electrode prepared by the preparation method, which comprises a carbonized framework, reduced graphene oxide and a catalyst material, wherein the reduced graphene oxide and the catalyst material are wrapped and filled on the surface and in gaps of the carbonized framework.
The invention further provides a lithium air battery comprising a three-dimensional self-supporting composite structure electrode of the invention.
The three-dimensional self-supporting composite structure electrode provided by the invention takes carbonized polyurethane sponge as a framework, so that an integral conductive network is provided, and simultaneously, reduced graphene oxide and a catalyst are wrapped and filled on polyurethane sponge fibers and gaps, so that the conductivity and the specific surface area of the electrode are increased, and a large number of active sites are provided for reaction. The electrode does not contain a binder, and can effectively prevent side reactions from occurring in the charging and discharging processes of the battery, thereby improving the energy density and the cycle performance of the battery. Compared with the prior art, the invention has the advantages of energy saving, environmental protection, simple manufacture and low cost.
Drawings
FIG. 1 is a schematic block diagram of a process for preparing a composite structured electrode according to the present invention;
wherein, PU: a polyurethane sponge; a CPU: carbonizing a polyurethane sponge; GO: graphene oxide;
rGO: reducing graphene oxide; CPU/GO is a carbonized polyurethane sponge/graphene oxide composite material;
CPU/rGO/M carbonized polyurethane sponge/reduced graphene oxide/metal catalyst (Ru, Pt, Fe, etc.) composite material
FIG. 2 is a schematic cross-sectional view of a composite structured electrode of the present invention;
FIG. 3 is a scanning electron micrograph of an electrode of the composite structure of the present invention;
fig. 4 is a charge-discharge curve diagram of the composite-structure electrode of the present invention applied to a lithium-air battery.
Detailed Description
Fig. 1 is a block flow diagram of a method for manufacturing a three-dimensional self-supporting composite structure electrode according to the present invention. The preparation method comprises the following steps:
1. cutting the polyurethane sponge into a required shape, such as a cylindrical body, in this embodiment, the polyurethane sponge is cut into a cylinder with the height of 1cm and the diameter of 1cm, and ultrasonically cleaning the cut material with deionized water and absolute ethyl alcohol for several times and drying the material; carbonizing at 750 deg.C for 2.5h in Ar or N atmosphere2And the like. The carbonization temperature can be selected as required: 600 ℃, 650 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃ for 2h, 3h, 3.5h and 4 h. As the carbonization temperature increases and the time increases, the electrode becomes more brittle and the deeper the carbonization, the more conductive.
2. Preparing a graphene oxide solution with the concentration of 2.5mg/ml, ultrasonically dispersing uniformly, immersing carbonized polyurethane sponge into the graphene oxide solution, taking out the carbonized polyurethane sponge, and drying to obtain the carbonized polyurethane sponge/graphene oxide composite material. The concentration of the graphene oxide solution can be selected to be 1-5 mg/ml according to needs. The greater the mass of the electrode, the more conductive as the concentration increases. The added reduced graphene oxide is wrapped on carbonized polyurethane sponge fibers and filled in gaps of the sponge fibers, so that the reduced graphene oxide serves as a conductive framework to increase the conductivity of the electrode on one hand, and can serve as a porous carbon material to provide a space for reaction on the electrode on the other hand, oxygen passes through the porous carbon material, and a proper catalytic action is provided. The traditional method for introducing reduced graphene oxide generally adopts a hydrothermal method to generate graphene hydrogel, and then the graphene aerogel is obtained through a vacuum freeze-drying method, so that the method is complex, time-consuming and labor-consuming, and the method provided by the invention is simple and efficient.
3. Preparing a catalyst solution, namely selecting a ruthenium chloride solution, wherein the concentration is 0.5M; soaking the dried composite material in the catalyst solution, taking out, drying at room temperature, reducing at 200 deg.C for 4 hr in Ar/H atmosphere25-10% of the total mass of the electrode, and finally preparing the three-dimensional self-supporting CPU/rGO/Ru/carbonized polyurethane sponge/reduced graphene oxide/ruthenium chloride composite structure electrode. According to the requirement, the temperature of the low-temperature reduction can be 190-210 ℃, and the time is 3.5-4.5 h. The catalyst solution of the present invention may be selected as a chloride solution, and the chloride in the chloride solution may be a chloride of one of Ru, Co, Pt or Fe. The concentration of the catalyst solution can be selected from 0.45-0.55M.
Fig. 2 and fig. 3 are schematic diagrams of embodiments of the three-dimensional self-supporting composite structure electrode prepared by the preparation method of the present invention. The three-dimensional self-supporting composite structure electrode is cut into a cylinder shape and comprises a carbonized framework, reduced graphene oxide and a catalyst material, wherein the reduced graphene oxide and the catalyst material are wrapped and filled on the outer surface of the carbon framework and in gaps. As shown in fig. 2, the carbonized skeleton is a spring-like carbonized polyurethane sponge fiber, the reduced graphene oxide material is a material wrapped on the fiber and filled in the fiber gap, and the catalyst material is distributed on the reduced graphene oxide.
The three-dimensional self-supporting composite structure electrode prepared by the method is directly used in a lithium air battery or a super capacitor.
As shown in FIG. 4, the lithium-air battery having the electrode of the three-dimensional self-supporting composite structure of the present invention was subjected to battery performance tests at a current density of 0.1mA/cm, respectively2、0.5mA/cm2The specific capacity of the battery reaches 2.7 mAh/cm respectively after charge and discharge tests2、4.9 mAh/cm2. Namely: the electrode has high-efficiency catalytic effect and the specific capacity of the battery is high.
The three-dimensional self-supporting composite structure electrode provided by the invention takes carbonized polyurethane sponge fiber as a framework, so that an integral conductive network is provided, and simultaneously, the polyurethane sponge fiber and gaps are coated and filled with a reduced graphene oxide catalyst, so that the conductivity and the specific surface area of the electrode are increased, and a large number of active sites are provided for reaction. The electrode does not contain a binder, and can effectively prevent side reactions from occurring in the charging and discharging processes of the battery, thereby improving the energy density and the cycle performance of the battery. Compared with the prior art, the invention has the advantages of energy saving, environmental protection, simple manufacture and low cost.
The foregoing is considered as illustrative only of the embodiments of the invention. It should be understood that any modifications, equivalents and changes made within the spirit and framework of the inventive concept are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of a three-dimensional self-supporting composite structure electrode comprises the following steps:
step 1: firstly, cutting a polyurethane sponge material into a required shape, and then carrying out carbonization treatment;
step 2: immersing the carbonized polyurethane sponge into a graphene oxide solution, taking out and drying;
and step 3: and soaking the dried material in a catalyst solution, taking out the material, airing the material at room temperature, and reducing the material at low temperature to obtain the three-dimensional self-supporting composite structure electrode.
2. The preparation method of claim 1, wherein the polyurethane sponge is cut into a column, and then ultrasonically cleaned with deionized water and absolute ethyl alcohol, and dried.
3. The method according to claim 1, wherein the carbonization treatment is carried out at 600 to 900 ℃ for 2.0 to 4.0 hours in Ar or N atmosphere2。
4. The preparation method according to claim 1, wherein the concentration of the graphene oxide solution is 1-5 mg/ml, the graphene oxide solution is uniformly dispersed by ultrasonic, and then is used for soaking the carbonized polyurethane sponge, and the carbonized polyurethane sponge is taken out and dried.
5. The method according to claim 1, wherein the catalyst solution is a chloride solution having a concentration of 0.45 to 0.55M.
6. The method of claim 5, wherein the chloride in the chloride solution is a chloride of one of Ru, Co, Pt, or Fe.
7. The preparation method of claim 1, wherein the temperature of the low-temperature reduction is 190-210 ℃ and the time is 3.5-4.5 h; the atmosphere is Ar/H2Atmosphere in which H25-10 percent.
8. A three-dimensional self-supporting composite structure electrode prepared by the preparation method according to any one of claims 1 to 7, comprising a carbonized skeleton, reduced graphene oxide wrapped and filled in the outer surface and voids of the carbonized skeleton, and a catalyst material.
9. A lithium-air battery comprising the three-dimensional self-supporting composite structure electrode of claim 8.
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