CN116960377A - Working electrode for sodium-carbon dioxide battery and preparation method thereof - Google Patents
Working electrode for sodium-carbon dioxide battery and preparation method thereof Download PDFInfo
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- CN116960377A CN116960377A CN202311212460.6A CN202311212460A CN116960377A CN 116960377 A CN116960377 A CN 116960377A CN 202311212460 A CN202311212460 A CN 202311212460A CN 116960377 A CN116960377 A CN 116960377A
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- NWYRNCMKWHKPAI-UHFFFAOYSA-N C(=O)=O.[Na] Chemical compound C(=O)=O.[Na] NWYRNCMKWHKPAI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- 239000002086 nanomaterial Substances 0.000 claims abstract description 72
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 150000003303 ruthenium Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000006262 metallic foam Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002064 nanoplatelet Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- JJKUOVDAMCXQFK-UHFFFAOYSA-H ruthenium(3+);tricarbonate Chemical compound [Ru+3].[Ru+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O JJKUOVDAMCXQFK-UHFFFAOYSA-H 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000013011 mating Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000002048 multi walled nanotube Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 239000002135 nanosheet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Abstract
The application relates to the technical field of electrode materials, in particular to a working electrode for a sodium-carbon dioxide battery and a preparation method thereof; the working electrode comprises a substrate and a catalyst supported on the substrate, wherein the raw materials of the catalyst comprise the following components in percentage by mass: ruthenium nano-particles modify multi-wall carbon nano-materials, binders and dispersants; wherein the mass ratio of the ruthenium nano-particle modified multi-wall carbon nano-material to the binder is 85-95:15-5, and the mass volume ratio of the ruthenium nano-particle modified multi-wall carbon nano-material to the dispersing agent is 5-19:1; since the introduced carbon nanomaterial also has excellent conductivity, the conductivity of the mating substrate can also significantly reduce the charge voltage at the time of operation of the working electrode and increase the discharge voltage at the time of discharge, thereby reducing the polarization voltage of the working electrode, and thus the battery performance and the battery cycle life including the working electrode can be improved.
Description
Technical Field
The application relates to the technical field of electrode materials, in particular to a working electrode for a sodium-carbon dioxide battery and a preparation method thereof.
Background
The sodium-carbon dioxide battery is a novel energy storage and conversion device which takes carbon dioxide as anode gas and adopts a catalytic anode to catalyze the carbon dioxide reaction to generate electric energy, and the reaction of the battery is as follows:
because of the excellent energy storage characteristic of the sodium-carbon dioxide battery, the sodium-carbon dioxide battery has wide application potential in the fields of space exploration (the atmosphere of Mars and Mars contains rich carbon dioxide content), industrial tail gas treatment and the like. However, there are few catalytic materials currently associated with the positive electrode, and among them, carbon-based ruthenium-based catalysts have been widely recognized due to their excellent catalytic activity and electrochemical properties.
However, the existing carbon-based catalyst has poor catalytic activity, and the polarization voltage of the whole battery is too large, so that the overall performance and the cycle life of the battery are reduced, and therefore, how to provide a working electrode for a sodium-carbon dioxide battery, which has high catalytic activity and can reduce the polarization voltage of the battery, is a technical problem to be solved at present.
Disclosure of Invention
The application provides a working electrode for a sodium-carbon dioxide battery and a preparation method thereof, which are used for solving the technical problems that the catalytic activity of the working electrode in the sodium-carbon dioxide battery is poor and the polarization voltage of the working electrode is too high so as to reduce the overall performance and the cycle life of the battery in the prior art.
In a first aspect, the present application provides a working electrode for a sodium-carbon dioxide battery, the working electrode comprising a substrate and a catalyst supported on the substrate, the raw materials of the catalyst comprising, in mass fraction: ruthenium nano-particles modify multi-wall carbon nano-materials, binders and dispersants;
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 85-95:15-5, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 5-19:1.
Optionally, the mass ratio of the ruthenium nano particles to the carbon nano material in the ruthenium nano particle modified multiwall carbon nano material is 1:1-2.
Optionally, the carbon nanomaterial includes at least one of carbon nanotubes, graphene, and carbon nanoplatelets.
Optionally, the substrate comprises a sheet-like carbon material or a metal foam material.
Optionally, the sheet-like carbon material includes at least one of carbon paper, carbon cloth, and carbon felt.
Optionally, the metal foam material comprises nickel foam and/or iron foam.
Optionally, the binder comprises polyvinylidene fluoride.
Optionally, the dispersant comprises N-methylpyrrolidone.
In a second aspect, the present application provides a method of preparing the working electrode of the first aspect, the method comprising:
adding ruthenium salt into an organic solvent, stirring, adding a multi-wall carbon nanomaterial, and stirring to obtain a mixed solution;
carrying out high-temperature reaction on the mixed solution, cooling and washing, and then carrying out vacuum drying to obtain the ruthenium nanoparticle modified multiwall carbon nanomaterial;
respectively adding the ruthenium nanoparticle modified multiwall carbon nanomaterial and a binder into a dispersing agent, and stirring to obtain catalyst slurry;
and coating the catalyst slurry on the surface of the substrate, and drying to obtain the working electrode.
Optionally, the ruthenium salt includes at least one of ruthenium chloride, ruthenium nitrate, ruthenium oxide, and ruthenium carbonate.
Optionally, the temperature of the high-temperature reaction is 150-200 ℃, and the time of the high-temperature reaction is more than or equal to 3 hours.
Optionally, the vacuum drying comprises a heat preservation section and a heating section;
the temperature of the heat preservation section is 75-85 ℃, and the time of the heat preservation section is 4-6 hours;
the temperature of the heating section is 175-185 ℃, and the time of the heating section is 10-14 h.
Optionally, the drying includes air drying and high temperature drying;
the temperature of the blast drying is 75-85 ℃, and the time of the blast drying is 2-4 hours;
the high-temperature drying temperature is 105-115 ℃, and the high-temperature drying time is 8-12 h.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the working electrode for the sodium-carbon dioxide battery, provided by the embodiment of the application, the catalyst comprising the ruthenium nano-particle modified multi-wall carbon nano-material is introduced into the working electrode, the multi-wall carbon nano-material is used for supporting simple substance ruthenium and is used as the catalyst, on one hand, the multi-wall carbon nano-material has a good pore structure, so that the working electrode can disperse carbon dioxide in a normal working stage, and the carbon dioxide can be fully contacted with the simple substance ruthenium, on the other hand, the porous structure of the multi-wall carbon nano-material can contain enough simple substance ruthenium, so that the catalytic activity of the simple substance ruthenium in unit time can be improved, meanwhile, the mass-volume ratio of the ruthenium nano-particle modified multi-wall carbon nano-material to the binder is controlled, and the ruthenium nano-particle modified multi-wall carbon nano-material is uniformly dispersed and fixed on the surface of the substrate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic diagram of a transmission electron microscope of a ruthenium nanoparticle-modified multiwall carbon nanomaterial provided in an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for preparing the working electrode according to an embodiment of the present application;
FIG. 3 is a schematic diagram showing the comparison of X-ray diffraction patterns of ruthenium nanoparticle modified multiwall carbon nanotubes and multiwall carbon nanotubes according to an embodiment of the present application;
FIG. 4 is a schematic diagram of a scanning electron microscope of a ruthenium nanoparticle-modified multiwall carbon nanomaterial provided in an embodiment of the present application;
FIG. 5 is a schematic diagram showing the element distribution of ruthenium nanoparticle-modified multiwall carbon nanomaterial provided in an embodiment of the present application;
fig. 6 is a schematic diagram of practical application of a sodium-carbon dioxide battery according to an embodiment of the present application;
FIG. 7 is a schematic diagram of the cycling performance of a sodium-carbon dioxide cell provided by an embodiment of the present application;
FIG. 8 shows a discharge capacity of 7730 mAh.g according to an embodiment of the present application -1 Is a full charge-discharge performance curve diagram.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
As shown in fig. 1, an embodiment of the present application provides a working electrode for a sodium-carbon dioxide battery, the working electrode including a substrate and a catalyst supported on the substrate, the raw materials of the catalyst including, in mass fraction: ruthenium nano-particles modify multi-wall carbon nano-materials, binders and dispersants;
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 85-95:15-5, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 5-19:1.
According to the embodiment of the application, the specific mass ratio of the ruthenium nanoparticle modified multiwall carbon nanomaterial to the binder is controlled, and the specific mass volume ratio of the ruthenium nanoparticle modified multiwall carbon nanomaterial to the dispersing agent is controlled, so that the ruthenium nanoparticle modified multiwall carbon nanomaterial can be firmly adhered to the substrate by the binder, and meanwhile, the dispersing agent can uniformly disperse the ruthenium nanoparticle modified multiwall carbon nanomaterial on the surface of the substrate, so that the conductivity and the catalytic activity of the substrate are uniformly improved.
The mass ratio may be 85:15, 86:14, 87:13, 88:12, 89:11, 90:10, 91:9, 92:8, 93:7, 94:6, and 95:5.
The mass to volume ratio may be 5:1, or 7:1, or 9:1, or 11:1, or 13:1, or 15:1, or 17:1, or 19:1.
In some alternative embodiments, the mass ratio of ruthenium nanoparticles to carbon nanomaterial in the ruthenium nanoparticle modified multiwall carbon nanomaterial is from 1:1 to 2.
In the embodiment of the application, the specific mass ratio of the ruthenium nano particles to the carbon nano material in the ruthenium nano particle modified multiwall carbon nano material is controlled, so that the multiwall carbon nano material can load enough simple substance ruthenium, and the catalytic activity of the working electrode is effectively improved.
The mass ratio may be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, and 1:2.
In some alternative embodiments, the carbon nanomaterial comprises at least one of carbon nanotubes, graphene, and carbon nanoplatelets.
In some alternative embodiments, the substrate comprises a sheet-like carbon material or a metal foam material.
In the embodiment of the application, the specific types of the carbon nano materials are controlled, and the carbon nano materials with porous structures such as nano tubes, graphene and carbon nano sheets and specific surface areas can be used for effectively loading enough simple substance ruthenium, so that the catalytic activity of the working electrode is effectively improved.
The limiting substrate material adopts sheet carbon material or metal foam material, and can be finally prepared into flexible battery products, thereby facilitating the use of the final sodium-carbon dioxide battery.
In some alternative embodiments, the sheet-like carbon material includes at least one of carbon paper, carbon cloth, and carbon felt.
In some alternative embodiments, the metal foam material comprises nickel foam and/or iron foam.
In the embodiment of the application, the specific composition of the sheet-shaped carbon material and the metal foam material in the substrate is controlled, so that the prepared working electrode can form a flexible battery, and the use of a final sodium-carbon dioxide battery is convenient.
In some alternative embodiments, the binder comprises polyvinylidene fluoride.
In some alternative embodiments, the dispersant comprises N-methylpyrrolidone.
In the embodiment of the application, the specific types of the binder and the dispersing agent are controlled, the binder can be utilized to ensure that the ruthenium nanoparticle modified multiwall carbon nanomaterial is firmly adhered to the substrate, and meanwhile, the dispersing agent can ensure that the ruthenium nanoparticle modified multiwall carbon nanomaterial is uniformly dispersed on the surface of the substrate, so that the conductivity and the catalytic activity of the substrate are uniformly improved.
As shown in fig. 2, based on one general inventive concept, an embodiment of the present application provides a method of preparing the working electrode, the method comprising:
s1, adding ruthenium salt into an organic solvent, stirring, adding a multi-wall carbon nanomaterial, and stirring to obtain a mixed solution;
s2, carrying out high-temperature reaction on the mixed solution, cooling and washing, and then carrying out vacuum drying to obtain the ruthenium nanoparticle modified multiwall carbon nanomaterial;
s3, respectively adding the ruthenium nanoparticle modified multiwall carbon nanomaterial and the binder into a dispersing agent, and stirring to obtain catalyst slurry;
s4, coating the catalyst slurry on the surface of the substrate, and drying to obtain the working electrode.
In the embodiment of the application, ruthenium salt and multi-wall carbon nano materials are used as raw materials, then ruthenium nano particles are used for modifying the multi-wall carbon nano materials by a solvothermal method, and finally the ruthenium nano particles are used for modifying the multi-wall carbon nano materials by using a binder and a dispersing agent, so that the ruthenium nano particles can be stably adhered to the surface of a substrate, and further the conductivity and the catalytic activity of the substrate are uniformly improved.
The method is directed to the preparation method of the working electrode, the specific composition and the raw material proportion of the working electrode can refer to the above embodiment, and because the method adopts part or all of the technical schemes of the above embodiment, the method at least has all the beneficial effects brought by the technical schemes of the above embodiment, and the detailed description is omitted.
In some alternative embodiments, the ruthenium salt comprises at least one of ruthenium chloride, ruthenium nitrate, ruthenium oxide, and ruthenium carbonate.
In the embodiment of the application, the specific types of ruthenium salts are controlled, so that most of ruthenium sources can be covered, and the preparation cost of a solvothermal method is reduced.
In some alternative embodiments, the temperature of the high temperature reaction is 150 ℃ to 200 ℃ and the time of the high temperature reaction is more than or equal to 3 hours.
In the embodiment of the application, the specific temperature and the specific time of the high-temperature reaction are controlled, so that the mixed solution formed by the ruthenium salt and the multi-wall carbon nano material is sufficiently dried, and a coarse sample of the ruthenium nano particle modified multi-wall carbon nano material is obtained.
The high temperature reaction temperature may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃.
In some alternative embodiments, the vacuum drying comprises a soak section and a heating section;
the temperature of the heat preservation section is 75-85 ℃, and the time of the heat preservation section is 4-6 hours;
the temperature of the heating section is 175-185 ℃, and the time of the heating section is 10-14 h.
In the embodiment of the application, the temperature and the time of a specific heat preservation period of vacuum drying are controlled, and impurities in the crude sample of the ruthenium nanoparticle modified multiwall carbon nanomaterial can be primarily removed, so that the pure ruthenium nanoparticle modified multiwall carbon nanomaterial can be conveniently obtained later.
The temperature of a specific heating section and the time of the heating section of vacuum drying are controlled, so that impurities in the ruthenium nanoparticle modified multiwall carbon nanomaterial crude sample can be further removed, and the pure ruthenium nanoparticle modified multiwall carbon nanomaterial is obtained.
The temperature of the heat preservation section can be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ and 85 ℃.
The time of the heat preservation period can be 4 hours, can be 4.5 hours, can be 5.0 hours, can be 5.5 hours, and can be 6.0 hours.
The temperature of the heating section may be 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃ or 185 ℃.
The heating period may be 10 hours, or 10.5 hours, or 11.0 hours, or 11.5 hours, or 12.0 hours, or 12.5 hours, or 13.0 hours, or 13.5 hours, or 14.0 hours.
In some alternative embodiments, the drying includes forced air drying and high temperature drying;
the temperature of the blast drying is 75-85 ℃, and the time of the blast drying is 2-4 hours;
the high-temperature drying temperature is 105-115 ℃, and the high-temperature drying time is 8-12 h.
In the embodiment of the application, the specific temperature and the specific time of the forced air drying in the drying are controlled, and the catalyst slurry can be subjected to preliminary drying in an air drying mode, so that the working electrode product with uniformly distributed catalyst can be obtained later.
The catalyst can be further dried by controlling the specific temperature and the specific time of high-temperature drying, so that the working electrode product with uniformly distributed catalyst can be obtained.
The temperature of the forced air drying may be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃.
The time of the forced air drying may be 2 hours, or may be 2.5 hours, or may be 3.0 hours, or may be 3.5 hours, or may be 4.0 hours.
The high temperature drying temperature may be 105 deg.C, 106 deg.C, 107 deg.C, 108 deg.C, 109 deg.C, 110 deg.C, 111 deg.C, 112 deg.C, 113 deg.C, 114 deg.C, 115 deg.C
The high-temperature drying time may be 8 hours, or 8.5 hours, or 9.0 hours, or 9.5 hours, or 10.0 hours, or 10.5 hours, or 11.0 hours, or 11.5 hours, or 12.0 hours.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
An operating electrode for a sodium-carbon dioxide battery comprises a substrate and a catalyst supported on the substrate, wherein the catalyst comprises the following raw materials in mass percent: ruthenium nano-particles modify multi-wall carbon nano-materials, binders and dispersants;
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 85:15, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 17g:1L.
The mass ratio of the ruthenium nano particles to the carbon nano material in the ruthenium nano particle modified multiwall carbon nano material is 1:1.6.
The carbon nanomaterial is a carbon nanotube.
The substrate is carbon paper.
The binder is polyvinylidene fluoride.
The dispersing agent is N-methyl pyrrolidone.
A method of making a working electrode comprising:
s1, preparing a positive electrode material:
the Ru-CNTs catalytic anode is prepared by a simple solvothermal method: 30mg of RuCl 3 (Aladin) was dissolved in 60mL of ethylene glycol and stirred for 2h48mg of multi-walled carbon nanotubes (Qianfeng nanometer) are weighed and added into the solution, and the mixture is stirred for 30min to obtain a mixed solution.
The mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene having a capacity of 100 mL and placed in a high temperature oven at 170 ℃ for 3 hours, after cooling to room temperature, the black powder product was suction filtered out with ethanol several times.
The product was kept in a vacuum oven at 80 ℃ for 5h, then heated to 180 ℃ for 12h, and the black powder obtained was ground for further use.
S2, preparing a catalytic electrode:
17mg of Ru-CNTs and 3mg of polyvinylidene fluoride (polymerized from 1, 1-difluoroethylene) (PVDF) were added to 1mL of N-methylpyrrolidone (NMP) and stirred overnight to form a uniformly mixed slurry.
20. Mu.L of the slurry was coated on a carbon paper having a diameter of 14mm, and then dried in a forced air drying oven at 80℃for 3h and at 110℃for 10 hours at the working anode.
Example 2
Example 2 and example 1 were compared, and the difference between example 2 and example 1 is that:
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 90:10, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 5g:1L.
Example 3
Example 3 was compared with example 1, and the difference between example 3 and example 1 was:
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 95:5, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 19g:1L.
Example 4
Example 4 and example 1 were compared, and example 4 and example 1 differ in that:
the carbon nanomaterial is graphene.
The substrate is carbon cloth.
Example 5
Example 5 was compared with example 1, and the difference between example 5 and example 1 was:
the carbon nanomaterial is a carbon nanosheet.
The substrate is foam nickel.
Example 6
Comparing example 6 with example 1, example 6 differs from example 1 in that:
the temperature of the high-temperature reaction is 150 ℃, and the time of the high-temperature reaction is 4 hours.
The vacuum drying comprises a heat preservation section and a heating section;
the temperature of the heat preservation section is 75 ℃, and the time of the heat preservation section is 4 hours;
the temperature of the heating section was 175℃and the time of the heating section was 10 hours.
Drying includes air drying and high temperature drying;
the temperature of the air-blast drying is 75 ℃, and the time of the air-blast drying is 2 hours;
the high temperature drying temperature is 105 ℃, and the high temperature drying time is 8 hours.
Example 7
Example 7 was compared with example 1, and the difference between example 7 and example 1 was:
the temperature of the high temperature reaction was 200 ℃.
The vacuum drying comprises a heat preservation section and a heating section;
the temperature of the heat preservation section is 85 ℃, and the time of the heat preservation section is 6 hours;
the temperature of the heating section was 185℃and the time of the heating section was 14h.
Drying includes air drying and high temperature drying;
the temperature of the air-blast drying is 85 ℃, and the time of the air-blast drying is 4 hours;
the high temperature drying temperature is 115 ℃, and the high temperature drying time is 12 hours.
Related experiment and effect data:
the ruthenium nanoparticle-modified multiwall carbon nanotubes and multiwall carbon nanotubes obtained in example 1 were subjected to X-ray diffraction and a control pattern, and the results are shown in fig. 3. Fig. 3 shows, in order from top to bottom, an X-ray diffraction pattern measured on Carbon Nanotubes (CNTs), prepared Ru-CNTs using an X-ray diffractometer, and standard cards for X-ray diffraction of metallic Ru numbered 06-0663. According to the X-ray diffraction pattern curve of Ru-CNTs, the diffraction peak of Ru appears on the curve of CNTs, which proves that the prepared material is ruthenium nanoparticle modified multiwall carbon nanotube.
The ruthenium nanoparticle-modified multiwall carbon nanotube obtained in example 1 was observed by a scanning electron microscope, and the result is shown in fig. 4.
The ruthenium nanoparticle modified multiwall carbon nanotube obtained in example 1 was comprehensively analyzed for element distribution, and the result is shown in fig. 5.
Preparation of a battery:
the working electrode prepared in example 1 was assembled in a glove box filled with argon, and a battery case of model CR2032 was used, the positive electrode case of which was regularly perforated, in the order of negative electrode case, gasket, sodium metal sheet, glass fiber filter paper, a certain amount of electrolyte, catalytic positive electrode, shrapnel, followed by a perforated positive electrode case. The cells were then encapsulated using a sealer.
Testing of the battery:
the prepared cell was contained in a bottle in a glove box to constitute an apparatus as shown in fig. 6, after which the bottle was taken out of the glove box, and then the argon atmosphere in the bottle was replaced with pure CO 2 And (3) carrying out constant-current charge and discharge test on the gas by using a blue charge and discharge instrument.
And calculating the tested current according to the quality of the metal ruthenium, wherein the cut-off voltage is charged to 4.5V, and the discharge voltage is 2V, so that the cyclic test is carried out. As shown in FIG. 7, the current density was 200 mA.g -1 The charge-discharge cut-off capacity is 5000 mAh.g -1 The discharge voltage of the battery from the first cycle (1 st) to the 20th cycle (20 th) was still stable, and the charge voltage did not significantly rise, confirming that the prepared Na-CO 2 The battery has good cycle performance and stable structure in the reaction process. When the number of cycles reaches 120 times (120 th), the charging voltage is still lower than 4.5V, and the discharging voltage is higher than 2V, which shows that the prepared electrode pair has obvious effect of reducing voltage polarization. As shown in conjunction with FIG. 8, at the same timeTest at a current density of 200 mA.g -1 At the time of complete discharge, the specific capacity was 7730 mAh.g -1 Far higher than the current lithium ion battery material, and is 45 times of theoretical discharge capacity of the lithium iron phosphate anode material. In addition, the discharge voltage is stable, and the discharge platform is more than 2.2V.
As can be seen from fig. 7 and 8, the working electrode for a sodium-carbon dioxide battery provided by the embodiment of the application can significantly reduce the charging voltage, and improve the discharging voltage, thereby reducing the polarization voltage, and the prepared battery has excellent charging and discharging performance and good cycle performance.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
(1) The working electrode for the sodium-carbon dioxide battery provided by the embodiment of the application can fix carbon dioxide, use carbon dioxide in the fields of energy storage, energy supply and the like, and can achieve multiple purposes.
(2) The working electrode for the sodium-carbon dioxide battery provided by the embodiment of the application is beneficial to large-scale popularization because the use cost of sodium metal and carbon dioxide is lower.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (13)
1. A working electrode for a sodium-carbon dioxide battery, characterized in that the working electrode comprises a substrate and a catalyst supported on the substrate, wherein the raw materials of the catalyst comprise, in mass fraction: ruthenium nano-particles modify multi-wall carbon nano-materials, binders and dispersants;
the mass ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the binder is 85-95:15-5, and the mass volume ratio of the ruthenium nanoparticle modified multi-wall carbon nanomaterial to the dispersing agent is 5-19:1.
2. The working electrode of claim 1 wherein the mass ratio of ruthenium nanoparticles to carbon nanomaterial in the ruthenium nanoparticle modified multiwall carbon nanomaterial is 1:1-2.
3. The working electrode of claim 2 wherein the carbon nanomaterial comprises at least one of carbon nanotubes, graphene, and carbon nanoplatelets.
4. The working electrode of claim 2 wherein the substrate comprises a sheet-like carbon material or a metal foam material.
5. The working electrode of claim 4 wherein the sheet-like carbon material comprises at least one of carbon paper, carbon cloth, and carbon felt.
6. The working electrode of claim 4 wherein the metal foam material comprises nickel foam and/or iron foam.
7. The working electrode of claim 1 wherein the binder comprises polyvinylidene fluoride.
8. The working electrode of claim 1 wherein the dispersant comprises N-methyl pyrrolidone.
9. A method of preparing the working electrode for a sodium-carbon dioxide battery according to any one of claims 1-8, comprising:
adding ruthenium salt into an organic solvent, stirring, adding a multi-wall carbon nanomaterial, and stirring to obtain a mixed solution;
carrying out high-temperature reaction on the mixed solution, cooling and washing, and then carrying out vacuum drying to obtain the ruthenium nanoparticle modified multiwall carbon nanomaterial;
respectively adding the ruthenium nanoparticle modified multiwall carbon nanomaterial and a binder into a dispersing agent, and stirring to obtain catalyst slurry;
and coating the catalyst slurry on the surface of the substrate, and drying to obtain the working electrode.
10. The method of claim 9, wherein the ruthenium salt comprises at least one of ruthenium chloride, ruthenium nitrate, ruthenium oxide, and ruthenium carbonate.
11. The method according to claim 9, wherein the high temperature reaction is carried out at a temperature of 150 ℃ to 200 ℃ for a time of not less than 3 hours.
12. The method of claim 9, wherein the vacuum drying comprises a soak zone and a heating zone;
the temperature of the heat preservation section is 75-85 ℃, and the time of the heat preservation section is 4-6 hours;
the temperature of the heating section is 175-185 ℃, and the time of the heating section is 10-14 h.
13. The method of claim 9, wherein the drying comprises forced air drying and high temperature drying;
the temperature of the blast drying is 75-85 ℃, and the time of the blast drying is 2-4 hours;
the high-temperature drying temperature is 105-115 ℃, and the high-temperature drying time is 8-12 h.
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