CN114300696B - Doped graphene material and preparation method and application thereof - Google Patents
Doped graphene material and preparation method and application thereof Download PDFInfo
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- CN114300696B CN114300696B CN202111581352.7A CN202111581352A CN114300696B CN 114300696 B CN114300696 B CN 114300696B CN 202111581352 A CN202111581352 A CN 202111581352A CN 114300696 B CN114300696 B CN 114300696B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 142
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 239000002184 metal Substances 0.000 claims abstract description 38
- 150000003624 transition metals Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 28
- 125000004429 atom Chemical group 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
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- 239000013543 active substance Substances 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract 1
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- 229910052760 oxygen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
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- 238000006722 reduction reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
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- 238000011161 development Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
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- 235000005074 zinc chloride Nutrition 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
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- 239000002002 slurry Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical group 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
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- 239000007888 film coating Substances 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- 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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- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a doped graphene material, a preparation method and application thereof, wherein the doped graphene material comprises metal atoms and graphene, and the mass percentage of the metal atoms in the doped graphene material is more than 0% and not more than 20%, wherein the metal atoms are doped into the graphene in an atomic-level chemical substitution manner, and the metal atoms are transition metal atoms. By using self-supporting graphene, transition metal monoatoms are used as catalytic active sites to carry out atomic-level chemical bonding with a highly conductive graphene base body, three-dimensional holes of the graphene are fully utilized to provide a gas diffusion channel, a binder and a conductive agent are not required to be added, and further compounding with a gas diffusion layer is not required. The complete self-supporting electrode structure ensures that the electrode can not fall off of active substances in the long-time use process, thereby remarkably improving the long-cycle stability of the electrode and prolonging the service life of the electrode while guaranteeing the catalytic performance.
Description
Technical Field
The invention relates to the field of batteries, in particular to a doped graphene material and a preparation method and application thereof.
Background
Along with the consumption of fossil fuel and the increase of human movable carbon emission, the development of clean and efficient novel renewable energy sources becomes an important research direction in the energy field. In recent years, the development of new energy devices has become a further research focus due to the development of the objective of carbon neutralization. The fuel cell uses fuel and oxygen as reaction raw materials, converts chemical energy into electric energy, is a clean and efficient power generation device, has the advantages of high power generation efficiency, high energy density, various selectable fuel types and the like, and is a new energy cell with great application prospect.
The air electrode is a positive electrode of the fuel cell, and mainly generates reduction reaction of oxygen and is a control step of the reaction speed of the cell, so that development of the air electrode with high performance is of great significance for improving the performance of the fuel cell. The traditional air electrode generally comprises a gas diffusion layer, a binder and a catalyst, wherein the catalyst, the conductive agent and the binder are mixed to prepare slurry, and the slurry is coated on a gas diffusion layer substrate through processes such as dipping, spraying and the like. However, in this preparation process, an interfacial resistance exists between the catalyst slurry and the substrate, which may affect the discharge efficiency of the battery to some extent. In addition, the long-term operation easily causes the catalyst to fall off from the substrate, so that the cycle stability of the air electrode is affected. Therefore, in recent years, a self-supporting air electrode is developed, and the self-supporting air electrode is directly used as the air electrode of a fuel cell without adding an additional conductive agent, an adhesive and a current collector, so that a film coating process in the process of preparing the electrode is omitted, and the manufacturing method of the air electrode is greatly simplified. At present, most common self-supporting electrodes are prepared by in-situ loading alloy and metal compound nano particles on conductive framework matrixes such as carbon paper, hydrogel, foam nickel and the like. However, the nano particles are agglomerated and fall off in the using process of the electrode loaded with the nano particles, so that the structure of the material is changed, and the catalytic performance of the electrode is affected.
Disclosure of Invention
Based on the above, it is necessary to provide a doped graphene material which is not easy to fall off of active substances, has good catalytic performance and battery electrode cycle stability, and a preparation method and application thereof.
The invention provides a doped graphene material, which comprises metal atoms and graphene, wherein the mass percentage of the metal atoms in the doped graphene material is more than 0% and not more than 20%;
the metal atoms are doped into the graphene in an atomic-level chemical substitution mode, and the metal atoms are transition metal atoms.
In one embodiment, the metal atom is at least one of a copper atom, an iron atom, a zinc atom, a cobalt atom, and a nickel atom.
In one embodiment, the doped graphene material has a thickness of 1 μm to 30 μm.
In one embodiment, the graphene is single-layer graphene or few-layer graphene with the number of layers of 2-10.
The invention further provides a preparation method of the doped graphene material, which comprises the following steps:
s10: uniformly mixing a first part of graphene and a first solvent by an ultrasonic or cell crushing method, carrying out suction filtration to form a film, and filtering out liquid to prepare a first dispersion raw material;
s20: mixing metal salt with a second solvent, and carrying out suction filtration on the basis of the first dispersion raw material film to remove liquid so as to prepare a second dispersion raw material;
s30: mixing a second part of graphene with a third solvent, and carrying out suction filtration on the basis of the second dispersion raw material to filter liquid to prepare a third dispersion raw material;
s40: and performing heat treatment on the third dispersed raw material.
In one embodiment, in step S10 to step S30, the suction filtration is vacuum filtration.
In one embodiment, in step S10 to step S30, the first solvent, the second solvent, and the third solvent are each independently selected from at least one of water and ethanol.
In one embodiment, in step S40, the temperature is raised from room temperature at a rate of 1 ℃ to 20 ℃ per minute to a heat treatment temperature of 500 ℃ to 900 ℃ for 15min to 60min.
In one embodiment, the mass ratio of the carbon atoms in the first part of graphene, the metal atoms in the metal salt and the carbon atoms in the second part of graphene is (1-100): 1 (1-100).
Furthermore, the invention also provides application of the doped graphene material in battery electrodes.
And taking self-supporting graphene as a framework, and performing atomic-level chemical bonding on a transition metal monoatom and a highly conductive graphene base body. The self-supporting structure not only provides a catalytic active site, but also is beneficial to electron transmission, and the three-dimensional holes of the graphene provide a gas diffusion channel, so that a self-supporting structure does not need to be added with a binder and a conductive agent, and does not need to be further compounded with a gas diffusion layer. The complete self-supporting electrode structure and the atomic bonding catalytic site enable the electrode not to fall off of active substances in the long-time use process, and the long-cycle stability of the electrode is remarkably improved. Furthermore, the transition metal replaces noble metal platinum commonly used in the air electrode, so that the production cost of the air electrode is reduced, the graphene doped with the transition metal atoms has a good catalytic effect, catalyst poisoning is not easy to occur, and the service life of the electrode is prolonged while the catalytic performance is ensured.
Drawings
FIG. 1 is a cross-sectional microtopography of the doped graphene material of example 1;
FIG. 2 is an X-ray photoelectron spectrum of the doped graphene material of example 1;
FIG. 3 is an X-ray photoelectron spectrum of the doped graphene material of example 2;
FIG. 4 is an X-ray photoelectron spectrum of the doped graphene material of example 4;
FIG. 5 is an atomic doping under a sphere difference electron microscope of the doped graphene material of example 3;
FIG. 6 is a graph of oxygen reduction catalytic performance of the doped graphene materials of examples 1-4;
FIG. 7 is an oxygen reduction catalytic performance of the doped graphene material of example 1 before and after 5000 long cycles;
fig. 8 is an oxygen reduction catalytic performance of the doped graphene material of comparative example 1 before and after 5000 long cycles.
Detailed Description
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a doped graphene material, which comprises metal atoms and graphene, wherein the mass percentage of the metal atoms in the doped graphene material is more than 0% and not more than 20%; wherein, the metal atoms are replaced and doped into the graphene by the chemistry of atomic level, and the metal atoms are transition metal atoms.
It will be appreciated that the chemical doping described above refers to substitutional doping, which is accomplished by the substitution of heteroatoms for carbon atoms in the graphene backbone.
The strong interaction of the metal monoatoms embedded in the graphene matrix can effectively regulate the electronic structure, and the graphene doped with the metal monoatoms has a unique energy level structure due to the quantum effect, so that the graphene has excellent activity and durability when used for oxygen reduction catalysis. The graphene doped with metal monoatoms is prepared by doping and modifying graphene at atomic level, and is directly used as an air electrode of a fuel cell, so that the manufacturing cost of the air electrode is reduced, the catalytic active sites are chemically bonded with a conductive graphene matrix, the active sites are not easy to separate from the matrix due to strong interaction of monoatoms doping, the problem of falling of active substances in a long-cycle process is solved by a self-supporting electrode structure, and the cycle stability of the electrode in operation can be remarkably improved.
Specifically, the atomic doping rate of the metal atoms may be, but is not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
In a specific example, the metal atom is at least one of a copper atom, an iron atom, a zinc atom, a cobalt atom, and a nickel atom.
In one specific example, the doped graphene material has a thickness of 1 μm to 30 μm.
Preferably, the thickness of the doped graphene material is 18 μm to 30 μm.
Further, the thickness of the doped graphene material may be, but is not limited to, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm.
It can be appreciated that the doped graphene material is self-supporting doped graphene paper, and the self-supporting electrode can be directly used as an electrode without additional binder, conductive agent and current collector.
In one specific example, the atomic percent of oxygen in the graphene is 0% -50%.
It is understood that the atomic percent of oxygen atoms may be, but is not limited to, 0%, 4%, 8%, 12%, 16%, 20%, 24%, 28%, 32%, 36%, 40%, 44%, or 50%.
Preferably, the atomic percentage of oxygen atoms in the graphene is 20% -50%.
In a specific example, the graphene is a single-layer graphene or a few-layer graphene with a layer number of 2 to 10.
Further, the number of layers of the few-layer graphene may be, but is not limited to, 2, 3, 4, 5, 6, 7, 8, 9, or 10 layers.
By taking self-supporting graphene as a framework, transition metal monoatoms serve as catalytic active sites to carry out atomic-level chemical bonding with a highly conductive graphene base body. The three-dimensional hole of the graphene provides a gas diffusion channel, a binder and a conductive agent are not required to be added, and further recombination with a gas diffusion layer is not required. The complete self-supporting electrode structure and the atomic bonding catalytic site enable the electrode not to fall off of active substances in the long-time use process, and the long-cycle stability of the electrode is remarkably improved. Furthermore, the transition metal replaces noble metal platinum commonly used in the air electrode, so that the production cost of the air electrode is reduced, the graphene doped with the transition metal atoms has a good catalytic effect, catalyst poisoning is not easy to occur, and the service life of the electrode is prolonged while the catalytic performance is ensured.
The invention further provides a preparation method of the doped graphene material, which comprises the following steps S10-S40.
Step S10: uniformly mixing the first part of graphene and a first solvent by an ultrasonic or cell crushing method, carrying out suction filtration to form a film, and filtering out liquid to prepare a first dispersion raw material.
It is understood that the first portion of graphene is uniformly dispersed in the first solvent.
Step S20: and mixing the metal salt with a second solvent, and carrying out suction filtration on the basis of the first dispersed raw material film to remove liquid so as to prepare a second dispersed raw material.
It is understood that after the metal salt is uniformly dispersed in the second solvent, the first dispersed raw material is covered for suction filtration.
Further, the above metal salt may be, but is not limited to, a metal chloride salt. In particular, the metal salt may be, but is not limited to, ferric chloride, nickel chloride, zinc chloride, cupric chloride, or cobalt chloride.
Step S30: and mixing the second part of graphene with a third solvent, and carrying out suction filtration on the basis of the second dispersed raw material to filter liquid to prepare a third dispersed raw material.
It can be appreciated that after the second portion of graphene is uniformly dispersed in the third solvent, the second portion of graphene is covered on the second dispersed raw material for suction filtration.
In a specific example, in step S10 to step S30, the suction filtration is vacuum filtration.
In a specific example, in step S10 to step S30, the first solvent, the second solvent, and the third solvent are each independently selected from at least one of water and ethanol.
Step S40: and carrying out heat treatment on the third dispersed raw material.
In a specific example, in step S40, the temperature is raised from room temperature at a temperature raising rate of 1 ℃/min to 20 ℃/min to a temperature of heat treatment, the temperature of heat treatment is 500 ℃ to 900 ℃, and the time of heat treatment is 15min to 60min.
Further, the rate of heating may be, but is not limited to, 1 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 15 ℃/min, 17 ℃/min, 19 ℃/min, or 20 ℃/min.
Further, the heat treatment temperature may be, but is not limited to, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, or 900 ℃.
In one specific example, the time of the heat treatment may be, but is not limited to, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, or 60min.
In a specific example, the mass ratio of the carbon atoms in the first graphene, the metal atoms in the metal salt, and the carbon atoms in the second graphene is (1-100): 1 (1-100).
Further, the mass ratio of the carbon atoms in the first graphene to the metal atoms in the metal salt to the carbon atoms in the second graphene is preferably (1 to 20): 1 (1 to 20).
Still further, the above heat treatment is performed under an inert gas atmosphere, and it is understood that the inert gas may be, but is not limited to, nitrogen or argon.
By taking self-supporting graphene as a framework, transition metal monoatoms serve as catalytic active sites to carry out atomic-level chemical bonding with a highly conductive graphene base body. The three-dimensional hole of the graphene provides a gas diffusion channel, a binder and a conductive agent are not required to be added, and further recombination with a gas diffusion layer is not required. The complete self-supporting electrode structure and the atomic bonding catalytic site enable the electrode not to fall off of active substances in the long-time use process, and the long-cycle stability of the electrode is remarkably improved. Furthermore, the transition metal replaces noble metal platinum commonly used in the air electrode, so that the production cost of the air electrode is reduced, the graphene doped with the transition metal atoms has a good catalytic effect, catalyst poisoning is not easy to occur, and the service life of the electrode is prolonged while the catalytic performance is ensured.
Furthermore, the invention also provides application of the doped graphene material as a battery electrode.
It will be appreciated that the doped graphene materials described above may be, but are not limited to, application in electrode materials suitable for use in fuel cells or metal-oxygen cells.
Specific examples are provided below to illustrate the doped graphene materials of the present invention and methods of making the same in further detail. The raw materials according to the following embodiments may be commercially available unless otherwise specified.
Example 1
The preparation method of the doped graphene material provided by the embodiment comprises the following steps:
step S10: and weighing 500mg of graphene oxide with the oxygen atom content of 40at percent, uniformly dispersing in 20mL of deionized water, and drying after vacuum suction filtration to obtain a first dispersion raw material.
Step S20: 133.65mg of ferric chloride FeCl is weighed 3 Uniformly dispersing in deionized water to obtain ferric chloride FeCl 3 A solution. Suction filtering ferric chloride FeCl on the first dispersed raw material film 3 And drying the solution to obtain a second dispersed raw material.
Step S30: 600mg of graphene oxide which is the same as that in the step S10 is weighed and uniformly dispersed in 20mL of deionized water, suction filtration is carried out on the second dispersed raw material film, and a third dispersed raw material is obtained after drying.
Step S40: and (3) carrying out heat treatment on the third dispersion raw material film under the protection of argon, heating to 700 ℃ at the heating rate of 10 ℃/min, preserving heat for 60min, and then cooling to room temperature.
The number of layers of graphene in the doped graphene material provided in this embodiment is 2, the doping amount of iron atoms is 5.62wt%, the thickness of the doped graphene material is 26 μm, as shown in fig. 1, which is a microscopic morphology diagram of a cross section of the doped graphene material in this embodiment, and fig. 2, which is an X-ray photoelectron spectrum of the doped graphene material in this embodiment.
The doped graphene material provided in this embodiment is directly used as an oxygen electrode, 0.1M KOH solution is used as an electrolyte, hg/HgO is used as a reference electrode, and a platinum wire is usedFor the counter electrode, an oxygen reduction catalytic performance test was carried out in an oxygen-saturated three-electrode system, the initial potential of which was-0.089V (vs RHE), and the limiting current density was 6.41mA/cm 2 . As shown in fig. 7, the above battery system can still maintain high oxygen reduction catalytic activity after 5000 times of long-cycle oxygen reduction catalytic tests.
Example 2
This example differs from example 1 in ferric chloride FeCl 3 The preparation method of the doped graphene material provided by the embodiment comprises the following steps of:
step S10: and weighing 500mg of graphene oxide with the oxygen atom content of 40at percent, uniformly dispersing in 20mL of deionized water, and drying after vacuum suction filtration to obtain a first dispersion raw material.
Step S20: 400.95mg of ferric chloride FeCl is weighed 3 Uniformly dispersing in deionized water to obtain ferric chloride FeCl 3 A solution. Suction filtering ferric chloride FeCl on the first dispersed raw material film 3 And drying the solution to obtain a second dispersed raw material.
Step S30: 600mg of graphene oxide which is the same as that in the step S10 is weighed and uniformly dispersed in 20mL of deionized water, suction filtration is carried out on the second dispersed raw material film, and a third dispersed raw material is obtained after drying.
Step S40: and (3) carrying out heat treatment on the third dispersion raw material film under the protection of argon, heating to 700 ℃ at the heating rate of 10 ℃/min, preserving heat for 60min, and then cooling to room temperature.
The number of layers of graphene in the doped graphene material provided in this embodiment is 2, the doping amount of iron atoms is 16.25wt%, and the thickness of the doped graphene material is 25 μm, as shown in fig. 3, which is an X-ray photoelectron spectrum of the doped graphene material of this embodiment.
The doped graphene material provided in this embodiment is directly used as an oxygen electrode, 0.1M KOH solution is used as an electrolyte, hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and oxygen reduction catalytic performance test is performed in an oxygen saturated three-electrode system, wherein the initial potential is-0.024V (vs RHE), and the limiting current density is 8.11mA/cm 2 。
Example 3
The preparation method of the doped graphene material provided by the embodiment comprises the following steps:
step S10: and weighing 500mg of graphene oxide with the oxygen atom content of 35at percent, uniformly dispersing in 20mL of deionized water, and drying after vacuum suction filtration to obtain a first dispersion raw material.
Step S20: 179.52mg of zinc chloride ZnCl is weighed 2 Uniformly dispersing in deionized water to obtain zinc chloride ZnCl 2 A solution. Suction filtering zinc chloride ZnCl on the first dispersed raw material film 2 And drying the solution to obtain a second dispersed raw material.
Step S30: 600mg of graphene oxide which is the same as that in the step S10 is weighed and uniformly dispersed in 20mL of deionized water, suction filtration is carried out on the second dispersed raw material film, and a third dispersed raw material is obtained after drying.
Step S40: and (3) carrying out heat treatment on the third dispersion raw material film under the protection of argon, heating to 700 ℃ at the heating rate of 10 ℃/min, preserving heat for 60min, and then cooling to room temperature.
The number of layers of graphene in the doped graphene material provided in this embodiment is 3, the doping amount of zinc atoms is 9.37wt%, and the thickness of the doped graphene material is 25 μm, as shown in fig. 5, which is an atom doping condition under the spherical aberration electron microscope in this embodiment.
The doped graphene material provided in this embodiment is directly used as an oxygen electrode, 0.1M KOH solution is used as an electrolyte, hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and oxygen reduction catalytic performance test is performed in an oxygen saturated three-electrode system, wherein the initial potential is-0.162V (vs RHE), and the limiting current density is 6.76mA/cm 2 。
Example 4
The preparation method of the doped graphene material provided by the embodiment comprises the following steps:
step S10: and weighing 500mg of graphene oxide with the oxygen atom content of 35at percent, uniformly dispersing in 20mL of deionized water, and drying after vacuum suction filtration to obtain a first dispersion raw material.
Step S20: 334.57mg of copper acetate Cu (CH) was weighed 3 COO) 2 Uniformly dispersing in deionized water to obtain copper acetate Cu (CH) 3 COO) 2 A solution. Suction filtering copper acetate Cu (CH) on first dispersed raw material film 3 COO) 2 And drying the solution to obtain a second dispersed raw material.
Step S30: 600mg of graphene oxide which is the same as that in the step S10 is weighed and uniformly dispersed in 20mL of deionized water, suction filtration is carried out on the second dispersed raw material film, and a third dispersed raw material is obtained after drying.
Step S40: and (3) carrying out heat treatment on the third dispersion raw material film under the protection of nitrogen, heating to 900 ℃ at the heating rate of 15 ℃/min, preserving heat for 40min, and then cooling to room temperature.
The number of layers of graphene in the doped graphene material provided in this embodiment is 3, the doping amount of copper atoms is 11.97wt%, and the thickness of the doped graphene material is 20 μm, as shown in fig. 4, which is an X-ray photoelectron spectrum of the doped graphene material of this embodiment.
The doped graphene material provided in this embodiment is directly used as an oxygen electrode, 0.1M KOH solution is used as an electrolyte, hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and oxygen reduction catalytic test is performed in an oxygen saturated three-electrode system, wherein the initial potential is-0.025V (vs RHE), and the limiting current density is 7.23mA/cm 2 。
The comparison of oxygen reduction catalytic performance of the doped graphene materials of examples 1-4 is shown in fig. 6.
The doped graphene materials of examples 1 to 4 were used as electrode materials to give batteries having good electrochemical performance with a limiting current density of 6.41mA/cm 2 ～8.11mA/cm 2 The battery remained well stable in cycling even after 5000 cycles.
Comparative example 1
The preparation method of the doped graphene doped powder provided by the comparative example comprises the following steps:
step S10: 1100mg of graphene oxide with the oxygen atom content of 40at% is weighed and uniformly dispersed in 40mL of deionized water to obtain a first dispersion raw material.
Step S20: 133.65mg of ferric chloride FeCl is weighed 3 Uniformly dispersing in deionized water to obtain ferric chloride FeCl 3 A solution. Ferric chloride FeCl 3 Solution additionThe first dispersed raw materials are uniformly mixed and dried to obtain the second dispersed raw materials.
Step S30: and (3) carrying out heat treatment on the second dispersion raw material under the protection of argon, heating to 700 ℃ at the heating rate of 10 ℃/min, preserving heat for 60min, and then cooling to room temperature to obtain the doped graphene powder.
4mg of doped graphene powder provided in the comparative example, 2mg of carbon black and 50 mu L of 5% naphthol solution are dispersed in 2mL of ethanol to prepare electrode liquid, and 16 mu L of electrode liquid is dripped into an area of 0.196cm 2 The platinum electrode surface of (c) was dried and used as an oxygen electrode. The catalytic performance of the doped graphene material of this comparative example was measured by 5000 times of long-cycle oxygen reduction in a three-electrode system saturated with oxygen using 0.1M KOH solution as electrolyte, hg/HgO as reference electrode, and platinum wire as counter electrode, as shown in fig. 8.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted in accordance with the contents of the claims.
Claims (10)
1. A doped graphene material, characterized in that its composition comprises metal atoms and graphene, the mass percentage of the metal atoms in the doped graphene material being greater than 0% and not greater than 20%;
the metal atoms are doped into the graphene in an atomic-level chemical substitution manner, and the metal atoms are transition metal atoms;
the preparation method of the doped graphene material comprises the following steps:
s10: uniformly mixing a first part of graphene and a first solvent by an ultrasonic or cell crushing method, carrying out suction filtration to form a film, and filtering out liquid to prepare a first dispersion raw material;
s20: mixing metal salt with a second solvent, and carrying out suction filtration on the basis of the first dispersion raw material film to remove liquid so as to prepare a second dispersion raw material;
s30: mixing a second part of graphene with a third solvent, and carrying out suction filtration on the basis of the second dispersion raw material to filter liquid to prepare a third dispersion raw material;
s40: and performing heat treatment on the third dispersed raw material.
2. The doped graphene material of claim 1, wherein the metal atoms are at least one of copper atoms, iron atoms, zinc atoms, cobalt atoms, and nickel atoms.
3. The doped graphene material of claim 1, wherein the doped graphene material has a thickness of 1 μιη to 30 μιη.
4. A doped graphene material according to any one of claims 1 to 3, wherein the graphene is a single layer graphene or a few layer graphene with a number of layers of 2 to 10.
5. The doped graphene material of claim 1, wherein the mass percentage of metal atoms in the doped graphene material is 5% -17%.
6. The doped graphene material of claim 1, wherein in step S10-step S30, the suction filtration is vacuum filtration.
7. The doped graphene material of claim 1, wherein in step S10-step S30, the first solvent, the second solvent, and the third solvent are each independently selected from at least one of water and ethanol.
8. The doped graphene material of claim 1, wherein in step S40, the temperature is raised from room temperature at a temperature rise rate of 1 ℃/min to 20 ℃/min to a heat treatment temperature of 500 ℃ to 900 ℃ and the heat treatment time is 15min to 60min.
9. The doped graphene material according to claim 1, wherein the mass ratio of carbon atoms in the first portion of graphene, metal atoms in the metal salt, and carbon atoms in the second portion of graphene is (1-100): 1 (1-100).
10. Use of a doped graphene material according to any one of claims 1 to 9 as a battery electrode.
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| KR20130099535A (en) * | 2012-02-29 | 2013-09-06 | 중앙대학교 산학협력단 | Increase of work function using doped graphene |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| CN106115667A (en) * | 2016-06-20 | 2016-11-16 | 南京工程学院 | The low temperature preparation method of S, N codope Graphene and application |
| CN110642245A (en) * | 2019-09-29 | 2020-01-03 | 北京石墨烯技术研究院有限公司 | Preparation method of metal monoatomic doped graphene |
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| KR20130099535A (en) * | 2012-02-29 | 2013-09-06 | 중앙대학교 산학협력단 | Increase of work function using doped graphene |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| CN106115667A (en) * | 2016-06-20 | 2016-11-16 | 南京工程学院 | The low temperature preparation method of S, N codope Graphene and application |
| CN110642245A (en) * | 2019-09-29 | 2020-01-03 | 北京石墨烯技术研究院有限公司 | Preparation method of metal monoatomic doped graphene |
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