CN115472440B - Graphene-based N, S doped electrode material and preparation method thereof - Google Patents
Graphene-based N, S doped electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 239000007772 electrode material Substances 0.000 title claims abstract description 68
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 15
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
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- 238000002635 electroconvulsive therapy Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
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- 238000004146 energy storage Methods 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 239000003990 capacitor Substances 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
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- 239000002033 PVDF binder Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
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- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000010534 mechanism of action Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The application discloses a graphene-based N, S doped electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor; adding graphene oxide into the dispersion liquid to obtain a mixed solution; carrying out solvothermal treatment on the mixed solution; and washing and drying the product subjected to the solvent heat treatment, and then performing thermal shock treatment to obtain the electrode material. According to the preparation method, the carbon nanomaterial is inserted between the graphene oxide layers to form an inter-embedded structure, so that the conductivity of the graphene oxide layers is improved, and the carbon nanomaterial is inserted to prevent the graphene oxide layers from being stacked; according to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transport is promoted, and the conductivity and energy storage effect of the material are improved.
Description
Technical Field
The application belongs to the technical field of preparation of capacitor materials, and particularly relates to a graphene-based N, S doped electrode material and a preparation method thereof.
Background
The wide use of fossil energy such as coal and petroleum can produce negative effects such as environmental pollution to climate change, so clean pollution-free green energy system is used for replacing traditional fossil energy and an efficient and convenient energy use mode becomes a hot problem of current research. In the existing energy system, the green energy system such as solar energy, wind energy, tidal energy and the like is subjected to the problems of climate conditions, intermittence, low energy density and the like, and the generated electric energy is difficult to directly grid-connected for use. Therefore, the development of new energy storage and energy supply devices with high power density, high energy density, and high conversion efficiency has become an important research topic.
In order to solve these problems, new energy storage technologies, such as electrochemical, compressed air, heat pump water and electricity, have been proposed in recent years. Among these technologies, electrochemical energy storage has the characteristics of green, high efficiency, sustainability and the like, and is a primary choice for solving the problems of effective conversion and storage of renewable energy sources and providing stable energy output. The electrochemical energy storage technology commonly used at present comprises a secondary battery such as an air battery, a lithium ion battery, a lithium sulfur battery and the like, and a novel electrochemical energy storage technology such as a super capacitor and the like. At present, electrochemical energy storage systems represented by lithium ion batteries and supercapacitors are widely applied in the fields of standby power supplies, base station communication, portable mobile equipment and the like. However, they are limited by the mechanism of action and neither lithium ion batteries nor supercapacitors can meet the high energy density, high power density and good cycling stability required in many applications.
Electrode materials play a critical role in the electrochemical performance of lithium ion capacitors. Common cathode materials include carbon materials, metal oxides, lithium titanate and the like, and positive electrode materials include carbon materials, metal oxides, conductive polymers and the like. Although the theoretical capacity of the carbon material is low, the carbon material has the characteristics of no toxicity, high conductivity, low cost, abundant raw materials, strong reproducibility, high specific surface area, stable physicochemical properties and the like, so the carbon material is suitable as an electrode, in particular to a graphene material. However, a major problem with graphene materials as electrodes is that graphene tends to stack from layer to reduce surface energy, resulting in significantly lower conductivity and specific surface area than single or few layers of graphene, resulting in reduced capacitor electrochemical performance of the graphene material.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a graphene-based N, S doped electrode material and a preparation method thereof, so as to solve the technical problems of low capacity and poor cycling stability of the existing graphene-based electrode material.
In order to achieve the above object, according to a first aspect of the present application, there is provided a preparation method of a graphene-based N, S doped electrode material, including the steps of:
preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor;
adding graphene oxide into the dispersion liquid to obtain a mixed solution;
carrying out solvothermal treatment on the mixed solution;
and washing and drying the product subjected to the solvothermal treatment, and then performing thermal shock treatment to obtain the electrode material.
Further, the temperature of the solvothermal treatment is 150-200 ℃ and the time is 10-20 h.
Further, the temperature of the thermal shock treatment is 150-300 ℃, and the temperature rising rate is 5-15 ℃/min.
Further, in the dispersion liquid, the mass ratio of the nano carbon material to the heteroatom precursor is 1 (0.8-10), and the concentration of the dispersion liquid is 0.5-2 mg/ml.
Further, the nano carbon material is at least one of carbon nano fiber, nano mesoporous carbon, carbon nano tube, fullerene, graphene quantum dot or carbon quantum dot.
Further, the heteroatom precursor is at least one of thiophene, thiourea, ammonium sulfate, ammonium sulfide and ammonium sulfite.
Further, the mass ratio of the graphene oxide to the dispersion liquid is (0.8-2): 1.
Further, the solvent of the mixed solution is any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
Further, the drying is freeze drying, and the temperature is-60 to-35 ℃.
In a second aspect of the present application, there is provided a graphene-based N, S doped electrode material prepared using the preparation method of any one of the above.
Compared with the prior art, the application has the following technical effects:
according to the preparation method of the graphene-based N, S doped electrode material, the heteroatom precursor is combined with the nano carbon material through molecular self-assembly by utilizing the electrostatic effect, N, S co-doping is introduced through solvothermal reaction, more active sites are introduced, and the conductivity and electrochemical performance of the carbon material are improved.
According to the preparation method, the carbon nanomaterial is inserted between the graphene oxide layers to form an inter-embedded structure, so that the conductivity of the graphene oxide layers is improved, and the carbon nanomaterial is inserted to prevent the graphene oxide layers from being stacked; the nano carbon material and the graphene oxide are self-assembled into a three-dimensional porous nano network structure, so that the specific surface area is greatly increased, the high specific surface area is provided for charge transfer, the ion transmission distance is shortened, and the electrochemical performance of the material is improved.
According to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transport is promoted, and the conductivity and energy storage effect of the material are improved.
The preparation method is simple, convenient to operate, beneficial to large-scale production and capable of providing possibility for commercialization.
The electrode material can be used for the positive electrode or the negative electrode of the lithium ion capacitor, and when the electrode material is applied to the positive electrode and the negative electrode of the lithium ion capacitor, the electrode material has excellent high-capacity characteristic, cycle stability performance and ultrahigh rate performance.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a CV curve of the positive electrode of the lithium ion capacitor provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which 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. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means 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.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms "first" and "second" 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 for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
In a first aspect, an embodiment of the present application provides a method for preparing a graphene-based N, S doped electrode material, including the following steps:
(1) Preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor;
(2) Adding graphene oxide into the dispersion liquid to obtain a mixed solution;
(3) Carrying out solvothermal treatment on the mixed solution;
(4) And washing and drying the product subjected to the solvent heat treatment, and then performing thermal shock treatment to obtain the electrode material.
In the above step (1), in the dispersion liquid of the embodiment of the present application, the mass ratio of the nanocarbon material to the heteroatom precursor is 1: (0.8-10), the concentration of the dispersion is 0.5-2 mg/ml. The nano carbon material can be at least one of carbon nano fiber, nano mesoporous carbon, carbon nano tube, fullerene, graphene quantum dot or carbon quantum dot, and the specific embodiment of the application takes the carbon nano tube as an example for illustration; the heteroatom precursor can be at least one of thiophene, thiourea, ammonium sulfate, ammonium sulfide and ammonium sulfite, and the specific embodiments of the application are described by taking thiourea and ammonium sulfate as examples. In the prepared dispersion liquid, under the action of static electricity, the heteroatom precursor is combined with the nano carbon material through molecular self-assembly, and the heteroatom precursor is used as a source of N, S.
In the step (2), the mass ratio of the added graphene oxide to the dispersion liquid is (0.8-2): 1. After the graphene oxide is added, the dispersion of the graphene oxide in the mixed solution can be promoted by adopting ultrasonic dispersion, the power of the ultrasonic dispersion is 200-500W, and the time of the ultrasonic dispersion is 5-30 min.
In the step (3), N, S co-doping is introduced through solvothermal reaction, so that more active sites are introduced, and the conductivity and electrochemical performance of the prepared carbon material are improved. The temperature of the solvothermal treatment is 150-200 ℃ and the time is 10-20 h. The solvent can be any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
In the step (4), freeze drying can be adopted, and the temperature is between-60 ℃ and-35 ℃. The temperature of the thermal shock treatment in the embodiment of the application is 150-300 ℃, and the temperature rising rate is 5-15 ℃/min. In the process of rapid temperature rise, heat is transferred to the graphene oxide sheets, so that expansion of the graphene oxide sheets is promoted, and stacking among the graphene oxide sheets is further reduced.
According to the preparation method, the carbon nanomaterial is inserted between the graphene oxide layers to form an inter-embedded structure, so that the conductivity of the graphene oxide layers is improved, and the carbon nanomaterial is inserted to prevent the graphene oxide layers from being stacked; the nano carbon material and the graphene oxide are self-assembled into a three-dimensional porous nano network structure, so that the specific surface area is greatly increased, the high specific surface area is provided for charge transfer, the ion transmission distance is shortened, and the electrochemical performance of the material is improved. According to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transport is promoted, and the conductivity and energy storage effect of the prepared material are improved.
The preparation method of the embodiment of the application is simple, convenient to operate, beneficial to large-scale production and provides possibility for commercialization.
In a second aspect of the embodiments of the present application, a graphene-based N, S doped electrode material obtained by the above preparation method is provided, where the electrode material of the embodiments of the present application may be used in a positive electrode or a negative electrode of a lithium ion capacitor, and when the electrode material of the embodiments of the present application is applied to the positive electrode and the negative electrode of a lithium ion capacitor, the electrode material of the embodiments of the present application all exhibits excellent high capacity characteristics, cycle stability performance, and ultra-high rate capability.
A graphene-based N, S doped electrode material and a method for preparing the same according to embodiments of the present application are illustrated in the following examples.
Example 1
Embodiment 1 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, comprising the following steps:
(1) 50ml of deionized water is added into 6mg of carbon nano tube and 25mg of thiourea, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Fig. 1 is a CV curve of the positive electrode of the lithium ion capacitor of example 1 of the present application, and it is seen from fig. 1 that a good rectangular shape can be maintained even at a high scan speed. The test result shows that the positive electrode of the lithium ion capacitor has surface adsorption capacitance behavior and good reversibility.
Example 2
Embodiment 2 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, comprising the following steps:
(1) 50ml of deionized water is added into 3mg of carbon nano tube and 25mg of thiourea, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Example 3
Embodiment 3 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, including the following steps:
(1) 50ml of deionized water is added into 10mg of carbon nano tube and 25mg of thiourea, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Example 4
Embodiment 4 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, comprising the following steps:
(1) 50ml of deionized water is added into 30mg of carbon nano tube and 25mg of thiourea, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Example 5
Embodiment 5 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, comprising the following steps:
(1) 50ml of deionized water is added into 15mg of carbon nano tube and 25mg of thiourea, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Example 6
Embodiment 6 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, comprising the following steps:
(1) 50ml of deionized water is added into 10mg of carbon nano tube and 25mg of ammonium sulfate, and the mixture is stirred for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and performing ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle into an electrothermal blowing drying oven for solvothermal treatment at 180 ℃ for 12h;
(4) And heating to 260 ℃ (heating rate 15 ℃/min) after suction filtration, washing and freeze drying, and preserving heat for 2 hours to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methylpyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8:1:1, and the negative electrode and the positive electrode of the lithium ion capacitor are obtained after the electrode active material is subjected to blade coating, drying at 50 ℃ for 12 hours, heating to 80 ℃ and drying for 10 hours.
Comparative example 1
It is different from example 3 in that the carbon nanotubes are not added in step (1), and other process steps are the same.
Comparative example 2
This differs from example 3 in that in step (4) no thermal shock treatment is performed and the other process steps are the same.
Performance tests were performed on graphene-based N, S doped electrode materials prepared in examples 1-6 and comparative examples 1-2 of the present application. The test conditions were: the current density is 0.1A/g, and the voltage window of the negative electrode is as follows: the voltage window of the positive electrode is 0.01-3V: 2-4.5V, the results are shown in the following table:
from the table above, graphene-based N, S doped electrode materials prepared in examples 1-6 of the application all show higher positive and negative electrode capacity, high ploidy and cycling stability. Compared with comparative examples 1 and 2, the preparation method of the embodiment of the application adopts the nano carbon material for composite modification and synergistic thermal shock treatment, and can remarkably improve the capacity, the multiplying power and the cycling stability of the prepared electrode material.
The foregoing examples represent only a few embodiments of the present application, which are described in more detail and are not thereby to be construed as limiting the scope of the present application. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (6)
1. The preparation method of the graphene-based N, S doped electrode material is characterized by comprising the following steps of:
preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor; in the dispersion liquid, the mass ratio of the nano carbon material to the heteroatom precursor is 1 (0.8-10), and the concentration of the dispersion liquid is 0.5-2 mg/ml;
adding graphene oxide into the dispersion liquid to obtain a mixed solution; the mass ratio of the graphene oxide to the dispersion liquid is (0.8-2) 1;
carrying out solvothermal treatment on the mixed solution; the temperature of the solvothermal treatment is 150-200 ℃ and the time is 10-20 hours;
and washing and drying the product subjected to the solvothermal treatment, and then performing thermal shock treatment to obtain the electrode material, wherein the temperature of the thermal shock treatment is 150-300 ℃ and the heating rate is 5-15 ℃/min.
2. The method for preparing a graphene-based N, S doped electrode material according to claim 1, wherein the nano carbon material is at least one of carbon nanofibers, nano mesoporous carbon, carbon nanotubes, fullerenes, graphene quantum dots or carbon quantum dots.
3. The method for preparing a graphene-based N, S doped electrode material according to claim 1, wherein the heteroatom precursor is at least one of thiophene, thiourea, ammonium sulfate, ammonium sulfide and ammonium sulfite.
4. The method for preparing a graphene-based N, S doped electrode material according to claim 1, wherein the solvent of the mixed solution is any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
5. The method for preparing a graphene-based N, S doped electrode material according to claim 1, wherein the drying is freeze drying, and the temperature is-60 to-35 ℃.
6. A graphene-based N, S doped electrode material, which is prepared by the preparation method according to any one of claims 1 to 5.
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