CN116564717B - Bi-based composite electrode material, preparation method and application thereof - Google Patents
Bi-based composite electrode material, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 17
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- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
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- 239000011669 selenium Substances 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 27
- 239000002608 ionic liquid Substances 0.000 claims description 19
- -1 1-butyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 9
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- 230000000052 comparative effect Effects 0.000 description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 239000012153 distilled water Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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Classifications
-
- 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
-
- 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 invention discloses a Bi-based complexA composite electrode material comprising: heterojunction structure material consisting of BiOBr and Bi doped with nonmetallic atoms 2 X 3 Constructing; the nonmetallic atoms include N atoms, B atoms, and F atoms; the X includes one of O, S, se and Te. The preparation method of the Bi-based composite electrode material comprises the following steps: step 1, preparing substances including BiOBr doped with nonmetallic atoms by adopting a solvothermal method; and 2, adding an X source into the substance prepared in the step 1, and reducing the substance in the reducing gas atmosphere to obtain substances including heterojunction structure materials serving as Bi-based composite electrode materials. The Bi-based composite electrode material provided by the invention is expected to show excellent performance in a super capacitor.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a Bi-based composite electrode material, a preparation method and application.
Background
In recent years, the high energy and power density of supercapacitors (also known as electrochemical capacitors), better cycling stability and higher charge/discharge rates make this technology promising in energy storage.
Along with the promotion of the environment-friendly and simple and rapid concepts of people's life, super capacitors have been widely applied to high-power electronic equipment such as aerospace, military industry, electric vehicles, hybrid electric vehicles and the like. Electrode materials are the core of supercapacitors and are the key factors determining capacitor performance. At present, the commercial supercapacitor electrode is made of carbon materials, the energy density of the commercial supercapacitor electrode is generally only 3-5 Wh.kg, and the requirements of various portable electronic devices and electric automobiles on high-energy-density supercapacitors can not be met far. Therefore, there is an urgent need to find and develop a novel high-performance supercapacitor electrode material.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides a Bi-based composite electrode material for solving the problems, a preparation method and application thereof.
The invention is realized by the following technical scheme:
a Bi-based composite electrode material comprising: heterojunction structure material consisting of BiOBr and Bi doped with nonmetallic atoms 2 X 3 Constructing; the nonmetallic atoms include N atoms, B atoms, and F atoms; the X includes one of O, S, se and Te.
The heterojunction provided by the invention is a three-dimensional petal-shaped material, bismuth selenide is arranged at the edges of petals, and BiOBr is arranged at the centers of the petals.
Further optionally, a substrate for supporting the heterojunction electrode material is also included.
Further alternatively, the substrate comprises an MXene substrate.
Further alternatively, the MXene substrate is selected from Mo 2 CT x Substrate, ti 3 C 2 T x Substrate, ti 2 CT x Substrate, cr 2 CT x Substrate and V 2 CT x One or more of the substrates.
A preparation method of a Bi-based composite electrode material is used for preparing the Bi-based composite electrode material, and comprises the following steps:
step 1, preparing substances including BiOBr doped with nonmetallic atoms by adopting a solvothermal method;
and 2, adding an X source into the substance prepared in the step 1, and reducing the substance in the reducing gas atmosphere to obtain substances including heterojunction structure materials serving as Bi-based composite electrode materials.
In step 1, the bismuth source comprises bismuth nitrate salt; the bromine source comprises one or more than two of cetyl-3-methyl ammonium bromide (CTAB), sodium bromide and potassium bromide; the solvent comprises one or more of ethylene glycol, ethanol and isopropanol.
Preferably, in step 1, bismuth nitrate is used as the bismuth source and cetyl-3-methyl ammonium bromide (CTAB) is used as the bromine source. Ethylene glycol and/or ethanol is used as solvent.
The bromine source cetyl-3-methyl ammonium bromide (CTAB) can also be used as a forming agent, and is favorable for forming petal-shaped heterojunction structures.
Further optionally, in the step 1, an ionic liquid is used as a doped nonmetallic source;
preferably, the ionic liquid comprises one or more of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, and 1-ethyl-3-methylimidazolium tetrafluoroborate.
Specifically, step 1 includes the preparation steps of:
(1-1) adding bismuth source and ionic liquid into ethylene glycol to obtain a mixed solution A;
(1-2) dissolving a bromine source in ethanol to obtain a solution B;
(1-3) mixing the mixed solution a and the solution B; then the reaction is carried out by heating. And centrifuging and drying the reacted solution to obtain a substance including BiOBr doped with nonmetallic atoms.
More preferably, the mixed solution A and the solution B are mixed and stirred uniformly (e.g., stirred at a temperature of 0 ℃ to 300 ℃ for 30min to 60 min); and (3) placing the stirred solution into a reaction kettle, and heating for 5-10 h at 120-200 ℃. And centrifuging and drying the reacted solution to obtain a substance including BiOBr doped with nonmetallic atoms.
Further optionally, in the step 2, the method includes:
mixing the substance prepared in the step 1 with an X source, and heating under the atmosphere of reducing gas to perform a reduction reaction.
Further alternatively, the X source is a corresponding elemental powder.
If X is used for representing O, directly reducing; when X represents S, sulfur powder is adopted; when X represents Se, selenium powder is adopted; when X represents Te, tellurium powder is used.
Specifically, step 2 includes the preparation steps of:
mixing the substance prepared in the step 1 with simple substance powder of an X source, and placing the mixture in a reducing gas atmosphere for reduction reaction to obtain the composite electrode material. Preferably, the reduction reaction temperature is 300 ℃ to 600 ℃.
Further optionally, in step 1, adding a base material as a carrier of the heterojunction structure material is further included.
For the amount of each component, for example, the amount of the ionic liquid is preferably 0 to 2 parts by weight, and the amount of the bismuth source is preferably 0.1 to 2 parts by weight; the consumption of the bromine source is 0.1-2 parts; the amount of the carrier is 0-1 part. The ratio of the X source to the BiOBr doped with nonmetallic atoms is 0-1.
Specifically, for example: wherein the dosage of the ionic liquid is 0-2ml; the dosage of bismuth source is 0.1-2g; the dosage of the bromine source is 0.1-2g; the amount of carrier is 0-1g.
An application of a Bi-based composite electrode material is used for a super capacitor.
The invention has the following advantages and beneficial effects:
1. the Bi-based composite electrode material provided by the invention consists of BiOBr doped with nonmetallic atoms and Bi 2 X 3 The heterojunction structure formed by (X=O, S, se) has large specific surface area, so that the electrocatalytic performance is improved; biOBr/Bi 2 X 3 The heterojunction has rich oxygen vacancies, so that more active sites are exposed, and the spin state of the central Bi ions is made more active; co-doping N atoms, B atoms and F atoms into BiOBr/Bi 2 X 3 In the heterojunction, the number of active sites can be further increased, and electronegativity can be improved, so that the capability of capturing protons is further enhanced.
2. The Bi-based composite electrode material provided by the invention adopts an MXene material as a substrate for growing NBF-BiOBr/Bi 2 X 3 A heterojunction; because the MXene material has excellent metal conductivity, the conductivity of the whole rhenium disulfide nano sheet can be further improved by introducing the MXene material, and the electron transmission is accelerated. In addition, the MXene has a two-dimensional lamellar structure, so that the phenomenon of heterojunction agglomeration can be relieved to a great extent, the specific surface area is increased, and the number of active binding sites is further increased.
3. The Bi-based composite electrode material provided by the invention is expected to show excellent performance in a super capacitor.
4. The preparation method of the Bi-based composite electrode material provided by the invention has the advantages that the raw materials are cheap and easy to obtain, the preparation method is mainly based on a hydrothermal method and a reduction reaction, three hetero-atom doping can be realized by only adding one additive (ionic liquid), and the whole operation method is simple.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
figure 1 is an XRD spectrum of the different samples.
FIG. 2 is an SEM image of a sample prepared according to example 1
Fig. 3 is an SEM image of different samples.
FIG. 4 is an EPR spectrum of the sample provided in example 1.
FIG. 5 is a graph of CV curves for samples at different scan rates.
Figure 6 is a graph of GCD plots for samples at different scan rates.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
Example 1
The implementation provides a Bi-based composite electrode material which is prepared from BiOBr and Bi doped with nonmetallic atoms 2 X 3 The formed heterojunction structure material is named NBF-BiOBr/Bi 2 Se 3 . The preparation method comprises the following steps:
step 1, preparing NBF-BiOBr by a solvothermal method.
The ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 0.25mL, 0.48g bismuth nitrate was dissolved in 10mL ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. Bismuth oxybromide doped with nitrogen, boron and fluorine, namely NBF-BiOBr, is obtained.
Step 2, preparing NBF-BiOBr/Bi through reduction reaction 2 Se 3 。
30mg of dried NBF-BiOBr and 500mg of selenium powder are taken and put into an OTF-1200X tube furnace together, and are put into Ar/H 2 Under the atmosphere, at 5 ℃ for min -1 Is heated to 450 ℃ and is kept at the temperature for 1h. Taking out the sample after cooling to obtain a heterojunction structure material named NBF-BiOBr/Bi 2 Se 3 。
Example 2
The implementation provides a Bi-based composite electrode material, which consists of a substrate and a heterojunction structure material loaded on the substrate, and is named NBF-BiOBr/Bi 2 Se 3 /Mo 2 CT x . The preparation method comprises the following steps:
step 1, preparing Mo 2 CT x A substrate.
Mo 2 CT x MXene nanoplatelets are obtained from bulk Mo by HF 2 Ga 2 And C, selectively etching the Ga layer to synthesize the semiconductor.
First, mo is taken up in 2 Ga 2 Powder C (2 g) was milled for 30min and then slowly added to 20mL HF solution without dilution.
The mixture was then placed on a magnetic stir heated sleeve at 55 ℃ and stirred for 7 days.
And centrifuging at 10000rpm for 10min to obtain the product, and washing with deionized water for several times until the pH value of the solution reaches about 6. Finally, the resulting powder was dried in a freeze dryer.
Step 2, preparing NBF-BiOBr/Mo by a solvothermal method 2 CTx。
Ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 0.25ml, bismuth nitrate 0.48g and Mo 0.05g 2 CT x Dissolved in 10mL of glycol to form solution A。
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. To obtain bismuth oxybromide doped with nitrogen, boron and fluorine, i.e. NBF-BiOBr/Mo, supported on the substrate 2 CT x 。
Step 3, preparing NBF-BiOBr/Bi through reduction reaction 2 Se 3 /Mo 2 CT x 。
30mg of dried NBF-BiOBr/Mo was taken 2 CT x Placing into an OTF-1200X tube furnace together with 500mg selenium powder, under Ar/H conditions 2 Under the atmosphere, at 5 ℃ for min -1 Is heated to 450 ℃ and is kept at the temperature for 1h. Taking out the sample after cooling to obtain the composite electrode material named NBF-BiOBr/Bi 2 Se 3 /Mo 2 CT x 。
Comparative example 1
The present case provides a composite electrode material BiOBr/Bi 2 Se 3 /Mo 2 CT x The preparation method is as follows:
step 1, preparing BiOBr/Mo by solvothermal method 2 CT x 。
Will be 0.48 g Bismuth nitrate, 0.05g Mo 2 CT x (the carrier was prepared as in example 2) was dissolved in 10mL of ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. To obtain bismuth oxybromide supported on the substrate, i.e. BiOBr/Mo 2 CT x 。
Step 2, preparing BiOBr/Bi through reduction reaction 2 Se 3 /Mo 2 CT x 。
30mg of dried BiOBr/Mo was taken 2 CT x Placing into an OTF-1200X tube furnace together with 500mg selenium powder, under Ar/H conditions 2 Under the atmosphere, at 5 ℃ for min -1 Is heated to 450 ℃ and is kept at the temperature for 1h. Taking out the sample after cooling to obtain the composite electrode material, named BiOBr/Bi 2 Se 3 /Mo 2 CT x 。
Comparative example 2
The present case provides a composite electrode material NBF-Bi 2 Se 3 /Mo 2 CT x The preparation method is as follows:
step 1, preparing NBF-BiOBr/Mo by solvothermal method 2 CT x 。
Ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 0.25ml, bismuth nitrate 0.48g and Mo 0.05g 2 CT x Dissolved in 10mL of ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. To obtain bismuth oxybromide doped with nitrogen, boron and fluorine, i.e. NBF-BiOBr/Mo, supported on the substrate 2 CT x 。
Step 2, preparing NBF-Bi through reduction reaction 2 Se 3 /Mo 2 CT x 。
30mg of dried NBF-BiOBr/Mo was taken 2 CT x Placing into an OTF-1200X tube furnace together with 1g selenium powder, and adding into Ar/H 2 Under the atmosphere, at 5 ℃ for min -1 Is heated to 450 ℃ and is kept at the temperature for 1h. Taking out the sample after cooling to obtain the composite electrode material named NBF-Bi 2 Se 3 /Mo 2 CT x 。
Comparative example 3
The present case provides a composite electrode material NBF-BiOBr/Mo 2 CT x The preparation method is as follows:
step 1, preparing NBF-BiOBr/Mo by solvothermal method 2 CT x 。
Ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 0.25ml, bismuth nitrate 0.48g and Mo 0.05g 2 CT x Dissolved in 10mL of ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. To obtain bismuth oxybromide doped with nitrogen, boron and fluorine, i.e. NBF-BiOBr/Mo, supported on the substrate 2 CT x As a composite electrode material.
Comparative example 4
The present case provides a composite electrode material BiOBr/Mo 2 CT x The preparation method is as follows:
step 1, preparing BiOBr/Mo by solvothermal method 2 CT x 。
Bismuth nitrate 0.48g and Mo 0.05g 2 CT x Dissolved in 10mL of ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. To obtain bismuth oxybromide supported on the substrate, i.e. BiOBr/Mo 2 CT x 。
Comparative example 5
The present case provides a composite electrode material NBF-BiOBr, and the preparation method is as follows:
step 1, preparing NBF-BiOBr by a solvothermal method.
The ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 0.25mL, 0.48g bismuth nitrate was dissolved in 10mL ethylene glycol to form solution A.
0.77g of cetyl-3-methyl ammonium bromide (CTAB) was dissolved in 60mL of ethanol to form solution B.
Liquids A and B were mixed, stirred with a magnetic stirrer for 30min, and sealed in a 100mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted at 160℃for 8h.
The autoclave was naturally cooled to room temperature, centrifuged several times with distilled water and dried at 80℃for 2h. The bismuth oxybromide doped with nitrogen, boron and fluorine, namely NBF-BiOBr, is obtained as a composite electrode material.
1. Characterization analysis
1. XRD characterization analysis.
The crystal structure of the samples was systematically studied by XRD pattern. Sample BiOBr/Bi of comparative example 1 2 Se 3 /Mo 2 CT x Sample BiOBr/Mo of comparative example 4 2 CTx、Mo 2 CT x The XRD patterns (obtained from step 1 of example 2) are shown in FIG. 1, labeled BiOBr and Bi 2 Se 3 Is a standard substance card corresponding to two substances.
As can be seen from FIG. 1, biOBr/Bi 2 Se 3 /Mo 2 CT x And BiOBr/Mo 2 CT x The diffraction peaks of (2) are the basic superposition of the diffraction peaks of the constituent substances, and the XRD pattern has no other impurity peaks, which indicates that the crystal structure of the ionic liquid is not changed when the ionic liquid is doped.
2. SEM characterization analysis.
(1) Fig. 2 is an SEM image of the sample prepared in example 1. As can be seen from the figure, the heterojunction provided in this embodiment is a three-dimensional petal-shaped material, bismuth selenide is arranged at the edges of petals, and the center of the petals is BiOBr.
(2) Fig. 3 is an SEM image of different samples. In the drawing the view of the figure,
(a) Represents the sample BiOBr/Mo provided in comparative example 4 2 CT x SEM images of (a);
(b) Represents the sample NBF-BiOBr/Mo provided in comparative example 3 2 CT x SEM images of (a);
(c) Represents the sample BiOBr/Bi provided in comparative example 1 2 Se 3 /Mo 2 CT x SEM images of (a);
(d) Sample NBF-BiOBr/Bi representing example 2 2 Se 3 /Mo 2 CT x SEM images of (a);
(e) Representing the sample NBF-BiOBr/Bi provided in example 1 2 Se 3 SEM images of (a);
(f) Representation of sample NBF-Bi provided in comparative example 2 2 Se 3 /Mo 2 CT x SEM images of (a);
(g) SEM image of sample NBF-BiOBr of comparative example 5.
As can be seen from the figure, biOBr/Mo without ionic liquid 2 CT x Is in a flower ball shape and distributed in clusters; after selenization, it was found that finely divided lamellar structures were formed on the surface of the flower ball. After the ionic liquid is added, the two-dimensional nano-sheets on the original sphere of the BiOBr or the sheet-shaped B generated after selenizing are adopted i2 Se 3 The number of the units is increased. Therefore, the addition of the ionic liquid is supposed to increase the contact area of electrochemical reaction, and provide more reaction sites for ion migration and electrocatalytic processes, thereby improving the electrochemical performance.
3. EPR characterization analysis.
FIG. 4 is an EPR spectrum of the sample provided in example 1. As shown in the figure, the appearance of a peak of 2.003 indicates that the crystal contains oxygen vacancies, biOBr/Bi 2 X 3 The heterojunction has abundant oxygen vacancies, which not only exposes more active sites, but also makes the spin state of the central Bi ion more active.
2. Electrochemical performance test
1. Test method.
(1) Preparing a working electrode:
using electrochemical workstations CHI760E (CHI Instruments, inc., shanghai) the electrochemical performance of the active materials provided in the examples and comparative examples was tested with three electrodes and a 3M KOH solution was used as the electrolyte. Pt sheet electrode (1 cm) 2 ) And Hg/HgO electrode as counter electrode and reference electrode; the active material, acetylene black and polyvinylidene fluoride (PVDF) were poured into a mortar at a mass ratio of 7:2:1 for grinding. After grinding for 15min, the mixture was poured into N-methyl-2-pyrrolidone (NMP) solvent and stirred on a magnetic stirrer for 8h to give a viscous black slurry. And finally, uniformly coating the prepared slurry on foam nickel, putting the foam nickel into a vacuum oven, and drying the foam nickel at 80 ℃ for 16 hours to obtain the working electrode.
(2) The testing method comprises the following steps:
1) CV curve testing method: the scanning speed is 5mV-100mV, and the voltage range is 0 to-1V.
2) GCD curve test method: current density of 1Ag -1 -20Ag -1 And scanning the voltage range of 0 to-1V.
2. And (5) testing results.
(1) Cyclic voltammogram test results.
FIG. 5 is a graph of CV curves for samples at different scan rates. The scanning rate is 5-100 mV.s -1 . In the drawing the view of the figure,
(a) Representing the sample NBF-BiOBr/Bi provided in example 2 2 Se 3 /Mo 2 CT x Is a CV curve of (c);
(b) Represents the sample BiOBr/Bi provided in comparative example 1 2 Se 3 /Mo 2 CT x Is a CV curve of (c);
(c) Representation of sample NBF-Bi provided in comparative example 2 2 Se 3 /Mo 2 CT x Is a CV curve of (c);
(d) Represents the sample NBF-BiOBr/Mo provided in comparative example 3 2 CT x Is a CV curve of (c);
(e) CV plots showing the sample NBF-BiOBr provided in comparative example 5;
(f) Representing the sample NBF-BiOBr/Bi provided in example 1 2 Se 3 Is a CV curve of (c).
As shown in figure 5 of the drawings,the shape of these curves remained good at different scan rates, indicating that the material exhibited good rate performance. Each CV curve shows several distinct redox peaks representing typical cellular behavior. NBF-/BiOBr/Bi compared to other electrode materials 2 Se 3 /Mo 2 CT x Shows the widest redox peak and the largest integrated area under the peak, thus indicating the highest specific capacity during redox.
(2) And testing results of constant-current charge-discharge curves.
Figure 4 is a graph of GCD plots for samples at different scan rates. In the drawing the view of the figure,
(a) Representing the sample NBF-BiOBr/Bi provided in example 2 2 Se 3 /Mo 2 CT x Is a GCD graph of (C);
(b) Represents the sample BiOBr/Bi provided in comparative example 1 2 Se 3 /Mo 2 CT x Is a GCD graph of (C);
(c) Representation of sample NBF-Bi provided in comparative example 2 2 Se 3 /Mo 2 CT x Is a GCD graph of (C);
(d) Represents the sample NBF-BiOBr/Mo provided in comparative example 3 2 CT x Is a GCD graph of (C);
(e) A GCD graph showing the NBF-BiOBr of the sample provided in comparative example 5;
(f) Representing the sample NBF-BiOBr/Bi provided in example 1 2 Se 3 Is a GCD graph of (C).
As shown in FIG. 6, the content of the active ingredients is 1-20A.g -1 The constant current charge-discharge (GCD) curves of the different samples were measured at the current densities of (4), and as can be seen from FIG. 4, NBF-BiOBr/Bi 2 Se 3 /Mo 2 CT x Electrode 1 A.g -1 The discharge time at the current density was the longest, which also indicates the maximum specific capacity (637.2 C.g -1 )。
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A Bi-based composite electrode material comprising: the heterojunction structure material is characterized in that,
the heterojunction structure material is formed by Bi 2 X 3 And a BiOBr doped with non-metal atoms;
the nonmetallic atoms include N atoms, B atoms, and F atoms;
the X includes one of O, S, se and Te.
2. The Bi-based composite electrode material of claim 1, further comprising a substrate for supporting the heterojunction structure material.
3. The Bi-based composite electrode material of claim 2, wherein the substrate comprises an MXene substrate.
4. A Bi-based composite electrode material according to claim 3, wherein the MXene substrate is selected from Mo 2 CT x Substrate, ti 3 C 2 T x Substrate, ti 2 CT x Substrate, cr 2 CT x Substrate and V 2 CT x One or more of the substrates.
5. A method for producing a Bi-based composite electrode material according to any one of claims 1 to 4, characterized by comprising the steps of:
step 1, preparing substances including BiOBr doped with nonmetallic atoms by adopting a solvothermal method;
step 2, adding an X source into the substance prepared in the step 1, and reducing the substance in the reducing gas atmosphere to obtain substances including heterojunction structure materials serving as Bi-based composite electrode materials;
in the step 1, an ionic liquid is adopted as a doped nonmetallic source; the ionic liquid comprises one or more of 1-butyl-3-methylimidazole tetrafluoroborate, 1-methyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate;
step 1, adding ionic liquid into glycol;
step 2, mixing the substance prepared in the step 1 with an X source, and heating under a reducing gas atmosphere to perform a reduction reaction;
the X source adopts corresponding simple substance powder; comprising the following steps: x represents O, and then directly reducing; or when X represents S, sulfur powder is adopted; or when X represents Se, selenium powder is adopted; or when X represents Te, tellurium powder is used.
6. The method of claim 5, further comprising adding a base material as a carrier for the heterojunction structure material in step 1.
7. The application of the Bi-based composite electrode material is characterized in that the Bi-based composite electrode material is used for a super capacitor; the Bi-based composite electrode material is a Bi-based composite electrode material according to any one of claims 1 to 4, or a Bi-based composite electrode material prepared by a method for preparing a Bi-based composite electrode material according to claim 5 or 6.
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| CN104826637A (en) * | 2015-02-10 | 2015-08-12 | 西北师范大学 | Preparation method of BiOBr/Bi2O3 heterojunction composite catalyst |
| CN106938340A (en) * | 2016-08-30 | 2017-07-11 | 江苏大学 | A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope |
| CN110911170A (en) * | 2019-12-02 | 2020-03-24 | 武汉轻工大学 | Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof |
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| CN104826637A (en) * | 2015-02-10 | 2015-08-12 | 西北师范大学 | Preparation method of BiOBr/Bi2O3 heterojunction composite catalyst |
| CN106938340A (en) * | 2016-08-30 | 2017-07-11 | 江苏大学 | A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope |
| CN110911170A (en) * | 2019-12-02 | 2020-03-24 | 武汉轻工大学 | Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof |
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