CN110844939B - Molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and preparation method thereof - Google Patents
Molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and preparation method thereof Download PDFInfo
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 35
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- HWRJVZIUPBOVBP-UHFFFAOYSA-N [C].[Mo]=S Chemical compound [C].[Mo]=S HWRJVZIUPBOVBP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 74
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 74
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 66
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 40
- 239000008103 glucose Substances 0.000 claims abstract description 40
- 239000000017 hydrogel Substances 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 33
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 33
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000004964 aerogel Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000001580 bacterial effect Effects 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000011807 nanoball Substances 0.000 claims 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
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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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: step S1, preparing a sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material; step S2, converting the sodium molybdate/thiourea in the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material into molybdenum disulfide, converting the glucose into carbon nanospheres, and converting the bacterial cellulose into carbon nanofibers to serve as electrode materials of the supercapacitor. By adopting the technical scheme of the invention, a carbon nanofiber mesh structure can be constructed, and the molybdenum disulfide in the structure grows along the carbon nanofibers, compared with a molybdenum disulfide/carbon nanofiber structure, the added glucose can be converted into carbon nanospheres, so that the electronic conductivity in the electrode is increased, and the transmission efficiency of electrons in the electrode is improved. The technical scheme can provide a novel preparation method for manufacturing the electrode material.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and a preparation method thereof.
Background
The super capacitor has the advantages of ultrahigh power density, longer cycle life, high cycle stability, low cost, high safety and the like, is a green chemical energy source which is concerned in recent years, can be used as a power supply, and shows excellent electrochemical performance. Electrode materials are the key factors determining the super capacitive performance, and among them, the most widely reported are porous carbon materials, mainly including: porous carbon materials, activated carbon fibers, carbon aerosols, carbon nanotubes, and the like. Different materials have respective advantages and disadvantages, such as a porous carbon material having a great specific surface area and a high cycle life, but a low discharge capacity.
More recently, two-dimensional metal sulfides (e.g., CoS, WS)2And MoS2) Is considered to be an electrochemical active material of a new generation of super capacitor due to its higher electrical conductivity and high specific surface area. Among them, molybdenum disulfide is considered as the most promising material in the fields of lithium ion batteries, supercapacitors and the like because of its graphene-like layered structure.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and a preparation method thereof.
In order to solve the technical scheme existing in the prior art, the invention provides a preparation method of a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material, which comprises the following steps of:
step S1, preparing a sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material;
step S2, converting sodium molybdate/thiourea in the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material into molybdenum disulfide, converting glucose into carbon nanospheres, and converting bacterial cellulose into carbon nanofibers; thereby preparing the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material as a supercapacitor electrode material;
wherein the step S1 further comprises the steps of:
s10: repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel;
s11: preparing a sodium molybdate/thiourea/glucose mixed solution, and soaking the bacterial cellulose in the solution for 10-90 minutes to enable the bacterial cellulose to fully absorb the solution, so as to obtain sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel;
the step S2 further includes the steps of:
s20: putting the sodium molybdate/thiourea/glucose/bacterial fiber hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction, naturally cooling, and taking out to obtain a molybdenum disulfide/carbon nanosphere/bacterial cellulose hydrogel composite material;
s21: soaking the bacterial cellulose containing the molybdenum disulfide/carbon nanospheres in deionized water after hydrothermal treatment to remove impurities in the solution, naturally drying the molybdenum disulfide/carbon nanospheres/bacterial cellulose composite material, and obtaining molybdenum disulfide/carbon nanospheres/bacterial cellulose gel after 6-24 hours;
s22: and putting the molybdenum disulfide/carbon nanospheres/bacterial cellulose gel into a tube furnace, heating to 600-900 ℃ under the protection of argon atmosphere, calcining for 1-6 hours, and naturally cooling to obtain the finished product of the molybdenum disulfide/carbon nanospheres/carbon nanofiber aerogel material.
Preferably, in step S10, the bacterial cellulose from which water is removed has a thickness of 0.5 mm.
Preferably, in step S11, the mass ratio of sodium molybdate, thiourea, glucose and water is 9:11.6:16:360 at room temperature.
Preferably, in step S20, the hydrothermal reaction temperature is 220 ℃.
Preferably, in step S21, the natural drying time is 18 hours.
In a preferred embodiment, in step S22, the mixture is heated to 800 ℃ at a rate of 3 ℃/min under an argon atmosphere and held for 2 hours.
The invention also discloses a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material which is prepared by adopting the steps.
The invention also discloses a super capacitor, and the electrode material of the super capacitor adopts the prepared molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) molybdenum disulfide is a two-dimensional metal sulfide, the two-dimensional metal sulfide is combined with carbon nanofiber, the formed molybdenum disulfide/carbon nanofiber aerogel compound is of a three-dimensional structure, glucose is added into bacterial fiber, and the formed molybdenum sulfide/carbon nanosphere/carbon nanofiber structure (MoS)2-C), with molybdenum sulphide/carbon nanofibrous structure (MoS)2) In contrast, this structure can increase the electron conductivity of the electrode and greatly improve the effective transport of the active material.
(2) The bacterial cellulose has a fine nano-scale net structure, the carbon nano-fiber net structure is formed after high-temperature carbonization, the carbon nanospheres are formed after glucose water is heated, and the combination of the net structure and the carbon nanospheres is beneficial to effective transmission of electrons in the electrode and ion transmission in electrolyte.
(3) The constructed electrode is a self-supporting electrode, so that a conductive agent and an adhesive are not required to be added, the electronic conduction of the electrode is facilitated, the content and the loading capacity of active substances in the electrode are improved, and the installation process of the super capacitor can be simplified.
Drawings
FIG. 1 is a flow chart of the steps of the preparation method of the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material of the present invention;
FIG. 2 is a graph showing the charge/discharge curves of the electrode according to the present invention at different current densities (0.1A/g,0.2A/g,0.5A/g,1A/g, 2A/g);
FIG. 3 is a molybdenum sulfide/carbon nanofiber structure electrode (MoS) at a scan rate of 2mV/s2) And the molybdenum sulfide/carbon nanosphere/carbon nanofiber structure electrode (MoS) of the invention2-C) cyclic voltammogram;
FIG. 4 is a molybdenum sulfide/carbon nanofiber structure electrode (MoS) at various scan rates (2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/s, 500mV/s)2) And the molybdenum sulfide/carbon nanosphere/carbon nanofiber structure electrode (MoS) of the invention2-C) specific capacity versus plot.
The following specific embodiments will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
In order to better explain the process and scheme of the present invention, the following invention is further described with reference to the accompanying drawings and examples. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Referring to fig. 1, the invention provides a preparation method of a molybdenum sulfide/carbon nanosphere/carbon nanofiber composite electrode material, which is used for preparing the electrode material based on bacterial cellulose hydrogel, wherein the bacterial cellulose is a porous reticular nano-scale biopolymer synthesized by microbial fermentation, and has a hyperfine reticular structure, higher water absorption and retention performance, higher biocompatibility, adaptability and good biodegradability.
The method specifically comprises the following steps:
wherein the step S1 further comprises the steps of:
s10: repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel;
s11: preparing a sodium molybdate/thiourea/glucose mixed solution, and soaking the bacterial cellulose in the solution for 10-90 minutes to enable the bacterial cellulose to fully absorb the solution, so as to obtain sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel;
the step S2 further includes the steps of:
s20: putting the sodium molybdate/thiourea/glucose/bacterial fiber hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction, naturally cooling, and taking out to obtain a molybdenum disulfide/carbon nanosphere/bacterial cellulose hydrogel composite material;
s21: soaking the bacterial cellulose containing the molybdenum disulfide/carbon nanospheres in deionized water after hydrothermal treatment to remove impurities in the solution, naturally drying the molybdenum disulfide/carbon nanospheres/bacterial cellulose composite material, and obtaining molybdenum disulfide/carbon nanospheres/bacterial cellulose gel after 6-24 hours;
s22: and putting the molybdenum disulfide/carbon nanospheres/bacterial cellulose gel into a tube furnace, heating to 600-900 ℃ under the protection of argon atmosphere, calcining for 1-6 hours, and naturally cooling to obtain the finished product of the molybdenum disulfide/carbon nanospheres/carbon nanofiber aerogel material.
Among the above-mentioned technical scheme, turn into molybdenum disulfide with sodium molybdate/thiourea through hydrothermal method earlier, turn into carbon nanosphere with glucose, the bacterial cellulose form after the rethread natural drying makes the hydrothermal is unchangeable, keeps leveling, nevertheless gets rid of original moisture, makes molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite through high temperature carbonization at last. Therefore, a novel structure for preparing the electrode of the super capacitor is provided, and no adhesive is required to be added in the process of preparing the electrode.
EXAMPLE 1
And repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel. Preparing sodium molybdate, thiourea, glucose and an aqueous solution at room temperature according to the mass ratio of 9:11.6:16:360, and soaking the bacterial cellulose in the solution for 30 minutes to enable the bacterial cellulose to fully absorb the solution, thereby obtaining the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel. And (3) putting the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 15 hours at 220 ℃, naturally cooling, and taking out to obtain the molybdenum disulfide/glucose/bacterial cellulose gel. And (3) placing the bacterial cellulose after the hydrothermal treatment in a normal temperature environment, naturally drying for 18 hours, and taking out to obtain the molybdenum disulfide/carbon nanosphere/bacterial cellulose gel. And (3) putting the gel into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the protection of an argon atmosphere environment, calcining for 2 hours, and then self-heating and cooling to obtain the finished product of the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material.
Instantiation 2
And repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel. Preparing sodium molybdate, thiourea and glucose aqueous solution according to the mass ratio of 1:1:1:180 at room temperature, and soaking the bacterial cellulose in the solution for 30 minutes to enable the bacterial cellulose to fully absorb the solution, thereby obtaining the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel. And (3) putting the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 15 hours at 220 ℃, naturally cooling, and taking out to obtain the molybdenum disulfide/glucose/bacterial cellulose gel. And (3) placing the bacterial cellulose after the hydrothermal treatment in a normal temperature environment, naturally drying for 24 hours, and taking out to obtain the molybdenum disulfide/carbon nanosphere/bacterial cellulose gel. And (3) putting the gel into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the protection of an argon atmosphere environment, calcining for 2 hours, and then self-heating and cooling to obtain the finished product of the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material.
Instantiation 3
And repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel. Preparing sodium molybdate, thiourea and glucose aqueous solution according to the mass ratio of 9:11.6:16:360 at room temperature, and soaking the bacterial cellulose in the solution for 60 minutes to enable the bacterial cellulose to fully absorb the solution, thereby obtaining the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel. And (3) putting the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 210 ℃, naturally cooling, and taking out to obtain the molybdenum disulfide/glucose/bacterial cellulose gel. And (3) placing the bacterial cellulose after the hydrothermal treatment in a normal temperature environment, naturally drying for 18 hours, and taking out to obtain the molybdenum disulfide/carbon nanosphere/bacterial cellulose gel. And (3) putting the gel into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the protection of an argon atmosphere environment, calcining for 2 hours, and then self-heating and cooling to obtain the finished product of the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material.
Instantiation 4
And repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel. Preparing sodium molybdate, thiourea and glucose aqueous solution according to the mass ratio of 9:11.6:16:360 at room temperature, and soaking the bacterial cellulose in the solution for 60 minutes to enable the bacterial cellulose to fully absorb the solution, thereby obtaining the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel. And (3) putting the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 18 hours at 220 ℃, naturally cooling, and taking out to obtain the molybdenum disulfide/glucose/bacterial cellulose gel. And (3) placing the bacterial cellulose after the hydrothermal treatment in a normal temperature environment, naturally drying for 20 hours, and taking out to obtain the molybdenum disulfide/carbon nanosphere/bacterial cellulose gel. And (3) putting the gel into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the protection of an argon atmosphere environment, calcining for 3 hours, and then self-heating and cooling to obtain the finished product of the molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite material.
FIG. 2 is a graph showing the charge and discharge curves of the electrode according to the present invention at different current densities (0.1A/g,0.2A/g,0.5A/g,1A/g, 2A/g). The triangular charging and discharging curves show that the electrode can show good symmetry and linearity under different current densities, and further prove that the electrode material has ideal capacitance performance. Wherein, when the current density is 0.1A/g, the specific capacity of the material can reach 117.8F/g, and when the current density is increased, the specific capacity attenuation is smaller, and when the current is 2A/g, the specific capacity is still as high as 80F/g.
FIG. 3 is a molybdenum sulfide/carbon nanofiber structure electrode (MoS) at a scan rate of 2mV/s2) And the molybdenum sulfide/carbon nanosphere/carbon nanofiber structure electrode (MoS) of the invention2-C) cyclic voltammogram. From the figure, MoS can be seen2Cyclic voltammogram of-C having an absolute area greater than MoS2The absolute area of the electrode shows that the electrode has larger specific capacity.
FIG. 4 is a molybdenum sulfide/carbon nanofiber structure electrode (MoS) at various scan rates (2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/s, 500mV/s)2) And the molybdenum sulfide/carbon nanosphere/carbon nanofiber structure electrode (MoS) of the invention2-C) specific capacity versus plot. From the figure canIt is seen that the specific capacities of both electrodes are gradually reduced as the scan rate is increased, but the MoS prepared by this method2The specific capacity of the-C electrode is always higher than that of MoS2The electrode shows that the specific capacity of the super capacitor can be increased by the method.
Further, the obtained molybdenum disulfide/carbon nanofiber aerogel composite material is formed into an area of about 0.7cm2And (4) sheet electrodes of the size, which are used as electrodes for assembling the positive super capacitor for testing.
The specific assembly process is as follows: the supercapacitor was assembled using CR2016 coin cells. The two electrodes are prepared molybdenum disulfide/carbon nanosphere/carbon nanofiber aerogel composite electrodes, the TF4030 cellulose diaphragm is used as a diaphragm, and 6mol/L KOH solution is used as electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 0V-1V.
From the analysis, the method can be used for directly manufacturing the composite electrode without adding an adhesive, so that the electronic conductivity is increased, and the specific capacity of the assembled super capacitor can be greatly increased and the performance of the super capacitor is improved under different scanning rates compared with the electrode without adding glucose.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A preparation method of a molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material is characterized by comprising the following steps of:
step S1, preparing a sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material;
step S2, converting sodium molybdate/thiourea in the sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel composite material into molybdenum disulfide, converting glucose into carbon nanospheres, and converting bacterial cellulose into carbon nanofibers; thereby preparing the molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material;
wherein the step S1 includes the steps of:
s10: repeatedly washing the bacterial cellulose hydrogel in deionized water to remove impurities and remove water in the hydrogel;
s11: preparing a sodium molybdate/thiourea/glucose mixed solution, and soaking the bacterial cellulose in the solution for 10-90 minutes to enable the bacterial cellulose to fully absorb the solution, so as to obtain sodium molybdate/thiourea/glucose/bacterial cellulose hydrogel;
the step S2 includes the steps of:
s20: putting the sodium molybdate/thiourea/glucose/bacterial fiber hydrogel into a hydrothermal reaction kettle, carrying out hydrothermal reaction, naturally cooling, and taking out to obtain a molybdenum disulfide/carbon nanosphere/bacterial cellulose hydrogel composite material;
s21: soaking the bacterial cellulose containing the molybdenum disulfide/carbon nanospheres in deionized water after hydrothermal treatment to remove impurities in the solution, naturally drying the molybdenum disulfide/carbon nanospheres/bacterial cellulose composite material, and obtaining molybdenum disulfide/carbon nanospheres/bacterial cellulose gel after 6-24 hours;
s22: putting the molybdenum disulfide/carbon nanospheres/bacterial cellulose gel into a tube furnace, heating to 600-900 ℃ under the protection of argon atmosphere, calcining for 1-6 hours, and naturally cooling to obtain a finished product of the molybdenum disulfide/carbon nanospheres/carbon nanofiber aerogel material;
in step S11, the mass ratio of the sodium molybdate to the thiourea to the glucose to the water is 9:11.6:16:360 at room temperature;
in step S20, the hydrothermal reaction temperature was 220 ℃.
2. The method for preparing a molybdenum sulfide carbon nanoball carbon nanofiber composite electrode material according to claim 1, wherein the thickness of the bacterial cellulose from which moisture is removed is 0.5 mm in step S10.
3. The method for preparing a molybdenum sulfide carbon nanoball carbon nanofiber composite electrode material according to claim 1, wherein the natural drying time is 18 hours in step S21.
4. The method for preparing a molybdenum sulfide carbon nanoball carbon nanofiber composite electrode material according to claim 1, wherein in step S22, it is heated to 800 ℃ at a rate of 3 ℃/min under the protection of argon atmosphere and kept for 2 hours.
5. A molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material, which is prepared by the preparation method of any one of claims 1-4.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006570A (en) * | 2015-06-10 | 2015-10-28 | 中南大学 | Molybdenum selenide based composite cathode material for sodium-ion battery and preparation method thereof |
| CN105293581A (en) * | 2015-10-25 | 2016-02-03 | 复旦大学 | Molybdenum sulfide/graphene/carbon nanoball composite material and preparing method thereof |
| RO131882A2 (en) * | 2015-11-18 | 2017-05-30 | Institutul Naţional De Cercetare-Dezvoltare Pentru Chimie Şi Petrochimie - Icechim | Composition and process for preparing nanocomposites from polyhydroxyalkanoates and bacterial cellulose nanofibres |
| CN107069035A (en) * | 2017-03-31 | 2017-08-18 | 合肥国轩电池材料有限公司 | A kind of preparation method of molybdenum disulfide/carbosphere lithium ion battery negative material |
| CN107188230A (en) * | 2017-05-24 | 2017-09-22 | 岭南师范学院 | A kind of molybdenum disulfide carbon is combined bouquet and its preparation method and application |
| CN107275609A (en) * | 2017-06-16 | 2017-10-20 | 南京理工大学 | A kind of selenizing molybdenum/carbonization bacteria cellulose lithium ion battery negative material and preparation method thereof |
| CN108269982A (en) * | 2018-01-09 | 2018-07-10 | 中国科学院福建物质结构研究所 | A kind of composite material, preparation method and the application in lithium ion battery |
| CN109546139A (en) * | 2019-01-07 | 2019-03-29 | 合肥学院 | A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material |
| CN109999835A (en) * | 2019-03-27 | 2019-07-12 | 武汉理工大学 | A kind of carbonization bacteria cellulose-cadmium sulfide composite photocatalyst material and its preparation method and application |
| CN110212180A (en) * | 2019-05-22 | 2019-09-06 | 杭州电子科技大学 | A kind of preparation method and lithium-sulfur cell of lithium sulfide self-supporting carbon ball/carbon nano-fiber composite material |
-
2019
- 2019-11-12 CN CN201911096768.2A patent/CN110844939B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006570A (en) * | 2015-06-10 | 2015-10-28 | 中南大学 | Molybdenum selenide based composite cathode material for sodium-ion battery and preparation method thereof |
| CN105293581A (en) * | 2015-10-25 | 2016-02-03 | 复旦大学 | Molybdenum sulfide/graphene/carbon nanoball composite material and preparing method thereof |
| RO131882A2 (en) * | 2015-11-18 | 2017-05-30 | Institutul Naţional De Cercetare-Dezvoltare Pentru Chimie Şi Petrochimie - Icechim | Composition and process for preparing nanocomposites from polyhydroxyalkanoates and bacterial cellulose nanofibres |
| CN107069035A (en) * | 2017-03-31 | 2017-08-18 | 合肥国轩电池材料有限公司 | A kind of preparation method of molybdenum disulfide/carbosphere lithium ion battery negative material |
| CN107188230A (en) * | 2017-05-24 | 2017-09-22 | 岭南师范学院 | A kind of molybdenum disulfide carbon is combined bouquet and its preparation method and application |
| CN107275609A (en) * | 2017-06-16 | 2017-10-20 | 南京理工大学 | A kind of selenizing molybdenum/carbonization bacteria cellulose lithium ion battery negative material and preparation method thereof |
| CN108269982A (en) * | 2018-01-09 | 2018-07-10 | 中国科学院福建物质结构研究所 | A kind of composite material, preparation method and the application in lithium ion battery |
| CN109546139A (en) * | 2019-01-07 | 2019-03-29 | 合肥学院 | A kind of metal sulfide/carbon composite, preparation method and its application in cell negative electrode material |
| CN109999835A (en) * | 2019-03-27 | 2019-07-12 | 武汉理工大学 | A kind of carbonization bacteria cellulose-cadmium sulfide composite photocatalyst material and its preparation method and application |
| CN110212180A (en) * | 2019-05-22 | 2019-09-06 | 杭州电子科技大学 | A kind of preparation method and lithium-sulfur cell of lithium sulfide self-supporting carbon ball/carbon nano-fiber composite material |
Non-Patent Citations (2)
| Title |
|---|
| facile synthesis method and electrochemical studies of a hierarchical structured MoS2/C nanocomposite;Zhenyou Li et al.;《RCS Advances》;20160729;第6卷;第76085页第3和5段、第76086页第4段和图3 * |
| In-situ assembly of three-dimensional MoS2 nanoleaves/carbon nanofiber composites derived from bacterial cellulose as flexible and binder-free anodes for enhanced lithium-ion batteries;Fan Zhang et al.;《Electrochimica Acta》;20160616;第211卷;第406页第3段 * |
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Application publication date: 20200228 Assignee: Shenzhen Huaxinhui Technology Co.,Ltd. Assignor: HANGZHOU DIANZI University Contract record no.: X2022330000482 Denomination of invention: A kind of molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and preparation method thereof Granted publication date: 20220301 License type: Common License Record date: 20220904 |
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