CN114142014A - Self-supporting carbon nanofiber loaded molybdenum disulfide composite material and preparation method and application thereof - Google Patents
Self-supporting carbon nanofiber loaded molybdenum disulfide composite material and preparation method and application thereof Download PDFInfo
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- CN114142014A CN114142014A CN202111463508.1A CN202111463508A CN114142014A CN 114142014 A CN114142014 A CN 114142014A CN 202111463508 A CN202111463508 A CN 202111463508A CN 114142014 A CN114142014 A CN 114142014A
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- -1 aluminum ion Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims description 3
- 239000011831 acidic ionic liquid Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000282465 Canis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a self-supporting carbon nanofiber loaded molybdenum disulfide composite material and a preparation method and application thereof, and belongs to the field of aluminum ion batteries. The invention directly utilizes (NH)4)2MoS4Reduction to MoS2The carbon nanofiber has the unique property of flexible self-support, can be directly used as an electrode, avoids the phenomena of reduced conductivity, no high temperature resistance, falling of active substances in the circulating process and the like caused by a complicated electrode preparation process and the use of a binder, can be used as a support substrate of molybdenum sulfide during charging and dischargingIn the cycle process, the structural damage of molybdenum sulfide in the cycle process can be avoided, the cycle performance is stable, and meanwhile, the carbon nanofiber carbon nano-composite material has a unique molybdenum disulfide mosaic structure, is very favorable for the embedding and the de-embedding of aluminum ions in the battery charging and discharging process, and can meet the practical application.
Description
The application is a divisional application with application date of 2019, 1, 11 and application number of 201910026673.7, and the invention name of "a self-supporting carbon nanofiber load molybdenum disulfide composite material and a preparation method and application thereof".
Technical Field
The invention belongs to the technical field of aluminum ion batteries, and particularly relates to a self-supporting carbon nanofiber load molybdenum disulfide composite material, and a preparation method and application thereof.
Background
Because of the limited storage capacity, high price, flammability and explosiveness of lithium metal, a low-cost and safe rechargeable battery is needed to replace lithium ion batteries. Aluminum, a metal abundant in reserves, is much less expensive than lithium and highly safe, so that aluminum ion batteries are promising alternatives to lithium ion batteries. Since the advent of aluminum ion batteries, the limiting factor has been the lack of suitable cathode materials. The aluminum ion battery meets the requirements of practical application on cathode materials: 1) the cost is low, and the process flow is simple; 2) high specific volume; 3) the circulation stability is good; 4) the multiplying power performance is good, and the device can adapt to large-current charging and discharging.
In the cathode material of the aluminum ion battery in the prior art, an active material is bonded on a current collector through a bonding agent, and the cathode material can fall off in the circulation process, so that the performance of the battery is reduced, and the problem of poor circulation stability exists.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-supporting carbon nanofiber-supported molybdenum disulfide composite material, and a preparation method and an application thereof. The carbon nanofiber in the self-supporting carbon nanofiber load molybdenum disulfide composite material provided by the invention is used as a supporting substrate of molybdenum sulfide, so that the structural damage of the molybdenum sulfide in the circulating process can be avoided, and the circulating stability is good.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a self-supporting carbon nanofiber loaded molybdenum disulfide composite material, which comprises the following steps:
preparing an electrostatic spinning precursor: will be (NH)4)2MoS4Grinding with agate mortar to powder less than 100 μm, and weighing (NH)4)2MoS4Dissolving the micro powder in N, N-dimethylformamide solution, adding polyacrylonitrile (Mw of 120,000, and (NH) and magnetically stirring at 50 ℃ for 8 hours after the micro powder is fully dissolved to obtain an electrostatic spinning precursor4)2MoS4The mass ratio of the polyacrylonitrile to the polyacrylonitrile is 0.5: 1, the concentration of the electrostatic spinning precursor is 8%;
the electrostatic spinning process comprises the following steps: sucking the electrostatic spinning precursor into a 10mL medical injector, and carrying out spinning injection by using a needle head with the diameter of 1.6mm to obtain fibers, wherein the electrostatic spinning voltage is 20KV, the distance between the needle head and a receiving plate is 15cm, and the propelling speed is 10 mu L/min;
and (3) heat treatment process: pre-oxidizing the fiber, heating the fiber to 230 ℃ at a heating rate of 3 ℃/min in an air atmosphere from room temperature, and keeping the temperature for 1 h; after pre-oxidation, at 93% Ar-7% H2Heating to 450 deg.C in atmosphere, heating at a rate of 5 deg.C/min, and maintaining for 1h (NH)4)2MoS4Finally, heating to 830 ℃ in Ar atmosphere to carbonize the fibers, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h to obtain the self-supporting flexible carbon nanofiber-loaded MoS2A composite material.
The invention also provides the self-supporting carbon nanofiber load molybdenum disulfide composite material prepared by the preparation method in the technical scheme, and the molybdenum disulfide is embedded in the carbon nanofiber.
The invention also provides application of the self-supporting carbon nanofiber loaded molybdenum disulfide composite material in the technical scheme as an aluminum ion battery cathode material.
The invention also provides an aluminum ion battery, which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the anode is an aluminum foil, the thickness of the aluminum foil is 0.2mm, and the purity of the aluminum foil is 99.999 percent; the cathode is the self-supporting carbon nanofiber-supported molybdenum disulfide composite material as claimed in claim 2; the membrane is Whatman (GF/D); the electrolyte is an acidic ionic liquid, and the electrolyte is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a weight ratio of 1.3: 1, and the molar ratio of the components is 1.
The invention provides a preparation method of a self-supporting carbon nanofiber loaded molybdenum disulfide composite material, which comprises the following steps: will be (NH)4)2MoS4Dissolving the powder in N, N-dimethylformamide, and then adding polyacrylonitrile to obtain an electrostatic spinning precursor; spinning and spraying the electrostatic spinning precursor to obtain fibers; pre-oxidizing the fiber in an air atmosphere to obtain a pre-oxidized product; subjecting the pre-oxidized product to Ar-H2Reducing in the mixed atmosphere to obtain a reduction product; and carbonizing the reduction product in an inert atmosphere to obtain the self-supporting flexible carbon nanofiber loaded molybdenum disulfide composite material. The invention directly utilizes (NH)4)2MoS4Reduction to MoS2The carbon nanofiber has the unique property of flexible self-support, can be directly used as an electrode, avoids the phenomena of reduced conductivity, no high temperature resistance, falling of active substances in a circulation process and the like caused by a complicated electrode preparation process and the use of a binder, can be used as a support substrate of molybdenum sulfide, and Al can be used as a support substrate of the molybdenum sulfide in the charge-discharge circulation process3+The embedding and the releasing in the molybdenum sulfide can generate stress action on the structure of the molybdenum sulfide to cause structural damage, the support protection of the carbon nanofiber substrate can avoid the structural damage of the molybdenum sulfide in the circulation process, the stable performance can be still kept after 500 times of circulation, and meanwhile, the unique embedded structure of the molybdenum disulfide in the carbon nanofiber is provided, so that the embedding and the releasing of aluminum ions in the battery charging and discharging process are very favorable, and the guiding value is provided for meeting the requirement of practical application. And because the carbon nano fiber has excellent conductivity, compared with molybdenum sulfide, the molybdenum sulfide material compounded with the carbon nano fiber has good conductivity, and canIs suitable for large-current charging and discharging batteries (100 mAh.g)-1，200mAh·g-1，300mAh·g-1And 500mAh · g-1) And the feasibility is provided for the practical application of the aluminum ion battery.
Drawings
FIG. 1 is a diagram of the self-supporting flexible carbon nanofiber-supported MoS of example 12A physical representation of the composite;
FIG. 2(a) is a MoS-loaded self-supporting flexible carbon nanofiber as in example 12LED experimental plots of the composite; 2(b) is an open circuit voltage test curve;
FIG. 3 shows the MoS loaded on the self-supporting flexible carbon nanofiber in example 12Constant current cyclic charge-discharge specific volume and coulombic efficiency curve of the composite material;
FIG. 4 shows the MoS loaded on the self-supporting flexible carbon nanofiber in example 12Voltage-capacity plot of the first three cycles of the composite;
FIG. 5 shows the MoS loaded on the self-supporting flexible carbon nanofiber in example 12A multiplying power performance test curve of the composite material;
FIG. 6 shows the MoS loaded on the self-supporting flexible carbon nanofiber in example 12Cyclic voltammetry test curves of the composite;
FIG. 7 shows the self-supporting flexible carbon nanofiber-loaded MoS of example 12Testing spectrograms of the composite material under a scanning electron microscope under different multiplying powers;
FIG. 8 shows the MoS loaded on the self-supporting flexible carbon nanofiber in example 12A transmission electron microscopy image of the composite;
FIG. 9 shows the self-supporting flexible carbon nanofiber-loaded MoS of example 12The element distribution of the composite materials C, Mo and S;
fig. 10 is an XRD pattern of the flexible self-supporting carbon nanofiber loaded molybdenum disulfide composite of example 1.
Detailed Description
The invention provides a preparation method of a self-supporting carbon nanofiber loaded molybdenum disulfide composite material, which comprises the following steps:
will be (NH)4)2MoS4Dissolving the powder in N, N-dimethylAdding polyacrylonitrile after formamide to obtain an electrostatic spinning precursor;
spinning and spraying the electrostatic spinning precursor to obtain fibers;
pre-oxidizing the fiber in an air atmosphere to obtain a pre-oxidized product;
subjecting the pre-oxidized product to Ar-H2Reducing in the mixed atmosphere to obtain a reduction product;
and carbonizing the reduction product in an inert atmosphere to obtain the self-supporting flexible carbon nanofiber loaded molybdenum disulfide composite material.
The invention will be described in (NH)4)2MoS4And dissolving the powder in N, N-dimethylformamide, and then adding polyacrylonitrile to obtain the electrostatic spinning precursor. In the present invention (NH) is first dissolved4)2MoS4The powder is added with polyacrylonitrile, so that the raw materials can be dissolved uniformly.
In the present invention, the (NH)4)2MoS4The particle size of the powder is preferably below 100 microns. Preferred (NH) is4)2MoS4Grinding into (NH) with an agate mortar4)2MoS4And (3) powder.
In the present invention, the (NH)4)2MoS4The mass ratio of the powder to the polyacrylonitrile is preferably 0.5-1: 1.
in the present invention, the Mw of the polyacrylonitrile is preferably 120000-150000.
In the invention, the mass concentration of the electrostatic spinning precursor is preferably 8-10%.
In the present invention, the (NH)4)2MoS4The dissolution of the powder in N, N-dimethylformamide and the addition of polyacrylonitrile are preferably carried out under magnetic stirring. In the present invention, the temperature of the magnetic stirring is preferably 50 ℃, the time of the magnetic stirring is preferably 8 hours, and the power of the magnetic stirring is not particularly limited in the present invention.
After the electrostatic spinning precursor is obtained, the invention carries out spinning jet on the electrostatic spinning precursor to obtain the fiber. In the invention, the spinning jet is preferably carried out by a medical injector, the voltage of the spinning jet is preferably 18-20 KV, the distance between a needle head of the medical injector and a receiving plate is preferably 15-18 cm, and the propelling speed is preferably 10-12 muL/min.
In the present invention, the diameter of the needle of the medical syringe is preferably 1.6 mm. In the present invention, the volume of the medical syringe is preferably 10 mL.
After the fiber is obtained, the fiber is pre-oxidized in the air atmosphere to obtain a pre-oxidized product. In the invention, the preoxidation can convert fiber linear molecules into a heat-resistant ladder-shaped structure, so that the fiber form is kept in the subsequent high-temperature carbonization process, and melting and doubling are avoided. In the invention, the pre-oxidation temperature is preferably 230-250 ℃, more preferably 235-245 ℃, and the time is preferably 1-2 h.
In the present invention, it is preferable to raise the temperature from room temperature to the temperature of the pre-oxidation. In the present invention, the rate of temperature rise to the pre-oxidation temperature is preferably 3 to 5 ℃/min.
After obtaining the pre-oxidation product, the invention puts the pre-oxidation product in Ar-H2Reducing in the mixed atmosphere to obtain a reduction product. In the present invention, the reduction takes place in (NH)4)2MoS4To obtain MoS2。
In the present invention, Ar-H in the mixed atmosphere2Is preferably 93: 7.
In the invention, the reduction temperature is preferably 450-480 ℃, more preferably 460-470 ℃, and the time is preferably 1-2 h. In the present invention, the rate of temperature rise to the reduction temperature is preferably 3 to 5 ℃/min.
After obtaining the reduction product, carbonizing the reduction product in an inert atmosphere to obtain the self-supporting flexible carbon nanofiber load molybdenum disulfide composite material.
In the present invention, the inert atmosphere is preferably Ar.
In the invention, the carbonization temperature is preferably 830-850 ℃, more preferably 835-845 ℃, and the time is preferably 1-2 h. In the present invention, the rate of temperature rise to the carbonization temperature is preferably 3 to 5 ℃/min.
The invention also provides the self-supporting carbon nanofiber load molybdenum disulfide composite material prepared by the preparation method in the technical scheme, and the molybdenum disulfide is embedded in the carbon nanofiber.
In the invention, the mass content of molybdenum disulfide in the self-supporting carbon nanofiber-loaded molybdenum disulfide composite material is preferably 55-60%.
The invention also provides application of the self-supporting carbon nanofiber loaded molybdenum disulfide composite material in the technical scheme as an aluminum ion battery cathode material. The nanofiber-loaded molybdenum disulfide composite material has the unique property of flexibility and self-support, is preferably directly used as an electrode, avoids the phenomena of reduction of conductivity, no high temperature resistance, falling of active substances in a circulation process and the like caused by a complicated electrode preparation process and the use of a binder, can be used as a support substrate of molybdenum sulfide, and can be used for Al in a charge-discharge circulation process3+The embedding and the releasing in the molybdenum sulfide can generate stress action on the structure of the molybdenum sulfide to cause structural damage, the support protection of the carbon nanofiber substrate can avoid the structural damage of the molybdenum sulfide in the circulation process, the stable performance can be still kept after 500 times of circulation, and meanwhile, the unique embedded structure of the molybdenum disulfide in the carbon nanofiber is provided, so that the embedding and the releasing of aluminum ions in the battery charging and discharging process are very favorable, and the guiding value is provided for meeting the requirement of practical application. And because the carbon nanofiber has excellent conductivity, compared with molybdenum sulfide, the molybdenum sulfide material compounded with the carbon nanofiber has good conductivity, can adapt to large-current charge-discharge batteries, and provides feasibility for putting aluminum ion batteries into practical application.
The self-supporting carbon nanofiber-supported molybdenum disulfide composite material provided by the invention and the preparation method and application thereof are described in detail below with reference to examples, but the materials should not be construed as limiting the scope of the invention.
Example 1
Step 1: self-supporting flexible carbon nanofiber loaded MoS2Preparation of composite materials
Preparing an electrostatic spinning precursor:
will be (NH)4)2MoS4Grinding into micrometer (below 100 micrometer) powder with agate mortar, and weighing (NH)4)2MoS4Dissolving in N, N-dimethyl formamide solution, adding polyacrylonitrile (Mw 120,000) to obtain electrostatic spinning precursor (NH)4)2MoS4The mass ratio of the polyacrylonitrile to the polyacrylonitrile is 0.5: 1, the concentration of the electrostatic spinning precursor is 8%, and the electrostatic spinning precursor is obtained after magnetic stirring is carried out for 8 hours at 50 ℃.
The electrostatic spinning process comprises the following steps:
the prepared electrospinning precursor was sucked into a 10mL medical syringe and subjected to spinning jet with a needle having a diameter of 1.6 mm. The electrostatic spinning voltage is 20KV, the distance between the needle head and the receiving plate is 15cm, and the advancing speed is 10 muL/min.
And (3) heat treatment process:
pre-oxidizing the fiber obtained by electrostatic spinning, heating to 230 ℃ at the heating rate of 3 ℃/min from room temperature in the air atmosphere, and keeping the temperature for 1 h. After the pre-oxidation, the (NH) is carried out4)2MoS4At 93% Ar-7% H2Heating to 450 ℃ in the atmosphere, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1 h. Finally, heating to 830 ℃ in Ar atmosphere to carbonize the fibers, wherein the heating rate is 5 ℃/min, and the temperature is kept for 1h, so that the self-supporting flexible carbon nanofiber-loaded MoS is obtained2A composite material.
FIG. 1 shows the MoS loaded on the self-supporting flexible carbon nanofiber in the embodiment2Figure 1a is a physical diagram of a composite material, wherein figure 1a is a flexible self-supporting carbon nanofiber loaded with molybdenum disulfide without cycle testing, and figure 1b is a flexible self-supporting carbon nanofiber loaded with molybdenum disulfide after 200 cycles. As can be read from FIG. 1, the material is a flexible self-supporting structure, and can be directly cut into electrodes with required size, and after 200 cycles, the electrodes still maintain good integrity and do not generate heatThe problems of green dusting and chipping indicate that the composite material has excellent cycle stability.
Step 2: battery system
Because the electrolyte used by the aluminum ion battery is acidic ionic liquid and has corrosivity on stainless steel, a button battery is not adopted, and a soft package battery is selected for testing.
The aluminum foil is used as an anode, the thickness of the aluminum foil is 0.2mm, and the purity of the aluminum foil is 99.999%. The self-supporting flexible carbon nanofiber loaded molybdenum sulfide composite material of the embodiment is directly used as a cathode. Whatman (GF/D) was used as a membrane. The electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a weight ratio of 1.3: 1, and the molar ratio of the components is 1.
And step 3: electrochemical testing
1) Open circuit voltage testing
The open circuit voltage is about 1.5V. The two batteries are connected in series, so that the LED small bulb can be lightened.
FIG. 2(a) is an experimental LED diagram; and 2(b) is an open circuit voltage test curve.
2) Constant current cycling test
Constant current circulation test is carried out by using a LAND CT2001A battery test system, and the current value is 100 mA.g-1The voltage range is 0.1-2V. Fig. 3 is a constant current cyclic charge-discharge specific volume and coulombic efficiency curve. As can be seen from FIG. 3, the first discharge specific volume was 293.2mAh g-1After 200 cycles, the specific discharge capacity can still be maintained at 126.6 mAh.g-1Coulombic efficiency was higher than 95%. It can be seen that the self-supporting flexible carbon nanofiber supports the MoS2The composite material has high specific capacity and good cycling stability when being used as the cathode material of the aluminum ion battery.
FIG. 4 is a voltage-capacity diagram of the previous three cycles, as can be seen from FIG. 4, the discharge voltage plateau is 0.7-0.8V and 0.5-0.6V, the charge voltage plateau is 0.9-1.0V and 1.1-1.2V, and the self-supporting carbon nanofiber load molybdenum disulfide composite material is used as the cathode material of the aluminum ion battery and has a stable charge and discharge voltage plateau.
3) Rate capability test
Multiplying power performance test is carried out by using LAND CT2001A battery test system. As can be seen from FIG. 5, the current density was 100mA · g-1The specific volume is stabilized at 146.2 mAh.g after 20 times of circulation-1About, when the current density was gradually increased to 150mA g-1，200mA·g-1And 250mA · g-1When the specific volume is reduced, the specific volume is very small, and the specific volume is respectively 128.4 mAh.g-1，118.3mAh·g-1And 111.9mAh · g-1When the current is recovered to 100mA g-1After that, the capacity was also completely recovered to 147.2mAh · g-1The flexible self-supporting carbon nanofiber loaded molybdenum disulfide composite material has excellent rate performance when being used as a cathode material of an aluminum ion battery.
4) Cyclic voltammetry test
Cyclic voltammetry tests were performed on a Gamry Reference 3000. The scanning speed is 5mV/s, and the scanning voltage range is 0.1-2V. Fig. 6 is a cyclic voltammetry test curve, and as can be seen from fig. 6, when the flexible self-supporting carbon nanofiber-loaded molybdenum disulfide composite material is used as the cathode of an aluminum ion battery, cathode peak currents appear at 0.6V and 0.8V, anode peak currents appear at 1.0V and 1.2V, respectively, and are very consistent with a charge-discharge voltage platform, and the first three cycles of cyclic voltammetry scan curves are basically coincident, which indicates that the battery has good stability.
And 4, step 4: topography characterization
1) Scanning Electron Microscope (SEM) tests at different magnifications are shown in fig. 7, wherein a and b are scanning electron microscope images of the flexible self-supporting carbon nanofiber-supported molybdenum disulfide composite material, and it can be seen that the morphology of the composite material is a three-dimensional network formed by continuous and uniform nanofibers. No visible substance exists outside the fiber, which indicates that molybdenum disulfide is loaded inside the carbon nanofiber, and c and d are scanning electron microscope images of the carbon nanofiber loaded with molybdenum disulfide after 200 cycles, so that a typical continuous and uniform three-dimensional network of the carbon nanofiber is still maintained after the cycles, and the carbon nanofiber has excellent structural stability.
2) Transmission electron microscope Test (TEM)
Fig. 8 is a transmission electron micrograph of flexible self-supporting carbon nanofibers loaded with molybdenum disulfide. It can be seen that the molybdenum disulfide is uniformly distributed inside the carbon nanofibers. FIG. 8c is a high resolution transmission electron micrograph, from a latticeThe spacing between the visible lattices of the fringes is 0.62nm, corresponding to MoS2(002) interplanar spacing of (iii).
3) Auger electron spectroscopy test (EDS)
FIG. 9 shows the element distribution of C, Mo and S. As can be seen from fig. 9, Mo and S are uniformly distributed in the carbon nanofibers, coinciding with the transmission electron microscope image.
4) X-ray diffraction (XRD)
Fig. 10 is an XRD pattern of the flexible self-supporting carbon nanofiber-supported molybdenum disulfide composite, and as can be seen from fig. 10, the XRD pattern of the flexible self-supporting carbon nanofiber-supported molybdenum disulfide composite shows diffraction peaks at 14 °, 32.5 ° and 58 °, corresponding to (002), (100) and (110) of molybdenum disulfide. The 24 ° diffraction peak corresponds to the (002) crystal face of the carbon nanofiber. XRD further proves the successful preparation of the flexible self-supporting carbon nanofiber loaded molybdenum disulfide composite material.
The prepared flexible self-supporting carbon nanofiber load molybdenum disulfide composite material can be directly used as a cathode of an aluminum ion battery, simplifies the battery preparation process and shows excellent electrochemical performance: 1) the open circuit voltage is higher than 1.5V; 2) the first discharge specific volume is 293.2mAh g-1(ii) a 3) After 200 cycles, the capacity was stably maintained at 126.6mAh g-1Coulombic efficiency higher than 95%; 4) in the rate capability test, 100mA · g-1，150mA·g-1，200mA·g-1，250mA·g-1After charge-discharge cycles at a current density of (1), the current was recovered to 100mA · g-1After that, the specific volume was almost completely recovered. 5) The charging and discharging voltage platform has stable charging and discharging voltage platforms, wherein the discharging voltage platforms are 0.7-0.8V and 0.5-0.6V, and the charging voltage platforms are 0.9-1.0V and 1.1-1.2V.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of a self-supporting carbon nanofiber loaded molybdenum disulfide composite material is characterized by comprising the following steps:
preparing an electrostatic spinning precursor: will be (NH)4)2MoS4Grinding with agate mortar to powder less than 100 μm, and weighing (NH)4)2MoS4Dissolving the micro powder in N, N-dimethylformamide solution, adding polyacrylonitrile (Mw of 120,000, and (NH) and magnetically stirring at 50 ℃ for 8 hours after the micro powder is fully dissolved to obtain an electrostatic spinning precursor4)2MoS4The mass ratio of the polyacrylonitrile to the polyacrylonitrile is 0.5: 1, the concentration of the electrostatic spinning precursor is 8%;
the electrostatic spinning process comprises the following steps: sucking the electrostatic spinning precursor into a 10mL medical injector, and carrying out spinning injection by using a needle head with the diameter of 1.6mm to obtain fibers, wherein the electrostatic spinning voltage is 20KV, the distance between the needle head and a receiving plate is 15cm, and the propelling speed is 10 mu L/min;
and (3) heat treatment process: pre-oxidizing the fiber, heating the fiber to 230 ℃ at a heating rate of 3 ℃/min in an air atmosphere from room temperature, and keeping the temperature for 1 h; after pre-oxidation, at 93% Ar-7% H2Heating to 450 deg.C in atmosphere, heating at a rate of 5 deg.C/min, and maintaining for 1h (NH)4)2MoS4Finally, heating to 830 ℃ in Ar atmosphere to carbonize the fibers, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h to obtain the self-supporting flexible carbon nanofiber-loaded MoS2A composite material.
2. The self-supporting carbon nanofiber-supported molybdenum disulfide composite material prepared by the preparation method of claim 1, wherein the molybdenum disulfide is embedded in the carbon nanofiber.
3. Use of the self-supporting carbon nanofiber loaded molybdenum disulfide composite as claimed in claim 2 as a cathode material for an aluminum ion battery.
4. An aluminum ion battery comprises an anode, a cathode, a diaphragm and electrolyte, and is characterized in that the anode is an aluminum foil, the thickness of the aluminum foil is 0.2mm, and the purity of the aluminum foil is 99.999%; the cathode is the self-supporting carbon nanofiber-supported molybdenum disulfide composite material as claimed in claim 2; the membrane is Whatman (GF/D); the electrolyte is an acidic ionic liquid, and the electrolyte is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride in a weight ratio of 1.3: 1, and the molar ratio of the components is 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114944476A (en) * | 2022-05-09 | 2022-08-26 | 桂林理工大学 | MoS 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
| CN115537973A (en) * | 2022-09-27 | 2022-12-30 | 河北师范大学 | Molybdenum sulfide/porous carbon nanofiber composite electrode material and preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111261854A (en) * | 2020-01-16 | 2020-06-09 | 易航时代(北京)科技有限公司 | Elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and preparation method and application thereof |
| CN113097466B (en) * | 2021-04-02 | 2023-09-01 | 山西君东新材料股份有限公司 | Negative electrode material MoS of lithium ion battery 2 Preparation method of @ CFs |
| CN113998740B (en) * | 2021-10-25 | 2022-10-14 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114300676B (en) * | 2021-11-01 | 2023-07-18 | 北京航空航天大学 | Flexible sodium ion battery negative electrode material, preparation method thereof and battery negative electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393290A (en) * | 2014-10-29 | 2015-03-04 | 北京科技大学 | Aluminum-ion battery using MoS2 as positive electrode material and preparation method of battery |
| CN105597791A (en) * | 2015-12-17 | 2016-05-25 | 复旦大学 | Molybdenum selenide/porous carbon nanofiber composite material and preparation method and application thereof |
| CN106450181A (en) * | 2016-09-26 | 2017-02-22 | 东华大学 | Molybdenum disulfide/nitrogen-doped carbon nanofiber composite material and preparation method and application thereof |
| CN106471660A (en) * | 2014-02-28 | 2017-03-01 | 里兰斯坦福初级大学理事会 | Ultrafast chargeable metal ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056642A (en) * | 2014-05-19 | 2014-09-24 | 浙江理工大学 | Preparation method of molybdenum disulfide/carbon nano-fiber hybrid material |
-
2019
- 2019-01-11 CN CN202111463508.1A patent/CN114142014A/en active Pending
- 2019-01-11 CN CN201910026673.7A patent/CN109742370A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106471660A (en) * | 2014-02-28 | 2017-03-01 | 里兰斯坦福初级大学理事会 | Ultrafast chargeable metal ion battery |
| CN104393290A (en) * | 2014-10-29 | 2015-03-04 | 北京科技大学 | Aluminum-ion battery using MoS2 as positive electrode material and preparation method of battery |
| CN105597791A (en) * | 2015-12-17 | 2016-05-25 | 复旦大学 | Molybdenum selenide/porous carbon nanofiber composite material and preparation method and application thereof |
| CN106450181A (en) * | 2016-09-26 | 2017-02-22 | 东华大学 | Molybdenum disulfide/nitrogen-doped carbon nanofiber composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOQIN XIONG 等: "Flexible Membranes of MoS2/C Nanofibers by Electrospinning as Binder-Free Anodes for High-Performance Sodium-Ion Batteries", 《SCIENTIFIC REPORTS》 * |
| 刘莎莎: "静电纺丝法制备MoS2纳米纤维及其表征", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114944476A (en) * | 2022-05-09 | 2022-08-26 | 桂林理工大学 | MoS 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
| CN114944476B (en) * | 2022-05-09 | 2023-10-13 | 桂林理工大学 | MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof |
| CN115537973A (en) * | 2022-09-27 | 2022-12-30 | 河北师范大学 | Molybdenum sulfide/porous carbon nanofiber composite electrode material and preparation method and application thereof |
| CN115537973B (en) * | 2022-09-27 | 2024-04-30 | 河北师范大学 | Molybdenum sulfide/porous carbon nanofiber composite electrode material and preparation method and application thereof |
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