CN114050248B - MXene/MnO x Electrostatic spinning preparation method of nanofiber - Google Patents
MXene/MnO x Electrostatic spinning preparation method of nanofiber Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 48
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 239000002134 carbon nanofiber Substances 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 230000037427 ion transport Effects 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 32
- 102000020897 Formins Human genes 0.000 description 12
- 108091022623 Formins Proteins 0.000 description 12
- 238000001523 electrospinning Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 230000002860 competitive effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a MXene (Ti 3 C 2 ) Manganese oxide (MnO) x ) A method for preparing nanofibers. MXene nano-sheets modified by electrostatic spinning manganese ions are carbonized to synthesize MnO x Three-dimensional high-speed electron ion transport network (MnO) with surface anchoring and internal intercalation x MXene/CNFs). The invention has the advantages of simple and controllable production process, high yield and low cost, and meets the actual demands. MnO (MnO) x The nano particles are uniformly dispersed, the specific surface area of the film is large, and the transfer of ions/electrons and the permeation of electrolyte can be effectively promoted. The flexible material is used as a high-performance lithium battery, and has high specific capacity, excellent multiplying power performance and cycle stability.
Description
Technical Field
The invention relates to the field of transition metal oxides and two-dimensional nano materials MXene, in particular to a MXene/MnO x An electrostatic spinning preparation method of nanofiber composite material.
Background
Manganese oxide (MnO) x ) As a transition metal oxide, it had a high specific capacity (1230 mAh g -1 ) The LIBs cathode material has the advantages of high power density, high natural abundance, environmental friendliness and the like, and is a very promising LIBs cathode material. MXene is a two-dimensional layered transition metal carbide, nitride or carbonitride, and is a graphene-like structure two-dimensional material. The material is mainly obtained by etching an interlayer (silicon or aluminum) of a lamellar MAX material and stripping under the action of ultrasonic or solvent intercalation. By virtue of its high electrical conductivity and bending stiffness, abundant surface functional groups and excellent dispersibility in various solvents, there is growing interest in energy storage and conversion applications and shows competitive properties.
Composite materials formed by MXene and some metal oxides can show excellent synergistic effects under certain conditions. MXene/MnO when applied to an energy storage device, such as a negative electrode material of a lithium ion battery or a sodium ion battery x The nanofiber composite can utilize the interfacial effect thereof to increase lithium (sodium) ionsStorage density and cycling stability of the seed; in addition, the MXene has higher carrier mobility, which is favorable for charge migration and increases the charge and discharge rate of the battery.
Zhi Chunyi et al report on Journal of Materials Chemistry A (2017) 20818-20823 that a composite product of trimanganese tetroxide and MXene was synthesized by hydrothermal method for research on zinc-air batteries. YuryGogotsi et al report on Journal of Materials Chemistry A (2019) 269-277 that a few layers of MXene and PAN were mixed in DMF solution to prepare an electrostatic spinning solution, and an MXene carbon nanofiber was prepared by an electrostatic spinning method for the study of supercapacitors. Jim Yang LEE et al report on Chemical Engineering Journal 420 (2021) 130452 that MnO was prepared by room temperature precipitation x the/MXene composite material is used for researching the performance of a lithium sulfur battery.
The existing research has a plurality of weaknesses in the preparation of the composite product, firstly, the synthesis method is complicated, the yield is low, and the large-scale preparation is not facilitated; on the other hand, the appearance of the composite product is poor, most of the prepared composite product is powder, the manganese oxide of the composite product is easy to agglomerate, and the MXene sheet layer is easy to re-stack, so that the surface active site of the composite product is not fully exposed, the material utilization rate is low, the electrochemical energy storage performance and the photocatalytic activity are not improved high, and the recovery and the reuse of the powder catalyst are also a difficult problem. Therefore, an environment-friendly, low-cost and simple-step preparation method for obtaining the MXene composite material with excellent morphology and improved performance is urgently needed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides an MXene/MnO which is economical and effective, has high yield and can be applied on a large scale x An electrostatic spinning preparation method of nanofiber composite material. The MXene/MnO prepared by the method x The nanofiber has controllable morphology, good stability, high conductivity and good flexibility.
The technical scheme is as follows: MXene/MnO according to the present invention x The electrostatic spinning preparation method of the nanofiber composite material is characterized by comprising the following steps of:the method comprises the following steps:
s1: 5mL of MXene in DMF (N, N-dimethylformamide) solution is subjected to ice bath ultrasonic treatment for 1-3 hours under the protection of gas to obtain 30mg mL -1 A stable MXene colloidal solution;
s2: adding 0.6g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath under the shielding gas for 30 minutes;
s3: 0.5g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. A positive voltage of 20kv was applied to the needle tip and the collecting cylinder covered with aluminum foil was grounded. The distance between the needle tip and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mLh -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ for min -1 。
The beneficial effects are that: compared with the prior art, the invention has the following beneficial effects:
1) The preparation method has simple preparation process and controllable morphology, and can be used for preparing a large amount of MXene/MnO with uniform morphology, good flexibility and high conductivity x A nanofiber membrane; the prepared nanofiber composite material has the advantages of high loading amount, large specific surface area, good conductivity, self-stacking prevention and the like; mnO in the prepared nanofiber composite material x The high dispersibility of MXene is good, and the use of MXene as a composite substrate takes full advantage of the high conductivity of MXene. At the same time, the unique three-dimensional structure of the fibrous membrane brings about a high specific surface area.
2) The invention utilizes the electrostatic spinning technology to make a part of MnO x The nano particles are uniformly anchored on the surface of the MXene carbon fiber, and the other part of MnO x The nanoparticles are uniformly absent within the one-dimensional nanofibers. The unique design of anchoring and embedding fully utilizes the excellent conductivity of MXene, so that electrons can be quickly and effectively transmitted in the photocatalytic degradation and electrochemical redox process, the charge transmission efficiency can be effectively improved, and MnO is fully exerted x Excellent photocatalytic and electrochemical energy storage properties; the porous structure of the three-dimensional fiber network is beneficial to the infiltration and migration of electrolyte ions, and the electrochemical performance of the composite material is further improved. In addition, mnO x Is also a low-cost and pollution-free raw material.
3) MXene/MnO prepared by the invention x The nanofiber membrane can increase the effective contact area of the active material and the conductive substrate on one hand; on the other hand, the constructed three-dimensional network structure can accelerate the transmission rate of electrons and electrolyte ions in the electrode, and finally the aim of improving the electrochemical performance of the material is achieved. In addition, the synthesized nano material can be directly used as an electrode, so that complicated procedures for preparing the electrode by using the traditional powder active material and addition of an insulating polymer binder are avoided; in the aspect of photocatalysis application, compared with a powder catalyst, the self-supporting film prepared by the electrostatic spinning method is more convenient to recycle, has good environmental protection advantage, can effectively promote the separation and transmission of carriers in the photocatalysis process, and can effectively improve the photocatalysis activity.
4) The invention prepares MXene/MnO by electrostatic spinning method x Nanofiber membranes with both high conductivity of MXene and MnO x Is a high electrochemical activity of (a). In addition, the high mechanical strength of the MXene enhances the stability of the composite material and buffers the volume change in the charge and discharge process. MnO (MnO) x The composite material with MXene can fully exert the advantages of the two materials, thereby constructing a composite material with a multi-stage structure, and the composite material can be used as an ideal electrode material of high-performance photocatalyst materials, novel energy sources such as lithium ion batteries, super capacitors and the like.
Drawings
FIG. 1 is a schematic illustration of the MXene/MnO synthesized in example 2 of the present invention x XRD pattern of nanofiber composite;
FIG. 2 is the presentInventive example 2 MXene/MnO synthesized x Scanning electron microscope pictures of the nanofiber composite at low magnification;
FIG. 3 is a schematic illustration of the MXene/MnO synthesized in example 2 of the present invention x Scanning electron microscope pictures of the nanofiber composite at high magnification;
FIG. 4 is a schematic illustration of the MXene/MnO synthesized in example 2 of the present invention x Transmission electron microscope photographs of the nanofiber composites;
FIG. 5 is a schematic illustration of the MXene/MnO synthesized in example 2 of the present invention x After the nanofiber composite is assembled into a battery, the battery is manufactured by 2Ag -1 Cycling performance plot at current density.
Detailed Description
The invention prepares MXene/MnO by an electrostatic spinning method through simple process design x A nanofiber membrane. The composite material has the obvious advantages that: MXene provides both a conductive path and stabilizes the material structure, serving as a penetrating bridge to connect MnO x The special structure of the three-dimensional conductive network also provides a good electron and ion diffusion channel for electrochemical reaction, shortens the diffusion distance of ions, reduces the internal resistance of the active electrode, and is beneficial to the transfer of electrons, ions and the like between electrolyte and electrode materials. By utilizing the electrostatic spinning technology, not only a three-dimensional conductive network can be constructed, but also MnO is inhibited x The agglomeration of (C) and the self-stacking effect of MXene; the porous structure of the three-dimensional conductive network is also beneficial to the migration of ions in the electrochemical reaction process, and shortens the transfer path from the electrolyte to the active site. Therefore, the two materials are effectively compounded, and good synergistic effect can be realized, so that the high-activity composite material can be prepared.
The technical scheme of the invention is further described below with reference to the embodiment and the attached drawings.
Example 1:
this example discloses a MXene/MnO x The electrostatic spinning preparation method of the nanofiber composite material comprises the following steps:
s1: 3mL of MXene in DMF (N, N-dimethylformamide)Amide) solution under protective gas ice bath ultrasonic treatment for 1-3 hours to obtain 30mg mL concentration -1 A stable MXene colloidal solution;
s2: adding 0.3g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath ultrasonic treatment under the shielding gas for 30 minutes;
s3: 0.5g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. A positive voltage of 20kv was applied to the needle tip and the collecting cylinder covered with aluminum foil was grounded. The distance between the needle tip and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mLh -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ for min -1 。
Example 2:
this example discloses a MXene/MnO x The electrostatic spinning preparation method of the nanofiber composite material comprises the following steps:
s1: 5mL of MXene in DMF (N, N-dimethylformamide) solution is subjected to ice bath ultrasonic treatment for 1-3 hours under the protection of gas to obtain 30mg mL -1 A stable MXene colloidal solution;
s2: adding 0.6g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath under the shielding gas for 30 minutes;
s3: 0.5g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. Applying a positive voltage of 20kv to the needle tip and covering the needle tip with aluminum foilThe collecting cylinder is grounded. The distance between the needle tip and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mLh -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ for min -1 。
MXene/MnO prepared in this example x The XRD pattern of the nanofiber composite is shown in figure 1. The results show that: MXene/MnO x The nanofiber composite has a diffraction peak at 2θ=6.5°, corresponding to the (002) crystal plane of MXene; in addition, other diffraction peaks may correspond to Mn, respectively 3 O 4 (PDF # 89-4837) and MnO (PDF # 77-2363). Description of MXene/MnO x The nanofiber composite material was successfully prepared.
MXene/MnO prepared in this example x SEM pictures of nanofiber composites, as shown in FIGS. 2 and 3, MXene/MnO x The nanofiber composite material has rich pore structure and is constructed into three-dimensional nano-network structure, granular MnO x Uniformly anchored on the surface of the fiber, the particle size is about 20-30nm, and the diameter of the fiber is about 500nm. MXene/MnO prepared x The nanofiber composite material has a unique porous structure, mnO x Firmly anchored to the fiber. Effectively inhibit MnO x Self-agglomeration of the particles and self-stacking of the MXene.
MXene/MnO prepared in this example x TEM image of nanofiber composite, as shown in FIG. 4, mnO x The nanoparticles are anchored to the MXene flakes and form ribbon-like fibers. The design greatly improves the number of active sites available for the material, and enhances the rate capability and stability of the electrode in the charge and discharge process.
MXene/MnO prepared in this example x Assembled into a battery with 2Ag by the nanofiber composite material -1 The cycle performance at current density is shown in fig. 5. The reversible capacity can reach 1098 even after 2000 cyclesmAhg -1 And only 0.007208% capacity fade rate.
Example 3:
this example discloses a MXene/MnO x The electrostatic spinning preparation method of the nanofiber composite material comprises the following steps:
s1: 5mL of MXene in DMF (N, N-dimethylformamide) solution is subjected to ice bath ultrasonic treatment for 1-3 hours under the protection of gas to obtain 30mg mL -1 A stable MXene colloidal solution;
s2: adding 0.4g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath under the shielding gas for 30 minutes;
s3: 0.5g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. A positive voltage of 20kv was applied to the needle tip and the collecting cylinder covered with aluminum foil was grounded. The distance between the needle tip and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mLh -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ for min -1 。
Example 4:
this example discloses a MXene/MnO x The electrostatic spinning preparation method of the nanofiber composite material comprises the following steps:
s1: 5mL of MXene in DMF (N, N-dimethylformamide) solution is subjected to ice bath ultrasonic treatment for 1-3 hours under the protection of gas to obtain 30mg mL -1 A stable MXene colloidal solution;
s2: adding 0.6g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath under the shielding gas for 30 minutes;
s3: 0.4g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. A positive voltage of 20kv was applied to the needle tip and the collecting cylinder covered with aluminum foil was grounded. The distance between the needle point and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mL h -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ for min -1 。
Example 5:
this example discloses a MXene/MnO x The electrostatic spinning preparation method of the nanofiber composite material comprises the following steps:
s1: 5mL of MXene in DMF (N, N-dimethylformamide) solution is subjected to ice bath ultrasonic treatment for 1-3 hours under the protection of gas to obtain 30mg mL -1 A stable MXene colloidal solution;
s2: adding 0.6g of manganese acetate to the MXene solution in the step S1 and carrying out ice bath under the shielding gas for 30 minutes;
s3: 0.5g of PAN (polyacrylonitrile, molecular weight: 1500000) was added to the solution in step S2, and stirring was continued for 12 hours to form a viscous black dope;
s4: and carrying out electrostatic spinning by a single-shaft electrostatic spinning device. The electrospinning solution obtained in step S3 was charged into a 5mL plastic syringe equipped with an 18G blunt needle. A positive voltage of 20kv was applied to the needle tip and the collecting cylinder covered with aluminum foil was grounded. The distance between the needle tip and the collector is 15cm, and the injection speed of the solution is controlled to be 1.2mLh -1 The air humidity is less than 30%.
S5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ for min -1 。
S6: carbonizing the nanofiber membrane obtained in the step S4 for 3 hours under argon, wherein the carbonization temperature is 500 ℃, and the heating rate is 2 ℃ for min -1 。
Claims (1)
1. MXene/MnO x The preparation method of the nanofiber composite material is characterized by comprising the following steps of: the method comprises the following steps:
s1: 5mL of MXene DMF solution is subjected to ice bath ultrasound under the protection of gas for 1-3 hours, and the concentration of 30 mg.mL is obtained -1 A stable MXene colloidal solution;
s2: adding 0.6. 0.6g manganese acetate into the MXene colloidal solution in the step S1 and carrying out ice bath ultrasonic treatment under the protection gas for 30 minutes;
s3: adding 0.5g of polyacrylonitrile into the solution in the step S2, and continuously stirring for 12 hours to form a viscous black spinning solution, wherein the molecular weight of the polyacrylonitrile is 1500000;
s4: carrying out electrostatic spinning by a single-shaft electrostatic spinning device; filling the electrostatic spinning solution obtained in the step S3 into a 5mL plastic injector provided with an 18G blunt needle; applying a positive voltage of 20kv to the needle tip and grounding the aluminum foil covered collection cylinder; the distance between the needle tip and the collector is 15cm, and the solution injection speed is controlled to be 1.2 mL.h -1 The air humidity is less than 30%;
s5: stabilizing the nanofiber membrane obtained in the step S4 in air for 2 hours at the temperature of 280 ℃ and the heating rate of 5 ℃ and min -1 ；
S6: carbonizing the nanofiber membrane obtained in the step S5 for 3 hours under argon, wherein the carbonization temperature is 800 ℃, and the heating rate is 2 ℃ and min -1 。
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