CN114335458A - Ti3C2Tx @ g-C3N4 composite material and preparation method and application thereof - Google Patents
Ti3C2Tx @ g-C3N4 composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims description 50
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000007710 freezing Methods 0.000 claims description 15
- 230000008014 freezing Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000001465 metallisation Methods 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- -1 DCD compound Chemical class 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YCLCFZRBVJIBMF-UHFFFAOYSA-N [Li].FC(F)(F)S(=N)C(F)(F)F Chemical compound [Li].FC(F)(F)S(=N)C(F)(F)F YCLCFZRBVJIBMF-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
Images
Classifications
-
- 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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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a Ti3C2Tx@g‑C3N4A composite material and a preparation method and application thereof relate to the technical field of composite materials. Ti provided by the invention3C2Tx@g‑C3N4The composite material has excellent cycle stability, and the Ti provided by the invention3C2Tx@g‑C3N4When the composite material is applied to a lithium metal cathode, three-dimensional Ti3C2TxThe skeleton is used as a lithium metal deposition substrate with a three-dimensional structure, and the surfaceG to C of3N4The layer is used as a uniform artificial Solid Electrolyte Interface (SEI), so that the interface stability of the lithium metal negative electrode can be improved, and the electrochemical performance is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to Ti3C2Tx@g-C3N4Composite material and its preparation method and application.
Background
At present, graphite is used as a negative electrode of a commercial lithium ion battery, and the theoretical specific capacity is 372 mAh/g. However, as the energy demand of industries such as portable electronic products and electric vehicles is increasing, the development of a storage system with high energy density becomes more critical. Lithium metal has the highest theoretical specific capacity (3860mAh/g) and the lowest electrochemical potential (-3.04Vvs. RHE), and attracts wide attention as an ideal negative electrode material of a lithium battery. Despite the unique advantages of rechargeable lithium metal batteries, their practical application still faces some technical challenges. The high-activity Li reacts spontaneously with the organic electrolyte to form an unstable Solid Electrolyte Interface (SEI) at the Li/electrolyte interface, resulting in low coulombic efficiency, short cycle life and serious potential safety hazard.
The construction of the lithium metal deposition substrate with the three-dimensional structure is beneficial to reducing the local current density and improving the cycle stability to a certain extent. However, electrolyte-derived SEI's do not protect lithium metal from the continued corrosion of the electrolyte, ultimately leading to uncontrolled growth of lithium dendrites and irreversible capacity loss.
Disclosure of Invention
The object of the present invention is to provide a Ti3C2Tx@g-C3N4Composite material, preparation method and application thereof, and Ti provided by the invention3C2Tx@g-C3N4The composite material has excellent cycling stability, and when the composite material is applied to a lithium metal negative electrode, the interface stability of the lithium metal negative electrode can be improved, and the electrochemical performance is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Ti3C2Tx@g-C3N4Composite material comprising Ti3C2TxNanosheets and nanoparticles attached to the Ti3C2Txg-C of nanosheet surface3N4A film;
in atomic percent, the Ti3C2Tx@g-C3N4The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti, 5-15% of O and 2-12% of F.
Preferably, the Ti3C2Tx@g-C3N4The composite material is of a three-dimensional lamellar structure, and the thickness of each lamellar is independently 2-5 nm; the Ti3C2Tx@g-C3N4The specific surface area of the composite material is 20-30 m2/g。
The invention provides the Ti in the technical scheme3C2Tx@g-C3N4The preparation method of the composite material comprises the following steps:
mixing Ti3C2TxMixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion liquid; the Ti3C2TxThe mass ratio of the nanosheet to the carbon nitride precursor is 1: 3-9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid composite to obtain Ti3C2Tx@g-C3N4A composite material.
Preferably, the carbon nitride precursor comprises urea, cyanamide, thiourea, melamine or dicyandiamide.
Preferably, the freezing temperature is-35 to-50 ℃; the freezing time is 10-15 h.
Preferably, the drying is vacuum drying.
Preferably, the calcining temperature is 400-600 ℃; the calcining time is 1-3 h.
Preferably, the heating rate of the temperature from room temperature to the calcining temperature is 3-8 ℃/min.
Preferably, the calcination is carried out under a protective atmosphere.
The invention provides the Ti in the technical scheme3C2Tx@g-C3N4Composite material or Ti prepared by the preparation method of the technical scheme3C2Tx@g-C3N4The composite material is applied to a lithium metal negative electrode material.
The invention provides a Ti3C2Tx@g-C3N4Composite material comprising Ti3C2TxNanosheets and nanoparticles attached to the Ti3C2Txg-C of nanosheet surface3N4A film; in atomic percent, the Ti3C2Tx@g-C3N4The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti, 5-15% of O and 2-12% of F. Ti provided by the invention3C2Tx@g-C3N4When the composite material is applied to a lithium metal cathode, three-dimensional Ti3C2TxFramework as three-dimensional structure lithium metal deposition substrate, g-C of surface3N4The layer is used as a uniform artificial Solid Electrolyte Interface (SEI), so that the interface stability of the lithium metal negative electrode can be improved, and the electrochemical performance is improved. The invention controls Ti3C2Tx@g-C3N4The percentage of each atom in the composite material is such that g-C3N4Is suitable in content, and avoids the problem of g-C when being applied to a lithium metal anode material3N4Too high a content of (A), excessive g-C3N4Has serious side reaction with lithium and avoids the problem of g-C3N4Too low a content to form uniform Ti3C2Tx/g-C3N4A problem of a heterojunction interface. Ti provided by the invention3C2Tx@g-C3N4The composite material is used as an active component of a lithium metal negative electrode material, is assembled with a lithium sheet into a half cell, and is tested for electrochemical performance, and the results of the examples show that Ti3C2Tx@g-C3N4The composite material has excellent cycle performance and the current density is 0.5 mA-cm-2And a circulation capacity of 1mAh · cm-2Of Ti3C2Tx@g-C3N4The composite material can stably circulate for more than 400 circles, and the circulation stability is obviously superior to that of three-dimensional Ti3C2TxNanosheets and pure g-C3N4As a lithium metal negative electrode material.
Drawings
FIG. 1 shows Ti prepared in example 13C2TxNanosheet, g-C3N4And Ti3C2Tx@g-C3N4An X-ray diffraction pattern of the composite;
FIG. 2 shows Ti prepared in example 13C2Tx@g-C3N4Scanning electron microscopy spectra of the composite;
FIG. 3 shows Ti prepared in example 13C2Tx@g-C3N4An Atomic Force Microscope (AFM) spectrum of the composite material;
FIG. 4 shows Ti prepared in example 13C2Tx@g-C3N4Nitrogen adsorption and desorption isotherms of the composite material;
FIG. 5 shows Ti prepared in example 13C2Tx@g-C3N4Coulombic efficiency plots of constant current charge-discharge cycles of the composite; the current density is 0.5mA/cm2The circulation capacity is 1mAh/cm2；
FIG. 6 shows Ti prepared in example 13C2Tx@g-C3N4Coulombic efficiency plots of constant current charge-discharge cycles of the composite; the current density is 2mA/cm2The circulation capacity is 2mAh/cm2；
FIG. 7 shows Ti prepared in example 23C2Tx@g-C3N4Coulombic efficiency plots of constant current charge-discharge cycles of the composite;
FIG. 8 shows Ti prepared in example 33C2Tx@g-C3N4Coulombic efficiency plots of constant current charge-discharge cycles of the composite;
FIG. 9 shows Ti of comparative example 13C2TxCoulombic efficiency graph of constant current charge-discharge cycle of the nano-sheet;
FIG. 10 is g-C of comparative example 23N4Coulombic efficiency plots of constant current charge-discharge cycles of the electrodes.
Detailed Description
The invention provides a Ti3C2Tx@g-C3N4Composite material comprising Ti3C2TxNanosheets and nanoparticles attached to the Ti3C2Txg-C of nanosheet surface3N4A film;
in atomic percent, the Ti3C2Tx@g-C3N4The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti, 5-15% of O and 2-12% of F.
Ti provided by the invention3C2Tx@g-C3N4The composite material comprises Ti3C2TxNanosheets, in the present invention, the Ti3C2TxThe nano sheet is of a three-dimensional sheet structure; the thickness of the lamellae is preferably 2.9 nm. In the present invention, the Ti is3C2TxT in (3) preferably comprises-OH, -O, -F.
Ti provided by the invention3C2Tx@g-C3N4The composite material comprises Ti adhered to the surface of the substrate3C2Txg-C of nanosheet surface3N4And (3) a membrane. In the present invention, the g-C3N4Film and Ti3C2TxThe nanosheets are connected by hydrogen bonds. In the present invention, the g-C3N4A film is uniformly adhered to the Ti3C2TxAnd (3) the surface of the nanosheet.
In the present invention, the Ti is present in atomic percentage3C2Tx@g-C3N4The composite material preferably comprises C46.01%, N25.46%, Ti 18.51%, O6.73%, F3.29%.
In the present invention, the Ti is3C2Tx@g-C3N4The composite material is of a three-dimensional lamellar structure, the thickness of each lamellar is preferably 2-5 nm independently, and more preferably 3.2 nm; the Ti3C2Tx@g-C3N4The specific surface area of the composite material is preferably 20 to E30m2A,/g, more preferably 24.9m2/g。
The invention also provides the Ti of the technical scheme3C2Tx@g-C3N4The preparation method of the composite material comprises the following steps:
mixing Ti3C2TxMixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion liquid; the Ti3C2TxThe mass ratio of the nanosheet to the carbon nitride precursor is 1: 3-9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid composite to obtain Ti3C2Tx@g-C3N4A composite material.
The invention prepares Ti by self-assembly and in-situ calcination reaction3C2Tx@g-C3N4Composite materials, in a self-assembly process, carbon nitride precursors are deposited on Ti by weak interactions (e.g. hydrogen bonding)3C2TxThe carbon nitride precursor is uniformly distributed on the surface of the nano sheet3C2TxThe surface of the nanosheet; during calcination, the carbon nitride precursor is polycondensed to form g-C3N4So that Ti is3C2TxA layer of uniform g-C grows on the surface of the nanosheet in situ3N4Film to obtain Ti3C2Tx@g-C3N4A composite material. The invention adopts the mode of in-situ growth to ensure that g-C3N4Film and Ti3C2TxFirm combination is realized between the nano sheet substrates, and the stability is improved.
The invention is to mix Ti3C2TxAnd mixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion liquid. In the present invention, the Ti is3C2TxThe method of preparation of the nanoplatelets preferably comprises: mixing Ti3AlC2Mixing with etching liquid, and etching to obtain an etching system; sequentially feeding the etching systemWashing and centrifuging to obtain a suspension; freezing and drying the suspension liquid in sequence to obtain Ti3C2TxNanosheets.
In the invention, the etching liquid is preferably a mixed solution of lithium fluoride and hydrochloric acid or a hydrofluoric acid solution. In the present invention, the amount ratio of the lithium fluoride to the hydrochloric acid solution in the mixed solution of lithium fluoride and hydrochloric acid is preferably 0.8 g: 10 mL; the concentration of the hydrochloric acid solution is preferably 9 mol/L. In the present invention, the method for preparing the mixed solution of lithium fluoride and hydrochloric acid is preferably: the lithium fluoride and hydrochloric acid solution were mixed and stirred for 10 min. In the present invention, the concentration of the hydrofluoric acid solution is preferably 15 wt%. In the present invention, the Ti is3AlC2The method of mixing with the etching liquid preferably includes: mixing Ti3AlC2Adding into etching solution, and stirring for 24 h. In the present invention, the Ti is3AlC2The preferable dosage ratio of the etching solution to the etching solution is 0.3-0.8 g: 6-16 mL, more preferably 0.5 g: 10 mL.
After the etching system is obtained, the invention preferably washes and centrifuges the etching system in sequence to obtain the suspension. In the present invention, the washing liquid is preferably deionized water; the invention has no special requirement on the washing times, and the pH value of the filtrate is preferably 6. In the present invention, it is preferable that after the washing, the washed solid matter is mixed with water and centrifuged. In the present invention, the rotation speed of the centrifugation is preferably 3500rpm, and the time of the centrifugation is preferably 1 h. In the present invention, the concentration of the suspension is preferably 5 mg/mL.
After obtaining the suspension, the invention preferably freezes and dries the suspension in order to obtain Ti3C2TxNanosheets. In the present invention, the freezing temperature is preferably-35 to-50 ℃, more preferably-40 ℃; the freezing time is preferably 10-15 h, and more preferably 12 h. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 1-30 Pa, and more preferably 5 Pa; the drying temperature is preferably 25 ℃, and the drying time is preferably 48-54 h, and more preferably 50 h.
In the present invention, the Ti is3C2TxThe nano sheet is a dry and fluffy black nano sheet.
Preparation of Ti3C2TxAfter nanosheet, the present invention provides Ti3C2TxAnd mixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion liquid. In the present invention, the Ti is3C2TxThe mass ratio of the nanosheet to the carbon nitride precursor is preferably 1: 3-9, more preferably 1:5 to 7. In the present invention, the Ti is3C2TxThe mass ratio of the nanosheets to water is preferably 1: 500. In the present invention, the carbon nitride precursor preferably includes urea, cyanamide, thiourea, melamine or dicyandiamide; the water is preferably deionized water. In the present invention, the Ti is3C2TxThe method of mixing the nanoplatelets, the carbon nitride precursor and water preferably comprises: mixing Ti3C2TxDispersing the nano-sheets in water, and then adding a carbon nitride precursor for stirring. In the present invention, the stirring time is preferably 3 hours.
After the mixed dispersion liquid is obtained, the mixed dispersion liquid is sequentially frozen and dried to obtain the solid compound. In the present invention, the freezing temperature is preferably-35 to-50 ℃, more preferably-40 ℃; the freezing time is preferably 10-15 h, and more preferably 12 h. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 1-30 Pa, and more preferably 5 Pa; the drying temperature is preferably 25 ℃, and the drying time is preferably 48-54 h, and more preferably 50 h. The invention changes the mixed dispersion liquid into a solid compound through freezing and drying, and is convenient for subsequent calcination. The invention adopts a freeze drying method to remove the solvent, which is beneficial to maintaining Ti3C2TxIn the form of a sheet.
The invention carries out self-assembly in the mixing process, and the carbon nitride precursor is deposited on Ti through weak interaction (such as hydrogen bond)3C2TxThe carbon nitride precursor is uniformly distributed on the surface of the nano sheet3C2TxAnd (3) the surface of the nanosheet.
After obtaining the solid compound, the invention calcines the solid compound to obtain Ti3C2Tx@g-C3N4A composite material. In the invention, the calcining temperature is preferably 400-600 ℃, and more preferably 500-550 ℃; the heat preservation time is preferably 1-3 h, and more preferably 2 h; the heating rate from room temperature to the calcining temperature is preferably 3-8 ℃/min, and more preferably 5-7 ℃/min. In the present invention, the calcination is preferably performed under a protective atmosphere, more preferably under a nitrogen or argon atmosphere. In the present invention, the calcination is preferably carried out in a tube furnace. In the calcination process, the carbon nitride precursor is condensed to form g-C3N4So that Ti is3C2TxA layer of uniform g-C grows on the surface of the nanosheet in situ3N4Film to obtain Ti3C2Tx@g-C3N4A composite material.
In the invention, preferably, after the calcination, the obtained solid is naturally cooled to room temperature to obtain Ti3C2Tx@g-C3N4A composite material.
The invention also provides the Ti of the technical scheme3C2Tx@g-C3N4Composite material or Ti prepared by the preparation method of the technical scheme3C2Tx@g-C3N4The composite material is applied to a lithium metal negative electrode material. In the present invention, the lithium metal negative electrode material preferably includes a current collector and an active coating layer attached to the surface of the current collector; the composition of the active coating preferably comprises Ti3C2Tx@g-C3N4Composite material, conductive carbon black and polyvinylidene fluoride. In the present invention, the Ti is3C2Tx@g-C3N4The mass ratio of the composite material, the conductive carbon black and the polyvinylidene fluoride is preferably 8:1: 1.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1)Ti3C2TxAnd (3) synthesis of the nanosheet.
Adding 0.8g of lithium fluoride into 10mL of hydrochloric acid solution (the concentration is 9mol/L), and stirring for 10 min; then 0.5g Ti3AlC2Slowly adding the mixture into the solution, and stirring for 24 hours; washing with deionized water until the pH value of the filtrate is 6; centrifuging at 3500rpm for 1h to obtain stable suspension; freezing the suspension at-40 deg.C for 12h, and drying under 5Pa for 50h to obtain dry fluffy black Ti3C2TxNanosheets.
(2)Ti3C2Tx-synthesis of DCD complex.
100mg of the Ti3C2TxDispersing the nanosheets in 50mL of deionized water, adding 500mg of dicyandiamide (DCD), and stirring for 3 hours to obtain a mixed dispersion liquid; freezing the mixed dispersion liquid at-40 deg.C for 12h, and drying under 5Pa vacuum environment for 50h to obtain Ti3C2Tx-a DCD complex.
(3)Ti3C2Tx@g-C3N4And (4) synthesizing the composite material.
Adding the Ti3C2TxPlacing the DCD compound in a crucible, placing the DCD compound in a tube furnace, preserving the heat for 2 hours at 550 ℃ under the protective atmosphere of argon, wherein the heating rate is 5 ℃/min, and collecting the DCD compound after cooling to room temperature to obtain Ti3C2Tx@g-C3N4A composite material.
Example 2
The procedure was as in example 1, except that the amount of DCD was adjusted from "500 mg" to "700 mg".
Example 3
The procedure was as in example 1, except that the amount of DCD was adjusted from "500 mg" to "300 mg".
Comparative example 1
Ti prepared as in example 13C2TxNanosheets were used as comparative example 1.
Comparative example 2
Substantially the same as in example 1 except that Ti was not added3C2TxPlacing DCD into a crucible, placing the crucible into a tube furnace, keeping the temperature at 550 ℃ for 2h under the protective atmosphere of argon, increasing the temperature at the rate of 5 ℃/min, cooling to room temperature, and collecting to obtain g-C3N4。
Test example 1
FIG. 1 shows Ti prepared in example 13C2TxNanosheet, g-C3N4And Ti3C2Tx@g-C3N4An X-ray diffraction (XRD) pattern of the composite material. As can be seen from FIG. 1, with Ti3C2TxNanosheet phase, Ti3C2Tx@g-C3N4The (002) crystal face diffraction peak in the XRD pattern of the composite material is shifted to the left, which shows that the g-C is caused3N4Of Ti3C2TxThe interlayer spacing of (a) increases. Ti3C2Tx@g-C3N4The XRD pattern of the composite material does not show obvious g-C3N4Diffraction peaks, indicating that g-C was not generated3N4Bulk and Ti3C2TxThe original crystal structure is maintained.
FIG. 2 shows Ti prepared in example 13C2Tx@g-C3N4Scanning Electron Microscope (SEM) spectra of the composite material. As can be seen from FIG. 2, Ti3C2Tx@g-C3N4The composite material microscopically exhibits a three-dimensional lamellar structure.
FIG. 3 shows Ti prepared in example 13C2Tx@g-C3N4Atomic Force Microscope (AFM) spectra of the composite materials. As can be seen from FIG. 3, Ti3C2Tx@g-C3N4The thickness of the composite nanosheet is 3.2 nm.
FIG. 4 shows Ti prepared in example 13C2Tx@g-C3N4Nitrogen adsorption and desorption isotherms of the composite material. From FIG. 4, Ti3C2Tx@g-C3N4The specific surface area of the composite material was 24.9m2/g。
Test example 2
The half-cells are assembled. Ti prepared by examples 1 to 33C2Tx@g-C3N4Composite material, Ti of comparative example 13C2TxNanosheets and g-C of comparative example 23N4Respectively serving as lithium metal cathode materials, assembling the lithium metal cathode materials and a lithium sheet into a half cell, taking a mesoporous polypropylene film as a diaphragm (Celgard 2400), and taking an electrolyte as a mixed solution of 1, 3-dioxolane and glycol dimethyl ether containing 1mol/L bis (trifluoromethyl) sulfimide Lithium (LiTFSI), wherein the volume ratio of the 1, 3-dioxolane to the glycol dimethyl ether is 1: 1; a CR2025 type button cell was assembled in a glove box, and a constant current charge-discharge test was performed on the cell using a cell test system (Neware BTS 4000).
FIG. 5 shows Ti prepared in example 13C2Tx@g-C3N4Coulombic efficiency of constant current charge-discharge cycle of the composite material. At a current density of 0.5mA/cm2The circulation capacity is 1mAh/cm2Of Ti3C2Tx@g-C3N4The composite material can be stably circulated for more than 400 circles, and the average coulombic efficiency is 98.4%.
FIG. 6 shows Ti prepared in example 13C2Tx@g-C3N4Coulombic efficiency of constant current charge-discharge cycle of the composite material. At a current density of 2mA/cm2The circulation capacity is 2mAh/cm2Of Ti3C2Tx@g-C3N4The composite material can be cycled for 105 cycles.
FIG. 7 shows Ti prepared in example 23C2Tx@g-C3N4Coulombic efficiency of constant current charge-discharge cycle of the composite material. The addition ratio of dicyandiamide is increased, so that the finally obtained Ti3C2Tx@g-C3N4g-C in the composite3N4The content is higher. At a current density of 2mA/cm2The circulation capacity is 2mAh/cm2Of Ti3C2Tx@g-C3N4The composite material can be stably cycled for 150 cycles.
FIG. 8 shows Ti prepared in example 33C2Tx@g-C3N4Coulombic efficiency of constant current charge-discharge cycle of the composite material. The addition ratio of dicyandiamide is reduced, so that the finally obtained Ti3C2Tx@g-C3N4g-C in the composite3N4The content is low. At a current density of 2mA/cm2The circulation capacity is 2mAh/cm2Of Ti3C2Tx@g-C3N4The composite material can be stably cycled for 80 cycles.
FIG. 9 shows Ti of comparative example 13C2TxCoulombic efficiency of constant current charge-discharge cycle of the nanosheets. At a current density of 0.5mA/cm2The circulation capacity is 1mAh/cm2Of Ti3C2TxThe nanosheets can be stably cycled for 170 cycles. Ti3C2TxThe cycling stability of the nano-sheet is obviously lower than that of Ti3C2Tx@g-C3N4A composite material.
FIG. 10 is g-C of comparative example 23N4Coulombic efficiency of constant current charge-discharge cycles of the electrodes. At a current density of 0.5mA/cm2The circulation capacity is 1mAh/cm2When g-C3N4The electrode can cycle stably for 120 cycles. Pure g-C3N4Has a significantly lower cycling stability than Ti3C2Tx@g-C3N4A composite material.
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 (10)
1. Ti3C2Tx@g-C3N4Composite material comprising Ti3C2TxNanosheets and nanoparticles attached to the Ti3C2Txg-C of nanosheet surface3N4A film;
in atomic percent, the Ti3C2Tx@g-C3N4The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti, 5-15% of O and 2-12% of F.
2. The Ti of claim 13C2Tx@g-C3N4Composite material, characterized in that the Ti is3C2Tx@g-C3N4The composite material is of a three-dimensional lamellar structure, and the thickness of each lamellar is independently 2-5 nm; the Ti3C2Tx@g-C3N4The specific surface area of the composite material is 20-30 m2/g。
3. The Ti as set forth in any one of claims 1 to 23C2Tx@g-C3N4The preparation method of the composite material comprises the following steps:
mixing Ti3C2TxMixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion liquid; the Ti3C2TxThe mass ratio of the nanosheet to the carbon nitride precursor is 1: 3-9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid composite to obtain Ti3C2Tx@g-C3N4A composite material.
4. The method of claim 3, wherein the carbon nitride precursor comprises urea, cyanamide, thiourea, melamine, or dicyandiamide.
5. The method of claim 3, wherein the freezing temperature is-35 to-50 ℃; the freezing time is 10-15 h.
6. The method according to claim 3, wherein the drying is vacuum drying.
7. The preparation method according to claim 3, wherein the temperature of the calcination is 400 to 600 ℃; the heat preservation time is 1-3 h.
8. The method according to claim 3 or 7, wherein a temperature rise rate from room temperature to the calcination temperature is 3 to 8 ℃/min.
9. The method according to claim 3 or 7, wherein the calcination is carried out under a protective atmosphere.
10. The Ti as set forth in any one of claims 1 to 23C2Tx@g-C3N4Composite material or Ti prepared by the preparation method of any one of claims 3 to 93C2Tx@g-C3N4The composite material is applied to a lithium metal negative electrode material.
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