CN114335458B - 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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- CN114335458B CN114335458B CN202111535805.2A CN202111535805A CN114335458B CN 114335458 B CN114335458 B CN 114335458B CN 202111535805 A CN202111535805 A CN 202111535805A CN 114335458 B CN114335458 B CN 114335458B
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- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000001465 metallisation Methods 0.000 claims abstract description 4
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 4
- 239000002135 nanosheet Substances 0.000 claims description 30
- 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
- 239000002064 nanoplatelet Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000007710 freezing Methods 0.000 claims description 16
- 230000008014 freezing Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 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
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 16
- 238000010586 diagram Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 238000005530 etching Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 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
- 210000004027 cell Anatomy 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
- 238000012360 testing method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000012010 growth Effects 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
- 238000013507 mapping Methods 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
- -1 DCD compound Chemical class 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-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
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect 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
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
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
Abstract
The invention provides a Ti 3 C 2 T x @g‑C 3 N 4 A composite material, a preparation method and application thereof relate to the technical field of composite materials. Ti provided by the invention 3 C 2 T x @g‑C 3 N 4 The composite material has excellent cycle stability, and the Ti provided by the invention 3 C 2 T x @g‑C 3 N 4 When the composite material is applied to a lithium metal anode, three-dimensional Ti 3 C 2 T x Skeleton as three-dimensional structure lithium metal deposition substrate, g-C on surface 3 N 4 The layer is used as a uniform artificial Solid Electrolyte Interface (SEI), so that the interface stability of the lithium metal anode can be improved, and the electrochemical performance can be improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a Ti alloy 3 C 2 T x @g-C 3 N 4 Composite materials, methods of making and uses thereof.
Background
At present, the commercial lithium ion battery takes graphite as a negative electrode, and the theoretical specific capacity is 372mAh/g. However, with the increasing energy demands of industries such as portable electronic products and electric automobiles, it is becoming more critical to develop a storage system with high energy density. Lithium metal has the highest theoretical specific capacity (3860 mAh/g) and the lowest electrochemical potential (-3.04vvs. RHE), and has attracted considerable attention as an ideal lithium battery negative electrode material. While rechargeable lithium metal batteries have unique advantages, 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 safety hazards.
The lithium metal deposition substrate with the three-dimensional structure is constructed, so that the local current density is reduced, and the cycle stability is improved to a certain extent. However, electrolyte-derived SEI cannot protect lithium metal from sustained corrosion by the electrolyte, ultimately leading to uncontrolled growth of lithium dendrites and irreversible capacity loss.
Disclosure of Invention
The invention aims to provide Ti 3 C 2 T x @g-C 3 N 4 Composite material, preparation method and application thereof, and the Ti provided by the invention 3 C 2 T x @g-C 3 N 4 The composite material has excellent cycle stability, and can improve the interface stability of the lithium metal negative electrode and the electrochemical performance when being applied to the lithium metal negative electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Ti 3 C 2 T x @g-C 3 N 4 Composite material comprising Ti 3 C 2 T x Nanoplatelets and attached to the Ti 3 C 2 T x g-C of nanoplatelet surface 3 N 4 A membrane;
in atomic percent, the Ti is 3 C 2 T x @g-C 3 N 4 The 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 Ti is 3 C 2 T x @g-C 3 N 4 The composite material is of a three-dimensional lamellar structure, and the thickness of each lamellar is independently 2-5 nm; the Ti is 3 C 2 T x @g-C 3 N 4 The specific surface area of the composite material is 20-30 m 2 /g。
The invention provides the Ti 3 C 2 T x @g-C 3 N 4 The preparation method of the composite material comprises the following steps:
ti is mixed with 3 C 2 T x Nanometer scaleMixing the sheet, the carbon nitride precursor and water to obtain a mixed dispersion; the Ti is 3 C 2 T x The mass ratio of the nanosheets to the carbon nitride precursor is 1:3 to 9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid compound to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material.
Preferably, the carbon nitride precursor comprises urea, melamine, 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 temperature of the calcination is 400-600 ℃; the calcination time is 1-3 h.
Preferably, the temperature rising rate from room temperature to the calcining temperature is 3-8 ℃/min.
Preferably, the calcination is performed under a protective atmosphere.
The invention provides the Ti 3 C 2 T x @g-C 3 N 4 Composite material or Ti prepared by the preparation method in the technical scheme 3 C 2 T x @g-C 3 N 4 The application of the composite material in the lithium metal anode material.
The invention provides a Ti 3 C 2 T x @g-C 3 N 4 Composite material comprising Ti 3 C 2 T x Nanoplatelets and attached to the Ti 3 C 2 T x g-C of nanoplatelet surface 3 N 4 A membrane; in atomic percent, the Ti is 3 C 2 T x @g-C 3 N 4 The 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 invention 3 C 2 T x @g-C 3 N 4 Composite material applicationsIn the lithium metal anode, three-dimensional Ti 3 C 2 T x Skeleton as three-dimensional structure lithium metal deposition substrate, g-C on surface 3 N 4 The layer is used as a uniform artificial Solid Electrolyte Interface (SEI), so that the interface stability of the lithium metal anode can be improved, and the electrochemical performance can be improved. The invention controls Ti 3 C 2 T x @g-C 3 N 4 The percentage of atoms in the composite material is such that g-C 3 N 4 Is suitable in content, and avoids the generation of g-C when applied to lithium metal anode materials 3 N 4 Is too high, excessive g-C 3 N 4 Has serious side reaction with lithium, and avoids the problem of g-C 3 N 4 Is too low to form uniform Ti 3 C 2 T x /g-C 3 N 4 Heterojunction interface problems. Ti provided by the invention 3 C 2 T x @g-C 3 N 4 The composite material is used as an active component of a lithium metal anode material, and is assembled into a half cell with a lithium sheet, the electrochemical performance is tested, and the results of the examples show that Ti 3 C 2 T x @g-C 3 N 4 The composite material has excellent cycle performance, and the current density is 0.5mA cm -2 The circulation capacity is 1mAh cm -2 When Ti is 3 C 2 T x @g-C 3 N 4 The composite material can stably circulate for more than 400 circles, and the circulation stability is obviously better than three-dimensional Ti 3 C 2 T x Nanoplatelets and pure g-C 3 N 4 As a lithium metal anode material.
Drawings
FIG. 1 is a diagram of Ti prepared in example 1 3 C 2 T x Nanosheets, g-C 3 N 4 And Ti is 3 C 2 T x @g-C 3 N 4 X-ray diffraction pattern of the composite material;
FIG. 2 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Scanning electron microscope mapping of the composite material;
FIG. 3 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Atomic Force Microscope (AFM) mapping of the composite material;
FIG. 4 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Nitrogen adsorption and desorption isotherms of the composite material;
FIG. 5 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Coulomb efficiency plot of constant current charge-discharge cycles of the composite material; the current density was 0.5mA/cm 2 The circulation capacity is 1mAh/cm 2 ；
FIG. 6 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Coulomb efficiency plot of constant current charge-discharge cycles of the composite material; the current density was 2mA/cm 2 The circulation capacity is 2mAh/cm 2 ；
FIG. 7 is a diagram of Ti prepared in example 2 3 C 2 T x @g-C 3 N 4 Coulomb efficiency plot of constant current charge-discharge cycles of the composite material;
FIG. 8 is a Ti prepared in example 3 3 C 2 T x @g-C 3 N 4 Coulomb efficiency plot of constant current charge-discharge cycles of the composite material;
FIG. 9 is Ti of comparative example 1 3 C 2 T x Coulomb efficiency plot of constant current charge-discharge cycle of nanoplates;
FIG. 10 is g-C of comparative example 2 3 N 4 Coulomb efficiency plot for constant current charge-discharge cycles of the electrodes.
Detailed Description
The invention provides a Ti 3 C 2 T x @g-C 3 N 4 Composite material comprising Ti 3 C 2 T x Nanoplatelets and attached to the Ti 3 C 2 T x g-C of nanoplatelet surface 3 N 4 A membrane;
in atomic percent, the Ti is 3 C 2 T x @g-C 3 N 4 The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti and 5-1% of O5％，F 2～12％。
Ti provided by the invention 3 C 2 T x @g-C 3 N 4 The composite material comprises Ti 3 C 2 T x Nanoplatelets, in the present invention, the Ti 3 C 2 T x The nano sheet is of a three-dimensional lamellar structure; the thickness of the platelet is preferably 2.9nm. In the present invention, the Ti is 3 C 2 T x Preferably, T in (C) comprises-OH, -O, -F.
Ti provided by the invention 3 C 2 T x @g-C 3 N 4 The composite material comprises Ti attached to the material 3 C 2 T x g-C of nanoplatelet surface 3 N 4 And (3) a film. In the present invention, the g-C 3 N 4 Film and Ti 3 C 2 T x The nanoplatelets are connected by hydrogen bonds. In the present invention, the g-C 3 N 4 The film is uniformly adhered to the Ti 3 C 2 T x The surface of the nano-sheet.
In the present invention, the Ti is in atomic percent 3 C 2 T x @g-C 3 N 4 The composite material preferably comprises C46.01%, N25.46%, ti 18.51%, O6.73%, F3.29%.
In the present invention, the Ti is 3 C 2 T x @g-C 3 N 4 The composite material is of a three-dimensional lamellar structure, and the thickness of each lamellar is independently preferably 2-5 nm, more preferably 3.2nm; the Ti is 3 C 2 T x @g-C 3 N 4 The specific surface area of the composite material is preferably 20-30 m 2 Preferably 24.9m 2 /g。
The invention also provides the Ti 3 C 2 T x @g-C 3 N 4 The preparation method of the composite material comprises the following steps:
ti is mixed with 3 C 2 T x Mixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion; the Ti is 3 C 2 T x The mass ratio of the nanosheets to the carbon nitride precursor is 1:3 to 9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid compound to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material.
The invention prepares Ti through self-assembly and in-situ calcination reaction 3 C 2 T x @g-C 3 N 4 Composite materials, in which carbon nitride precursors deposit on Ti through weak interactions (e.g., hydrogen bonding) during self-assembly 3 C 2 T x The carbon nitride precursor is uniformly distributed on the surface of the nano-sheet 3 C 2 T x The surfaces of the nano-sheets; during calcination, the carbon nitride precursor is condensed to form g-C 3 N 4 So that Ti is 3 C 2 T x In-situ growth of a layer of uniform g-C on the surface of the nano-sheet 3 N 4 Film to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material. The invention adopts an in-situ growth mode to lead the g-C 3 N 4 Film and Ti 3 C 2 T x Firm combination is realized between the nano sheet substrates, and stability is improved.
The invention uses Ti 3 C 2 T x The nanoplatelets, the carbon nitride precursor and water are mixed to obtain a mixed dispersion. In the present invention, the Ti is 3 C 2 T x The preparation method of the nano-sheet preferably comprises the following steps: ti is mixed with 3 AlC 2 Mixing the etching solution and etching to obtain an etching system; washing and centrifuging the etching system in sequence to obtain a suspension; freezing and drying the suspension in sequence to obtain Ti 3 C 2 T x A nano-sheet.
In the present invention, the etching solution is preferably a mixed solution of lithium fluoride and hydrochloric acid or a hydrofluoric acid solution. In the present invention, the ratio of the amount of the lithium fluoride and the hydrochloric acid solution in the mixed solution of lithium fluoride and hydrochloric acid is preferably 0.8g:10mL; the concentration of the hydrochloric acid solution is preferably 9mol/L. In the invention, the preparation of the mixed solution of lithium fluoride and hydrochloric acidThe method is preferably as follows: mixing lithium fluoride and hydrochloric acid solution, and stirring for 10min. In the present invention, the concentration of the hydrofluoric acid solution is preferably 15wt%. In the present invention, the Ti is 3 AlC 2 The method for mixing the etching liquid preferably comprises the following steps: ti is mixed with 3 AlC 2 Adding the mixture into etching solution, and stirring for 24 hours. In the present invention, the Ti is 3 AlC 2 And the etching solution is preferably used in an amount of 0.3 to 0.8g:6 to 16mL, more preferably 0.5g:10mL.
After the etching system is obtained, the invention preferably carries out washing and centrifugation on the etching system in sequence to obtain 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, preferably, after the washing, the washed solid matter is mixed with water and centrifuged. In the present invention, the rotational speed of the centrifugation is preferably 3500rpm, and the time of the centrifugation is preferably 1h. In the present invention, the concentration of the suspension is preferably 5mg/mL.
After obtaining the suspension, the invention preferably carries out freezing and drying on the suspension in sequence to obtain Ti 3 C 2 T x A nano-sheet. In the present invention, the temperature of the freezing is preferably-35 to-50 ℃, more preferably-40 ℃; the time for the freezing is preferably 10 to 15 hours, more preferably 12 hours. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 1 to 30Pa, more preferably 5Pa; the drying temperature is preferably 25 ℃, and the drying time is preferably 48 to 54 hours, more preferably 50 hours.
In the present invention, the Ti is 3 C 2 T x The nano-sheets are dry and fluffy black nano-sheets.
Preparing Ti 3 C 2 T x After nano-sheets, the invention uses Ti 3 C 2 T x The nanoplatelets, the carbon nitride precursor and water are mixed to obtain a mixed dispersion. In the present invention, the Ti is 3 C 2 T x The mass ratio of the nanoplatelets to the carbon nitride precursor is preferably 1:3 to 9, more preferably 1:5 to 7. In the present invention,the Ti is 3 C 2 T x The mass ratio of the nano-sheet to the 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 is 3 C 2 T x The method of mixing the nanoplatelets, the carbon nitride precursor and the water preferably comprises: ti is mixed with 3 C 2 T x The nanoplatelets are dispersed in water, and then the carbon nitride precursor is added 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 temperature of the freezing is preferably-35 to-50 ℃, more preferably-40 ℃; the time for the freezing is preferably 10 to 15 hours, more preferably 12 hours. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 1 to 30Pa, more preferably 5Pa; the drying temperature is preferably 25 ℃, and the drying time is preferably 48 to 54 hours, more preferably 50 hours. The invention converts the mixed dispersion liquid into a solid compound by freezing and drying, which is convenient for subsequent calcination. The invention adopts a freeze drying method to remove the solvent, which is favorable for keeping Ti 3 C 2 T x Is a laminated structure of (a) a substrate.
The invention performs self-assembly in the mixing process, and the carbon nitride precursor is deposited on Ti through weak interaction (such as hydrogen bond) 3 C 2 T x The carbon nitride precursor is uniformly distributed on the surface of the nano-sheet 3 C 2 T x The surface of the nano-sheet.
After obtaining a solid compound, the invention calcines the solid compound to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material. In the present invention, the temperature of the calcination is preferably 400 to 600 ℃, more preferably 500 to 550 ℃; the heat preservation time is preferably 1 to 3 hours, more preferably 2 hours; the rate of temperature increase from room temperature to the calcination temperature is preferably 3 to 8℃per minute, more preferably 5 to 7℃per minute. In the present invention, the calcination is preferably carried out in a shielding gasThe reaction is carried out under an atmosphere, more preferably under a nitrogen or argon atmosphere. In the present invention, the calcination is preferably performed in a tube furnace. In the calcining process, the carbon nitride precursor is condensed to form g-C 3 N 4 So that Ti is 3 C 2 T x In-situ growth of a layer of uniform g-C on the surface of the nano-sheet 3 N 4 Film to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material.
The invention preferably naturally cools the obtained solid to room temperature after the calcination to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material.
The invention also provides the Ti 3 C 2 T x @g-C 3 N 4 Composite material or Ti prepared by the preparation method in the technical scheme 3 C 2 T x @g-C 3 N 4 The application of the composite material in the lithium metal anode material. In the present invention, the lithium metal anode material preferably includes a current collector and an active coating layer attached to a surface of the current collector; the components of the active coating preferably include Ti 3 C 2 T x @g-C 3 N 4 Composite materials, conductive carbon black and polyvinylidene fluoride. In the present invention, the Ti is 3 C 2 T x @g-C 3 N 4 The mass ratio of the composite material, the conductive carbon black and the polyvinylidene fluoride is preferably 8:1:1.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1)Ti 3 C 2 T x And (3) synthesizing the nano-sheets.
0.8g of lithium fluoride was added to 10mL of hydrochloric acid solution (concentration is9 mol/L), stirring for 10min; then 0.5g of Ti 3 AlC 2 Slowly adding into the solution, and stirring for 24 hours; washing with deionized water until the pH value of the filtrate is 6; centrifuging for 1h at 3500rpm to obtain a stable suspension; freezing the suspension at-40deg.C for 12 hr, and drying under 5Pa vacuum for 50 hr to obtain dry fluffy black Ti 3 C 2 T x A nano-sheet.
(2)Ti 3 C 2 T x Synthesis of DCD complex.
100mg of the Ti 3 C 2 T x Dispersing the nano-sheets in 50mL of deionized water, adding 500mg of dicyandiamide (DCD), and stirring for 3h to obtain a mixed dispersion liquid; freezing the mixed dispersion liquid at a low temperature of-40 ℃ for 12 hours, and drying for 50 hours in a vacuum environment of 5Pa to obtain Ti 3 C 2 T x -DCD complex.
(3)Ti 3 C 2 T x @g-C 3 N 4 And (3) synthesizing a composite material.
Subjecting the Ti to 3 C 2 T x Placing the DCD compound in a crucible, placing in a tubular furnace, preserving heat for 2 hours at 550 ℃ under the protection of argon, heating at a speed of 5 ℃/min, cooling to room temperature, and collecting to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material.
Example 2
Substantially the same as in example 1, except that the amount of DCD was changed from "500mg" to "700mg".
Example 3
Substantially the same as in example 1, except that the amount of DCD was changed from "500mg" to "300mg".
Comparative example 1
Ti prepared in example 1 3 C 2 T x Nanoplatelets are used as comparative example 1.
Comparative example 2
Substantially the same as in example 1, except that Ti was not added 3 C 2 T x Putting DCD into crucible, placing in tubular furnace, maintaining at 550deg.C for 2h under argon protection atmosphere at a heating rate of 5deg.C/min, cooling to room temperature, and collecting to obtain g-C 3 N 4 。
Test example 1
FIG. 1 is a diagram of Ti prepared in example 1 3 C 2 T x Nanosheets, g-C 3 N 4 And Ti is 3 C 2 T x @g-C 3 N 4 X-ray diffraction (XRD) pattern of the composite material. As can be seen from FIG. 1, with Ti 3 C 2 T x Compared with nano-sheet, ti 3 C 2 T x @g-C 3 N 4 The (002) plane diffraction peak in the XRD pattern of the composite material was shifted to the left, indicating that the diffraction peak was due to g-C 3 N 4 Covering of Ti 3 C 2 T x The interlayer spacing of (c) increases. Ti (Ti) 3 C 2 T x @g-C 3 N 4 No apparent g-C appears in XRD patterns of the composite material 3 N 4 Diffraction peaks, indicating no g-C production 3 N 4 Block and Ti 3 C 2 T x The original crystal structure is maintained.
FIG. 2 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Scanning Electron Microscope (SEM) profile of the composite material. As can be seen from FIG. 2, ti 3 C 2 T x @g-C 3 N 4 The composite material microscopically exhibits a three-dimensional lamellar structure.
FIG. 3 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Atomic Force Microscope (AFM) mapping of the composite material. As can be seen from FIG. 3, ti 3 C 2 T x @g-C 3 N 4 The thickness of the composite nano-sheet is 3.2nm.
FIG. 4 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Nitrogen adsorption desorption isotherms for composite materials. As can be seen from FIG. 4, ti 3 C 2 T x @g-C 3 N 4 Composite materialThe specific surface area of the material is 24.9m 2 /g。
Test example 2
And assembling the half cells. Ti prepared in examples 1 to 3 3 C 2 T x @g-C 3 N 4 Composite material, ti of comparative example 1 3 C 2 T x Nanosheets and g-C of comparative example 2 3 N 4 Respectively used as a lithium metal anode material and assembled with a lithium sheet to form a half battery, a mesoporous polypropylene film is used as a diaphragm (Celgard 2400), and the electrolyte is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether containing 1mol/L lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI), wherein the volume ratio of the 1, 3-dioxolane to the ethylene glycol dimethyl ether is 1:1; CR2025 type coin cells were assembled in a glove box and the cells were subjected to constant current charge and discharge testing using a battery test system (new BTS 4000).
FIG. 5 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Coulomb efficiency of constant current charge-discharge cycles of the composite material. At a current density of 0.5mA/cm 2 The circulation capacity is 1mAh/cm 2 When Ti is 3 C 2 T x @g-C 3 N 4 The composite material can be stably cycled over 400 cycles with an average coulombic efficiency of 98.4%.
FIG. 6 is a diagram of Ti prepared in example 1 3 C 2 T x @g-C 3 N 4 Coulomb efficiency of constant current charge-discharge cycles of the composite material. At a current density of 2mA/cm 2 The circulation capacity is 2mAh/cm 2 When Ti is 3 C 2 T x @g-C 3 N 4 The composite material can be stably circulated for 105 circles.
FIG. 7 is a diagram of Ti prepared in example 2 3 C 2 T x @g-C 3 N 4 Coulomb efficiency of constant current charge-discharge cycles of the composite material. The proportion of dicyandiamide added is increased, and finally the Ti is obtained 3 C 2 T x @g-C 3 N 4 g-C in composite material 3 N 4 The content is higher. At a current density of 2mA/cm 2 The circulation capacity is 2mAh/cm 2 When Ti is 3 C 2 T x @g-C 3 N 4 The composite material can be stably circulated for 150 circles.
FIG. 8 is a Ti prepared in example 3 3 C 2 T x @g-C 3 N 4 Coulomb efficiency of constant current charge-discharge cycles of the composite material. Due to the reduced proportion of dicyandiamide, the final Ti 3 C 2 T x @g-C 3 N 4 g-C in composite material 3 N 4 The content is low. At a current density of 2mA/cm 2 The circulation capacity is 2mAh/cm 2 When Ti is 3 C 2 T x @g-C 3 N 4 The composite material can be stably circulated for 80 circles.
FIG. 9 is Ti of comparative example 1 3 C 2 T x Coulomb efficiency of constant current charge-discharge cycles of the nanoplates. At a current density of 0.5mA/cm 2 The circulation capacity is 1mAh/cm 2 When Ti is 3 C 2 T x The nanoplatelets can be stably cycled for 170 turns. Ti (Ti) 3 C 2 T x The cyclic stability of the nano-sheet is obviously lower than that of Ti 3 C 2 T x @g-C 3 N 4 A composite material.
FIG. 10 is g-C of comparative example 2 3 N 4 Coulomb efficiency of constant current charge-discharge cycles of the electrode. At a current density of 0.5mA/cm 2 The circulation capacity is 1mAh/cm 2 g-C at the time of 3 N 4 The electrode may be cycled steadily for 120 turns. Pure g-C 3 N 4 Is significantly lower than Ti 3 C 2 T x @g-C 3 N 4 A composite material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. Ti (titanium) 3 C 2 T x @g-C 3 N 4 Application of composite material in negative electrode material of lithium metal battery, and application of composite material in negative electrode material of lithium metal batteryTi 3 C 2 T x @g-C 3 N 4 Composite material comprising Ti 3 C 2 T x Nanoplatelets and attached to the Ti 3 C 2 T x g-C of nanoplatelet surface 3 N 4 A membrane;
in atomic percent, the Ti is 3 C 2 T x @g-C 3 N 4 The composite material comprises 30-50% of C, 15-35% of N, 13-20% of Ti, 5-15% of O and 2-12% of F;
the Ti is 3 C 2 T x @g-C 3 N 4 The preparation method of the composite material comprises the following steps:
ti is mixed with 3 C 2 T x Mixing the nanosheets, the carbon nitride precursor and water to obtain a mixed dispersion; the Ti is 3 C 2 T x The mass ratio of the nanosheets to the carbon nitride precursor is 1: 7-9;
sequentially freezing and drying the mixed dispersion liquid to obtain a solid compound;
calcining the solid compound to obtain Ti 3 C 2 T x @g-C 3 N 4 A composite material;
with the Ti as 3 C 2 T x @g-C 3 N 4 Composite material used as lithium metal battery cathode material and three-dimensional Ti 3 C 2 T x Skeleton as three-dimensional structure lithium metal deposition substrate, g-C on surface 3 N 4 The layer acts as a uniform artificial solid electrolyte interface.
2. The use according to claim 1, characterized in that the Ti 3 C 2 T x @g-C 3 N 4 The composite material is of a three-dimensional lamellar structure, and the thickness of each lamellar is independently 2-5 nm; the Ti is 3 C 2 T x @g-C 3 N 4 The specific surface area of the composite material is 20-30 m 2 /g。
3. The use according to claim 1, wherein the carbon nitride precursor comprises urea, melamine, thiourea, melamine or dicyandiamide.
4. The use according to claim 1, wherein the temperature of the freezing is-35 to-50 ℃; the freezing time is 10-15 h.
5. The use according to claim 1, wherein the drying is vacuum drying.
6. The use according to claim 1, wherein the calcination temperature is 400-600 ℃; the heat preservation time is 1-3 h.
7. Use according to claim 1 or 6, characterized in that the rate of rise from room temperature to the calcination temperature is 3-8 ℃/min.
8. Use according to claim 1 or 6, characterized in that the calcination is carried out under a protective atmosphere.
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