CN116812934A - Ti (titanium) 3 C 2 Base composite material and preparation method and application thereof - Google Patents
Ti (titanium) 3 C 2 Base composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010936 titanium Substances 0.000 title claims description 251
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 52
- 229910012672 LiTiO Inorganic materials 0.000 claims description 47
- 238000001291 vacuum drying Methods 0.000 claims description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 238000005530 etching Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000005119 centrifugation Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011232 storage material Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 description 70
- 239000011734 sodium Substances 0.000 description 36
- 230000008569 process Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000003860 storage Methods 0.000 description 9
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000755 effect on ion Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The application provides a Ti 3 C 2 A base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the Ti is as follows 3 C 2 The mass percentage of the substrate material is 80% -96%, and the mass percentage of the nano particles is 4% -20%. The book is provided withThe application also provides the Ti 3 C 2 A preparation method and application of a base composite material. Ti of the application 3 C 2 The particle size of the base composite material is uniform, and Ti can be effectively inhibited 3 C 2 Collapse and re-stacking of the accordion-like sheet structure of material while being able to provide a large number of active sites; and Ti is 3 C 2 The shape of the base composite material is well maintained, the purity is high, and the initial shape can be maintained after the hydrothermal reaction. The preparation method is simple, easy to operate and short in experimental period.
Description
Technical Field
The application relates to the technical field of materials, in particular to a Ti 3 C 2 A base composite material, a preparation method and application thereof.
Background
Excessive use of fossil fuels presents many environmental pollution problems such as global warming, atmospheric haze, etc. The advent of lithium ion batteries has greatly improved the current situation of energy shortage, and lithium ion batteries are one of the most competitive candidates for power storage devices due to their long cycle performance and high energy density. Graphite as one kind of widely used negative electrode material for commercial lithium cell with theoretical specific capacity of only 370 mA/hr g -1 The specific capacity is lower, and the current market demand of the lithium ion battery cannot be met.
Two-dimensional (2D) materials are crystalline materials with one or several atomic layers, while mxnes is an emerging two-dimensional layered transition metal carbide or nitride that has received increasing attention from researchers due to its unique "accordion" layered structure, good hydrophilicity, and adaptability to intercalation of ions with different electrolytes. In a plurality of MXenes, ti 3 C 2 As a negative electrode material of a lithium ion battery, it is widely studied that the capacity of the lithium ion battery can be increased by introducing additional reaction sites through loading reaction sites or surface functional group modification; furthermore, the two-dimensional voids between the layers can also provide diffusion channels for lithium ions, making two-dimensional materials of great interest in electrochemical energy storage and conversion. However, ti is 3 C 2 The material has weak conductivity and small specific surface area, and is easy to accumulate into slices in the charging and discharging processes, thereby greatly limiting the application of the electrochemical performance.
Disclosure of Invention
Based on this, the embodiment of the application provides a Ti 3 C 2 Base composite material, preparation method and application thereof, aiming at solving the problem of Ti 3 C 2 The material has weak conductivity and small specific surface area, is easy to accumulate into slices in the charging and discharging processes, and greatly limits the application of electrochemical performance and the like.
To achieve the above object, in one aspect, an embodiment of the present application providesFor Ti to 3 C 2 Base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the Ti is as follows 3 C 2 The mass percentage of the substrate material is 80% -96%, and the mass percentage of the nano particles is 4% -20%.
By controlling Ti 3 C 2 The mass ratio of the base material to the nano particles can effectively inhibit Ti 3 C 2 Collapse and re-stacking of the accordion-like sheet structure of the base material while providing a large number of active sites (such as active sites for insertion and extraction of lithium ions) such that T i 3 C 2 The shape of the base composite material is well maintained, the purity is high, and the initial shape can be still maintained after the hydrothermal reaction, thereby effectively improving Ti 3 C 2 Electrochemical properties of the substrate material.
As a preferred embodiment, the nanoparticle is LiTiO 2 Nanoparticles or Na 2 Ti 3 O 7 And (3) nanoparticles.
On the other hand, the embodiment of the application also provides the Ti 3 C 2 A method of preparing a base composite comprising the steps of:
SO1, ti 3 C 2 Adding the powder into the first solution, and uniformly stirring to obtain a mixed solution; 50 to 200 mg of Ti is added into each 30 to 100ml of the first solution 3 C 2 A powder;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 A base composite material; the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 2-16 h at 75-185 ℃.
In a preferred embodiment, in step S01,
according to the practical requirement, 50 mg Ti can be added into 30ml of the first solution 3 C 2 Powder, or 150% Ti per 50ml of the first solution 3 C 2 Powder, or 200 Ti per 100ml of the first solution 3 C 2 Powder, or 50% Ti per 100ml of the first solution 3 C 2 Powder, etc., preferably 100 mg of Ti per 50ml of the first solution 3 C 2 And (3) powder. Thus, ti can be effectively suppressed 3 C 2 Collapse and re-stacking of the accordion-like sheet structure of the base material while providing a large number of active sites (such as active sites for insertion and extraction of lithium ions) such that Ti 3 C 2 The shape of the base composite material is well maintained.
The Ti is 3 C 2 The powder is prepared by the following method: adding MAX precursor into the second solution for etching, centrifuging, collecting precipitate, washing, and drying to obtain Ti 3 C 2 A powder; and adding 0.5 g-2 g of MAX precursor into every 10 ml-40 ml of the second solution.
According to the actual use, 0.5g of MAX precursor is added to 10ml of the second solution, or 2g of MAX precursor is added to 40ml of the second solution, or 2g of MAX precursor is added to 30ml of the second solution, etc., preferably 1g of MAX precursor is added to 20ml of the second solution. Thus, ti can be ensured 3 C 2 And (3) generating powder. The MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is an HF solution, preferably a 40wt% HF solution. Adopts HF solution, has mature and perfect process preparation and is easy to etch ideal lamellar Ti 3 C 2 And (3) powder.
The etching temperature is 40-60 ℃ (which can be 40 ℃, 45 ℃, 50 ℃ or 60 ℃ and the like according to the actual use requirement), and is preferably 50 ℃; the etching time is 36h.
The centrifugation speed is 2000r min -1 ～9000r min -1 Preferably 6000r min -1 ～9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time is 4-6 min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying.
The temperature of the vacuum drying is preferably 75-85 ℃ (75 ℃, 78 ℃, 80 ℃ or 85 ℃ and the like according to the actual use requirement), and the time of the vacuum drying is preferably 10-20 h (10 h, 12h, 15h, 18h or 20h and the like according to the actual use requirement).
The first solution is LiOH aqueous solution or NaOH aqueous solution.
The LiOH aqueous solution is 1mol L -1 Is an aqueous solution of LiOH; the NaOH aqueous solution is 1mol L -1 NaOH aqueous solution of (a).
The stirring is magnetic stirring.
In a preferred embodiment, in step S02,
the conditions of the hydrothermal reaction are that the hydrothermal reaction is carried out for 4-12 h (4 h, 6h, 8h, 10h or 12h and the like according to the actual use requirement) at 100-165 ℃ (100 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 165 ℃ and the like according to the actual use requirement).
During the hydrothermal reaction, ti 3 C 2 Oxidized to produce TiO 2 ，Li + /Na + Substituted anatase TiO 2 In situ LiTiO production 2 /Ti 3 C 2 (or Na 2 Ti 3 O 7 /Ti 3 C 2 ) A nanocomposite. Ti (Ti) 3 C 2 Is used as a substrate material and provides a large number of active sites for insertion and extraction of lithium ions. Since the size of the in-situ grown nanoparticles is controllable and the nanoparticles are uniformly distributed, this is advantageous for stabilizing Ti during cycling 3 C 2 Thus, the Ti of the application 3 C 2 Based composite materials (e.g. LiTiO 2 /Ti 3 C 2 Nanocomposite or Na 2 Ti 3 O 7 /Ti 3 C 2 Nanocomposite) exhibits a specific ratio of Ti 3 C 2 Better electrochemical performance.
If the temperature of the hydrothermal reaction is too low, nanoparticles cannot be generated; if the temperature of the hydrothermal reaction is too high, ti 3 C 2 The substrate material is heated and oxidized to cause the collapse of the layered structure, thereby reducing the electricity of the composite materialChemical properties. If the hydrothermal reaction is too long, ti 3 C 2 The material is heated and oxidized to cause the collapse of the layered structure, so that the electrochemical performance of the composite material is reduced; if the hydrothermal reaction time is too short, the generation of nanoparticles is not favored.
The hydrothermal reaction is carried out in an autoclave.
The centrifugation speed is 2000r min -1 ～9000r min -1 (2000 r min may be used according to the actual use requirement) -1 、5000r min -1 、6000r min -1 、7000r min -1 Or 9000r min -1 Etc.), preferably 6000r min -1 ～9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time is 4-6 min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying.
The temperature of the vacuum drying is 75-85 ℃ (75 ℃, 78 ℃, 80 ℃ or 85 ℃ and the like according to the actual use requirement), and the temperature is preferably 80 ℃; the time of the vacuum drying is 10h to 20h (10 h, 12h, 15h, 18h or 20h, etc. according to the actual use requirement), preferably 12h.
In yet another aspect, an embodiment of the present application further provides the Ti 3 C 2 Use of a base composite material, said Ti 3 C 2 The base composite material can be applied to battery materials, hydrogen storage materials and supercapacitors.
As a preferred embodiment, the battery material is a lithium ion battery anode material.
Compared with the prior art, the embodiment of the application has the following technical effects:
(1) Ti of the application 3 C 2 The particle size of the base composite material is uniform, and Ti can be effectively inhibited 3 C 2 Collapse and re-stacking of the accordion-like sheet structure of material while providing a large number of active sites (such as active sites for insertion and extraction of lithium ions); and Ti is 3 C 2 The shape of the base composite material is well maintained, the purity is high, and the base composite material can still be maintained after hydrothermal reactionInitial form.
(2) The preparation method is simple, easy to operate and short in experimental period; during the hydrothermal reaction, the byproduct TiO 2 The nano particles play an important role in purposefully introducing lithium/sodium ions, and greatly enhance Ti 3 C 2 So that the prepared Ti 3 C 2 The base composite material has good electrochemical performance, can be applied to the fields of battery materials, hydrogen storage materials, supercapacitors and the like, and has good performance.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Ti as an embodiment of the application 3 AlC 2 、Ti 3 C 2 、LiTiO 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 X-ray diffraction (XRD) pattern of the nanocomposite;
FIG. 2 is a view of Ti as an embodiment of the application 3 C 2 、LiTiO 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 FESEM images of nanocomposite;
FIG. 3 shows LiTiO according to an embodiment of the present application 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 HRTEM images of nanocomposite;
FIG. 4 shows LiTiO according to an embodiment of the present application 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 XPS spectrum of nanocomposite;
FIG. 5 is a schematic view of a displayLiTiO of the embodiment of the application 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 Electrochemical performance-long cycling capacity performance and corresponding coulombic efficiency of the nanocomposite;
FIG. 6 shows LiTiO according to an embodiment of the present application 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 A power-variable performance map of the nanocomposite;
FIG. 7 shows LiTiO according to an embodiment of the present application 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 CV curve of nanocomposite;
FIG. 8 shows LiTiO according to an embodiment of the present application 2 /Ti 3 C 2 The CV curves of the nanocomposite at different scan rates and the non-diffusion limited current contributions at different scan rates.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described in the following embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that, if there is a description of "first", "second", etc. in the embodiments of the present application, the description of "first", "second", etc. is only for descriptive purposes, and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present application.
In the embodiment of the application, various reagents and raw materials are all commercial products; the concentration of the HF solution was 40wt%; the lithium hydroxide in the embodiment of the application is lithium hydroxide (monohydrate); lithium hydroxide (monohydrate) and sodium hydroxide are both analytically pure; the purity of MAX precursor is 98 percent and 200 meshes.
The embodiment of the application can effectively control the appearance and the size of the product, has simple process, and the obtained product has high purity, good dispersibility of nano particles, uniform size and particle diameter and good electrochemical performance.
Example 1
Ti (titanium) 3 C 2 Base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the Ti is as follows 3 C 2 The mass percentage of the substrate material is 80%, and the mass percentage of the nano particles is 20%.
The nano particles are LiTiO 2 And (3) nanoparticles.
The Ti is 3 C 2 A method of preparing a base composite comprising the steps of:
SO1, will be 100 mg Ti 3 C 2 Adding the powder into 50ml of the first solution, and uniformly stirring to obtain a mixed solution;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 Base composite (i.e. LiTiO 2 /Ti 3 C 2 A nanocomposite material); the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 12 hours at 160 ℃.
In the step S01 of the process,
the Ti is 3 C 2 The powder is prepared by the following method: iceUnder the bath condition, adding 1g MAX precursor into 20ml second solution (the adding time is 30 min) for etching, centrifuging, taking precipitate, washing, and drying to obtain Ti 3 C 2 And (3) powder.
The MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is a 40wt% hf solution. The etching temperature is 50 ℃; the etching time is 36h.
The centrifugal speed is 7000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 6min.
The washing is carried out by deionized water (the pH value of the supernatant liquid is about 6).
The drying is vacuum drying. The temperature of the vacuum drying is 75 ℃, and the time of the vacuum drying is 20h.
The first solution is LiOH aqueous solution and is prepared by the following method: 2.098g of lithium hydroxide (monohydrate) was added to 50mL of deionized water and magnetically stirred for 30min to give an aqueous LiOH solution.
The stirring is magnetic stirring.
In step S02 of the process,
the hydrothermal reaction was performed in an autoclave (100 mL polytetrafluoroethylene-lined stainless steel autoclave).
The centrifugal speed is 8000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 5min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying. The temperature of the vacuum drying is 80 ℃; the time of the vacuum drying is 12 hours.
The Ti is 3 C 2 The base composite material can be used in battery materials. The battery material is a lithium ion battery cathode material.
Example 2
Ti (titanium) 3 C 2 Base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the T is as followsi 3 C 2 The mass percentage of the substrate material is 96%, and the mass percentage of the nano particles is 4%.
The nano particles are Na 2 Ti 3 O 7 And (3) nanoparticles.
The Ti is 3 C 2 A method of preparing a base composite comprising the steps of:
SO1, will be 100 mg Ti 3 C 2 Adding the powder into 50ml of the first solution, and uniformly stirring to obtain a mixed solution;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 Base composite (i.e. Na 2 Ti 3 O 7 /Ti 3 C 2 A nanocomposite material); the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 10 hours at 180 ℃.
In the step S01 of the process,
the Ti is 3 C 2 The powder is prepared by the following method: under ice bath condition, adding 1g MAX precursor into 20ml second solution (30 min), etching, centrifuging, collecting precipitate, washing, and drying to obtain Ti 3 C 2 And (3) powder.
The MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is a 40wt% hf solution.
The etching temperature is 60 ℃; the etching time is 36h.
The centrifugal speed is 9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 4min.
The washing is carried out by deionized water (the pH value of the supernatant liquid is about 6).
The drying is vacuum drying. The temperature of the vacuum drying is 85 ℃, and the time of the vacuum drying is 10 hours.
The first solution is NaOH aqueous solution and is prepared by the following method: 2g of sodium hydroxide was added to 50mL of deionized water and magnetically stirred for 30min to obtain an aqueous NaOH solution.
The stirring is magnetic stirring.
In step S02 of the process,
the hydrothermal reaction was performed in an autoclave (100 mL polytetrafluoroethylene-lined stainless steel autoclave).
The centrifugal speed is 8000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 6min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying.
The temperature of the vacuum drying is 80 ℃; the time of the vacuum drying is 12 hours.
The Ti is 3 C 2 The base composite material can be used in battery materials. The battery material is a lithium ion battery cathode material.
Example 3
Ti (titanium) 3 C 2 Base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the Ti is as follows 3 C 2 The mass percentage of the substrate material is 90%, and the mass percentage of the nano particles is 10%.
The nano particles are LiTiO 2 And (3) nanoparticles.
The Ti is 3 C 2 A method of preparing a base composite comprising the steps of:
SO1, will be 100 mg Ti 3 C 2 Adding the powder into 50ml of the first solution, and uniformly stirring to obtain a mixed solution;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 Base composite (i.e. LiTiO 2 /Ti 3 C 2 A nanocomposite material); the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 6 hours at 120 ℃.
In the step S01 of the process,
the Ti is 3 C 2 The powder is prepared by the following method: under ice bath condition, adding 1g MAX precursor into 20ml second solution (30 min), etching, centrifuging, collecting precipitate, washing, and drying to obtain Ti 3 C 2 And (3) powder.
The MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is a 40wt% hf solution.
The etching temperature is 40 ℃; the etching time is 36h.
The centrifugal speed is 9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 4min.
The washing is carried out by deionized water (the pH value of the supernatant liquid is about 6).
The drying is vacuum drying.
The temperature of the vacuum drying is 75 ℃, and the time of the vacuum drying is 20h.
The first solution is LiOH aqueous solution and is prepared by the following method: 1.2g of lithium hydroxide was added to 50mL of deionized water and magnetically stirred for 30min to give an aqueous LiOH solution. The stirring is magnetic stirring.
In step S02 of the process,
the hydrothermal reaction was performed in an autoclave (100 mL polytetrafluoroethylene-lined stainless steel autoclave).
The centrifugal speed is 9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 4min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying. The temperature of the vacuum drying is 75 ℃; the time of the vacuum drying is 20h.
The Ti is 3 C 2 The base composite material can be used in battery materials. The battery material is a lithium ion battery cathode material.
Example 4
Ti (titanium) 3 C 2 Base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite materialThe amount is 100 percent, the Ti is 3 C 2 The mass percentage of the substrate material is 85%, and the mass percentage of the nano particles is 15%.
The nano particles are LiTiO 2 And (3) nanoparticles.
The Ti is 3 C 2 A method of preparing a base composite comprising the steps of:
SO1, will be 100 mg Ti 3 C 2 Adding the powder into 50ml of the first solution, and uniformly stirring to obtain a mixed solution;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 Base composite (i.e. LiTiO 2 /Ti 3 C 2 A nanocomposite material); the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 2 hours at 185 ℃.
In the step S01 of the process,
the Ti is 3 C 2 The powder is prepared by the following method: under ice bath condition, adding 1g MAX precursor into 20ml second solution (30 min), etching, centrifuging, collecting precipitate, washing, and drying to obtain Ti 3 C 2 And (3) powder.
The MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is a 40wt% hf solution. The etching temperature is 60 ℃; the etching time is 36h.
The centrifugal speed is 7000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 6min.
The washing is carried out by deionized water (the pH value of the supernatant liquid is about 6).
The drying is vacuum drying. The temperature of the vacuum drying is 85 ℃, and the time of the vacuum drying is 10 hours.
The first solution is LiOH aqueous solution and is prepared by the following method: 1.2g of lithium hydroxide was added to 50mL of deionized water and magnetically stirred for 30min to give an aqueous LiOH solution. The stirring is magnetic stirring.
The stirring is magnetic stirring.
In step S02 of the process,
the hydrothermal reaction was performed in an autoclave (100 mL polytetrafluoroethylene-lined stainless steel autoclave).
The centrifugal speed is 9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time was 5min.
The washing is carried out by adopting deionized water.
The drying is vacuum drying. The temperature of the vacuum drying is 75 ℃; the time of the vacuum drying is 18 hours.
The Ti is 3 C 2 The base composite material can be used in battery materials. The battery material is a lithium ion battery cathode material.
Effect examples
For the prepared Ti 3 C 2 Electrochemical energy of the base composite was tested: first, 80mg of LiTiO of example 1 was respectively 2 /Ti 3 C 2 Nanocomposite was added to a first agate mortar containing 10mg of conductive carbon black, 80mg of Na of example 2 2 Ti 3 O 7 /Ti 3 C 2 The nanocomposite was put into a second agate mortar containing 10mg of conductive carbon black, ground for 0.5h under an argon atmosphere, put into a glass vial after sufficient grinding, and 200. Mu.L of the prepared PVDF/NMP solvent (concentration of 0.05g mL was added -1 ) An appropriate amount of NMP solvent was added and stirring was continued on a stirrer for 12h to form a black slurry. The slurry is uniformly coated on a copper foil (the thickness is about 150 mu m) by using a four-side wet film preparation device, the copper foil is wiped by absolute ethyl alcohol before being used, the surface of the copper foil is clean and free of impurities, the copper foil is placed in a vacuum drying oven at 120 ℃ to be dried for 12 hours, the dried copper foil is pressed by using an electric pair roller to ensure stable contact between the slurry and the copper foil, and an electrode plate with the diameter of 14mm is cut by a slicing machine and is weighed for use. A metallic lithium sheet with the thickness of about 0.4mm and the diameter of 14mm is used as a counter electrode, and the button cell is assembled in an argon glove box. The oxygen content in the glove box is lower than 0.01ppm, and the water content is lower than 0.01ppm.
To confirm Ti 3 AlC 2 、Ti 3 C 2 LiTiO of example 1 2 /Ti 3 C 2 Nanocomposite and Na of example 2 2 Ti 3 O 7 /Ti 3 C 2 The phase composition and crystal structure of the nanocomposite were analyzed by XRD pattern, and the results are shown in FIG. 1. At Ti 3 C 2 The 39℃peak disappeared in the XRD pattern corresponding to Ti 3 AlC 2 The diffraction peaks of (104), (002) were shifted to lower angles, indicating Ti 3 AlC 2 Is successfully dissolved by the HF solution. In addition, na 2 Ti 3 O 7 /Ti 3 C 2 The diffraction peak (002) of the nanocomposite was shifted from 9.70 ° to 9.02 ° after NaOH treatment, whereas LiTiO 2 /Ti 3 C 2 The peak of the nanocomposite then moves to a lower angle of 7.15 deg., which indicates a corresponding increase in interlayer spacing. Calculated by Bragg equation, ti 3 C 2 、LiTiO 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 The interlayer spacing of the nanocomposite was 0.91, 0.98 and 1.20nm, respectively. At the same time, a (110) peak appears in all samples, indicating Ti 3 C 2 The reaction with LiOH and NaOH does not completely destroy Ti 3 C 2 Is a layered structure of (a). LiTiO 2 /Ti 3 C 2 XRD of nanocomposite shows LiTiO 2 And Ti is 3 C 2 Is shown to form a new phase LiTiO in the composite material 2 。Na 2 Ti 3 O 7 /Ti 3 C 2 XRD of the nanocomposite showed that only new Na could be detected in the composite 2 Ti 3 O 7 And (3) phase (C). LiTiO 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 Ti in nanocomposite material 3 C 2 Shows partial oxidation during hydrothermal treatment to form TiO 2 . From the XRD results, na 2 Ti 3 O 7 /Ti 3 C 2 There are two types of TiO in nanocomposites 2 : anatase TiO 2 (ICDD PDF#21-1272) and rutileTiO 2 (ICDD PDF # 21-1276). However, in Ti 3 C 2 And LiTiO 2 /Ti 3 C 2 Rutile TiO with narrow band gap can only be detected in nanocomposite 2 This helps to improve electrochemical performance.
As shown in FIG. 2 (a-c), ti was treated by FESEM 3 C 2 LiTiO of example 1 2 /Ti 3 C 2 Nanocomposite and Na of example 2 2 Ti 3 O 7 /Ti 3 C 2 The microstructure of the nanocomposite was characterized. In FIG. 2 (a), ti 3 C 2 Exhibiting a typical layered structure. FIGS. 2 (b) and (c) show LiTiO, respectively 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 Microcosmic morphology of nanocomposite, it can be seen that LiTiO 2 And Na (Na) 2 Ti 3 O 7 Grown in Ti 3 C 2 On the layer of Ti 3 C 2 As a carrier, the layered structure is also well maintained. In addition, liTiO 2 /Ti 3 C 2 LiTiO in nanocomposite material 2 Nanoparticle ratio Na 2 Ti 3 O 7 /Ti 3 C 2 Na in nanocomposite 2 Ti 3 O 7 The nanoparticles are smaller, finer, and more uniformly distributed. LiTiO 2 The presence of nanoparticles increases Ti 3 C 2 The spacing of the layers and support the layered structure.
FIG. 3 shows LiTiO prepared in example 1 2 /Ti 3 C 2 HRTEM images of nanocomposite. As shown in the figure, liTiO 2 Is distributed in Ti 3 C 2 On the layer. From the analysis of the fast Fourier transform and inverse fast Fourier transform processes in FIG. 3, the calculated interplanar spacing was 0.205nm, corresponding to LiTiO 2 The results are consistent with the SEM conclusion that nanoparticles are grown in Ti (200) 3 C 2 The surface of the sheet.
LiTiO of example 1 2 /Ti 3 C 2 Nanocomposite materialNa of example 2 2 Ti 3 O 7 /Ti 3 C 2 The structural information of the nanocomposite was further determined by XPS. Ti, O, C and F are the main elements in the sample. The F element is a residue of the etching process. The high resolution XPS spectra of Ti 2p (fig. 4 (a), (b)), C1s (fig. 4 (C), (d)) and O1s (fig. 4 (e) and (f) were further analyzed. Six different peaks can be observed in high resolution Ti 2 p. According to LiTiO 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 The 2p orbital binding energy of the nanocomposite material can be found that the Ti element contains three valence states, namely Ti 2+ 、Ti 3 + And Ti is 4+ . Of these three Ti states (C-Ti-C, C-Ti-O and O-Ti-O), the binding energy pairs 455.2 and 461.8eV, 456.3 and 463.2eV, and 468.6 and 464.5eV correspond to 2p3/2 and 2p1/2 spin states, respectively. The high resolution C1s spectra of the two samples (FIG. 4 (C), (d)) included three peaks corresponding to Ti-C (281.9 eV), C-O (288.7 eV) and C-C (285.1 eV), respectively. The above results also confirm that in the manufacture of Ti 3 C 2 In the process of (2), the Ti-C bond is not mostly broken, and is not completely oxidized into the Ti-O bond, so that the original structure is well preserved.
FIG. 5 shows a voltage range of 0.1V to 3.0V and 0.1A g -1 LiTiO of example 1 at current density 2 /Ti 3 C 2 Nanocomposite and Na of example 2 2 Ti 3 O 7 /Ti 3 C 2 Nanocomposite battery performance data and long-term cycling capability. LiTiO 2 /Ti 3 C 2 The initial discharge capacity of the nanocomposite material is 551.5mA h g -1 Higher than Na 2 Ti 3 O 7 /Ti 3 C 2 Nanocomposite (470 mA h g) -1 )。LiTiO 2 /Ti 3 C 2 Nanocomposite having an Initial Coulombic Efficiency (ICE) of 52.3%, an SEI film in which an initial capacitance was formed, and Li + With Ti 3 C 2 Is attenuated by the partial irreversible reaction between the surface groups (-OH, -F and-O). LiTiO for the second and third periods 2 /Ti 3 C 2 The specific discharge capacities of the nanocomposite materials were 312.3 and 287.1mA hg, respectively -1 . At 0.1A g -1 LiTiO at a current density of (C) 2 /Ti 3 C 2 The nanocomposite showed better cycle performance and a slight upward trend after 200 cycles, while Na 2 Ti 3 O 7 /Ti 3 C 2 The trend of the nano composite material is stable, and the final capacity is 321.1mA h g -1 . This phenomenon can be explained by the insertion and discharge of lithium ions during charge/discharge to cause Ti 3 C 2 Increased interlayer spacing, liTiO 2 And Na (Na) 2 Ti 3 O 7 The nano particles play a role in supporting the layered structure, and the LiTiO is caused by the changes 2 /Ti 3 C 2 Nanocomposite and Na 2 Ti 3 O 7 /Ti 3 C 2 Nanocomposite materials can provide more active sites to improve ion mobility kinetics.
As shown in FIG. 6, liTiO of example 1 2 /Ti 3 C 2 Nanocomposite material exhibited a ratio of Na to example 2 2 Ti 3 O 7 /Ti 3 C 2 The nanocomposite has better rate performance. With current density from 0.1A g -1 To 5A g -1 ，LiTiO 2 /Ti 3 C 2 The specific capacity of the nanocomposite material is 337.2mA h g -1 Down to 101.8mA hg -1 . Thereafter, the current density was restored to 0.1A g -1 ，LiTiO 2 /Ti 3 C 2 The capacity of the nanocomposite material increased to 372.3mA h g -1 Indicating LiTiO 2 /Ti 3 C 2 The two-dimensional structure of the nanocomposite has good rate capability. As with Na at the same current density 2 Ti 3 O 7 /Ti 3 C 2 Compared with nano composite material, liTiO 2 /Ti 3 C 2 Nanocomposite materials exhibit higher capacities. At 0.1 and 0.2. 0.2A g -1 LiTiO within the current density range of (2) 2 /Ti 3 C 2 Nanocomposite material shows a high affinity for Na 2 Ti 3 O 7 /Ti 3 C 2 The different capacities of the nanocomposite material, which increase in capacity as the cycle proceeds, may be related to electrolyte permeation through successive activations, which may be presumed to be an improvement in ion diffusion kinetics.
The lithium storage behavior of the composite material was studied by Cyclic Voltammetry (CV). FIG. 7 shows LiTiO of example 1 on the left and right, respectively 2 /Ti 3 C 2 Nanocomposite and Na of example 2 2 Ti 3 O 7 /Ti 3 C 2 Nanocomposite at 0.1mV s -1 The scanning rate and the first three CV curves obtained in the potential range of 0.01V to 3.0V. In the first cathodic sweep, one cathodic peak appears at about 1.516V when lithium ions are intercalated into the interlayer, and then the cathodic peak shifts to 1.566V and 1.614V in the following cycle, due to electrolyte decomposition and Solid Electrolyte Interface (SEI) layer formed at the electrode surface, which illustrates a significantly irreversible cathodic peak of 0.431V. In the following anodic scan, a relatively strong peak of 1.801V and a relatively weak peak of 2.644V appear. In the subsequent cycle, both the anode and cathode peaks were shifted to the right, which shows Li + Is extracted stepwise. In contrast, na 2 Ti 3 O 7 /Ti 3 C 2 The nanocomposite showed irreversible cathodic peaks at 0.46V and 1.62V. In the first cycle, insertion of lithium ions resulted in a cathode peak of 1.31V, which was transferred to about 1.4V in the subsequent cycle.
To further investigate the storage mechanism of the electrode, the storage mechanism was respectively changed at 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0 mV.s -1 LiTiO of example 1 2 /Ti 3 C 2 The nanocomposite was subjected to CV testing. As shown in fig. 8 (a), the anode current peak gradually increases with the increase of the scanning speed. The relationship between peak current (i) and scan rate (v) can be described by equation (1):
log(i)＝b*log(v)+log(a) (0.5≤b≤1) (1)
where a and b are two variable parameters. The storage mechanism of lithium ions is determined by the value of b. In general, b=0.5 indicates that diffusion completely controls the storage of lithium ions, and b=1 indicates that storage is completely controlled by capacitance. In the present example, the b values of the anode and cathode peaks of the electrode were calculated to be 0.852 and 0.932, respectively (fig. 8 (b)), indicating that the lithium ion storage process in the lithium electrode is controlled by the capacitance and diffusion processes.
The contribution of the capacitive process is further quantified according to equation (2):
(v)＝k 1 v+k 2 v 1 /(2i(v)) (2)
wherein k is 1 And k 2 Is two variables; k (k) 1 v and k 2 v 1 And/2 represents the contribution of the capacitance and diffusion control processes, respectively. As shown in FIG. 8 (c), the scan rate was 0.4 mV.s for the Li electrode -1 At this time, the capacitance contribution was 62.7%. While the percentage of capacitance contribution gradually increases with increasing scan rate from 0.1 mV.s -1 46.5% to 1 mV.s -1 76.7% (FIG. 8 (d)). This suggests that lithium ion intercalation/deintercalation can be more effectively achieved at higher scan rates due to the rapid reaction kinetics of the capacitive storage mechanism. Thus, a higher capacitance contribution will have a conductive effect on ion transport and improve the high rate performance of the electrode.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the application, and all equivalent structural changes made by the content of the present application or direct/indirect application in other related technical fields are included in the scope of the present application.
Claims (10)
1. Ti (titanium) 3 C 2 A base composite material comprising Ti 3 C 2 A base material supported on the Ti 3 C 2 Nanoparticles on a substrate material; with the Ti as 3 C 2 The mass of the base composite material is 100 percent, and the Ti is as follows 3 C 2 The mass percentage of the substrate material is 80% -96%, and the mass percentage of the nano particles is 4% -20%.
2. Ti according to claim 1 3 C 2 The base composite material is characterized in that the nano particles are LiTiO 2 Nanoparticles or Na 2 Ti 3 O 7 And (3) nanoparticles.
3. Ti according to claim 1 or 2 3 C 2 The preparation method of the base composite material is characterized by comprising the following steps:
SO1, ti 3 C 2 Adding the powder into the first solution, and uniformly stirring to obtain a mixed solution; 50 to 200 mg of Ti is added into each 30 to 100ml of the first solution 3 C 2 A powder;
SO2, carrying out hydrothermal reaction on the mixed solution in the step S01 to obtain a reaction product; centrifuging the reaction product, taking precipitate, washing, and drying to obtain Ti 3 C 2 A base composite material; the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 2-16 h at 75-185 ℃.
4. A Ti according to claim 3 3 C 2 A method for producing a base composite material, characterized in that in step S01, the Ti is 3 C 2 The powder is prepared by the following method: adding MAX precursor into the second solution for etching, centrifuging, collecting precipitate, washing, and drying to obtain Ti 3 C 2 A powder; and adding 0.5 g-2 g of MAX precursor into every 10 ml-40 ml of the second solution.
5. Ti according to claim 4 3 C 2 The preparation method of the matrix composite material is characterized in that the MAX precursor is Ti 3 AlC 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solution is an HF solution;
the etching temperature is 40-60 ℃; the etching time is 36h;
the centrifugation speed is 2000r min -1 ～9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time is 4-6 min;
the drying is vacuum drying; the temperature of the vacuum drying is 75-85 ℃, and the time of the vacuum drying is 10-20 h.
6. A Ti according to claim 3 3 C 2 The preparation method of the base composite material is characterized in that in the step S01, the first solution is LiOH aqueous solution or NaOH aqueous solution; the stirring is magnetic stirring.
7. A Ti according to claim 3 3 C 2 The preparation method of the base composite material is characterized in that in the step S02, the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 4-12 hours at 100-165 ℃.
8. A Ti according to claim 3 3 C 2 A method for preparing a base composite material is characterized in that in the step S02, the centrifugal speed is 2000r min -1 ～9000r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The centrifugation time is 4-6 min;
the drying is vacuum drying; the temperature of the vacuum drying is 75-85 ℃; the time of vacuum drying is 10-20 h.
9. Ti according to claim 1 or 2 3 C 2 Use of a matrix composite, characterized in that the Ti is 3 C 2 The base composite material is applied to battery materials, hydrogen storage materials and supercapacitors.
10. Ti according to claim 9 3 C 2 The application of the matrix composite material is characterized in that the battery material is a lithium ion battery anode material.
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