CN117534040B - Multilayer titanium nitride material and preparation method thereof - Google Patents
Multilayer titanium nitride material and preparation method thereof Download PDFInfo
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 51
- 239000010410 layer Substances 0.000 claims abstract description 25
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
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- 238000005406 washing Methods 0.000 claims description 8
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- 229910052719 titanium Inorganic materials 0.000 claims description 4
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- 238000001291 vacuum drying Methods 0.000 claims description 3
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 229910052744 lithium Inorganic materials 0.000 description 5
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- 239000000376 reactant Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- -1 Lewis acid salt Chemical class 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- 239000012670 alkaline solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
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- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
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- 159000000001 potassium salts Chemical class 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
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- 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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- 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
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention relates to a multilayer titanium nitride which has an accordion-like multilayer structure, an interlayer spacing of 50-300nm and a specific surface area of 20-150 m 2 And/g, wherein the surface of the multilayer titanium nitride is provided with an oxide layer, and the X-ray photoelectron spectrum of Ti 2p is provided with the following characteristic peaks: 456.4 + -0.1 eV, 458.2+ -0.1 eV. The invention prepares the multilayer TiN (M-TiN) with the MXene-like accordion structure by a simple preparation method, successfully combines the conductive framework and the high specific surface area of the MXene with the chemical stability and the excellent conductive performance of the TiN, and provides a new solving path for solving the problem of the stability of the MXene. The novel TiN material with unique structure and excellent performance has wide application prospect and huge market potential in the fields of catalysis, energy storage, sensing and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to multilayer titanium nitride and a preparation method thereof.
Background
MXene is a type of two-dimensional material obtained by etching an a-element layer from a MAX-phase material, a layered ceramic material containing a transition metal M element, an a element (group IIIA or IVA element), and an X element (carbon or nitrogen). Since 2011 was first discovered, MXene is rapidly becoming a hotspot for research due to its excellent physicochemical properties, such as high conductivity, high mechanical strength, and excellent electrochemical activity. The production of MXene relies mainly on wet chemical methods, i.e. etching with strong oxidants (e.g. fluorides) to remove the a element from the MAX phase material and thereby obtain MXene. MXene has a typical layered structure, with each layer of transition metal atoms sandwiched by two layers of X element atoms. This unique layered structure imparts many of the superior properties of MXene. For example, MXene exhibits extremely high electrical conductivity, which is comparable to metals. Meanwhile, the MXene has high mechanical strength and good flexibility, and can be bent and folded while maintaining high strength. In addition, the layered structure of MXene imparts excellent electrochemical activity to it, making it excellent in energy storage and conversion devices. Due to its unique properties, MXene has shown a broad application potential in a number of fields. In the energy storage field, MXene is widely used in supercapacitor and battery electrode materials, exhibiting high specific capacity and long cycle life. In the sensor field, the high conductivity and high specific surface area of MXene make it exhibit excellent performance in gas sensors and biosensors. In addition, MXene also has great application potential in the fields of catalysis, electromagnetic shielding, photoelectric equipment and the like. Although MXene exhibits many excellent properties and broad application potential, its stability problem has been a major factor limiting its further development. The abundant terminal functional groups (e.g., -OH, -F, -O) in the MXene layered structure are susceptible to react with moisture and oxygen in the environment, leading to rapid oxidation and corrosion of the material. This not only damages the layered structure of MXene, reducing its conductivity and mechanical strength, but also affects its performance in electrochemical devices. Therefore, how to improve the chemical stability of MXene and prolong the service life of MXene is an important direction of current research.
Titanium nitride (TiN) is a hard ceramic material having a high melting point (about 2950 ℃ C.), a high hardness (about 8-9 Mohs), and excellent chemical stability. TiN belongs to a face-centered cubic structure, each titanium atom of which is surrounded by six nitrogen atoms, and each nitrogen atom of which is also surrounded by six titanium atoms, forming a compact three-dimensional network structure. Due to its unique structure, tiN exhibits extremely high electrical conductivity, and is one of a few ceramic materials with metallic conductivity. This has led to the wide application of TiN in conductive films, electronic devices, and cutting tool coatings. The high hardness and wear resistance properties of TiN also make it important to play an important role in the coating of tools and wear parts. Compared with other materials such as MXene, the biggest advantage of TiN is extremely high chemical stability. TiN can remain stable under extreme conditions and is not easily reacted with moisture and oxygen in the environment. This allows TiN to maintain good performance in high temperature, high pressure and corrosive environments, and is an ideal choice for making high performance devices and materials. Although TiN has many advantages, it also has some limitations. For example, conventional TiN materials are typically present in bulk or thin film form with a relatively small specific surface area, which limits their performance in areas where high specific surface area materials are required (e.g., catalyst and battery electrode materials, etc.). In recent years, scientists have modified and optimized TiN materials by various methods, including controlling their morphology and structure, introducing other elements for doping, etc., to increase their specific surface area and conductivity. However, these methods often involve complicated preparation processes and cannot be prepared in batch, which limits their application in industrial scale production.
In order to solve the problems of chemical instability of MXene and small specific surface area of common TiN, the development of a novel TiN material which has stable structure, excellent conductivity and easy mass preparation is a hot spot for research. The advent of accordion-like TiN materials provides new possibilities for solving this problem. The direct conversion from bulk TiN to accordion-like TiN is almost impossible to achieve. Therefore, we designed by transforming bulk TiN into MAX phase Ti 4 AlN 3 Then through molten salt and NiCl 2 Etching the Al layer by Lewis acid salt, and obtaining an intermediate product MXene Ti 4 N 3 The structure is unstable, and the material is in situ converted into more stable-structure accordion-shaped multilayer TiN at high temperature. This innovative strategy solves the stability problem of MXene while maintaining the excellent conductivity and chemical stability of TiN. In addition, the method can synthesize the accordion-shaped TiN rapidly in a large scale, does not need chemical post-treatment, is environment-friendly, and can remove impurities by only needing one magnet. The method provides powerful support for realizing the industrial production and wide application of the accordion-shaped TiN, and predicts that the novel material will show great application potential and market value in a plurality of fields in the future. The accordion-shaped TiN material not only inherits the chemical stability and the electric conductivity of TiN, but also provides the characteristic of high specific surface area through the unique structure. This makes it possible to show great potential for applications in the fields of catalysis, energy storage and sensing, etc., in particular in improving the stability of MXene materials, and to show unique advantages.
Disclosure of Invention
In order to overcome the problems of the MXene material that the chemical instability and the specific surface area are small, and the catalyst activity can not be fully exerted as a catalyst carrier, the invention provides a preparation method and application of multilayer titanium nitride (M-TiN). The invention prepares the multilayer TiN (M-TiN) with the MXene-like accordion structure by a simple preparation method, successfully combines the conductive framework and the high specific surface area of the MXene with the chemical stability and the excellent conductive performance of the TiN, and provides a new solving path for solving the problem of the stability of the MXene. The novel TiN material with unique structure and excellent performance has wide application prospect and huge market potential in the fields of catalysis, energy storage, sensing and the like.
The first object of the present invention is to provide a multilayer titanium nitride which exhibits an accordion-like multilayer structure having a layer spacing of 50 to 300nm and a specific surface area of 20 to 150 m 2 And/g, wherein the surface of the multilayer titanium nitride is provided with an oxide layer, and the X-ray photoelectron spectrum of Ti 2p is provided with the following characteristic peaks: 456.4 + -0.1 eV, 458.2+ -0.1 eV.
Further, the X-ray photoelectron spectrum of Ti 2p has the following characteristic peaks: 456.4 + -0.05 eV, 458.2+ -0.05 eV.
Further, the multilayer titanium nitride has an average pore diameter of 2.2-2.5nm and a specific surface area of 50-100 m 2 /g, preferably 70-90m 2 Preferably 80-90m 2 /g。
Further, the multilayer titanium nitride crystal has a face-centered cubic structure, has a lattice parameter of 4.25 a, belongs to the space group Fm-3m (225), and has a face spacing of 0.245, 0.212, 0.150, 0.128, and 0.123 and nm, respectively.
The multilayer titanium nitride provided by the invention is different from the titanium nitride with the known block structure, and has a multilayer structure similar to an accordion structure. The multilayer structure is a material with large specific surface area and microstructure similar to MXene, but overcomes the chemical instability of MXene materials, has the excellent performance of MXene materials, and solves the instability problems of alkali resistance and oxidation resistance.
The multilayer titanium nitride obtained by the invention has characteristic peaks of 456.4 eV and 458.2 eV corresponding to Ti-N-O and Ti-O respectively through XPS energy spectrum of Ti 2p, but no obvious oxidation phase of M-TiN is observed from XRD test. The atomic ratio of Ti to N to O, as determined by EDS, was about 1:0.94:0.12, confirming that the M-TiN surface was covered with a thin oxide layer. The oxide layer can protect the M-TiN from further oxidation under severe synthesis conditions and strong alkaline solution, so that the M-TiN has more excellent oxidation resistance than the MXene, has more excellent chemical stability, solves the problem that the multilayer MXene is difficult to store under the conditions of decomposition of the strong alkaline solution and air, and has wider application space than the MXene.
The second object of the present invention is to provide a method for preparing the above multilayer titanium nitride, comprising the steps of:
(P1) mixing a nickel source, a sodium source and a potassium source, and grinding to obtain eutectic salt; the nickel source serves as Lewis acid salt to etch the aluminum layer in the titanium aluminum nitride, the melting point of the mixture of the sodium source and the potassium source is far lower than the temperature of the nickel source for etching the aluminum layer, and the mixture of the sodium source and the potassium source can be melted before etching, so that oxygen is isolated, and the severe oxidation of the titanium aluminum nitride is prevented.
(P2) placing titanium aluminum nitride MAX phase material at the bottom of a crucible, and covering the titanium aluminum nitride MAX phase material with the eutectic salt obtained in the step (P1), wherein the dosage proportion of the titanium aluminum nitride MAX phase material and the eutectic salt satisfies the mole ratio of Al in the titanium aluminum nitride MAX phase material to Ni in the eutectic salt as Al: ni=1-8:10, high temperature treatment;
and (P3) cooling the product obtained in the step (P2) to room temperature, washing, magnetic separation, suction filtration and drying to obtain the multilayer TiN.
Further, in the step (P1), the nickel source, sodium source and potassium source are nickel, sodium and potassium salts, preferably metal halogen salts; more specifically, the nickel source is selected from NiF 2 、NiCl 2 、NiBr 2 、NiI 2 At least one of the sodium sources is selected from NaF, naCl, naBr, naI and the potassium source is selected from KF, KCl, KBr, KI; the nickel source, the sodium source and the potassium source are prepared according to the following steps of: na: the molar ratio of K is 1:4-5:4-5.
When the crucible is heated to 550 ℃ or higher in the muffle furnace under an air atmosphere, the nickel source starts etching the titanium aluminum nitride MAX phase. During heating, the sodium source/potassium source/nickel source eutectic salt begins to melt at about 300 c, which is well below the reaction temperature of the nickel source etching MAX phase, so that the liquid molten salt provides a shield separating the titanium aluminum nitride MAX phase from the air.
Further, in step (P2), the titanium aluminum nitride MAX phase material is selected from Ti 4 AlN 3 、Ti 2 AlN、TiAlN、Ti 3 AlN 2 、Ti 6 AlN 5 、Ti 3 At least one of AlN.
Further, in the step (P2), the high temperature treatment is to heat to 550-800 ℃, and the heat preservation treatment is to heat for 20-60min. When the high-temperature treatment is performed, the system is ensured to be sealed, and the rapid evaporation loss of inorganic salt is prevented.
Further, in the step (P3), the washing is to remove the excessive inorganic salt generated during the reaction by washing with deionized water a plurality of times, for example, 3 to 5 times.
Further, in the step (P3), the magnetic separation is to adsorb Ni byproducts generated in the washing process by using a magnet, and the suction filtration is carried out by a sand core funnel, and the process is repeated for 3-5 times until no Ni particles remain at the bottom of the beaker.
Further, in the step (P3), the drying is vacuum drying, for example, drying at 60-80 ℃ for 10-15 hours, and finally obtaining the brown black accordion-shaped multilayer TiN material.
In the post-treatment process of the step (P3), it is necessary to ensure thorough removal of all byproducts during the cleaning stage, avoiding residues of impurities. In the magnetic separation process, all Ni particles are adsorbed by the magnet, and the purity of the product is ensured. In the drying stage, the product is ensured to be completely dried, and the subsequent storage and application are convenient.
The invention innovatively prepares the accordion-shaped multilayer TiN material (M-TiN) with the TiN and MXene conductive frameworks, and the specific technical characteristics are as follows:
in the invention, the M-TiN is prepared by in-situ phase transformation process at high temperature, thus the M-TiN is not provided with high chemical stability, and is not converted into an accordion-shaped multilayer TiN structure with high chemical stability by the non-corrosion MXene, meanwhile, the layered skeleton of the MXene is reserved, the excellent mechanical strength and conductivity of the MXene material are inherited, and meanwhile, the M-TiN also has excellent chemical stability and prolonged service life.
2, M-TiN has higher conductivity. Is suitable for the fields of conductive films, electronic equipment and the like which need high conductive performance.
3, M-TiN maintains the excellent electrochemical activity of MXene, so that it shows excellent performance in energy storage and conversion devices.
The M-TiN has the characteristic of high specific surface area, which is an important advantage for the application fields of catalysts, battery electrode materials and the like, can improve the catalytic activity and the catalytic efficiency, and can improve the battery capacity and the like.
And 5, the preparation process of the M-TiN material does not need chemical post-treatment, is green and environment-friendly, can be quickly synthesized in a large scale, and is easy for industrial production.
Drawings
FIG. 1 is reactant Ti 4 AlN 3 And XRD patterns of the product M-TiN of example 1;
FIG. 2 is an SEM image of a multilayer titanium nitride (M-TiN) and bulk titanium nitride obtained in example 1;
FIG. 3 is a graph showing the adsorption/desorption isotherm (a) and the pore size distribution (b) of nitrogen obtained in example 1 for M-TiN and bulk TiN;
FIG. 4 is a Ti 2p X ray photoelectron spectrum (XPS) of M-TiN obtained in example 1;
FIG. 5 is an elemental distribution diagram of M-TiN obtained in example 1;
FIG. 6 is an SEM image of M-TiN obtained in examples 2-5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
Example 1
1. Mixing and pretreatment: will be anhydrous NiCl 2 : naCl: the KCl mixture was mixed in a molar ratio of 1:5:5 and finely ground in a mortar for 20 minutes to ensure uniform distribution of the mixture.
High temperature reaction: to a certain amount of Ti 4 AlN 3 Powder (Ti) 4 AlN 3 ：NiCl 2 Molar ratio=1:8) is placed at the bottom of an alumina crucible, the eutectic salt uniformly mixed in the previous step is placed in the alumina crucible, and Ti is covered 4 AlN 3 And heating the powder to 750 ℃ in a muffle furnace, and preserving heat for 20min to finish etching of an Al layer and formation of TiN.
Cooling and cleaning: after naturally cooling to room temperature, deionized water was used for 3 times to remove the excess inorganic salts generated during the reaction.
Magnetic separation and filtration: and (3) carrying out suction filtration through a sand core funnel by utilizing Ni byproducts generated in the magnet adsorption flushing process, and repeating for 3 times until no Ni particles remain at the bottom of the beaker.
Drying and obtaining a product: and finally, putting the filtered product into a vacuum drying oven, and drying at 60 ℃ for 12 hours to finally obtain the brownish-black accordion-shaped TiN material with excellent performance.
FIG. 1 is reactant Ti 4 AlN 3 And XRD patterns of the product M-TiN. Ti (Ti) 4 AlN 3 After high temperature reaction, the TiN is completely converted into multilayer TiN. FIG. 1 shows Ti as a hexagonal system of reactants 4 AlN 3 And standard cards with PDF card numbers of 96-152-6339. By comparing raw material Ti 4 AlN 3 The diffraction peaks of the standard card can be found to have extremely high matching degree, and the purity of the reactant can be judged to be high. The products M-TiN and standard cards of TiN in FIG. 1 have PDF card numbers 01-087-0632. By comparing the diffraction peaks of the product M-TiN and the standard card, the matching degree of the diffraction peaks of the product M-TiN and the standard card is extremely high, and Ti in the product 4 AlN 3 The diffraction peak of the by-product Ni completely disappears, so that the synthesized material is basically determined to be TiN-type material and does not contain Ti 4 AlN 3 And impurities of a byproduct Ni, and the purity of the product is extremely high. Diffraction peak of the product is divided by indexing diffraction peaksThe crystal face spacing is 0.245, 0.212, 0.150, 0.128 and 0.123. 0.123 nm corresponding to the crystal faces (111), (200), (220), (311) and (222), respectively, and the crystal lattice is of a face-centered cubic structure, the lattice parameter is 4.25A, and the crystal lattice belongs to a space group Fm-3m (225). At the same time, FIG. 1 also shows the structure of M-TiN after soaking in 6M KOH for 7 days, and the XRD test result is still TiN, indicating that M-TiN is not converted into TiO under strong alkali as Ti-based MXene reported in the literature 2 。
FIG. 2 is an SEM image of multilayer titanium nitride (M-TiN) and bulk titanium nitride. Wherein, (a) is M-TiN, and (b) is bulk TiN. The M-TiN has a unique multi-layer accordion-like structure similar to MXene, and has good ordering among layers, and the layers are flat, smooth, clear and distinguishable, so that the M-TiN not only imitates the structural characteristics of the MXene in appearance, but also has higher chemical and mechanical stability in layer cleanliness. Conventional bulk TiN only shows a general amorphous bulk structure, lacking any specific topographical features. The electron microscopy image of M-TiN further demonstrates that while maintaining the excellent chemical and mechanical stability characteristics of TiN itself, it successfully incorporates the structural advantages of MXene, suggesting its potential enhanced performance in a variety of applications.
FIG. 3 is a nitrogen adsorption and desorption isotherm (a) and pore size distribution diagram (b) of M-TiN and TiN. We performed detailed specific surface area and pore size distribution measurements on modified M-TiN as well as conventional bulk TiN using BET specific surface analyzer. The nitrogen adsorption isotherms of M-TiN and bulk TiN and their pore size distribution are clearly shown. By careful analysis, M-TiN showed the characteristic of a typical type IV adsorption isotherm in the relative pressure range of 0.0 to 1.0, indicating that M-TiN has a composite structure of micropores and mesopores. The specific surface area of the M-TiN is 82.5M g -1 The pore size distribution is a fit obtained by the BJH method and has an average pore size of about 2.44nm. In contrast, the specific surface area of bulk TiN is only 0.990 m g. When etching was performed using 550 ℃, the specific surface area was measured to be 23.2 m g due to incomplete etching of the Al layer -1 When the etching is performed at 800 ℃, the specific surface area of the M-TiN is close to 150M g -1 But oxidizeAnd is more serious. When Ti is used 4 AlN 3 ：NiCl 2 At a molar ratio of=1:4, because NiCl 2 Less, incomplete etching of the Al layer results in less interlayer spacing, a minimum interlayer spacing of 50nm as measured by SEM scale, when Ti is used 4 AlN 3 ：NiCl 2 Molar ratio of = 1:10, al layer is effectively etched, excess Ni 2+ Acting as intercalation ions causes the interlayer spacing to be further enlarged so that the maximum value measured by the scale of SEM image is 300nm. Obviously, the multilayer accordion-like structure of M-TiN significantly increases its specific surface area. The high specific surface area of the multilayer titanium nitride of the invention gives special performance and advantages, and realizes exposure of more active sites, which is of great significance for catalytic reaction. These active sites can provide more reaction opportunities, thereby significantly increasing the activity and reaction rate of the catalyst. Therefore, the multilayer titanium carbide provided by the invention has the unique advantage in a catalyst carrier, an enzyme carrier or other active substance carriers.
When the high-specific-surface-area M-TiN is used as an electrode material of energy storage equipment such as a battery or a super capacitor, the high-specific-surface-area M-TiN directly promotes excellent electrochemical performance, the contact area with electrolyte is increased, the capacitance of the electrode is improved, and the energy storage efficiency is improved. In the electrochemical reaction process, the M-TiN can realize a shorter diffusion path and a faster substance transmission rate due to the large specific surface area, and has important promotion effect on the rapid transmission of protons, electrons and reactants in the catalytic and electrochemical reactions.
The invention adopts a four-probe method to conduct conductivity measurement on the multi-layer accordion-shaped M-TiN and a comparison sample thereof under the constant pressure condition of 3 MPa. The control sample included the reported halogen functionality MXene, i.e., ti, obtained by the same treatment with Lewis acid etching 3 C 2 Cl x 、Ti 3 C 2 Br x And Ti is 4 N 3 Cl x . The measurements revealed that M-TiN significantly preceded other MXene materials with a conductivity of 94.25S/M. Specifically Ti 3 C 2 Br x Is 31.26S/m，Ti 3 C 2 Cl x Is 1.879/S/m, and Ti 4 N 3 Cl x Only 0.05771S/m. This significant difference indicates that despite Ti 3 C 2 Cl x And Ti is 3 C 2 Br x Are all obtained by lewis acid etching, but they are much lower in conductivity than M-TiN. Such differences may result from differences in their interlayer chemical structure, chemical composition, and electron transport properties. The excellent conductivity of M-TiN not only highlights its great potential in the field of electronic materials, but also opens a new door for its potential application in high-end energy conversion and storage facilities. In conclusion, the excellent performance of the M-TiN material in terms of conductivity clearly shows its competitiveness in the high-performance conductive material market.
FIG. 4 is a Ti 2p X ray photoelectron spectrum (XPS) of the multilayer titanium nitride (M-TiN) obtained in example 1. It has a characteristic peak of Ti-O (458.2 eV) and a characteristic peak of Ti-N-O (456.4 ev) in addition to the characteristic peak of conventional TiN. The multilayer titanium nitride obtained by the preparation method of the invention has a thin oxide layer and is a nitrogen oxide compound of titanium or an oxide of titanium.
Ti 2p X ray photoelectron spectroscopy (XPS) showed that exposure to air during synthesis of M-TiN would be unavoidable, resulting in the formation of a thin oxynitride (456.4 ev) or oxide surface layer (458.2 ev), but no significant oxidation phase of M-TiN was observed from XRD testing. The atomic ratio of Ti to N to O, as determined by EDS, was about 1:0.94:0.12, confirming that the M-TiN surface was covered with a thin oxide layer. The oxide layer can protect the M-TiN from further oxidation under severe synthesis conditions and strong alkaline solution, so that the M-TiN has more excellent oxidation resistance than the MXene, has more excellent chemical stability, solves the problem that the multilayer MXene is difficult to store under the conditions of decomposition of the strong alkaline solution and air, and has wider application space than the MXene.
FIG. 5 is an elemental distribution diagram of a multilayer titanium nitride (M-TiN) obtained in example 1. The resulting M-TiN surface may also be demonstrated to have an oxide layer.
Example 2
OthersThe conditions were the same as in example 1, except that NiCl 2 Respectively replacing NaCl and KCl with NiBr with equimolar quantity 2 ，NaBr、KBr；Ti 4 AlN 3 Powder replacement with Ti 2 AlN，Ti 2 AlN is used in an amount such that Ti 2 AlN and NiBr 2 The molar ratio of (2) is 1:8.
Example 3
Other conditions were the same as in example 1 except that the temperature of the high temperature reaction was 550 ℃.
Example 4
Other conditions were the same as in example 1 except that Ti 4 AlN 3 ：NiCl 2 Molar ratio = 1:10.
Example 5
Other conditions were the same as in example 1, except that NiCl 2 : naCl: the KCl mixture was mixed in a molar ratio of 1:4:4.
FIG. 6 is an SEM image of the multilayer carbon nitride obtained in examples 2-5. It can be seen that a multilayer structure similar to the accordion-like structure of example 1 was also successfully produced. Wherein (a), (b), (c) and (d) correspond to example 2, example 3, example 4 and example 5, respectively.
Application example
Weighing the raw materials: first, the active material (M-TiN, or bulk TiN, or MXene prepared in example 1), an acetylene black (ACET) conductive additive, and a polyvinylidene fluoride (PVDF) binder were accurately weighed in a mass ratio of 7:2:1.
Solvent treatment: the PVDF binder was dispersed in an N-methylpyrrolidone (NMP) organic solvent and stirred in a closed bottle for 10 minutes to prevent the solvent from absorbing excessive moisture in the air.
Mixing raw materials: at the same time, the M-TiN/TiN/MXene material and acetylene black were mixed and then ground in an agate mortar for 10 minutes to ensure uniform mixing.
Adding a binder: next, the PVDF binder solution which has been dispersed is poured into an agate mortar containing MAX/MXene and acetylene black, and mixed for further 10 minutes. NMP is added in an appropriate amount as needed to obtain a moderately flowable electrode slurry.
Coating and drying: the mixed electrode paste was uniformly coated on the copper foil by a doctor blade and preheated at 60 c using a heating type coater to remove most of the organic solvent. Subsequently, the coated electrode was transferred to an oven and dried under vacuum at 100 ℃ for 12 hours.
Cutting and weighing: cutting the dried electrode material into round electrode slices with the diameter of 12 mm by using a punching machine. The mass of the active material was calculated by weighing with a high precision balance and the electrode sheet with a mass loading in the range of 0.8 to 1.6 mg/cm was selected for testing.
Storage and protection: after weighing, the electrode plates were transferred as soon as possible into a glove box filled with high purity argon to prevent water absorption and to influence the subsequent test results.
The lithium ion battery test was performed using a button cell battery model CR 2032. The key conditions for battery assembly and testing are as follows:
1, material preparation: a CR2032 type button cell was used, comprising a positive and negative electrode casing, a leaf spring and a gasket. These parts are subjected to ultrasonic cleaning and drying treatment before use.
2, electrode specification: the diameter of the electrode sheet was set to 12 mm.
3, lithium metal sheet: the lithium metal sheet used as the counter electrode and the reference electrode had a diameter of 16 mm and a thickness of 0.6 mm.
4, separator and electrolyte: using a GFA separator with a diameter of 19 mm, the electrolyte was 1M LiPF6 dissolved in a mixed solvent of EC: dmc=1:1.
5, testing environment: all tests were performed in a high purity argon glove box with water and oxygen content less than 0.01 ppm to ensure accuracy and safety of the experiment.
6, battery assembly: the casing of the CR2032 type button cell had a diameter of 20 mm and a thickness of 3.2 mm. This larger volume button cell design can accommodate more electrolyte. The stainless steel gasket is used for supporting the lithium metal sheet with softer texture, ensuring the uniform stress of the lithium metal sheet and avoiding the generation of sharp burrs so as to prevent short circuit. Meanwhile, the spring piece ensures that all components in the battery are in close contact, and dislocation is prevented.
All test materials were electrochemically tested in the form of lithium ion half-cells.
Test parameter setting: the voltage interval of the constant current charge and discharge test is set to 0.01 to 3 volts. Test frequency range of chemical alternating current impedance Spectroscopy (EIS) 10 -2 To 10 6 Hertz.
And (3) battery pretreatment: to ensure adequate wetting of the electrode material and separator, all button cells were left to stand for 12 hours before electrochemical testing was performed. The results are shown in Table 1 below.
TABLE 1 Capacity values of different active materials at 50mA/g current density
。
M-TiN materials exhibit excellent lithium storage properties, mainly due to their MXene-like multilayer structure, which provides convenience for intercalation and deintercalation of lithium ions. Meanwhile, M-TiN exhibits higher chemical stability than conventional MXene materials. In addition, the material has better conductivity than the similar MXene material, so that the material is a material with important application potential in the field of lithium ion batteries.
Claims (8)
1. A multilayer titanium nitride is characterized by exhibiting an accordion-like multilayer structure having an interlayer spacing of 50 to 300nm and a specific surface area of 70 to 90m 2 And/g, wherein the surface of the multilayer titanium nitride is provided with a thin oxide layer, and the X-ray photoelectron spectrum of Ti 2p is provided with the following characteristic peaks: 456.4 + -0.1 eV, 458.2+ -0.1 eV; the atomic ratio of Ti to N to O of the multilayer titanium nitride measured by EDS is 1:0.94:0.12;
the preparation method of the multilayer titanium nitride comprises the following steps:
(P1) mixing a nickel source, a sodium source and a potassium source, and grinding to obtain eutectic salt;
(P2) placing titanium aluminum nitride MAX phase material at the bottom of a crucible, and covering the titanium aluminum nitride MAX phase material with the eutectic salt obtained in the step (P1), wherein the dosage proportion of the titanium aluminum nitride MAX phase material and the eutectic salt satisfies the mole ratio of Al in the titanium aluminum nitride MAX phase material to Ni in the eutectic salt as Al: ni=1-8:10, high temperature treatment;
and (P3) cooling the product obtained in the step (P2) to room temperature, washing, magnetic separation, suction filtration and drying to obtain the multilayer TiN.
2. The multilayer titanium nitride according to claim 1, characterized in that its specific surface area is 80-90m 2 /g。
3. The multilayer titanium nitride according to claim 1, which has a face-centered cubic structure, a lattice parameter of 4.25 a, belongs to space group Fm-3m (225), and has a face spacing of 0.245, 0.212, 0.150, 0.128, 0.123 and nm, respectively.
4. The multilayer titanium nitride according to claim 1, wherein in step (P1), the nickel source, sodium source, potassium source are salts of nickel, sodium, potassium.
5. The multilayer titanium nitride according to claim 4, wherein the nickel source is selected from the group consisting of NiF 2 、NiCl 2 、NiBr 2 、NiI 2 At least one of the sodium sources is selected from NaF, naCl, naBr, naI and the potassium source is selected from KF, KCl, KBr, KI; the nickel source, the sodium source and the potassium source are prepared according to the following steps of: na: the molar ratio of K is 1:4-5:4-5.
6. The multilayer titanium nitride according to claim 1, wherein in step (P2), the titanium aluminum nitride MAX phase material is selected from the group consisting of Ti 4 AlN 3 、Ti 2 AlN、TiAlN、Ti 3 AlN 2 、Ti 6 AlN 5 、Ti 3 At least one of AlN.
7. The multilayer titanium nitride according to claim 1, wherein in step (P2), the high temperature treatment is heating to 550 to 800 ℃ and the heat preservation treatment is performed for 20 to 60 minutes.
8. The multilayer titanium nitride according to claim 1, wherein in step (P3), washing is performed with 3 to 5 times of washing to remove the excessive inorganic salt generated during the reaction; the magnetic separation is to adsorb Ni byproducts generated in the washing process by using a magnet, and the suction filtration is carried out by a sand core funnel, and the process is repeated for 3 to 5 times until no Ni particles remain at the bottom of the beaker; the drying is vacuum drying.
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