CN115872404A - Metal intercalation two-dimensional compound and preparation method thereof - Google Patents
Metal intercalation two-dimensional compound and preparation method thereof Download PDFInfo
- Publication number
- CN115872404A CN115872404A CN202310193194.0A CN202310193194A CN115872404A CN 115872404 A CN115872404 A CN 115872404A CN 202310193194 A CN202310193194 A CN 202310193194A CN 115872404 A CN115872404 A CN 115872404A
- Authority
- CN
- China
- Prior art keywords
- intercalation
- metal
- dimensional compound
- dimensional
- mxene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of two-dimensional nano materials, and relates to a metal intercalation two-dimensional compound and a preparation method thereof. The molecular general formula of the metal intercalation two-dimensional compound is M (n+1)m I m‑1 X nm T x M is selected from any one or any combination of more than two of III B, IV B, V B, VI B and VII B elements, I is an intercalation element, X is carbon or/and nitrogen element, and T is a surface terminal group; wherein n is any number of 1~3, x is any number of 1~3, and m is any number of 2-20. The metal intercalation two-dimensional compound has the stable structure characteristic of MAX phase materials and the abundant surface chemical characteristics of MXene, and has great application prospect in the fields of energy storage, catalysis and the like.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nano materials, and relates to a metal intercalation two-dimensional compound and a preparation method thereof.
Background
Since the discovery of graphene in 2004, the material researchers have attracted considerable attention to other two-dimensional materials. Along with the development of other two-dimensional materials with excellent performance, such as hexagonal boron nitride (h-BN), transition metal sulfides (TMDS), black Phosphorus (BP), two-dimensional transition metal carbonitride (MXene) and the like, the two-dimensional material has a great application prospect in the research fields of catalysis, energy storage, photoelectric devices, spinning electronic devices and the like. The MAX phase is a non-van der Waals layered material with a hexagonal structure, has the characteristics of metal and ceramic due to the unique element composition and structural characteristics, and has good thermal shock resistance and oxidation resistance as well as high electrical conductivity and thermal conductivity of metal. MXene is mainly obtained by selectively etching A-site element of non-van der Waals layered MAX phase precursor material, and its chemical formula is represented as M n+1 X n T x 。T x The MXene material surface termination agent is characterized by representing different surface groups terminated on the surface in the etching process, and the surface groups have obvious influence on the surface chemistry and the physical and chemical properties of the MXene material. However, MXene materials are easily oxidized in an unprotected environment (containing water, oxygen, etc.) due to the presence of active transition metals and structural defects, resulting in poor stability. Therefore, if a two-dimensional structure which has the characteristics of MAX phase structure and has MXene surface end groups can be obtained, the defects of easy oxidation, unstable structure and the like of MXene materials can be effectively avoided, and the excellent physical and chemical properties similar to MXene can be simultaneously achieved. However, the synthesis of such two-dimensional compounds currently faces significant challenges.
Disclosure of Invention
The invention aims to provide a metal intercalation two-dimensional compound and a preparation method thereof aiming at the defects in the prior art.
One purpose of the invention is realized by the following technical scheme:
a metal intercalation two-dimensional compound with a molecular general formula of M (n+1)m I m- 1 X nm T x M is selected from any one or more than two of III B, IV B, V B, VI B and VII B elementsIn the synthesis, I is an intercalation element, X is carbon or/and nitrogen element, and T is a surface terminal group; wherein n is any number of 1~3, x is any number of 1~3, and m is any number of 2-20.
Preferably, m is an arbitrary number from 2 to 10.
In the metal intercalation two-dimensional compound, M is an early transition metal element, including but not limited to any one or any combination of two or more of Ti, V, nb, mn, Y, zr, cr, mo, hf, ta and W.
Preferably, M is any one of Ti, nb, and Ta, or any combination of two or more thereof.
In the metal intercalation two-dimensional compound, I includes but is not limited to any one or any combination of two or more of Al, ga, ge, in, sn, bi, fe, co, ni, cu, zn, pd, ir, au and Cd.
Preferably, I is any one or any combination of two or more of Al, ga, sn, fe, cu, zn and Cd.
Preferably, X is C a N b Wherein the sum of a and b is any number of 1~3.
In the above-mentioned metal-intercalated two-dimensional compound, T includes but is not limited to any one or any combination of two or more of-Cl, -Br, -I, -F, -O, -OH, -S, -Se, -Te, -P and-Sb.
Preferably, T is any one or any combination of two or more of-Cl, -Br, -I and-F.
Preferably, the metal intercalation two-dimensional compound is M (n+1)m X nm The structural unit and the I atomic layer are alternately stacked, wherein M is (n+1)m X nm The surface of the structural unit is connected with a surface terminal group T.
In the metal intercalation two-dimensional compound, the metal intercalation two-dimensional compound is a two-dimensional sheet, and the thickness of the two-dimensional sheet is 1 to 50nm, preferably 1 to 20nm, more preferably 1 to 15nm, 1 to 10nm, 1 to 5nm, 2 to 20nm, 2 to 15nm, 2 to 10nm, 3 to 20nm, 3 to 15nm, 3 to 10nm, and the like.
The other purpose of the invention is realized by the following technical scheme:
a preparation method of a metal intercalation two-dimensional compound comprises the following steps:
s1, etching treatment: etching the MAX phase material by a Lewis acid molten salt method to obtain an MXene material;
s2, intercalation treatment: mixing the obtained MXene material, metal 'scissors' elements, intercalation elements or compounds containing the intercalation elements and inorganic salt, and reacting to obtain a primary intercalation MAX phase material;
and S3, repeating the etching treatment and the intercalation treatment to obtain the metal intercalation two-dimensional compound.
In the above preparation method of the metal intercalation two-dimensional compound, the lewis acid molten salt method of step S1 specifically includes the following steps: mixing MAX phase material, lewis acid salt and halide salt, reacting at 400-900 ℃, and then washing, filtering and drying to obtain MXene material.
Lewis acid salts include, but are not limited to FeO, coO, niO, cuO, znO, feCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 、CdCl 2 、FeBr 2 、CoBr 2 、NiBr 2 、ZnBr 2 、FeI 2 、CoI 2 、NiI 2 、CdI 2 、AgI、FeSO 4 、CoSO 4 、NiSO 4 、CdSO 4 Any one of or any combination of two or more of them.
In the preparation method of the metal intercalation two-dimensional compound, the preferable molar ratio of the MXene material, the metal 'scissors' element, the intercalation element or the compound containing the intercalation element and the inorganic salt is 1: (0.5 to 3): (0.5 to 3): (5 to 50).
In the preparation method of the metal intercalation two-dimensional compound, the general formula of the MXene material is M n+1 X n T' y Wherein, the M element is the same as the M element in the molecular general formula of the metal intercalation two-dimensional compound, the X element is the same as the X element in the molecular general formula of the metal intercalation two-dimensional compound, the value of n is the same as the value of n in the molecular general formula of the metal intercalation two-dimensional compound, T' is any one or any combination of more than two of-Cl, -Br, -I, -F, -O and-OH, y is 1~3Any number.
In the above preparation method of the metal intercalation two-dimensional compound, the metal "scissors" element includes but is not limited to any one or any combination of two or more of Li, na, K, mg, ca, al, ga, ge, in and Sn.
In the preparation method of the metal intercalation two-dimensional compound, the intercalation element includes but is not limited to any one or any combination of more than two of Al, ga, ge, in, sn, bi, fe, co, ni, cu, zn, pd, ir, au and Cd.
In the above method for producing a metal-intercalated two-dimensional compound, the inorganic salt is preferably a metal halide salt of a halogen element and a metal element, and examples of the metal element include Na, K, li, mg, ca, and the like. Preferably, the inorganic salt includes but is not limited to any one or more of NaF, liCl, naCl, KCl, naBr, KBr, KI and NaI. In the preparation method of the metal intercalation two-dimensional compound, the halogen end group and M (n+1)m X nm The structural units are connected so as to intercalate M of the two-dimensional compound in the metal (n+1) m X nm The surface of the structural unit is terminated with any one or any combination of more than two of surface end groups of-Cl, -Br, -I and-F.
In the preparation method of the metal intercalation two-dimensional compound, the reaction temperature in the step S2 is 400-900 ℃, and the reaction time is 4-15h.
In the preparation method of the metal intercalation two-dimensional compound, the step S3 preferably repeats the etching treatment and the intercalation treatment for 2 to 10 times, and more preferably 2~5 times.
Because the metal 'scissors' element has stronger reducibility, the metal 'scissors' element can react with the end group of MXene and knock the end group out of the MXene surface, MX layers are opened after the end group is knocked out, and the intercalation element atoms can enter the layers of the MX layers through intercalation reaction to obtain an intercalation product, but the surface of the intercalation product sheet layer can be terminated with the end group in the molten salt again, so that a new surface end group is generated on the surface of the intercalation product. The thinning of the sheet layer can be gradually realized by repeating the etching and intercalation processes, and new surface end groups are generated in each thinning process, so that the metal intercalation two-dimensional compound is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a novel metal intercalation two-dimensional compound for the first time, and the two-dimensional compound has rich element composition and has the stable structure characteristic of MAX phase materials and the rich surface chemical characteristic of MXene;
2. the metal intercalation two-dimensional compound is a two-dimensional lamellar structure, and compared with a two-dimensional MXene material, the two-dimensional structure effectively improves the structural stability;
3. the metal intercalation two-dimensional compound is obtained by repeatedly carrying out special etching treatment and special intercalation treatment to gradually thin the sheet layer;
4. in the intercalation treatment process, metal 'scissors' elements are adopted to remove end groups, so that the intercalation elements are promoted to enter MX layers, the end groups in molten salt are promoted to be terminated on the surface of an intercalation product through a molten salt environment provided by inorganic salt, and a new surface end group is generated on the surface of the intercalation product;
5. the metal intercalation two-dimensional compound can be used for regulating and controlling different structures and elements, realizes the regulation and control of the physicochemical properties, and has great application prospect in the fields of energy storage, catalysis and the like
Drawings
FIG. 1 is a schematic diagram of an etching/intercalation process in example 1 of the present invention;
FIG. 2 is an XRD pattern corresponding to a triple etch/intercalation product in example 1 of the present invention;
FIG. 3 shows Ti as a primary intercalation product in example 1 of the present invention 3m’ Al m’-1 C 2m’ T x SEM picture of (1);
FIG. 4 shows a secondary intercalation product Ti in example 1 of the present invention 3m’’ Al m’’-1 C 2m’’ T x SEM picture of (1);
FIG. 5 shows a three-etching product Ti in example 1 of the present invention 3 C 2 Cl 2 A TEM image of (D);
FIG. 6 shows a triple intercalation product Ti in example 1 of the present invention 3m Al m-1 C 2m T x SEM picture of (1);
FIG. 7 is a low power TEM image of a triple intercalation product in example 1 of the present invention;
FIG. 8 shows a triple intercalation product Ti in example 2 of the present invention 3m Sn m-1 C 2m T x XRD pattern of (a);
FIG. 9 shows a triple intercalation product Ti in example 2 of the present invention 3m Sn m-1 C 2m T x SEM picture of (1);
FIG. 10 shows a triple intercalation product Ti in example 2 of the present invention 3m Sn m-1 C 2m T x SEM-EDS diagram of (1);
FIG. 11 shows a triple intercalation product Ti in example 2 of the present invention 3m Sn m-1 C 2m T x Bright field STEM map of (a);
FIG. 12 shows a triple intercalation product Ti in example 2 of the present invention 3m Sn m-1 C 2m T x The atom-resolved STEM map and the corresponding atomic structure model map.
Detailed Description
The technical solutions of the present invention are further described below by way of specific embodiments and drawings, it should be understood that the specific embodiments described herein are only for the purpose of facilitating understanding of the present invention, and are not intended to be specific limitations of the present invention. And the drawings used herein are for the purpose of illustrating the disclosure better and are not intended to limit the scope of the invention. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
(1) Adding MAX phase material Ti 3 AlC 2 Powder, cdCl 2 Powder, naCl and KCl according to a molar ratio of 1:3:10:10, fully grinding and mixing to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing the reaction product with 2mol/L hydrochloric acid solution to remove inorganic substancesSalt NaCl, KCl and Cd metal elementary substance generated by reaction, and finally carrying out suction filtration and drying to obtain primary etched Ti 3 C 2 Cl 2 MXene powder.
(2) Will etch Ti once 3 C 2 Cl 2 MXene powder, al powder, naCl and KCl in a molar ratio of 1:3:10:10, fully grinding to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing the reaction product with 2mol/L hydrochloric acid solution to remove inorganic salts NaCl, KCl and unreacted Al metal simple substance, and finally performing suction filtration and drying to obtain Ti with thick primary intercalation layer 3m’ Al m’-1 C 2m’ T x And (3) powder. Because the thickness of the lamella of the primary intercalation is thicker, namely the m' value is larger, the lamella does not have the two-dimensional lamella characteristic.
(3) By inserting Ti in one step 3m’ Al m’-1 C 2m’ T x The powder is taken as a precursor material, and secondary etching treatment is carried out again according to the method in the step (1) to obtain secondary etching Ti 3 C 2 Cl 2 MXene powder; then, ti is etched twice 3 C 2 Cl 2 MXene powder is used as a precursor, and secondary intercalation Ti is obtained by carrying out secondary intercalation according to the method in the step (2) 3m’’ Al m’’-1 C 2m’’ T x And (3) powder. The lamellae of the secondary intercalation product are thinned, i.e. m ', compared to the lamellae of the primary intercalation product'<m’。
(4) Inserting Ti into the layer twice 3m’’ Al m’’-1 C 2m’’ T x Taking the powder as a precursor material, and carrying out third etching treatment again according to the method in the step (1) to obtain third etched Ti 3 C 2 Cl 2 MXene powder; then three times etching Ti 3 C 2 Cl 2 MXene powder is used as a precursor, and the third intercalation product is obtained according to the method in the step (2), namely the metal intercalation two-dimensional compound Ti 3m Al m-1 C 2m T x Wherein m is<m’’<m', m is a number of 2 to 20, and x is a number of 1~3.
Etching treatment in step (1) As shown in a to b of FIG. 1, MAX phase material Ti is subjected to Lewis acid molten salt deposition 3 AlC 2 Al atoms in the MXene are removed by etching to obtain the MXene material Ti with the surface having end group Cl 3 C 2 Cl 2 (ii) a The intercalation process of step (2) is shown in fig. 1 b to c, where Al diffuses into MXene material Ti 3 C 2 Cl 2 Further reacts with exposed Ti atoms at M position and effects healing of the van der Waals gap to obtain Ti 3m’ Al m’-1 C 2m’ T x 。
The different etched and intercalated products of example 1 were analyzed by X-ray diffraction spectroscopy (XRD) as shown in fig. 2. (0002) The structural evolution of the whole etching/intercalation process is proved by the change of characteristic peaks of the (0004) surface and the (0002) surface, and the intensity of the characteristic peaks of the (0004) surface is reduced along with the increase of the etching/intercalation times, so that the lamella becomes thinner along with the increase of the whole etching/intercalation times. FIG. 3 shows a primary intercalation product Ti 3m’ Al m’-1 C 2m’ T x The particles can be observed to have the shape of an MXene typical 'accordion' through a Scanning Electron Microscope (SEM) picture, and the condition that the Al atom intercalation only occurs in Ti 3 C 2 Cl 2 The MXene has van der Waals gaps, so that the large gaps generated by one time of etching of the MXene cannot be healed, and finally, the MXene has the appearance of the same 'accordion' shape. FIG. 4 is an SEM image of a secondary intercalation product, and it can be observed that further exfoliation was generated on the particle surface compared to the primary intercalation product. FIG. 5 shows a three-time etching product Ti 3 C 2 Cl 2 TEM image of MXene particle cross section, it can be observed that after three etches it forms a two-dimensional lamellar stacking structure, indicating that significant lamellar thinning occurs by the three etches. FIG. 6 is an SEM image of a triple intercalation product, and it can be observed that the particles thereof produce a significant exfoliation effect compared to a single intercalation; further TEM observation of the particle cross section (FIG. 7) was carried outAnd observing an obvious two-dimensional lamellar stacking structure, wherein the two-dimensional lamellar is a metal intercalation two-dimensional compound, and the thickness of the metal intercalation two-dimensional compound is about 2 to 20nm.
Example 2
(1) Adding a MAX phase Ti 3 AlC 2 Powder, cdCl 2 Powder, naCl and KCl according to a molar ratio of 1:3:10:10, fully grinding and mixing to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing the reaction product with 2mol/L hydrochloric acid solution to remove inorganic salts NaCl, KCl and Cd metal simple substance generated by the reaction, and finally performing suction filtration and drying to obtain primary etched Ti 3 C 2 Cl 2 MXene powder.
(2) Will etch Ti once 3 C 2 Cl 2 MXene powder, al powder, naCl and KCl in a molar ratio of 1:3:10:10, fully grinding to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing off inorganic salts NaCl, KCl and unreacted Al metal simple substances from the reaction product by using 2mol/L hydrochloric acid solution, and finally performing suction filtration and drying to obtain primary intercalation Ti 3m’ Al m’-1 C 2m’ T x And (3) powder.
(3) By inserting Ti in one step 3m’ Al m’-1 C 2m’ T x The powder is taken as a precursor material, and secondary etching treatment is carried out again according to the method in the step (1) to obtain secondary etching Ti 3 C 2 Cl 2 MXene powder; then, ti is etched twice 3 C 2 Cl 2 MXene powder is used as a precursor, and secondary intercalation Ti is obtained by carrying out secondary intercalation according to the method in the step (2) 3m’’ Al m’’-1 C 2m’’ T x And (3) powder.
(4) Inserting Ti into the layer twice 3m’’ Al m’’-1 C 2m’’ T x The powder is taken as a precursor material, and third etching treatment is carried out again according to the method in the step (1) to obtain third etched Ti 3 C 2 Cl 2 MXene powder.
(5) Etching three times to Ti 3 C 2 Cl 2 MXene powder, al powder, sn powder, naCl and KCl according to a molar ratio of 1:2:2:10:10, fully grinding (the molar content of Al is small, the Al is consumed as a metal 'scissors' element, and the metal 'scissors' element cannot be inserted into an MX layer) to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere, and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing the reaction product with 2mol/L hydrochloric acid solution to remove inorganic salts NaCl, KCl and unreacted Al and Sn metal simple substances, and finally performing suction filtration and drying to obtain a three-time intercalation product, namely a metal intercalation two-dimensional compound Ti 3m Sn m-1 C 2m T x Wherein m is<m’’<m', m is a number of 2 to 20, and x is a number of 1~3.
FIG. 8 shows a triple intercalation product Ti 3m Sn m-1 C 2m T x XRD pattern of the powder, from which Ti was observed 3m Sn m-1 C 2m T x Corresponding characteristic peak proves Ti 3m Sn m-1 C 2m T x And (4) generating. In addition, higher Al contents were also detected 2 O 3 Peak, indicating Al formation during the reaction 2 O 3 This is due to oxidation of the surface layer of the Al used. FIG. 9 shows Ti triple intercalation 3m Sn m-1 C 2m T x In the SEM image of the powder, the morphology of the powder stripped after multiple etching/intercalation can be observed to be a two-dimensional lamellar stacking morphology. Analysis of the particle elements of the reaction product by SEM-EDS (FIG. 10) revealed that the presence of Cl elements was observed, indicating that-Cl terminal groups were also formed during the stripping process. The bright field STEM map (fig. 11) demonstrates the effective exfoliation of its lamellae, resulting in a two-dimensional structure. Further analysis of the atomic structure by atom-resolved STEM (fig. 12) demonstrated the presence of-Cl end groups on the surface of the metal intercalated two-dimensional compound.
Example 3
(1) Adding a MAX phase Ti 2 AlC powder and CdCl 2 Powder, naCl and KCl according to a molar ratio of 1:3:10:10, fully grinding and mixing to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing off inorganic salts NaCl and KCl and Cd metal simple substance generated by reaction from reaction products by using 2mol/L hydrochloric acid solution, and finally performing suction filtration and drying to obtain primary etching Ti 2 CCl 2 MXene powder.
(2) Will etch Ti once 2 CCl 2 MXene powder, al powder, naCl and KCl in a molar ratio of 1:3:10:10, fully grinding to obtain mixed powder; putting the mixed powder into an alumina crucible, then putting the alumina crucible into a high-temperature vacuum tube furnace to react for 5 hours at 700 ℃ under the protection of inert atmosphere (argon), and taking out the alumina crucible after the sintering temperature is reduced to room temperature; washing the reaction product with 2mol/L hydrochloric acid solution to remove inorganic salts NaCl, KCl and unreacted Al metal simple substance, and finally performing suction filtration to obtain primary intercalation Ti 2m’ Al m’-1 C m’ T x And (3) powder.
(3) By inserting Ti in one step 2m’ Al m’-1 C m’ T x The powder is taken as a precursor material, and secondary etching treatment is carried out again according to the method in the step (1) to obtain secondary etching Ti 2 CCl 2 MXene powder; then, ti is etched twice 2 CCl 2 MXene powder is used as a precursor, and secondary Al intercalation Ti is obtained by carrying out secondary intercalation according to the method in the step (2) 2m’’ Al m’’-1 C m’’ T x And (3) powder.
(4) Inserting Ti into the layer twice 2m’’ Al m’’-1 C m’’ T x Taking the powder as a precursor material, and carrying out third etching treatment again according to the method in the step (1) to obtain third etched Ti 2 CCl 2 MXene powder; then etching Ti three times 2 C 2 Cl 2 MXene powder is used as a precursor, and the third intercalation product is obtained according to the method in the step (2), namely the metal intercalation two-dimensional compound Ti 2m Al m-1 C m T x Wherein m is<m’’<m', m is a number of 2 to 20, and x is a number of 1~3.
The aspects, embodiments, features of the present invention should be considered in all respects as illustrative and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In the preparation method of the present invention, the order of the steps is not limited to the listed order, and for those skilled in the art, the order of the steps is not changed without creative efforts, and the invention is also within the protection scope of the present invention. Further, two or more steps or actions may be performed simultaneously.
Finally, it should be noted that the specific examples described herein are merely illustrative of the spirit of the invention and do not limit the embodiments of the invention. Various modifications, additions and substitutions for the embodiments described herein will occur to those skilled in the art, and all such embodiments are neither required nor possible. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (10)
1. The metal intercalation two-dimensional compound is characterized in that the molecular general formula of the metal intercalation two-dimensional compound is M (n+1)m I m-1 X nm T x M is selected from any one or any combination of more than two of III B, IV B, V B, VI B and VII B elements, I is an intercalation element, X is carbon or/and nitrogen element, and T is a surface terminal group; wherein n is any number of 1~3, x is any number of 1~3, and m is any number of 2-20And (4) counting.
2. The metal intercalation two-dimensional compound of claim 1, wherein the metal intercalation two-dimensional compound is M (n+1)m X nm The structural unit and the I atomic layer are alternately stacked, wherein M is (n+1)m X nm The surface of the structural unit is connected with a surface terminal group T.
3. The metal intercalation two-dimensional compound according to claim 2, wherein the metal intercalation two-dimensional compound is in a two-dimensional sheet shape, and the thickness of the two-dimensional sheet is 1 to 50nm.
4. A metal intercalated two-dimensional compound according to claim 1 or 2 wherein M comprises any one or any combination of two or more of Ti, V, nb, mn, Y, zr, cr, mo, hf, ta, W.
5. A metal intercalated two-dimensional compound according to claim 1 or 2 wherein I comprises any one or any combination of two or more of Al, ga, ge, in, sn, bi, fe, co, ni, cu, zn, pd, ir, au, cd.
6. A metal intercalation two-dimensional compound according to claim 1 or 2, wherein T comprises any one or any combination of two or more of-Cl, -Br, -I, -F, -O, -OH, -S, -Se, -Te, -P, -Sb.
7. The process of claim 1, comprising the steps of:
s1, etching treatment: etching the MAX phase material by a Lewis acid molten salt method to obtain an MXene material;
s2, intercalation treatment: mixing the obtained MXene material, metal 'scissors' elements, intercalation elements or compounds containing the intercalation elements and inorganic salt, and reacting to obtain a primary intercalation MAX phase material;
and S3, repeating the etching treatment and the intercalation treatment to obtain the metal intercalation two-dimensional compound.
8. The process according to claim 7, wherein the molar ratio of MXene material, metal "scissors" element, intercalation element or compound containing intercalation element, inorganic salt is 1: (0.5 to 3): (0.5 to 3): (5 to 50).
9. The method of claim 7, wherein the metallic "scissors" elements comprise any one or any combination of two or more of Li, na, K, mg, ca, al, ga, ge, in, sn.
10. The production method according to claim 7, wherein the reaction temperature in the step S2 is from 400 to 900 ℃, and the reaction time is from 4 to 15h;
and/or in the step S3, repeating the etching treatment and the intercalation treatment for 2 to 10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310193194.0A CN115872404B (en) | 2023-03-03 | 2023-03-03 | Metal intercalation two-dimensional compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310193194.0A CN115872404B (en) | 2023-03-03 | 2023-03-03 | Metal intercalation two-dimensional compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115872404A true CN115872404A (en) | 2023-03-31 |
| CN115872404B CN115872404B (en) | 2023-07-11 |
Family
ID=85761807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310193194.0A Active CN115872404B (en) | 2023-03-03 | 2023-03-03 | Metal intercalation two-dimensional compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115872404B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN109437172A (en) * | 2018-10-09 | 2019-03-08 | 武汉科技大学 | A kind of sodium ion intercalation Ti3C2MXene material and preparation method thereof |
| CN112125307A (en) * | 2020-09-24 | 2020-12-25 | 北京大学 | Preparation method and application of manganese ion intercalated and nitrided MXene |
| CN112591752A (en) * | 2020-12-30 | 2021-04-02 | 松山湖材料实验室 | Rapid preparation of V by molten salt chemical reaction2AlC powder preparation method and powder application thereof |
| CN113113597A (en) * | 2020-01-13 | 2021-07-13 | 中国科学院宁波材料技术与工程研究所 | Novel MAX phase material for lithium ion battery anode and preparation method thereof |
| CN114835120A (en) * | 2021-01-30 | 2022-08-02 | 苏州北科纳米科技有限公司 | Preparation method for synthesizing MXene by element replacement MAX phase |
-
2023
- 2023-03-03 CN CN202310193194.0A patent/CN115872404B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN109437172A (en) * | 2018-10-09 | 2019-03-08 | 武汉科技大学 | A kind of sodium ion intercalation Ti3C2MXene material and preparation method thereof |
| CN113113597A (en) * | 2020-01-13 | 2021-07-13 | 中国科学院宁波材料技术与工程研究所 | Novel MAX phase material for lithium ion battery anode and preparation method thereof |
| CN112125307A (en) * | 2020-09-24 | 2020-12-25 | 北京大学 | Preparation method and application of manganese ion intercalated and nitrided MXene |
| CN112591752A (en) * | 2020-12-30 | 2021-04-02 | 松山湖材料实验室 | Rapid preparation of V by molten salt chemical reaction2AlC powder preparation method and powder application thereof |
| CN114835120A (en) * | 2021-01-30 | 2022-08-02 | 苏州北科纳米科技有限公司 | Preparation method for synthesizing MXene by element replacement MAX phase |
Non-Patent Citations (3)
| Title |
|---|
| AROLE, K ET AL.: "Water-dispersible T3C2Tz MXene nanosheets by molten salt etching", 《ISCIENCE》 * |
| CHEN, NJ ET AL.: "Tailoring Ti3CNTx MXene via an acid molecular scissor", 《NANO ENERGY》 * |
| 李超;杨磊;邹云麒;严明;: "NaF-KF熔盐体系制备Ti_2CT_x材料的研究", 陶瓷学报 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115872404B (en) | 2023-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ronchi et al. | Synthesis, structure, properties and applications of MXenes: Current status and perspectives | |
| Bhatt et al. | High capacity conversion anodes in Li-ion batteries: A review | |
| Tan et al. | Vanadium-based nanostructure materials for secondary lithium battery applications | |
| JP6987764B2 (en) | Lithium nickelate positive electrode active material particle powder and its manufacturing method, and non-aqueous electrolyte secondary battery | |
| Huang et al. | Recent advances and perspectives of lewis acidic etching route: an emerging preparation strategy for MXenes | |
| Xu et al. | Toward emerging two-dimensional nickel-based materials for electrochemical energy storage: Progress and perspectives | |
| Hu et al. | Improve the electrochemical performances of Cr2O3 anode for lithium ion batteries | |
| Xu et al. | A rising 2D star: novel MBenes with excellent performance in energy conversion and storage | |
| Deng et al. | Transition metal oxides based on conversion reaction for sodium-ion battery anodes | |
| TWI576312B (en) | Manganese-bearing metal phosphates and process for the production thereof | |
| Lou et al. | Novel one-step gas-phase reaction synthesis of transition metal sulfide nanoparticles embedded in carbon matrices for reversible lithium storage | |
| CN106892407B (en) | A kind of two-dimensional ultrathin duplex metal hydroxide nanometer piece and preparation method thereof | |
| CN110540236A (en) | MXene material and preparation method and application thereof | |
| CN101024249A (en) | Fine nickel powder and process for producing the same | |
| CN113206230B (en) | Carbon-coated Prussian blue or analogue thereof, and preparation and application thereof | |
| Jing et al. | Constructing tunable core-shell Co5Ge3@ Co nanoparticles on reduced graphene oxide by an interfacial bonding promoted Kirkendall effect for high lithium storage performances | |
| Liang et al. | Synthesis and characterisation of SnO2 nano-single crystals as anode materials for lithium-ion batteries | |
| CN114349006B (en) | Surface modification method of MXene material | |
| Zhu et al. | Carbon-confined ultrasmall T-Nb 2 O 5 nanocrystals anchored on carbon nanotubes by pyrolysing MLD-niobiumcone films for enhanced electrochemical applications | |
| CN114284477A (en) | TiO preparation based on two colloidal solution self-assembly methods2Method and use of/MXene heterostructure | |
| Jaramillo-Cabanzo et al. | One-dimensional nanomaterials in lithium-ion batteries | |
| CN115872404A (en) | Metal intercalation two-dimensional compound and preparation method thereof | |
| Zhang et al. | Fabrication of nanosized metallic copper by electrochemical milling process | |
| Wang et al. | Mesocrystalline effect in a NiTiO 3/TiO 2 nanocomposite for enhanced capacity of lithium-ion battery anodes | |
| CN116960335A (en) | Sodium ion battery positive plate, preparation method thereof and sodium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |