CN116715527A - Nitrogen-containing high-entropy MXene two-dimensional material, application thereof, battery diaphragm, composite aluminum foil, positive plate and battery - Google Patents
Nitrogen-containing high-entropy MXene two-dimensional material, application thereof, battery diaphragm, composite aluminum foil, positive plate and battery Download PDFInfo
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- CN116715527A CN116715527A CN202310499301.2A CN202310499301A CN116715527A CN 116715527 A CN116715527 A CN 116715527A CN 202310499301 A CN202310499301 A CN 202310499301A CN 116715527 A CN116715527 A CN 116715527A
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000000463 material Substances 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 title claims description 25
- 239000011888 foil Substances 0.000 title claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 22
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000012512 characterization method Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims 5
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 101100289192 Pseudomonas fragi lips gene Proteins 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 210000000088 lip Anatomy 0.000 abstract description 6
- 229910003003 Li-S Inorganic materials 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 27
- 239000005077 polysulfide Substances 0.000 description 22
- 229920001021 polysulfide Polymers 0.000 description 22
- 150000008117 polysulfides Polymers 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 21
- 238000000227 grinding Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
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- 239000002184 metal Substances 0.000 description 11
- 229910018091 Li 2 S Inorganic materials 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
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- 239000002243 precursor Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000013068 control sample Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- KOMLXUNAWWFLRU-UHFFFAOYSA-N lithium;trifluoromethanesulfonamide Chemical compound [Li].NS(=O)(=O)C(F)(F)F.NS(=O)(=O)C(F)(F)F KOMLXUNAWWFLRU-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 235000002639 sodium chloride Nutrition 0.000 description 1
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Classifications
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- H01M10/052—Li-accumulators
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3865—Aluminium nitrides
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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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
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Abstract
The application discloses a nitrogen-containing high-entropy MXene two-dimensional material, application thereof, a battery diaphragm and composite aluminumThe nitrogen-containing high-entropy MXene two-dimensional material comprises M ' and X elements, wherein M ' is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB groups, X is C and N elements, and X-ray photoelectron spectroscopy (XPS) characterization of the nitrogen-containing high-entropy MXene two-dimensional material contains M ' -N bonds. Under the action of mechanical strain and more than five metal-N bonds, the nitrogen-containing high-entropy MXene shows good adsorption and catalytic capability on LiPSs, and shows high Li 2 The S deposition capacity is applied to a lithium sulfur battery, and high rate performance and long cycle life are realized in the Li-S battery.
Description
The application relates to a divisional application, and the main application is an application patent application of which the application date is 2021, 12, 16, 202111546949.8 and the application name is nitrogen-containing high-entropy MXene with a sulfur catalytic function, a diaphragm composite material and a battery.
The parent application claims part of the priority of China patent application filed to China patent office on the 5 th month 21 of 2021, with the application number of 202110560272.7, the application name of "nitrogen-containing middle-entropy or high-entropy MAX phase material, and preparation method and application thereof", with the application number of 202110560245.X, and the application name of "preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material", part of the contents of both applications are incorporated herein by reference.
Technical Field
The application relates to the field of new materials, in particular to application of high-entropy MXene in a battery, and more particularly relates to a nitrogen-containing high-entropy MXene two-dimensional material and application thereof, a battery diaphragm, a composite aluminum foil, a positive plate and a battery.
Background
High Entropy Materials (HEMs) have great potential in the field of energy storage and conversion due to the diversity of their compositions and unexpected physicochemical properties. All HEMs reported at present are 3D blocky, and have strong chemical bonds in the HEMs, so that the atomic layer stripping is difficult and heavy. In addition, in the traditional synthesis process such as pyrometallurgy, the phases in the high-entropy atomic layer are easy to separate due to the reduction of the mixing entropy.
In recent years, researchers have found that M-site doping of a variety of transition metal atoms in the MAX phase, also known as M, can be a way to synthesize high entropy materials n+1 AX n (n=1, 2, 3), wherein M represents an early transition metal element, a is mainly an element from groups 13 to 16, and X represents C and/or N. In the previous research work, the inventor successfully synthesizes and obtains high-entropy MAX phase materials, such as: article Advanced Materials 2021,33 (39): 2101473, reports high entropy nitride Ti 1/5 V 1/5 Zr 1/5 Nb 1/5 Ta 1/5 ) 2 AlC, patent CN202110560272 discloses a high entropy carbon nitrogen compound (Ti 1/3 V 1/6 Zr 1/ 6 Nb 1/6 Ta 1/6 ) 2 AlC x N 1-x And the like, and the high-entropy MXene two-dimensional Material (MX) is further synthesized by etching the A component, such as: (Ti) 1/5 V 1/5 Zr 1/5 Nb 1/5 Ta 1/5 ) 2 C、(Ti 1/3 V 1/6 Zr 1/6 Nb 1/6 Ta 1/6 ) 2 C x N 1-x Etc.; wherein the five transition metal species are uniformly dispersed in the MX layer based on solid solution characteristics. Thanks to the high molar configuration entropy and the corresponding low gibbs free energy, the five size compatible transition metal elements stabilize the MXene in the atomic layer, and the resulting high entropy MXene exhibits significant lattice distortion, resulting in high mechanical strain in the atomic layer. How to utilize the special physical and chemical properties of the novel high-entropy MXene two-dimensional material to apply the material to industryIn production and life, the development of value is the problem to be solved next.
Disclosure of Invention
The application aims to provide an application of nitrogen-containing high-entropy MXene in a battery, which is applied to a lithium-sulfur battery by utilizing high mechanical strain characteristics of the high-entropy MXene and high sulfur-promoting catalytic activity cooperatively generated by transition metal-nitrogen chemical bonds.
The application provides a nitrogen-containing high-entropy MXene two-dimensional material, which comprises M ' and X elements, wherein M ' is at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB groups, X is C and N elements, and X-ray photoelectron spectroscopy (XPS) of the nitrogen-containing high-entropy MXene two-dimensional material is characterized by containing M ' -N bonds.
In some embodiments, the X-ray photoelectron spectroscopy (XPS) characterization of the nitrogen-containing high entropy MXene two-dimensional material contains M' -C bonds.
In some embodiments, the X-ray diffraction test (XRD) characterization of the nitrogen-containing high entropy MXene two-dimensional material contains a (002) peak.
In some embodiments, the M' is selected from five or more of the Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, pd, au, ag, cu elements.
In some embodiments, the M' is selected from Ti, zr, V, nb, ta, cr.
In some embodiments, the nitrogen-containing high entropy MXene two-dimensional material contains a functional group.
The second aspect of the application provides a use of the nitrogen-containing high-entropy MXene two-dimensional material for a lithium-sulfur battery.
The third aspect of the application provides an application of a nitrogen-containing high-entropy MXene two-dimensional material for a lithium sulfur battery, wherein the chemical formula of the nitrogen-containing high-entropy MXene two-dimensional material is represented as M' n+1 X n T x Wherein M is selected from at least five of Ti, zr, V, nb, ta, cr elements, X is carbon and nitrogen, T is a functional group, and n is 1,2 or 3.
In some embodiments, the chemical formula of the nitrogen-containing high entropy MXene two-dimensional material is represented by at least one of the following:
(Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 3 CNT x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 2 C 0.5 N 0.5 T x 、(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 3 CNT x 、
(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 4 C 1.5 N 1.5 T x 、(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、
(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 3 CNT x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 。
the fourth aspect of the present application provides the above nitrogen-containing high-entropy MXene two-dimensional material, or the nitrogen-containing high-entropy MXene two-dimensional material used in the above application, and the preparation method of the nitrogen-containing high-entropy MXene two-dimensional material, comprising the steps of: etching the nitrogen-containing high entropy M' AX phase into a component A; preferably, a is selected from any one or more of Al, si, P, S, fe, cu, zn, ga, ge, as, cd, in, sn, tl, pb or Bi elements.
In a fifth aspect, the present application provides a battery separator comprising the nitrogen-containing high-entropy MXene two-dimensional material described above.
The sixth aspect of the application provides a method for preparing a battery separator, comprising the steps of: dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a solvent, coating the solvent on the surface of a diaphragm material, and drying to obtain the nitrogen-containing high-entropy MXene two-dimensional material; or dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a polymer monomer, mixing, and carrying out polymerization reaction to obtain the high-entropy MXene two-dimensional material.
The seventh aspect of the application provides a composite aluminum foil comprising an aluminum foil and the nitrogen-containing high-entropy MXene two-dimensional material.
The eighth aspect of the present application provides a method for preparing a composite aluminum foil, comprising the steps of: dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a solvent to form slurry, coating the slurry on the surface of an aluminum foil, and drying to obtain the nitrogen-containing high-entropy MXene two-dimensional material.
The ninth aspect of the application provides a positive plate of a lithium-sulfur battery, which contains the nitrogen-containing high-entropy MXene two-dimensional material; or, the above composite aluminum foil.
The tenth aspect of the application provides a lithium sulfur battery, which contains the nitrogen-containing high-entropy MXene two-dimensional material; or at least one of the positive plate, the composite aluminum foil and the battery separator.
The nitrogen-containing high-entropy MXene can produce the following technical effects when applied to a lithium sulfur battery:
the nitrogen-containing high-entropy MXene material contains multiple metal-N bonds, and the application confirms that the multiple metal-N bonds have remarkable effect on effectively adsorbing polysulfide, so that the dissolution of soluble polysulfide in electrolyte is reduced, and the loss of active substances and the generation of shuttle effect are avoided.
The nitrogen-containing high-entropy MXene material belongs to a two-dimensional material, has super-large specific surface area, has exposed multi-element metal atoms on the surface, and particularly, the surface of the nitrogen-containing high-entropy MXene material has obvious mechanical stress characteristics due to the existence of multi-element (more than five) metal atoms to generate lattice distortion on M position, so that the metal atoms in the nitrogen-containing high-entropy MXene material can be better exposed, thereby promoting sulfur catalysis and accelerating the transition from solid sulfur to soluble polysulfide Li 2 S n To solid Li 2 S (solid-liquid-solid) process, further reduces the dissolution of soluble polysulfides in the electrolyte.
Experiments prove that the lithium sulfur battery containing the nitrogen-containing high-entropy MXene shows excellent capacity characteristics and cycle ratePerformance and stability. At a rate of 4C, the capacity of the lithium sulfur battery containing HE-CN-MXene is kept at 700mAh g -1 Is obviously higher than TiVC 1/2 N 1/2 T x (589mAh g -1 )、Ti 2 C 1/2 N 1/2 T x (491mAh g -1 )、HE-MXene(185mAh g -1 ) And the capacity of MXene has been reported so far (403 mAh g -1 ). At a rate of 1C, the capacity after 300 cycles is kept at 738mAh g -1 Exhibits excellent cycle stability.
Drawings
FIG. 1 is a schematic diagram of a method for preparing nitrogen-containing high-entropy MXene by etching nitrogen-containing high-entropy MAX phase in embodiment 1 of the application;
FIG. 2 is a nitrogen-containing high-entropy MAX phase (Ti) in example 1 of the present application 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 (a) With nitrogen-containing high entropy MXene (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x (b) SEM photographs of (2);
FIG. 3 is a nitrogen-containing high-entropy MAX phase (Ti) in example 1 of the present application 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 (a) With nitrogen-containing high entropy MXene (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x (b) An XRD pattern of (a);
FIG. 4 is a schematic diagram of a nitrogen-containing high-entropy two-dimensional material (Ti) according to example 1 of the present application 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x TEM, HRTEM, STEM photos and element distribution maps of (a);
FIG. 5 is a schematic diagram of a nitrogen-containing high-entropy two-dimensional material (Ti) according to example 1 of the present application 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x AFM photograph (a) and thickness analysis map (b);
FIG. 6 is a nitrogen-containing high entropy two in example 1 of the present applicationVitamin material (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Is a mechanical strain profile of (a);
FIG. 7 is a schematic diagram of a nitrogen-containing high-entropy two-dimensional material (Ti) according to example 1 of the present application 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x XPS test patterns of (a);
FIG. 8 is a photograph, surface SEM photograph and thickness test chart of different separator composites prepared in example 8 of the present application;
fig. 9 is a charge-discharge curve (a), a cycle comparison graph (b) and a cycle performance graph (C) at 1C rate of the lithium sulfur battery assembled in example 8 of the present application at different rates;
FIG. 10 is a photograph (a) and a UV-visible spectrum (b) of the adsorption performance test of different MXene in example 9 of the present application;
FIG. 11 shows CV test results (a) and Li for different MXene-containing products in example 10 of the present application 2 S deposition test results (b);
FIG. 12 is the CV test results of high entropy MXene containing no nitrogen for the comparative sample in example 10 of the present application.
Detailed Description
The technical scheme of the application is described below through specific examples. It is to be understood that the reference to one or more steps of the application does not exclude the presence of other methods and steps before or after the described combined steps, or that other methods and steps may be interposed between these explicitly mentioned steps. It should also be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application, which relative changes or modifications may be regarded as the scope of the application which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
In practical applications, the sulfur positive electrode of lithium sulfur batteries generally exhibits serious capacity fade and low rate capability due to the following:
(1) The electron conductivity and ion conductivity of elemental sulfur are poor, and the conductivity of sulfur materials at room temperature is extremely low (5.0X10) -30 Scm -1 ) Final product of the reaction Li 2 S 2 And Li (lithium) 2 S is also an electronic insulator, which is not beneficial to the high rate performance of the battery;
(2) The densities of sulfur and lithium sulfide were 2.07 and 1.66g cm, respectively -3 Up to 79% of the volume expands/contracts during charge and discharge, which causes changes in the morphology and structure of the positive electrode, resulting in separation of sulfur from the conductive backbone, and thus capacity decay;
(3) Intermediate discharge products of lithium-sulfur batteries (soluble polysulfides, liPS, li 2 S n N is more than or equal to 4 and less than or equal to 8) can be dissolved into the organic electrolyte, so that the viscosity of the electrolyte is increased, the ion conductivity is reduced, polysulfide ions can migrate between the anode and the cathode, and the loss of active substances and the waste of electric energy (shuttle effect) are caused;
(4) The discharge process of the sulfur positive electrode is from solid sulfur to soluble polysulfide Li 2 S n And solid Li 2 S (solid-liquid-solid) heterogeneous conversion has low kinetic reactivity.
The nitrogen-containing high-entropy MXene can produce the following technical effects when applied to a lithium sulfur battery:
the nitrogen-containing high-entropy MXene material contains multiple metal-N bonds, and the application confirms that the multiple metal-N bonds have remarkable effect on effectively adsorbing polysulfide, so that the dissolution of soluble polysulfide in electrolyte is reduced, and the loss of active substances and the generation of shuttle effect are avoided.
The nitrogen-containing high-entropy MXene material belongs to a two-dimensional material, has super-large specific surface area, has exposed multi-element metal atoms on the surface, and particularly, has lattice distortion at M position due to the existence of multi-element (more than five) metal atomsSignificant mechanical stress characteristics, which enable better exposure of metal atoms therein, thereby facilitating sulfur catalysis, accelerating the transition from solid sulfur to soluble polysulfide Li 2 S n To solid Li 2 S (solid-liquid-solid) process, further reduces the dissolution of soluble polysulfides in the electrolyte. In addition, the nitrogen-containing high-entropy MXene is a conductive material, and has a certain effect on improving the conductivity of elemental sulfur.
Experiments prove that the lithium sulfur battery containing the nitrogen-containing high-entropy MXene shows excellent capacity characteristics, cycle rate performance and stability.
It should be noted that, according to the definition of the MXene material and the high-entropy material in the art, the chemistry of the nitrogen-containing high-entropy MXene two-dimensional material of the present application can be expressed as M n+1 X n Or M n+1 X n T x Wherein M is selected from at least five or more elements among transition metal elements, or M is selected from at least five metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB group; x is C and N, T is a functional group element, X is an indeterminate value, X is 0.ltoreq.x.ltoreq.2 according to theoretical calculation, in the chemical formula, T is generally used in the art x Representing that the surface of MXene contains functional group elements.
The technical features of the present application are illustrated below by examples from the preparation, application, performance test of nitrogen-containing high entropy MXene, respectively.
Example 1
The present embodiment provides a nitrogen-containing high-entropy MXene two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 As shown in FIG. 1, by etching a nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Wherein the Al element is obtained.
Nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the high entropy MAX phase 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (mole ratio) of Ti is selected from 4 AlN 3 、V 2 AlC and (Nb) 1/3 Ta 1/3 Zr 1/3 ) 2 AlC is used as a raw material precursor, and the molar ratio of AlC is Ti 4 AlN 3 :V 2 AlC:(Nb 1/3 Ta 1/3 Zr 1/3 ) 2 AlC=1:1:3, accurately weighing all raw material precursors according to corresponding molar ratios;
grinding: manually grinding the raw materials in a mortar for 10min, and placing the mixed powder in a powder tabletting mold for cold pressing treatment after grinding, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 1/3 Nb 1/6 Ta 1/ 6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 And (3) powder.
Nitrogen-containing high-entropy two-dimensional material (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 Comprises the following steps:
etching: taking 40ml of concentrated hydrochloric acid, uniformly mixing 2g of LiF as an etchant, and taking 1g of nitrogen-containing high-entropy MAX phase (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Placing the mixture in an etchant, reacting for 24 hours at 50 ℃, centrifuging, washing with water and drying after the reaction is finished to obtain the nitrogen-containing high-entropy two-dimensional material (Ti) 1/3 Nb 1/ 6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x (wherein T x Representing the functional group contained).
For nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 And nitrogen-containing high-entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x (Nitrogen-containing high entropy MXene) was subjected to Scanning Electron Microscopy (SEM) tests, respectively, and the results are shown in FIGS. 2a and b, which can be seen by comparison, (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Has an irregular three-dimensional block structure, while the nitrogen-containing high-entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x The appearance of the nano-plate is ultrathin, transparent and soft large-area two-dimensional nano-plate, which shows that the nitrogen-containing high-entropy MAX phase (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The Al layer in the process is effectively etched and removed under the action of hydrochloric acid+LiF etchant, and the corresponding nitrogen-containing high-entropy two-dimensional material (nitrogen-containing high-entropy MXene) is obtained after the reaction is finished. For nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 And high entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x X-ray diffraction (XRD) analysis was performed, and the results are shown in FIG. 3, in which the raw material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The (002) peak of the (002) peak appears at the position of 12.3 DEG, while the (002) peak of the nitrogen-containing high-entropy two-dimensional material product after the reaction with the hydrochloric acid+LiF etchant shifts to 6.7 DEG towards a low angle, and the diffraction peaks corresponding to other nitrogen-containing high-entropy MAX phases disappear, which shows that the (Ti 1/3 Nb 1/6 Ta 1/ 6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The Al element in the alloy is a noble metal,nitrogen-containing high entropy MXene (Ti) with lamellar structure is generated 1/3 Nb 1/6 Ta 1/6 Zr 1/ 6 V 1/6 ) 2 C 0.5 N 0.5 T x The interlayer spacing is obviously increased, which is similar to (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x The scanning electron microscope photo results of (2) are consistent, and the comparison of XRD patterns can also show that the synthesized nitrogen-containing high-entropy MAX phase (Ti 1/3 Nb 1/ 6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Diffraction pattern of (C) and reported quaternary MAX phase Ti 2 AlC 0.5 N 0.5 Consistent, and no other carbide and nitride impurity peaks appear, indicating that the resulting nitrogen-containing high entropy MAX phase (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Is a single phase.
(Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Transmission Electron Microscope (TEM) and High Resolution Transmission Electron Microscope (HRTEM) photographs, as shown in FIGS. 4a and b, showing that the obtained nitrogen-containing high-entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Rock salt crystal structure with ultra-thin single crystalline phase. (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Scanning Transmission Electron Micrographs (STEMs) and atomic distribution results (FIGS. 4 c-i) show that the ultrathin two-dimensional nanoplatelets have uniform Ti, nb, ta, zr, V, C, N, O and F element distributions, indicating that the target product is a film containing O and F functional groups and N element (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/ 6 V 1/6 ) 2 C 0.5 N 0.5 T x High entropy two-dimensional material (nitrogen-containing high entropy MXene). By atomic force microscope AFM testing (as shown in FIGS. 5a and 5 b), the present example was madeThe obtained nitrogen-containing high-entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x The atomic layer of (C) was about 2nm, indicating that (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Has the characteristics of ultra-thin and soft structure.
FIG. 6 shows a graph of the high entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Is at e xx And e xy The stress profile of the face, wherein red, bright yellow, green, and dark blue correspond to tensile or compressive strain, respectively, in the data field, indicates that the high entropy two-dimensional material surface has significant mechanical strain characteristics.
FIG. 7 shows the high entropy two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x Can be demonstrated in which the presence of a metal-nitrogen chemical bond, such as: ti-N (456.7 and 462.3 eV), V-N (514.2 and 521.8 eV), zr-N (179.3 and 181.7 eV), nb-N (205.3 and 208 eV), ta-N (23.1 and 25 eV) and the corresponding transition metal-carbon chemical bonds are also present.
Example 2
The present embodiment provides a nitrogen-containing high-entropy MXene two-dimensional material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 By etching nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Wherein the Al element is obtained.
Nitrogen-containing high-entropy MAX phase material (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (mole ratio) of Ti 4 AlN 3 ，Nb 2 AlC and (V) 1/3 Ta 1/3 Zr 1/3 ) 2 AlC is used as a raw material precursor, and the molar ratio of AlC is Ti 4 AlN 3 :Nb 2 AlC:(V 1/3 Ta 1/3 Zr 1/3 ) 2 AlC=1:1:3, accurately weighing all raw material precursors according to corresponding molar ratios;
grinding: manually grinding the raw materials in a mortar for 10min, and placing the mixed powder in a powder tabletting mold for cold pressing treatment after grinding, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 1/3 Nb 1/6 Ta 1/ 6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 And (3) powder.
Nitrogen-containing high-entropy two-dimensional material (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 Comprises the following steps:
etching: 50ml of 48% hydrofluoric acid (HF) was used as an etchant, and 1g of the nitrogen-containing high-entropy MAX phase (Ti) obtained in the present example of step (1) was used 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 Placing the mixture in an etchant, reacting for 48 hours at 50 ℃, centrifuging, washing with water and drying after the reaction is finished to obtain the nitrogen-containing high-entropy two-dimensional material (Ti) 1/3 Nb 1/6 Ta 1/ 6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x (wherein T x Representing the functional group contained).
Example 3
This example the present application provides another method for preparing nitrogen-containing high entropyMAX phase (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x The preparation method of (2) is similar to that of example 1, except that: in the dosing step (Zr) 1/3 Nb 1/3 Ta 1/3 ) 2 AlC、Ti 2 AlN and V 2 AlC is used as a raw material and is prepared according to the mol ratio of 3:1:1.
Example 4
This example the present application provides another method for preparing a nitrogen-containing high entropy MAX phase (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x The preparation method of (2) is similar to that of example 1, except that: in the batching step, ti is used 4 AlN 3 、Nb 2 AlC、Ta 2 AlC and V 2 AlC is used as a raw material and is prepared according to the mol ratio of 1:1:1:1.
Example 5
The application provides another method for preparing the nitrogen-containing high-entropy MAX phase (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the high entropy MAX phase 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 AlC 0.4 N 0.6 The stoichiometric ratio (mole ratio) of Ti 4 AlN 3 、Nb 2 AlC、Ta 2 AlC、V 2 AlC, zrC and Al are used as raw material precursors, and the molar ratio of AlC, zrC and Al is Ti 4 AlN 3 :Nb 2 AlC:Ta 2 AlC:V 2 AlC: zrC: al=1:1:1:1:2:3.2, accurately weighing each raw material precursor according to the corresponding molar ratio;
grinding: manually grinding the raw materials in a mortar for 10min, and placing the mixed powder in a powder tabletting mold for cold pressing treatment after grinding, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled blocks into a corundum crucible,heating to 1500 ℃ at 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling with a furnace, taking out the cooled block, and grinding to obtain nitrogen-containing high-entropy MAX phase (Ti) 1/3 Nb 1/6 Ta 1/ 6 Zr 1/6 V 1/6 ) 2 AlC 0.5 N 0.5 And (3) powder.
The same etching method as in example 1 is adopted to obtain a high-entropy MXene two-dimensional material: (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/ 6 V 1/6 ) 2 C 0.5 N 0.5 。
Example 6
The application provides a method for preparing nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the high entropy MAX phase 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (molar ratio) of Ti, nb, ta, V, zr, alN, al and graphite is adopted as raw material precursors, the molar ratio is that Ti, ta, V, zr and Al are respectively calculated according to the corresponding molar ratio, and the raw material precursors are accurately weighed;
grinding: placing the raw materials into a ball milling tank for ball milling at 600rpm for 20h, and placing the mixed powder into a powder tabletting mold for cold pressing treatment after ball milling, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 And (3) powder.
The same etching method as in example 1 is adopted to obtain a high-entropy MXene two-dimensional material: (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 。
Example 7
The application provides another method for preparing the nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (molar ratio) of Ti, nb, ta, V, zr, tiC, nbC, taC, VC, zrC, alN and Al are adopted as raw material precursors, the molar ratio is that Ti, nb, V, tiC, nbC, VC, zrC, alN and Al=0.3:0.3:0.3:0.3:0.1:0.1:0.1:0.1:0.5:0.7, and the raw material precursors are accurately weighed according to the corresponding molar ratio;
grinding: placing the raw materials into a ball milling tank for ball milling at 600rpm for 20h, and placing the mixed powder into a powder tabletting mold for cold pressing treatment after ball milling, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 And (3) powder.
The same etching method as in example 1 is adopted to obtain a high-entropy MXene two-dimensional material: (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 。
By adopting a similar method, the nitrogen-containing high-entropy MXene synthesized by the inventor also comprises the following components: (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 3 CNT x ， (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 4 C 1.5 N 1.5 T x ，(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/ 6 V 1/6 Cr 1/6 ) 2 C 0.5 N 0.5 T x ， (Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 3 CNT x ，(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 4 C 1.5 N 1.5 T x ， (Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x ，(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x ， (Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x ，(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x ， (Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x ，(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x ， (Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x ，(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 3 CNT x ， (Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x ，(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x ， (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 3 CNT x ，(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x ， (Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x ，(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x ，(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 。
However, the nitrogen-containing high-entropy MXene is not limited to the above disclosed type, other types of nitrogen-containing high-entropy MXene can be prepared by adjusting the synthesized condition parameters by the method disclosed by the application, and the nitrogen-containing high-entropy MXene is applied to lithium sulfur batteries based on the sulfur promotion catalytic effect caused by the metal-N bond and mechanical strain in the nitrogen-containing high-entropy MXene, and belongs to the technical conception of the application.
Example 8
The present embodiment provides a separator composite material and application thereof to lithium sulfur batteries, wherein the nitrogen-containing high-entropy MXene (Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x For illustration (hereinafter labeled HE-CN-MXene), the preparation method comprises the steps of:
ketjen Black, HE-CN-MXene and PVDF are dispersed in NMP solvent according to the mass ratio of 7:2:1 to form uniform slurry, and then the slurry is coated on a polypropylene diaphragm (Celgard 2500) by using a scraper and dried in vacuum for 12 hours at 50 ℃ to obtain the diaphragm composite material.
As a material of the comparative sample, there were high entropy MXene (Ti) 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 CT x (hereinafter referred to as HE-MXene) and binary nitrogen-containing MXene TiVC 1/2 N 1/2 T x Monobasic nitrogen-containing MXene Ti 2 C 1/2 N 1/2 T x . The same method is adopted to prepare the diaphragm composite material.
In order to test the sulfur-promoting catalytic effect of the nitrogen-containing high-entropy MXene, the dried membrane composite material is cut into a wafer with the diameter of 20mm, please see FIG. 8, the thickness of the membrane surface material is about 8 μm, and the membrane surface material is assembled in a 2032 button test battery, and the specific assembly method is as follows:
the diaphragm composite material of the application is placed in the middle by taking a metal lithium sheet as a negative electrode and sulfur as a positive electrode, wherein one surface coated with nitrogen-containing high-entropy MXene is contacted with the sulfur positive electrode, 40 mu L of electrolyte containing 2wt.% LiNO is adopted 3 Additive 1.0M lithium bis (trifluoromethanesulfonamide) (LiTFSI), solvent DOL and DME (V/v=1:1).
The lithium-sulfur battery obtained by assembly is tested, all constant current tests are carried out on a blue-electricity CT2001A system, the voltage range is 1.7-2.8V, and the multiplying power (1C=1675 mAh g) -1 ). Cyclic Voltammetry (CV) measurements were performed at a scan rate of 0.1mV s between 1.7 and 2.8V -1 . Electrochemical Impedance Spectroscopy (EIS) is performed at a frequency in the range of 100kHz to 0.01 Hz.
As shown in FIGS. 9a and 9b, charge and discharge curves of lithium sulfur batteries containing HE-CN-MXene at different rates are shown, it can be seen that the lithium sulfur batteries containing HE-CN-MXene show excellent rate performance, and at a rate of 4C, the capacity of the lithium sulfur batteries containing HE-CN-MXene is maintained at 700mAh g -1 Is obviously higher than TiVC 1/2 N 1/2 T x (589mAh g -1 )、Ti 2 C 1/2 N 1/ 2 T x (491mAh g -1 )、HE-MXene(185mAh g -1 ) And the capacity of MXene has been reported so far (403 mAh g -1 ). FIG. 9C shows a graph of the cyclic performance of HE-CN-MXene, showing that the capacity after 300 cycles at a 1C rate is maintained at 738mAh g -1 Exhibits excellent cycle stability.
Example 9
To further explain why the HE-CN-MXene of the application produces excellent electrochemical performance in application to lithium-sulfur batteries, the present example conducted adsorption performance tests on HE-CN-MXene and its control, the test method comprising: 10mg of HE-CN-MXene and a control thereof were added to 2.0mL of 5.0mmol L, respectively -1 Li 2 S 4 Mixing the above solutions, and standingAfter overnight, photographs were collected and then qualitatively assessed for adsorption capacity using an ultraviolet-visible (UV-vis) spectrometer, wherein lithium polysulfide was prepared from sulfur powder and lithium sulfide (Li) 2 S) is obtained by stirring after reaction in a DME/DOL (v/v=1/1) mixture in a molar ratio of 3:1. The test results are shown in fig. 10a and b, and it can be seen that the color of the supernatant liquid is from light to dark: HE-CN-MXene and TiVC 1/2 N 1/2 T x 、Ti 2 C 1/ 2 N 1/2 T x HE-MXene; wherein the upper layer liquid of HE-CN-MXene is nearly transparent, and the upper layer liquid of HE-MXene is yellow, which shows that HE-CN-MXene has the best adsorption performance on polysulfide, and then TiVC 1/2 N 1/2 T x And Ti is 2 C 1/2 N 1/2 T x And HE-MXene, which contains no nitrogen, has the worst adsorption performance for polysulfide, and thus it can be seen that HE-CN-MXene, which contains the largest number of types of M-N chemical bonds, has the most excellent adsorption effect, and has a remarkable effect on adsorption of polysulfide. The excellent adsorption capacity can prevent polysulfide from being dissolved in electrolyte to generate a shuttle effect in the charge and discharge process, and can enable polysulfide to be in more contact with transition metal elements, so that the catalytic efficiency is improved.
Example 10
It is known that solid sulphur is converted into a liquid in an intermediate state and finally into a solid in an electrochemical process. Therefore, the use of Li is assembled in the present embodiment 2 S 6 Electrolyte symmetrical cell to study the catalytic ability of HE-CN-MXene on lithium polysulfide (LiPs), further explaining the sulfur-promoting catalytic effect of HE-CN-MXene of the application, this example was conducted polysulfide conversion test and Li 2 S deposition test.
The test method of polysulfide conversion test is as follows: HE-CN-MXene, ketjen black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 were milled in NMP solvent to form a uniform slurry, which was then coated on carbon coated aluminum foil having a diameter of 12.0 mm. The round electrode obtained was dried under vacuum at 50 ℃ overnight. Then, two identical working electrodes are combinedThe counter electrode was assembled into a 2032 button cell using a polypropylene (PP) separator and 40 μl of Li 2 S 6 (0.5M) electrolyte. In the voltage range of-1 to 1V, at 5mV s -1 Is used to acquire CV curves of symmetric cells. Li (Li) 2 The manufacturing method of the round pole piece tested in the S deposition test is similar to the polysulfide conversion test, except that the mass ratio of HE-CN-MXene, ketjen black and polyvinylidene fluoride (PVDF) is 7:2:1. The obtained circular electrode and lithium foil were used as a working electrode and a counter electrode, respectively. 20. Mu.L of Li was used 2 S 8 As catholyte, 20. Mu.L of the (0.5M) solution was used without L i2 S 8 As an anolyte. The HE-CN-MXene is respectively replaced by TiVC 1/2 N 1/2 T x And Ti is 2 C 1/2 N 1/2 T x A control sample was obtained. Button cell was first discharged to 2.06V at 0.1mA with constant current and then discharged at 2.05V with constant potential to realize Li 2 Nucleation and growth of S. When the current is lower than 10 -5 At A, the constant potential discharge is terminated. Calculation of Li by plotting the integral area of the curve according to Faraday's law 2 Deposition capacity of S. The HE-CN-MXene is respectively replaced by TiVC 1/2 N 1/2 T x 、Ti 2 C 1/2 N 1/2 T x And HE-MXene.
The polysulfide conversion test results are shown in FIG. 11a, cyclic Voltammetry (CV) curve, HE-CN-MXene showing a ratio of Ti 2 C 1/2 N 1/2 T x And TiVC 1/2 N 1/2 T x Higher current densities indicate faster redox kinetics for LiPSs. We have collected Li-free 2 S 6 CV curve of electrolyte to exclude capacitance contribution, and in addition, at 0.12, -0.15 and-0.5V, there are three distinct reduction peaks on HE-CN-MXene, respectively with S 8 To S 6 2- 、S 6 2- To S 4 2- And S is 4 2- To S 2- These reduction peaks are associated with the stepwise conversion process of Ti 2 C 1/2 N 1/2 T x And TiVC 1/2 N 1/2 T x Cannot be observed. This suggests that it has a high electrocatalytic capacity for the multistep conversion reactions of LiPSs, which benefits from the strong mechanical strain on the HE-CN-MXene layer. In contrast, the high entropy carbide MXene (HE-MXene) with the same transition metal elements did not show a distinct redox peak (see FIG. 12), indicating that the metal-N bond contributed greatly to the efficient conversion of LiPs. In addition to Ti 2 C 1/2 N 1/2 T x 、TiVC 1/2 N 1/2 T x HE-CN-MXene atomic layer pair Li as compared with HE-MXene 2 S 4 Shows stronger adsorption, as demonstrated by adsorption testing and reduced absorption intensity in the ultraviolet-visible (UV-vis) spectrum (fig. 10). As the number of metals increases and the polar metal-N bonds increase, the effective adsorption should result from the increased metal-N bonds. Because HE-CN-MXene has strong adsorption and catalytic capability to LiPSs, li is contained in the final liquid-solid conversion process 2 The precipitation of S should be well regulated. As shown in FIG. 11b, li precipitated on HE-CN-MXene 2 S capacity is 203.3mAh g -1 Is superior to Ti 2 C 1/2 N 1/2 T x (74.7mAh g -1 ) And TiVC 1/2 N 1/2 T x (108.4mAh g -1 )。
As can be seen from the above test, the nitrogen-containing high-entropy MXene of the application has good adsorption and catalytic ability to LiPSs due to the existence of mechanical strain and five metal-N bonds, and has higher Li 2 The S deposition capacity, high rate performance and longer cycle life are achieved in Li-S batteries. Based on the same mechanism, we can reasonably expect that the nitrogen-containing high-entropy MXene containing other metal elements has the same effect when applied to lithium-sulfur batteries. Since the metal-N bond has an influence on adsorption, the kinds of metal elements are different, and the polarities of the metal-N bond are different, we prefer to have a metal-N bond with high polarity for application in lithium sulfur batteries, and therefore, M in nitrogen-containing MXene is preferably five or more elements selected from Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, au, ag, pd, au, ag, cu or Bi elements.
Example 11
Because the nitrogen-containing high-entropy MXene is applied to a lithium sulfur battery, the application form of the nitrogen-containing high-entropy MXene is not limited to the embodiment 8, which is coated on a diaphragm material to be contacted with a sulfur positive electrode, based on mechanical strain and metal-N bond of the material, in the embodiment, we provide a sulfur positive electrode sheet containing nitrogen-containing high-entropy MXene, and the preparation method comprises the following steps: mixing 25-36 parts of water, 3-10 parts of elemental sulfur, 1-6 parts of conductive agent (Ketjen black) and 1-3 parts of nitrogen-containing high-entropy MXene to prepare slurry, coating the slurry on aluminum foil, and carrying out vacuum drying to obtain the high-entropy MXene. And assembling the dried sulfur positive plate and the metal lithium plate into a lithium sulfur battery. The nitrogen-containing high-entropy MXene in the positive plate can be contacted with sulfur, and the effect of promoting sulfur catalysis can be exerted, so that the electrochemical performance of the lithium-sulfur battery is improved.
Example 12
The embodiment provides another form of applying the nitrogen-containing high-entropy MXene to a lithium-sulfur battery, which comprises dispersing the nitrogen-containing high-entropy MXene in a solvent, (water is used as the solvent in the embodiment) to prepare slurry, coating the slurry on a metal aluminum foil, drying to obtain the aluminum foil with the nitrogen-containing high-entropy MXene on the surface, coating the slurry containing elemental sulfur on the upper layer of the nitrogen-containing high-entropy MXene, and drying to obtain the sulfur anode containing the nitrogen-containing high-entropy MXene. And assembling the dried sulfur positive plate and the metal lithium plate into a lithium sulfur battery.
Example 13
The embodiment provides another diaphragm composite material containing nitrogen and high in entropy MXene, which is obtained by adding the nitrogen and high in entropy MXene material of the application as a filler into propylene monomers and mixing, and obtaining a polypropylene film through polymerization reaction, wherein the nitrogen and high in entropy MXene material of the application exists in the polypropylene film.
The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.
Claims (13)
1. The nitrogen-containing high-entropy MXene two-dimensional material is characterized by comprising M ' and X elements, wherein M ' is at least five metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB groups, X is C and N elements, and an X-ray photoelectron spectroscopy (XPS) characterization of the nitrogen-containing high-entropy MXene two-dimensional material contains M ' -N bonds.
2. The nitrogen-containing high-entropy MXene two-dimensional material of claim 1, characterized by containing M' -C bonds by X-ray photoelectron spectroscopy (XPS) characterization of the nitrogen-containing high-entropy MXene two-dimensional material;
and/or, an X-ray diffraction test (XRD) characterization of the nitrogen-containing high entropy MXene two-dimensional material contains a (002) peak.
3. The nitrogen-containing high-entropy MXene two-dimensional material of claim 1 or 2, characterized in that M' is selected from five or more of the Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, pd, au, ag, cu elements; preferably, said M' is selected from Ti, zr, V, nb, ta, cr;
and/or the nitrogen-containing high-entropy MXene two-dimensional material contains functional groups.
4. Use of the nitrogen-containing high-entropy MXene two-dimensional material of any one of claims 1 to 3 for lithium sulfur batteries.
5. The application of the nitrogen-containing high-entropy MXene two-dimensional material in the lithium sulfur battery is characterized in that the chemical formula of the nitrogen-containing high-entropy MXene two-dimensional material is represented as M' n+1 X n T x Wherein M is selected from at least five of Ti, zr, V, nb, ta, cr elements, X is carbon and nitrogen, T is a functional group, and n is1. 2 or 3;
preferably, the chemical formula of the nitrogen-containing high-entropy MXene two-dimensional material is expressed as at least one of the following:
(Ti 1/3 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 3 CNT x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 2 C 0.5 N 0.5 T x 、(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 3 CNT x 、
(Ti 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Cr 1/6 ) 4 C 1.5 N 1.5 T x 、(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Ti 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、
(Ti 0.2 Nb 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Ti 0.2 Nb 0.2 Ta 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 3 CNT x 、
(Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 、(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 2 C 0.5 N 0.5 T x 、
(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 3 CNT x 、(Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 Cr 0.2 ) 4 C 1.5 N 1.5 T x 。
6. a method for preparing a nitrogen-containing high-entropy MXene two-dimensional material, characterized in that the nitrogen-containing high-entropy MXene two-dimensional material is the nitrogen-containing high-entropy MXene two-dimensional material according to any one of claims 1 to 3; or, the nitrogen-containing high-entropy MXene two-dimensional material being the nitrogen-containing high-entropy MXene two-dimensional material in the use as set forth in claim 4 or 5, the steps comprising: etching the nitrogen-containing high entropy M' AX phase into a component A; preferably, a is selected from any one or more of Al, si, P, S, fe, cu, zn, ga, ge, as, cd, in, sn, tl, pb or Bi elements.
7. The method for preparing a nitrogen-containing high-entropy MXene two-dimensional material according to claim 6, characterized in that the method for preparing a nitrogen-containing high-entropy M' AX phase material comprises: taking at least one nitrogen-containing MAX phase and a plurality of nitrogen-free MAX phases as raw materials for reaction;
or, taking at least one MAX phase containing nitrogen, simple substances or compounds of a plurality of transition metals and simple substances or compounds of A as raw materials for reaction;
or, taking an A-containing nitride, more than four transition metal simple substances or compounds and an A simple substance or compound as raw materials for reaction;
or, taking an M' AX phase material containing A nitride, at least one transition metal simple substance or compound and no nitrogen as a raw material for reaction.
8. A battery separator comprising the nitrogen-containing high-entropy MXene two-dimensional material according to any one of claims 1 to 3;
or, a nitrogen-containing high entropy MXene two-dimensional material in the use according to claim 4 or 5;
or, the nitrogen-containing high-entropy MXene two-dimensional material obtained by the preparation method of claim 6 or 7.
9. A method of preparing the battery separator of claim 8, comprising the steps of: dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a solvent, coating the solvent on the surface of a diaphragm material, and drying to obtain the nitrogen-containing high-entropy MXene two-dimensional material;
or dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a polymer monomer, mixing, and carrying out polymerization reaction to obtain the high-entropy MXene two-dimensional material.
10. A composite aluminum foil, characterized in that the composite aluminum foil comprises: aluminum foil;
and, the nitrogen-containing high-entropy MXene two-dimensional material of any one of claims 1 to 3; or, a nitrogen-containing high entropy MXene two-dimensional material in the use according to claim 4 or 5; or, the nitrogen-containing high-entropy MXene two-dimensional material obtained by the preparation method of claim 6 or 7.
11. A method of preparing the composite aluminum foil as recited in claim 10, comprising the steps of: and dispersing the nitrogen-containing high-entropy MXene two-dimensional material in a solvent, coating the solvent on the surface of an aluminum foil, and drying to obtain the nitrogen-containing high-entropy MXene two-dimensional material.
12. A positive electrode sheet of a lithium-sulfur battery, characterized in that the positive electrode sheet of the lithium-sulfur battery contains the nitrogen-containing high-entropy MXene two-dimensional material according to any one of claims 1 to 3;
or, a nitrogen-containing high entropy MXene two-dimensional material in the use according to claim 4 or 5;
or, the nitrogen-containing high-entropy MXene two-dimensional material obtained by the preparation method of claim 6 or 7;
or, the composite aluminum foil as claimed in claim 10;
or, the composite aluminum foil obtained by the preparation method according to claim 11.
13. A lithium sulfur battery comprising the battery separator of claim 8;
or, a battery separator comprising the battery separator obtained by the production method according to claim 9;
or, comprising the composite aluminum foil as claimed in claim 10;
or, a composite aluminum foil obtained by the production method according to claim 11;
or, a positive electrode sheet comprising the lithium-sulfur battery according to claim 12.
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