CN111943205A - Method for preparing MAX phase by adopting melt displacement reaction, prepared MAX phase and application - Google Patents

Method for preparing MAX phase by adopting melt displacement reaction, prepared MAX phase and application Download PDF

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CN111943205A
CN111943205A CN202010884092.XA CN202010884092A CN111943205A CN 111943205 A CN111943205 A CN 111943205A CN 202010884092 A CN202010884092 A CN 202010884092A CN 111943205 A CN111943205 A CN 111943205A
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max
phase
reaction
tin
indium
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CN111943205B (en
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丁军伟
王诗文
平丹
吴诗德
方少明
王恒
张勇
韩光鲁
郭东杰
杨许召
韩莉锋
罗河伟
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Zhengzhou University of Light Industry
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a method for preparing MAX phase by adopting melt displacement reaction, the MAX phase prepared by the method and application thereof, wherein A phase is 211 type MAX phase (TiVAlC, Mn) of aluminum2AlC and V2AlC) as a raw material, and obtaining MAX of gallium, MAX of indium or MAX of tin as an A phase by a displacement reaction in molten metal gallium, indium and tin; the melting displacement method overcomes the problem of very serious volatilization loss when corresponding MAX is directly synthesized by high-temperature solid-phase reaction of metal gallium, indium and tin, so that MAX phase with expected molar ratio can be obtained, and when the prepared MAX is used as a positive electrode material of a zinc ion battery, the specific capacity is higher than 150mAh/g, the voltage platform is high, and the cycle performance is good. The method can be prepared from an easily synthesized MAX phase through a process with high repeatability, simple process and less time consumption, and is suitable forAnd (4) industrial production.

Description

Method for preparing MAX phase by adopting melt displacement reaction, prepared MAX phase and application
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a method for preparing a MAX phase by adopting a melt displacement reaction, the prepared MAX phase and application.
Background
With the increasing demand for energy, multivalent ion batteries, such as magnesium ion batteries, calcium ion batteries, zinc ion batteries, aluminum ion batteries, and the like, have been rapidly developed, and among them, zinc ion batteries attract more and more attention due to their excellent properties, such as safety, environmental protection, and low cost. As a new battery, a zinc ion battery mainly uses a material capable of containing zinc ions as a positive electrode, zinc as a negative electrode, and an aqueous solution containing zinc ions (such as zinc sulfate and zinc trifluoromethanesulfonate) as an electrolyte. The charge and discharge of the battery are realized through reversible embedding and releasing of zinc ions in the anode material. Although the variety of positive electrode materials for zinc ion batteries is increasing with the progress of research, the need for developing positive electrode materials having high zinc storage capacity and excellent cycle stability is still urgent.
In recent years, manganese-based and vanadium-based cathode materials are widely used as cathode materials of zinc ion batteries, but because manganese and vanadium are easy to dissolve in the charging and discharging processes, the development of bimetallic manganese and vanadium-containing compounds capable of inhibiting the dissolution of manganese and vanadium is of great significance, and bimetallic materials can support lattice structures, thereby being beneficial to the improvement of the performance and the enhancement of the cycle stability of the zinc ion batteries.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the problem of very serious volatilization loss when corresponding MAX is synthesized by directly using metal gallium, indium and tin through high-temperature solid-phase reaction in the prior art, provide a MAX phase capable of obtaining an expected molar ratio, and greatly increase the MAX types of gallium, indium and tin which can be prepared. And the prepared MAX with A phase of gallium, indium and tin can be used as the anode material of the zinc ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing MAX by fusion replacement reaction uses 211 type MAX phase (TiVAlC, Mn) with A phase element as aluminium2AlC or V2AlC) as raw material, and carrying out displacement reaction in molten metal gallium, indium or tin to obtain MAX (TiVGaC, Mn) with phase A being gallium respectively2GaC or V2GaC), MAX (TiVINC, Mn) of indium2InC or V2InC) or MAX (TiVSnC, Mn) of tin2SnC or V2SnC); the melting substitution method overcomes the problem of very serious volatilization loss when corresponding MAX is synthesized by directly using metal gallium, indium and tin through high-temperature solid-phase reaction, and then MAX phase with expected molar ratio can be obtained, so that the types of MAX with gallium, indium and tin as phase A which can be prepared are greatly increased, and further the first experimental synthesis preparation of MAX phase which is predicted by various theories is realized.
According to a particular and preferred aspect of the invention, the preparation method comprises the following steps:
(1) respectively carrying out ball milling on the gallium block, the indium block and the tin block with the surface oxide layer removed and a 211 type MAX phase with an A phase element being aluminum under the protection of argon gas, and then carrying out a replacement reaction under the protection of argon gas;
(2) cooling to room temperature, removing excessive gallium, indium and tin by dilute hydrochloric acid or dilute sulfuric acid, and drying at 80 deg.C under vacuum for 12 hr to obtain MAX of phase A as gallium, MAX of indium or MAX of tin.
Further, in the step (1), the phase A element is 211 type MAX phase of aluminum, specifically TiVAlC and Mn2AlC or V2One kind of AlC.
Further, the metal blocks in the step (1) are gallium blocks, indium blocks or tin blocks.
Further, in the step (1), the oxide on the surface of the metal blocks (gallium blocks, indium blocks and tin blocks) needs to be removed, so that the replacement reaction is facilitated to occur.
Furthermore, the molar ratio of the metal blocks to the MAX in the step (1) is (2-50): 1.
Further, the temperature rise rate of the displacement reaction in the step (1) is 5-10 ℃ per minute, the temperature interval is 600-1300 ℃, and the reaction time is 1-24 hours.
The invention also relates to a MAX such as Mn prepared as described above2GaC、Mn2InC and Mn2Use of SnC as a positive electrode material for a zinc ion battery.
According to a specific aspect, the zinc-ion battery positive plate is prepared by adopting the following steps:
(1) mixing MAX, acetylene black and polyvinylidene fluoride uniformly according to the ratio of 7:2:1, preparing into paste with nitrogen methyl pyrrolidone, and uniformly coating on titanium foil;
(2) dried in a vacuum oven at 80 ℃ for 12 hours.
The electrochemical performance of the electrode material was tested as follows:
(1) the simulated battery adopts a button CR2032 type, wherein the electrolyte is 3M zinc trifluoromethanesulfonate aqueous solution, and the negative electrode is a zinc sheet.
(2) The reversible capacity and the cycle performance of the electrode material are tested and analyzed by constant current charging and discharging in experiments. The charging and discharging system is as follows: voltage range: 0.2-1.8V; the number of cycles is generally from 1 to 2000.
MAX prepared by the invention, such as Mn2GaC、Mn2InC and Mn2When the SnC is used as the positive electrode material of the zinc ion battery, the specific capacity is higher than 150mAh/g, the voltage platform is high, and the cyclicity is highThe performance is excellent.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the MAX phase which is easy to prepare by a solid-phase reaction method is used as a precursor raw material; (2) the method of fusion displacement reaction is utilized to overcome the problem of very serious volatilization loss when the corresponding MAX is synthesized by directly using the high-temperature solid-phase reaction of metal gallium, indium and tin; (3) obtaining MAX phase with expected molar ratio, thereby greatly increasing the types of MAX phase which can be prepared from gallium, indium and tin, and further realizing the first experimental synthesis preparation of MAX phase by various theoretical predictions; (4) obtained MAX such as Mn2GaC、Mn2InC and Mn2The capacity of the SnC used as the positive electrode material of the zinc ion battery is more than 150mAh/g, and the SnC has good cycle performance.
In conclusion, the method for preparing MAX phase by using fusion displacement reaction has the advantages that the MAX phase A which cannot be obtained by ordinary solid phase reaction is 211 MAX phase of gallium, indium and tin, and the obtained MAX is an ideal positive electrode material of a zinc ion battery; in addition, the preparation method is based on MAX which is easy to synthesize by solid phase reaction, is prepared by a process with high repeatability, simple process and less time consumption, and is very suitable for industrial production.
Drawings
FIG. 1 is V of example 12XRD of AlC precursor;
FIG. 2 is V from example 1 via a molten gallium displacement reaction2The purity of the obtained product is high by XRD of the GaC, which indicates that the melt displacement reaction occurs;
FIG. 3 is V of example 12Scanning Electron Micrographs (SEM) of AlC precursors;
FIG. 4 is V obtained by a molten gallium substitution reaction of example 12And the SEM of GaC shows that the obtained product has little difference with the shape of the precursor.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) removing gallium blocks of surface oxide layer and 211 type MAX phase (V) with Al as A phase element under the protection of argon2AlC) is ball milled, gallium/V2The molar ratio of AlC is 2; then reacting for 12 hours at 600 ℃ at the heating rate of 5 ℃ per minute under argon;
(2) cooling to room temperature, removing excessive gallium with dilute hydrochloric acid, vacuum drying at 80 deg.C for 12 hr to obtain MAX (V) with gallium as phase A2GaC）。
And (5) characterizing the crystal structure and the appearance of the obtained MAX. As can be seen from FIGS. 1 and 2, with respect to the precursor V2AlC is subjected to displacement reaction of molten gallium to obtain high-purity V2GaC; furthermore, as can be further seen from fig. 3 and 4, there is no significant change in morphology before and after the metathesis reaction.
The obtained MAX was made into a working electrode according to the method provided by the present invention and subjected to corresponding performance tests, and the results are shown in Table 1, where the first discharge specific capacity was 193 mAhg during 1C charge and discharge-1(ii) a The specific capacity after 1500 times of reverse circulation is 132 mAhg-1。
Example 2
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) removing gallium blocks of the surface oxide layer and 211 type MAX phase (Mn) of which the A phase element is aluminum under the protection of argon2AlC) ball milling, gallium/Mn2The molar ratio of AlC is 50; then reacting for 10 hours at 1300 ℃ at the heating rate of 10 ℃ per minute under argon;
(2) cooling to room temperature, removing excessive gallium with dilute hydrochloric acid, and vacuum drying at 80 deg.C for 12 hr to obtain MAX (Mn) with gallium as phase A2GaC）。
The obtained MAX is made into a working electrode and subjected to phase matching according to the method provided by the inventionThe results of the electrical property tests are shown in Table 1, and the specific first discharge capacity is 185 mAhg at 1C charging and discharging-1(ii) a The specific capacity is 122 mAhg after 1500 times of reverse circulation-1。
Example 3
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) ball-milling the gallium blocks with the surface oxide layer removed and 211 type MAX phase (TiVAlC) with the phase A element being aluminum under the protection of argon, wherein the molar ratio of gallium to TiVAlC is 25; then reacting for 8 hours at 1100 ℃ at the heating rate of 5 ℃ per minute under argon;
(2) then cooling to room temperature, removing excessive gallium by using dilute sulfuric acid, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain MAX (TiVGaC) with the phase A being gallium.
The obtained MAX was made into a working electrode according to the method provided by the present invention and subjected to corresponding electrical property tests, and the results are shown in Table 1, where the first discharge specific capacity was 177mAhg during 1C charging and discharging-1(ii) a The specific capacity after 1500 times of reverse circulation is 117 mAhg-1。
Example 4
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) under the protection of argon, the indium blocks with the surface oxide layers removed and 211 type MAX phase (TiVAlC) with aluminum as an A phase element are subjected to ball milling, and the molar ratio of indium to TiVAlC is 2; then reacting for 16 hours at 600 ℃ under argon at the heating rate of 5 ℃ per minute;
(2) then cooled to room temperature, excess indium is removed by dilute hydrochloric acid, and dried for 12 hours at 80 ℃ in vacuum to obtain MAX (TiVINC) with indium as phase A.
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 5
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) under the protection of argon, the indium blocks and A phase elements which are removed from the surface oxide layer areType 211 MAX phase (Mn) of aluminium2AlC) are ball milled, indium/Mn2The molar ratio of AlC is 30; then reacting for 12 hours at 1000 ℃ at the heating rate of 10 ℃ per minute under argon;
(2) then cooling to room temperature, removing excessive indium by using dilute hydrochloric acid, and drying at the temperature of 80 ℃ for 12 hours in vacuum to obtain MAX (Mn) with indium as phase A2InC）。
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 6
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) removing indium blocks of surface oxide layer and 211 type MAX phase (V) with Al as A phase element under the protection of argon2AlC) are ball milled, indium/V2The molar ratio of AlC is 25; then reacting for 10 hours at 800 ℃ at the heating rate of 5 ℃ per minute under argon;
(2) then cooling to room temperature, removing excessive indium by using dilute hydrochloric acid, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain MAX (V) with the phase A being indium2InC）。
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 7
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) under the protection of argon, ball-milling the tin blocks with the surface oxide layer removed and 211 type MAX phase (TiVAlC) with the phase A element being aluminum, wherein the molar ratio of tin to TiVAlC is 3; then reacting for 22 hours at 700 ℃ at the heating rate of 8 ℃ per minute under argon;
(2) then cooled to room temperature, excess tin is removed with dilute sulfuric acid, and dried under vacuum at 80 ℃ for 12 hours to obtain MAX (TiVSnC) with tin as phase A.
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 8
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) removing tin block of surface oxide layer and 211 type MAX phase (Mn) of which A phase element is aluminum under the protection of argon2AlC) were ball milled, tin/Mn2The molar ratio of AlC is 15; then reacting for 6 hours at 1100 ℃ at a heating rate of 10 ℃ per minute under argon;
(2) then cooling to room temperature, removing excessive tin by using dilute hydrochloric acid, and drying at the temperature of 80 ℃ for 12 hours in vacuum to obtain MAX (Mn) with tin as phase A2SnC）。
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 9
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) under the protection of argon, the tin blocks with the surface oxide layer removed and 211 type MAX phase (V) with the A phase element being aluminum are respectively treated2AlC) are ball milled, tin/V2The molar ratio of AlC is 20; then reacting for 6 hours at 900 ℃ under argon at the heating rate of 8 ℃ per minute;
(2) then cooling to room temperature, removing excessive tin by using dilute hydrochloric acid, and drying at the temperature of 80 ℃ for 12 hours in vacuum to obtain MAX (V) with tin as phase A2AlC）。
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
Example 10
The procedure for the preparation of the MAX phase by the melt metathesis reaction of this example was as follows:
(1) under the protection of argon, the tin blocks with the surface oxide layer removed and 211 type MAX phase (V) with the A phase element being aluminum are respectively treated2AlC) are ball milled, tin/V2The molar ratio of AlC is 2; then reacting for 24 hours at 1300 ℃ at the heating rate of 5 ℃ per minute under argon;
(2) then cooling to room temperatureRemoving excessive tin with dilute sulfuric acid, and vacuum drying at 80 deg.C for 12 hr to obtain MAX (V) with phase A being tin2SnC）。
The obtained MAX was made into a working electrode according to the method provided by the present invention and the corresponding performance test was performed, and the results are shown in table 1.
TABLE 1 shows the cycle performance of the batteries of examples 1-10
Figure DEST_PATH_IMAGE002
Table 1 shows the cycling performance of the cells in the different examples, indicating that the melt displacement reaction yielded MAX for the positive electrode of a zinc ion cell with long cycling stability.
Aiming at the problem of very serious volatilization loss when corresponding MAX is synthesized by directly using metal gallium, indium and tin through high-temperature solid-phase reaction, the MAX phase with an expected molar ratio is obtained through fusion displacement reaction, so that the types of MAX with gallium, indium and tin as the A phase which can be prepared are greatly increased, and further the first experimental synthesis preparation of MAX phases with various theoretical predictions is realized. And the obtained MAX can be used for the positive electrode material of the zinc ion battery. The method has very important significance for promoting the synthesis of novel functional MAX phases and the development of high-performance zinc ion batteries.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A method of preparing MAX by melt metathesis, characterised in that: the method takes a 211 type MAX phase with an A phase element being aluminum as a raw material, and obtains MAX of gallium, MAX of indium or MAX of tin as A phase respectively by a displacement reaction in molten metal gallium, indium or tin;
the 211 type MAX phase with the A phase element being aluminum is TiVAlC and Mn2AlC or V2AlC。
2. A method for preparing MAX by a meltsubstitution reaction according to claim 1, characterised in that it comprises the steps of:
(1) under the protection of argon, ball-milling the metal block with the surface oxide layer removed and a 211 type MAX phase with an A phase element being aluminum, and then carrying out a replacement reaction under the protection of argon;
(2) cooling to room temperature, removing excessive gallium, indium or tin by using dilute hydrochloric acid or dilute sulfuric acid, and drying to obtain MAX of A phase being gallium, MAX of indium or MAX of tin.
3. A method of producing MAX using a melt metathesis reaction, as claimed in claim 2, wherein: in the step (1), the 211 type MAX phase with the A phase element being aluminum is TiVAlC and Mn2AlC or V2AlC。
4. A method of producing MAX using a melt metathesis reaction, as claimed in claim 2, wherein: the metal blocks in the step (1) are gallium blocks, indium blocks or tin blocks.
5. A method for preparing MAX by a meltsubstitution reaction according to claim 2, characterised in that: the molar ratio of the metal blocks to the MAX in the step (1) is (2-50): 1.
6. A method for preparing MAX by a meltsubstitution reaction according to claim 2, characterised in that: the temperature rise rate of the displacement reaction in the step (1) is 5-10 ℃/min, the temperature of the displacement reaction is 600-1300 ℃, and the reaction time is 1-24 hours.
7. A method for preparing MAX by a meltsubstitution reaction according to claim 2, characterised in that: drying at the temperature of 80 ℃ for 12 hours in vacuum in the step (2),
MAX obtainable by a process according to any one of claims 1 to 6.
8. Use of a MAX according to claim 8 as a zinc ion battery positive electrode material.
9. Use according to claim 9, characterized in that: the MAX is used as the positive electrode material of the zinc ion battery, and has the advantages of specific capacity higher than 150mAh/g, high voltage platform and excellent cycle performance.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN115594181A (en) * 2021-07-08 2023-01-13 苏州北科纳米科技有限公司（Cn） Aluminum-excess MAX phase ceramic and preparation method thereof
CN115650729A (en) * 2022-11-04 2023-01-31 烟台大学 Di-titanium-vanadium-aluminum-carbon ceramic powder material and preparation method and application thereof

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WO2012000742A1 (en) * 2010-07-02 2012-01-05 Brandenburgische Technische Universität Cottbus Process for producing an adhesion- and scratch-resistant protective layer on a metallic workpiece
CN108821291A (en) * 2018-07-10 2018-11-16 中国科学院宁波材料技术与工程研究所 A kind of novel tertiary stratiform MAX phase material, preparation method and application
CN108910884A (en) * 2018-07-10 2018-11-30 中国科学院宁波材料技术与工程研究所 A kind of novel MAX phase material, preparation method and application
CN111470543A (en) * 2019-01-24 2020-07-31 中国科学院宁波材料技术与工程研究所 Composite material of magnetic element and magnetic MAX phase, preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040250334A1 (en) * 2003-06-13 2004-12-16 Tamer El-Raghy Max phase glove and condom formers
WO2012000742A1 (en) * 2010-07-02 2012-01-05 Brandenburgische Technische Universität Cottbus Process for producing an adhesion- and scratch-resistant protective layer on a metallic workpiece
CN108821291A (en) * 2018-07-10 2018-11-16 中国科学院宁波材料技术与工程研究所 A kind of novel tertiary stratiform MAX phase material, preparation method and application
CN108910884A (en) * 2018-07-10 2018-11-30 中国科学院宁波材料技术与工程研究所 A kind of novel MAX phase material, preparation method and application
CN111470543A (en) * 2019-01-24 2020-07-31 中国科学院宁波材料技术与工程研究所 Composite material of magnetic element and magnetic MAX phase, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115594181A (en) * 2021-07-08 2023-01-13 苏州北科纳米科技有限公司（Cn） Aluminum-excess MAX phase ceramic and preparation method thereof
CN115650729A (en) * 2022-11-04 2023-01-31 烟台大学 Di-titanium-vanadium-aluminum-carbon ceramic powder material and preparation method and application thereof
CN115650729B (en) * 2022-11-04 2023-05-12 烟台大学 Dititanium vanadium aluminum carbon ceramic powder material and preparation method and application thereof

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