CN112010305B - Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method - Google Patents

Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method Download PDF

Info

Publication number
CN112010305B
CN112010305B CN202010873464.9A CN202010873464A CN112010305B CN 112010305 B CN112010305 B CN 112010305B CN 202010873464 A CN202010873464 A CN 202010873464A CN 112010305 B CN112010305 B CN 112010305B
Authority
CN
China
Prior art keywords
alc
powder
submicron
process according
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010873464.9A
Other languages
Chinese (zh)
Other versions
CN112010305A (en
Inventor
许剑光
张宇
杨丹
刘志勇
姚为
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yancheng Institute of Technology
Original Assignee
Yancheng Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yancheng Institute of Technology filed Critical Yancheng Institute of Technology
Priority to CN202010873464.9A priority Critical patent/CN112010305B/en
Publication of CN112010305A publication Critical patent/CN112010305A/en
Application granted granted Critical
Publication of CN112010305B publication Critical patent/CN112010305B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 process for preparing (V, ti) 2 The method for preparing AlC submicron tablet and nano-particle includes such steps as mixing dried V powder, ti powder, al powder, sn powder and C powder (1.8-1) (0.2-1) (1-1.5) (0-0.35) (0.85-1.2) in ball mill, grinding, and high-temp self-spreading under argon atmosphere to obtain (V, ti) 2 Crushing AlCMX phase material, grinding, performing solvent ultrasound, standing the solution after ultrasound for 2-5 days, centrifuging the upper layer solution, and collecting the lower layer precipitate (V, ti) 2 AlC submicron tablet, supernatant liquid is (V, ti) 2 Colloidal solution of AlC nanoparticles. The method has low energy consumption, safety, environmental protection, simple operation, time saving and low cost, and the prepared (V, ti) 2 AlC submicron sheets and nanoparticles are suitable for use as lithium ion battery anode materials.

Description

Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method
Technical Field
The invention relates to a process for preparing (V, ti) 2 A method for preparing AlC submicron sheets and nanometer particles belongs to the technical field of preparation of lithium ion battery anode materials.
Background
The cathode material of the traditional lithium ion battery is graphite, but the graphite is only 372mAhg -1 And the theoretical specific capacity of the battery is poor, and the cycle life is poor, so that the requirement of the equipment on the high specific capacity of the battery is more and more difficult to meet. For this reason, many new negative electrode materials have been studied, such as amorphous carbon, si, siO x Sn, P, transition metal oxide, transition metal sulfide and the like, and the lithium ion battery cathode material is greatly enriched.
The concept of MAX phase was first proposed by Barsoum in 2000, where M represents a class of early transition metal elements, a represents some of the third or fourth main group elements, and X is C or N. At present, research on MAX phase is focused on bulk materials and some excellent properties thereof, such as low density, high melting point, good electric and thermal conductivity, high elastic modulus, high fracture toughness, oxidation resistance, thermal shock resistance, easy processing and good self-lubricity, but little research on electrochemical properties is conducted. MXenes prepared by HF etching of layer A in MAX phase have been shown to have good lithium ion storage properties, especially after complexing with other materials. Since a is a metal element and has excellent conductivity as compared with MXenes, the a layer may have excellent effect on improving the conductivity of the anode material. In 2016, we have found that by reducing the size of the MAX phase material, the MAX phase material (Ti 2 SC、Ti 2 SnC、Ti 3 SiC 2 ) The lithium ion storage performance is shown, and the capacity gradually increases along with the progress of circulation, so that the excellent cycle life is shown, and the energy storage sequence of the MAX phase material is pulled. In addition, since more of the current developments of commercial lithium ion batteries are restricted by the battery volume, the MAX phase material has a larger volume specific capacity compared with other anode materials because of a larger density.
V 2 AlC is used as one of MAX phases, and because the acting force between an MX layer and an A layer is large, the AlC is difficult to strip into a layered structure such as graphene and BN, and the application of the AlC in the field of negative electrode materials of lithium ion batteries is affected. The inventor adopts a solid solution method to introduce substitution atoms Ti to form a solid solution so as to weaken acting force between an MX layer and an A layer, and then peels the MX layer and the A layer by a solvent ultrasonic method to prepare the (V, ti) 2 AlC submicron flakes and nanoparticles, (V, ti) 2 AlC submicron sheets and nanometer particles can be used as negative electrode materials of lithium ion batteries, and the negative electrode materials show obvious lithium ion storage capacity, and the capacity is gradually increased along with the progress of circulation.
Disclosure of Invention
The invention aims to solve V 2 AlC is difficult to be peeled into a layered structure such as graphene and BN due to the large acting force between the MX layer and the A layer 2 AlC is improved to provide a preparation (V, ti) 2 AlC submicron sheet and nanometer particle method, which has low energy consumption, safety, environmental protection, simple operation and time saving, and the prepared (V, ti) 2 AlC submicron sheets and nano particles can be used as anode materials of lithium ion batteries.
Technical proposal
Preparation (V, ti) 2 A method of AlC submicron platelets and nanoparticles comprising the steps of:
(1) Grinding and mixing the dried V powder, ti powder, al powder, sn powder and C powder in a ball mill according to the molar ratio of (1.8-1): (0.2-1.5): (0-0.35): (0.85-1.2) to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and performing high-temperature self-propagating synthesis under the protection of argon atmosphere to obtain (V, ti) 2 AlC MAX phase material;
(3) Will (V, ti) 2 Crushing and grinding AlC MAX phase material to obtain (V, ti) 2 AlC powder is added into a solvent for solvent ultrasonic treatment;
(4) Standing the solution obtained after the ultrasonic treatment in the step (3) for precipitation for 2-5 days, centrifuging the upper layer solution, and obtaining a lower layer precipitate (V, ti) after centrifuging 2 AlC submicron tablet, supernatant liquid is (V, ti) 2 Colloidal solution of AlC nanoparticles.
Further, in the step (1), the molar ratio of V powder, ti powder, al powder, sn powder and C powder is preferably 1.3:0.7:1.15:0.12:1.
Further, in the step (1), the relative humidity is controlled to be less than or equal to 60% when grinding and mixing.
In the step (2), the high-temperature self-propagating synthesis temperature is 150-300 ℃ and the time is less than or equal to 5min.
In the step (2), the air pressure of argon in the high-temperature self-propagating synthesis reaction kettle is controlled to be 1.0-2.5 atmospheres.
Further, in the step (3), the solvent is selected from any one of water, absolute ethanol, acetone, ethylene glycol, dimethyl maple or N-methyl pyrrolidone.
In the step (3), argon is required to be introduced into the solvent as a protective gas during ultrasonic treatment, the ultrasonic power is 100w, and the frequency is 40KHz.
Further, in the step (4), the centrifugal speed is 500-5000 rpm, and the centrifugal time is 0.5-3 h.
The invention has the beneficial effects that: the invention provides a process for preparing (V, ti) 2 The AlC submicron sheet and nanometer particle method has low energy consumption, safety, environmental protection, simple operation, time saving and low cost, and the prepared (V, ti) 2 AlC submicron sheets and nanoparticles are suitable for use as lithium ion battery anode materials and exhibit significant lithium ion storage capacity with progressively increasing capacity as cycling proceeds.
Drawings
FIG. 1 shows the reaction mixture (V) obtained in example 1 0.65 Ti 0.35 ) 2 XRD diffraction pattern of AlC powder;
FIG. 2 shows the reaction mixture (V) obtained in example 1 0.65 Ti 0.35 ) 2 SEM images of AlC submicron sheets;
FIG. 3 shows the reaction mixture (V) obtained in example 1 0.65 Ti 0.35 ) 2 SEM images of AlC nanoparticles.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific drawings and the specific embodiments.
Example 1
Preparation (V, ti) 2 A method of AlC submicron platelets and nanoparticles comprising the steps of:
(1) Grinding and mixing the dried (dried at 50 ℃ for 18 hours) V powder, ti powder, al powder, sn powder and C powder in a molar ratio of 1.3:0.7:1.15:0.12:1 in a QB-BP ball mill for 3 hours under the relative humidity of about 40%, and controlling the rotating speed at 300rpm to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and under the protection of argon atmosphere (the argon pressure is controlled to be 1.5 in the reaction kettle)Local atmospheric pressure) to perform high-temperature self-propagating synthesis at 100-150deg.C for 4min to obtain (V) 0.65 Ti 0.35 ) 2 AlC MAX phase material;
(3) Will (V) 0.65 Ti 0.35 ) 2 Crushing AlC MAX phase material, grinding to 300 mesh to obtain (V) 0.65 Ti 0.35 ) 2 AlC powder, 5g (V) 0.65 Ti 0.35 ) 2 Adding AlC powder into 80ml absolute ethanol, and performing ultrasonic treatment (ultrasonic power is 100w, frequency is 40 KHz) for 2h;
(V 0.65 Ti 0.35 ) 2 XRD diffraction patterns of AlC powder are shown in figure 1, peak and V 2 AlC is substantially uniform but the position is slightly shifted to a small angle, indicating (V 0.65 Ti 0.35 ) 2 AlC crystal form and V 2 AlC is consistent but the cell parameters vary slightly due to the doping of Ti. That is, the method successfully synthesizes solid solution form (V 0.65 Ti 0.35 ) 2 AlC。
(4) Placing the solution obtained after the ultrasonic treatment in the step (3) into a refrigerator, standing and precipitating for 3 days, taking the upper layer solution, centrifuging at 500rpm for 1h, then taking out the centrifuged upper layer solution, adding the upper layer solution into a new centrifuge tube, centrifuging at 3500rpm for 1h, and obtaining a lower layer precipitate (V) 0.65 Ti 0.35 ) 2 AlC submicron tablet, supernatant liquid is (V) 0.65 Ti 0.35 ) 2 Colloidal solution of AlC nanoparticles.
FIG. 2 is (V) 0.65 Ti 0.35 ) 2 SEM image of AlC submicron sheet, FIG. 3 shows (V 0.65 Ti 0.35 ) 2 SEM images of AlC nanoparticles. As can be seen from fig. 2, the submicron flakes are typically less than 1 micron in size and very thin, less than 0.1 micron in thickness, and as can be seen from fig. 3, the nanoparticle size is only about tens of nanometers.
Taking the sample (V) obtained in example 1 0.65 Ti 0.35 ) 2 After the AlC submicron sheet is dried, the AlC submicron sheet, PVDF and acetylene black are added into N-methyl pyrrolidone according to the proportion of 8:1:1, and stirred for 24 hours to form uniform slurry. Uniformly coating the slurry on copper foil, airing, and vacuum drying the copper foilDrying in a drying box at 100deg.C for 12 hr, and cutting into round pieces with diameter of 12 mm. A mixed solution of 1M LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (V) EC :V DMC =1:1), the assembly of the coin cell was performed in an argon-filled glove box. After the assembled battery is kept stand for 24 hours, constant-current charge and discharge test and cycle test are carried out, and the specific capacity of the initial discharge reaches 502mAh g -1 The specific discharge capacity can be kept at 420mAh g after 1000 times of charge and discharge -1 。
Example 2
Preparation (V, ti) 2 A method of AlC submicron platelets and nanoparticles comprising the steps of:
(1) Grinding and mixing the dried (dried at 60 ℃ for 12 hours) V powder, ti powder, al powder and C powder in a molar ratio of 1.5:0.5:1:1 in a QB-BP ball mill for 3 hours under the relative humidity of about 40%, and controlling the rotating speed at 300rpm to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and performing high-temperature self-propagating synthesis under the protection of argon atmosphere (the argon pressure is controlled to be 1.5 local atmospheres in the reaction kettle), wherein the high-temperature self-propagating synthesis temperature is 100-150 ℃ and the time is 5min, thereby obtaining (V) 0.75 Ti 0.25 ) 2 AlC MAX phase material;
(3) Will (V) 0.75 Ti 0.25 ) 2 Crushing AlC MAX phase material, grinding to 300 mesh to obtain (V) 0.75 Ti 0.25 ) 2 AlC powder, 5g (V) 0.75 Ti 0.25 ) 2 Adding AlC powder into 80ml absolute ethanol, and performing ultrasonic treatment (ultrasonic power is 100w, frequency is 40 KHz) for 3h;
(4) Placing the solution obtained after the ultrasonic treatment in the step (3) into a refrigerator, standing and precipitating for 2 days, taking the upper layer solution, centrifuging at 500rpm for 1h, then taking out the centrifuged upper layer solution, adding the upper layer solution into a new centrifuge tube, centrifuging at 3500rpm for 10min, and obtaining a lower layer precipitate (V) 0.75 Ti 0.25 ) 2 AlC submicron tablet, supernatant liquid is (V) 0.75 Ti 0.25 ) 2 Colloidal solution of AlC nanoparticles.
Taking the sample (V) obtained in example 2 0.75 Ti 0.25 ) 2 After the AlC submicron sheet is dried, the AlC submicron sheet, PVDF and acetylene black are added into N-methyl pyrrolidone according to the proportion of 8:1:1, and stirred for 24 hours to form uniform slurry. And uniformly coating the slurry on a copper foil, airing, drying the copper foil in a vacuum drying oven at 100 ℃ for 12 hours, and cutting the copper foil into wafers with the diameter of 12mm after the drying. A mixed solution of 1M LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (V) EC :V DMC =1:1), the assembly of the coin cell was performed in an argon-filled glove box. After the assembled battery is kept stand for 24 hours, constant-current charge and discharge test and cycle test are carried out, and the specific capacity of the initial discharge reaches 487mAh g -1 The specific discharge capacity can be kept at 405mAh g after 1000 times of charge and discharge -1 。
Example 3
Preparation (V, ti) 2 A method of AlC submicron platelets and nanoparticles comprising the steps of:
(1) Grinding and mixing the dried (dried at 60 ℃ for 12 hours) V powder, ti powder, al powder and C powder in a molar ratio of 1.3:0.7:1:1 in a QB-BP ball mill for 3 hours under the relative humidity of about 40%, and controlling the rotating speed at 300rpm to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and performing high-temperature self-propagating synthesis under the protection of argon atmosphere (the argon pressure is controlled to be 1.5 local atmospheres in the reaction kettle), wherein the high-temperature self-propagating synthesis temperature is 100-150 ℃ and the time is 3min, thereby obtaining (V) 0.65 Ti 0.35 ) 2 AlC MAX phase material;
(3) Will (V) 0.65 Ti 0.35 ) 2 Crushing AlC MAX phase material, grinding to 300 mesh to obtain (V) 0.65 Ti 0.35 ) 2 AlC powder, 5g (V) 0.65 Ti 0.35 ) 2 Adding AlC powder into 80ml absolute ethanol, and performing ultrasonic treatment (ultrasonic power is 100w, frequency is 40 KHz) for 3h;
(4) Placing the solution obtained after the ultrasonic treatment in the step (3) into a refrigerator, standing and precipitating for 2 days, taking the upper layer solution, centrifuging at 500rpm for 1h, and then dissolving the centrifuged upper layerTaking out the solution, adding into a new centrifuge tube, centrifuging at 3500rpm for 40min, and collecting lower precipitate (V) 0.65 Ti 0.35 ) 2 AlC submicron tablet, supernatant liquid is (V) 0.65 Ti 0.35 ) 2 Colloidal solution of AlC nanoparticles.
Taking the sample (V) obtained in example 3 0.65 Ti 0.35 ) 2 After the AlC submicron sheet is dried, the AlC submicron sheet, PVDF and acetylene black are added into N-methyl pyrrolidone according to the proportion of 8:1:1, and stirred for 24 hours to form uniform slurry. And uniformly coating the slurry on a copper foil, airing, drying the copper foil in a vacuum drying oven at 100 ℃ for 12 hours, and cutting the copper foil into wafers with the diameter of 12mm after the drying. A mixed solution of 1M LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (V) EC :V DMC =1:1), the assembly of the coin cell was performed in an argon-filled glove box. After the assembled battery is kept stand for 24 hours, constant-current charge and discharge test and cycle test are carried out, and the specific capacity of initial discharge reaches 545mAh g -1 The specific discharge capacity after 1000 times of charge and discharge can be kept at 397mAh g -1 。
Example 4
Preparation (V, ti) 2 A method of AlC submicron platelets and nanoparticles comprising the steps of:
(1) Grinding and mixing the dried (dried at 50 ℃ for 18 hours) V powder, ti powder, al powder, sn powder and C powder in a molar ratio of 1.1:0.9:1.2:0.18:1 in a QB-BP ball mill for 3 hours under the relative humidity of about 40%, and controlling the rotating speed at 300rpm to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and performing high-temperature self-propagating synthesis under the protection of argon atmosphere (the argon pressure is controlled to be 1.5 local atmospheres in the reaction kettle), wherein the high-temperature self-propagating synthesis temperature is 100-150 ℃ and the time is 4min, thereby obtaining (V) 0.55 Ti 0.45 ) 2 AlC MAX phase material;
(3) Will (V) 0.55 Ti 0.45 ) 2 Crushing AlC MAX phase material, grinding to 300 mesh to obtain (V) 0.55 Ti 0.45 ) 2 AlC powder, 5g (V) 0.55 Ti 0.45 ) 2 Adding AlC powder into 80ml absolute ethanol, and performing ultrasonic treatment (ultrasonic power is 100w, frequency is 40 KHz) for 2h;
(4) Placing the solution obtained after the ultrasonic treatment in the step (3) into a refrigerator, standing and precipitating for 3 days, taking the upper layer solution, centrifuging at 500rpm for 1h, then taking out the centrifuged upper layer solution, adding the upper layer solution into a new centrifuge tube, centrifuging at 3500rpm for 1h, and obtaining a lower layer precipitate (V) 0.55 Ti 0.45 ) 2 AlC submicron tablet, supernatant liquid is (V) 0.55 Ti 0.45 ) 2 Colloidal solution of AlC nanoparticles.
Taking the sample (V) obtained in example 4 0.55 Ti 0.45 ) 2 After the AlC submicron sheet is dried, adding the AlC submicron sheet, PVDF and acetylene black into proper amount of N-methyl pyrrolidone according to the ratio of 8:1:1, and stirring for 24 hours to form uniform slurry. And uniformly coating the slurry on a copper foil, airing, drying the copper foil in a vacuum drying oven at 100 ℃ for 12 hours, and cutting the copper foil into wafers with the diameter of 12mm after the drying. A mixed solution of 1M LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (V) EC :V DMC =1:1), the assembly of the coin cell was performed in an argon-filled glove box. After the assembled battery is kept stand for 24 hours, constant-current charge and discharge test and cycle test are carried out, and the specific capacity of initial discharge reaches 432mAh g -1 The specific discharge capacity after 1000 times of charge and discharge can be kept at 369mAh g -1 。

Claims (8)

1. Preparation (V, ti) 2 The method for preparing the AlC submicron sheets and nano particles is characterized by comprising the following steps:
(1) Grinding and mixing the dried V powder, ti powder, al powder, sn powder and C powder in a ball mill according to the molar ratio of (1.8-1): (0.2-1.5): (0-0.35): (0.85-1.2) to obtain mixed powder;
(2) Adding the mixed powder into a graphite crucible, and performing high-temperature self-propagating synthesis under the protection of argon atmosphere to obtain (V, ti) 2 AlC MAX phase material;
(3) Will (V, ti) 2 AlC MAX phase material crushingGrinding to obtain (V, ti) 2 AlC powder is added into a solvent for solvent ultrasonic treatment;
(4) Standing the solution obtained after the ultrasonic treatment in the step (3) for precipitation for 2-5 days, centrifuging the upper layer solution, and obtaining a lower layer precipitate (V, ti) after centrifuging 2 AlC submicron tablet, supernatant liquid is (V, ti) 2 Colloidal solution of AlC nanoparticles.
2. The process according to claim 1 (V, ti) 2 The method for preparing the AlC submicron sheets and nano particles is characterized in that in the step (1), the molar ratio of V powder to Ti powder to Al powder to Sn powder to C powder is 1.3:0.7:1.15:0.12:1.
3. The process according to claim 1 (V, ti) 2 The method for preparing AlC submicron sheets and nanometer particles is characterized in that in the step (1), the relative humidity is controlled to be less than or equal to 60 percent during grinding and mixing.
4. The process according to claim 1 (V, ti) 2 The AlC submicron sheet and nanometer particle method is characterized in that in the step (2), the high-temperature self-propagating synthesis temperature is 150-300 ℃ and the time is less than or equal to 5min.
5. The process according to claim 1 (V, ti) 2 The AlC submicron sheet and nanometer particle method is characterized in that in the step (2), the air pressure of argon in a high-temperature self-propagating synthesis reaction kettle is controlled to be 1.0-2.5 atmospheres.
6. The process according to claim 1 (V, ti) 2 The method for preparing AlC submicron sheets and nanometer particles is characterized in that in the step (3), the solvent is selected from any one of water, absolute ethyl alcohol, acetone, glycol, dimethyl maple or N-methyl pyrrolidone.
7. The process according to claim 1 (V, ti) 2 The method for preparing AlC submicron sheets and nanometer particles is characterized in that argon is required to be introduced into a solvent as a protective gas during ultrasonic treatment in the step (3),the ultrasonic power is 100w and the frequency is 40KHz.
8. The process according to claim 1 to 7 (V, ti) 2 The AlC submicron tablet and nanoparticle method is characterized in that in the step (4), the centrifugal speed is 500-5000 rpm, and the centrifugal time is 0.5-3 h.
CN202010873464.9A 2020-08-26 2020-08-26 Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method Active CN112010305B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010873464.9A CN112010305B (en) 2020-08-26 2020-08-26 Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010873464.9A CN112010305B (en) 2020-08-26 2020-08-26 Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method

Publications (2)

Publication Number Publication Date
CN112010305A CN112010305A (en) 2020-12-01
CN112010305B true CN112010305B (en) 2023-06-27

Family

ID=73502574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010873464.9A Active CN112010305B (en) 2020-08-26 2020-08-26 Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method

Country Status (1)

Country Link
CN (1) CN112010305B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112938978A (en) * 2021-03-03 2021-06-11 盐城工学院 Preparation method of vanadium carbide nanosheet
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016012275A1 (en) * 2014-07-22 2016-01-28 Basf Se Composites comprising mxenes for cathodes of lithium sulfur cells
CN106699184A (en) * 2017-01-12 2017-05-24 盐城工学院 Preparation method for Ti3SnC2 ceramic powder and prepared ceramic powder
CN108075135A (en) * 2017-12-26 2018-05-25 盐城工学院 A kind of preparation method for mixing vanadium carbon titanium sulfide cell negative electrode material and its resulting materials and application
CN108726519A (en) * 2018-07-05 2018-11-02 盐城工学院 A method of preparing MXenes colloids using self-propagating high-temperature method synthesis MAX phase materials
CN109273685A (en) * 2018-09-07 2019-01-25 中南大学 A kind of nano-micro structure composite cathode material of lithium ion battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016012275A1 (en) * 2014-07-22 2016-01-28 Basf Se Composites comprising mxenes for cathodes of lithium sulfur cells
CN106699184A (en) * 2017-01-12 2017-05-24 盐城工学院 Preparation method for Ti3SnC2 ceramic powder and prepared ceramic powder
CN108075135A (en) * 2017-12-26 2018-05-25 盐城工学院 A kind of preparation method for mixing vanadium carbon titanium sulfide cell negative electrode material and its resulting materials and application
CN108726519A (en) * 2018-07-05 2018-11-02 盐城工学院 A method of preparing MXenes colloids using self-propagating high-temperature method synthesis MAX phase materials
CN109273685A (en) * 2018-09-07 2019-01-25 中南大学 A kind of nano-micro structure composite cathode material of lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Li, Xin.Synthesis of phase purity V2AlC via self-propagation high temperature sintering.International Journal of Materials Research.2013,第104卷(第6期),603–605. *
Zhou, J..Ti-enhanced exfoliation of V 2 AlC into V 2 C MXene for lithium-ion battery anodes.Ceramics International.2017,第43卷(第14期),11450–11454. *

Also Published As

Publication number Publication date
CN112010305A (en) 2020-12-01

Similar Documents

Publication Publication Date Title
CN107507972B (en) Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery
WO2021056981A1 (en) Preparation method for silicon-based composite negative electrode material for lithium battery
CN111326723B (en) Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof
CN112366301B (en) Silicon/silicon oxide/carbon composite negative electrode material for lithium ion battery and preparation method thereof
WO2021128603A1 (en) Modified silicon monoxide material for use in negative electrode of lithium-ion battery and preparation method therefor
CN109786670B (en) Preparation method of high-first-efficiency lithium ion secondary battery negative electrode active material
CN103708437B (en) Soft carbon negative material of lithium ion battery, preparation method of soft carbon negative material and lithium ion battery
EP3726628A1 (en) Lithium ion battery negative electrode material and preparation method therefor
CN110289408B (en) Nano silicon and silicon/carbon composite material based on cutting silicon waste material, preparation method and application
CN111710845A (en) Silica composite negative electrode material, preparation method thereof and lithium ion battery
WO2006125358A1 (en) A composite carbon material of negative electrode in lithium ion battery and its preparation method
CN111244438B (en) Graphene/carbon-coated lithium titanate composite material and preparation method thereof
CN106784741B (en) Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material
CN112010305B (en) Preparation (V, ti) 2 AlC submicron sheet and nanoparticle method
CN111048764A (en) Silicon-carbon composite material and preparation method and application thereof
CN103219168A (en) Li4Ti5O12/ grapheme composite electrode material and preparation method thereof
CN114044513B (en) Preparation method of coal-based graphite/carbon composite anode material for power lithium ion battery
CN112652742A (en) Silicon-carbon composite material and preparation method and application thereof
CN113851627A (en) Porous silicon-carbon negative electrode material and preparation method thereof
CN113363473A (en) Preparation method of high-first-efficiency SiO graphite composite negative electrode material
Wang et al. High-performance anode of lithium ion batteries with plasma-prepared silicon nanoparticles and a three-component binder
CN111564618A (en) High-capacity lithium ion battery cathode material capable of being industrially produced
CN108306002B (en) Li applied to negative electrode of lithium ion battery21Si5Preparation of graphene composite material
Song et al. A three-dimensional porous Si/SiOx decorated by nitrogen-doped carbon as anode materials for lithium-ion batteries
CN113054170B (en) Preparation method of nickel-nickel molybdenum oxide-graphene composite material and application of nickel-nickel molybdenum oxide-graphene composite material in lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20201201

Assignee: DONGTAI GAOKE TECHNOLOGY INNOVATION PARK Co.,Ltd.

Assignor: YANCHENG INSTITUTE OF TECHNOLOGY

Contract record no.: X2024980001369

Denomination of invention: A method for preparing (V, Ti)2AlC submicron sheets and nanoparticles

Granted publication date: 20230627

License type: Common License

Record date: 20240124

EC01 Cancellation of recordation of patent licensing contract

Assignee: DONGTAI GAOKE TECHNOLOGY INNOVATION PARK Co.,Ltd.

Assignor: YANCHENG INSTITUTE OF TECHNOLOGY

Contract record no.: X2024980001369

Date of cancellation: 20240407