CN114162866A - Vanadium oxide nanosheet and preparation method of two-dimensional composite material of vanadium oxide nanosheet and MXene - Google Patents

Vanadium oxide nanosheet and preparation method of two-dimensional composite material of vanadium oxide nanosheet and MXene Download PDF

Info

Publication number
CN114162866A
CN114162866A CN202111229654.8A CN202111229654A CN114162866A CN 114162866 A CN114162866 A CN 114162866A CN 202111229654 A CN202111229654 A CN 202111229654A CN 114162866 A CN114162866 A CN 114162866A
Authority
CN
China
Prior art keywords
vanadium oxide
mxene
nanosheet
vanadium
suspension
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111229654.8A
Other languages
Chinese (zh)
Other versions
CN114162866B (en
Inventor
黄娟娟
肖保全
陈杰
杨文静
胡长发
彭尚龙
闫德
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.)
Lanzhou University
Original Assignee
Lanzhou University
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 Lanzhou University filed Critical Lanzhou University
Priority to CN202111229654.8A priority Critical patent/CN114162866B/en
Publication of CN114162866A publication Critical patent/CN114162866A/en
Application granted granted Critical
Publication of CN114162866B publication Critical patent/CN114162866B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • 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
    • C01B32/914—Carbides of single elements
    • 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
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H01M2004/028—Positive 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a vanadium oxide nanosheet and a preparation method of a two-dimensional composite material of the vanadium oxide nanosheet and MXene, and vanadium oxideThe preparation method of the nano-sheet comprises the steps of vanadium source dispersion, vanadium oxide nucleation growth and vanadium oxide (V) preparation5O12·nH2O) nano-flakes, product freeze-drying; the preparation method of the two-dimensional composite material of the vanadium oxide nanosheet and the MXene comprises the steps of positive electricity pretreatment of the vanadium oxide nanosheet, self-assembly compounding of the vanadium oxide nanosheet and the MXene nanosheet, centrifugal washing and freeze-drying. According to the preparation method of the vanadium oxide nanosheet, a template agent is not required to be added, and the yield of the nanosheet can be increased to over 75%. When the two-dimensional composite material of the vanadium oxide nanosheet and MXene is applied to a water-based zinc-ion battery, the two-dimensional composite material shows a V-exceeding effect due to the interface effect of the composite material5O12·nH2O actual capacity of theoretical capacity.

Description

Vanadium oxide nanosheet and preparation method of two-dimensional composite material of vanadium oxide nanosheet and MXene
Technical Field
The invention belongs to the technical field of water-based zinc ion battery materials, and particularly relates to a vanadium oxide nanosheet and a preparation method of a two-dimensional composite material of the vanadium oxide nanosheet and MXene.
Background
In the field of water-based zinc ion batteries, methods for preparing vanadium oxide nano arrays and ultrathin titanium carbide nano sheets are disclosed in Chinese patent CN105271407A & lt & gt vanadium oxide nano arrays and preparation method thereof & lt & gt and CN109569494A & lt & gt MXene-Ti3C2The preparation method and the application of the nano-sheets are respectively disclosed in the specification.
The former is a hydrothermal synthesis method, and a vanadium oxide nano-sheet is formed and then self-assembled to form a vanadium oxide nano-array, however, the method can be completed only under the action of a specific template agent, and the so-called vanadium oxide nano-array is serious in self-stacking, thick in sheet layer, long in preparation period, and not beneficial to the exertion of material energy storage performance.
The product prepared by the latter has almost no capacity when being used in an aqueous zinc ion battery, and does not participate in Faraday redox reaction, so that the energy storage capacity of the simple MXene is very limited when being used as a positive electrode material of the aqueous zinc ion battery.
The literature Nano Energy 39(2017)151-161 mentions that commercial V is used2O5The powder is poured into deionized water and then V is directly added2O5The suspension is subjected to ultrasonic treatment to obtain V2O5The yield of the nano-sheets obtained by the method is low, and is only 20%, and the nano-sheets have serious breakage and nonuniform appearance.
In order to excavate a novel material suitable for an energy storage device and provide an effective preparation method and a nanosheet with good performance, a process technology for preparing a vanadium oxide nanosheet through in-situ liquid phase growth and ultrasonic stripping is provided; in addition, a two-dimensional composite material of a vanadium oxide nanosheet and an MXene nanosheet and a preparation method thereof are also provided.
Disclosure of Invention
The invention aims to provide a preparation method of vanadium oxide nanosheets, which aims to solve the problems of low yield and unsatisfactory product form of the preparation method of the vanadium oxide nanosheets.
The invention also aims to provide a preparation method of the two-dimensional composite material of the vanadium oxide nanosheet and MXene, so as to solve the problem that the energy storage capacity of the existing composite material is limited.
In order to solve the problems, the technical scheme of the invention is as follows:
a preparation method of a vanadium oxide nanosheet comprises the following steps:
step A, dispersing a vanadium source;
vanadium oxide as a vanadium source is dispersed in deionized water at a molar concentration of 0.022-0.047mol/L, hydrogen peroxide with a molar concentration of 10-40 times that of vanadium oxide and 8-12 drops of ethylene glycol (about 0.4-0.6mL) are added, and then the mixed solution is transferred into a water bath kettle and stirred magnetically at a constant temperature of 30-60 ℃ for 2-3.5 hours to uniformly disperse the vanadium source.
B, growing vanadium oxide nucleation;
taking out magnetons, preserving the dispersed clear yellow solution at 30-60 ℃ for 10-30 hours, and taking out the dark green suspension from the water bath after the vanadium oxide forms nuclei and grows.
Step C, preparation of vanadium oxide (V)5O12·nH2O) nanoflakes;
transferring the dark green suspension to an ultrasonic cleaner, and ultrasonically treating at 30-60 deg.C for 1-10 hr to remove V5O12·nH2And O, stripping.
On one hand, the step of utilizing ultrasonic waves to destroy Van der Waals bonds among material layers to enable the multilayer structure to be stripped into few layers or single layers V5O12·nH2O nanosheet; on the other hand, the oscillation effect of the ultrasonic waves can greatly hinder the further growth of crystal grains and prevent the crystal grains and the sheet layers with larger sizes from being generated, so that the growth of crystal nuclei can be controlled by adjusting the frequency and the action time of the ultrasonic waves, and the size of the nanosheets is controlled.
Centrifuging the solution at the rotating speed of 1000-3000r/min for 0.5-3 hours to obtain an upper layer suspension which is the vanadium oxide (V) successfully stripped5O12·nH2O) nanoflakes.
Step D: freeze-drying the product;
and D, quickly freezing the upper suspension obtained in the step C, and then putting the upper suspension into a freeze dryer to dry for 72-120 hours to obtain fluffy yellow-green flocculent vanadium oxide nanosheets.
Further, the vanadium oxide as the vanadium source in the step A is V2O5Or V2O5·nH2O。
A preparation method of a two-dimensional composite material of a vanadium oxide nanosheet and MXene is based on the preparation method of the vanadium oxide nanosheet, and further comprises the following steps:
step E: carrying out positive electricity pretreatment on the vanadium oxide nano sheet;
vanadium oxide nanosheet (HVO-NS) treated with ammonium dihydrogen phosphate (NH)4H2PO4) Or polyethylene propyl dimethyl ammonium chloride (PDDA) for pretreatment, and the specific steps refer toThe following: namely vanadium oxide nanosheet (HVO-NS) and ammonium dihydrogen phosphate (NH)4H2PO4) Or adding vanadium oxide nanosheets (HVO-NS) and polyvinyl propyl dimethyl ammonium chloride (PDDA) into a proper amount of deionized water according to the molar ratio of 1:1 to form suspension with the concentration of 1-3g/L, stirring for 1 hour at room temperature to enable the suspension to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets.
The purpose of this step of treatment is to make the vanadium oxide nanosheets positively charged, thereby facilitating self-assembly in the next step.
Step F: self-assembly compounding of positively charged vanadium oxide nanosheets and negatively charged MXene nanosheets;
and E, adding the positively charged vanadium oxide nanosheets and the negatively charged MXene nanosheets prepared in the step E into a proper amount of deionized water according to the mass ratio of 1:1-20:1, providing a necessary liquid phase environment to enable the materials to be compounded efficiently, forming a suspension with the concentration of 1-2g/L, and slowly stirring for 10-24 hours at the stirring speed of 100-300r/min to form a composite material suspension combined in a face-to-face manner.
Negatively charged MXene (Ti) in this step3C2) The nano-sheet is prepared by a preparation method in the prior art, and the details are shown in Chinese patent CN109569494A A MXene-Ti3C2Preparation method of nanosheet and application thereof, due to Ti3C2The functional groups (-O, -F and-OH) are self-negatively charged, so that the two are self-assembled in water due to electrostatic adsorption to form a composite material combined in a face-to-face mode.
Step G: centrifugal washing and freeze-drying;
and F, centrifugally washing the composite material suspension prepared in the step F by using deionized water, and freeze-drying for 48-72 hours to obtain the powdery two-dimensional composite material (V) of the vanadium oxide nanosheet and MXene5O12·nH2O@MXene)。
The invention has the following beneficial effects:
(1) the preparation method of the vanadium oxide nanosheet adopts in-situ liquid phase growth ultrasonic stripping, namely when a sample is prepared by using a sol-gel method, an ultrasonic environment is added in a curing stage of hydrogel formation for treatment, and the vanadium oxide nanosheet is prepared, a template agent is not required to be added in the preparation method, and the yield of the nanosheet can be increased to over 75%.
The product prepared is a compound with V5+And V4+V of mixed valence state5O12·nH2The thickness of the O nano sheet is about 1-10nm, the transverse dimension is about 10-30 mu m, and the O nano sheet has better dispersibility and stability in a liquid phase; due to its having
Figure BDA0003315517330000041
The anode material has the advantages of wide interlayer spacing, good morphological characteristics, stability and the like, and can be applied to the anode material of the water system zinc ion battery. Meanwhile, the energy band structure of the product is changed to a certain extent, and the photoluminescence spectrum can show that an obvious emission peak with higher intensity appears at 648nm under the action of exciting light with 365nm wavelength, which indicates that the product is also used as potential of luminescent materials. In addition, the product can be mixed with conventional carbon nanotubes, and a flexible thin film electrode with high conductivity and self-supporting function is prepared by ultrasonic spraying; or compounding with other layered materials to prepare a novel composite material with a sandwich structure; the vanadium oxide nanosheet can be used as a substrate material, and other substances can grow on the surface of the vanadium oxide nanosheet, so that the material can be conveniently subjected to deep modification and the like.
In addition, the method has good universality and high yield, and can realize sheet stripping for other layered two-dimensional materials which use a sol-gel method or can form nuclei in a solution besides vanadium oxide.
(2) In the implementation of the process, the vanadium oxide is usually composed of VO4Tetrahedron, VO5Pyramid or VO6Octahedron is connected by shared edges or shared angles to form a layered structure, adjacent layers are connected by weak van der Waals bonds, and the interlayer distance of the vanadium oxide is large after water molecules are inserted between the layersIncrease in amplitude, e.g. theoretically only the layer spacing
Figure BDA0003315517330000042
V of2O5After insertion of water molecules the interlayer spacing can be enlarged to
Figure BDA0003315517330000043
The bonding force of the secondary bonds between the layers can be further weakened, so that the possibility of ultrasonically peeling off few-layer nano sheets or single-layer nano sheets through in-situ liquid phase growth is provided. Meanwhile, according to the Ostwald ripening mechanism (Ostwald ripening), smaller grains have larger surface energy, and are spontaneously absorbed and combined by larger grains above the critical dimension, and grow into grains with larger volume or crystals to form precipitates, which is extremely unfavorable for preparing nano materials. Therefore, the ultrasonic wave not only has a stripping effect in the method, but also simultaneously utilizes the cavitation effect and the acoustic flow effect of the ultrasonic wave, and inhibits the growth of crystal grains while stripping, thereby preparing the nano-sheet with small crystal size and uniform distribution.
(3) The invention provides a preparation method of a two-dimensional composite material of a vanadium oxide nanosheet and MXene, which belongs to the initiative, and the novel two-dimensional composite material (V) of the vanadium oxide nanosheet and the MXene is formed in a way that the flaky vanadium oxide nanosheet and the MXene nanosheet with wide interlayer spacing are self-assembled by means of electrostatic adsorption5O12·nH2O@MXene)。
The composite material makes up and improves the defects of insufficient conductivity, unstable structure, poor mechanical property and the like of vanadium oxide by using the high conductivity, hydrophilicity, good structural stability and mechanical property of MXene, and improves the defects of poor conductivity and unstable structure when the conventional vanadium oxide is used as an Aqueous Zinc Ion Battery (AZIBs), thereby providing an electrode material with good comprehensive properties for AZIBs, supercapacitors and the like.
The two nano sheets are spontaneously assembled in an electrostatic adsorption mode, so that the nano sheets can be prevented from being broken, an open layered structure similar to a sandwich structure can be formed, intercalation/deintercalation of intercalation ions is facilitated, and due to the heterostructure generated by introduction of MXene with excellent conductivity, the overall conductivity of the material and active sites for ion storage are greatly increased, and the comprehensive performance of AZIBs is remarkably improved.
In addition, MXene compounded with vanadium oxide nanosheets selected for Ti removal3C2In addition, it may also be Ti3C2Two-dimensional layered materials of similar structure, or with negatively-charged functional groups, e.g. Ti2C、V2C、Nb2C, rGO and the like, all of which have good conductivity and have molecular weight ratio to Ti3C2Smaller, so that in Ti3C2In the case of possible combinations, several substances are additionally present with V5O12·nH2The O nano-sheet also has good compatibility, so that the O nano-sheet can be mixed with V5O12·nH2O constitutes the composite material by this method.
(4) The two-dimensional composite material (V) of the vanadium oxide nanosheet and MXene prepared by the method5O12·nH2O @ MXene) exhibits surpassing V5O12·nH2O actual capacity of theoretical capacity. The product prepared by the method activates the Faraday activity of MXene which has no energy storage capacity in water-based zinc ion batteries (AZIBs) originally through the interface effect generated by the composite heterostructure, provides more active sites for the storage of intercalation ions, and thus provides additional capacity contribution.
Drawings
FIG. 1 is SEM photographs of vanadium oxide nanosheets prepared according to the present invention at 8000 and 4000 times, respectively;
FIG. 2 is a TEM and SAED photograph of vanadium oxide nanosheets prepared in accordance with the present invention;
FIG. 3 is an XRD pattern of a vanadium oxide nanosheet prepared in accordance with the present invention;
FIG. 4 shows V prepared according to the present invention5O12·nH2SEM photograph of O @ MXene two-dimensional composite material;
FIG. 5 shows V prepared according to the present invention5O12·nH2TEM and SAED photographs of the O @ MXene two-dimensional composite material;
FIG. 6 shows V prepared according to the present invention5O12·nH2EDS photo of O @ MXene two-dimensional composite material;
FIG. 7 shows pure vanadium oxide nanosheets (HVO-NS) and V prepared in accordance with the present invention5O12·
nH2And (3) a multiplying power performance comparison graph of an electrode made of O @ MXene two-dimensional composite material (mass ratio of 3:1) when the electrode is used for AZIBs.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the claimed invention, but is merely representative of selected embodiments of the invention.
Example 1
This example, Steps A-D, are procedures for preparing vanadium oxide nanoplates (HVO-NS).
Step E-step G is to prepare the two-dimensional composite material of the vanadium oxide nanosheet and MXene by using the vanadium oxide nanosheet prepared in the step A-step D as a raw material (V)5O12·nH2O @ MXene), which was prepared as a starting material in the preceding step, was tested as a whole in the examples.
A preparation method of a vanadium oxide nanosheet comprises the following steps:
step A, dispersing a vanadium source;
weighing 2g of V serving as vanadium source2O5·H2O to 450mL of deionized waterIn the reaction system, 0.022mol/L of V is formed2O5The suspension was added with 45mL of 30% hydrogen peroxide solution and 8 drops of ethylene glycol (about 0.4mL as measured), and the mixture was transferred to a water bath and magnetically stirred at 60 ℃ for 2 hours to uniformly disperse the vanadium source.
B, growing vanadium oxide nucleation;
taking out magnetons, preserving the dispersed clear yellow solution at 60 ℃ for 10 hours, and taking out the suspension which becomes dark green from the water bath after the vanadium oxide nucleates and grows.
Step C, preparation of vanadium oxide (V)5O12·nH2O) nanoflakes;
transferring the dark green suspension obtained in step B to an ultrasonic cleaner, and carrying out constant-temperature ultrasonic treatment at 60 ℃ for 10 hours to remove newly formed V5O12·nH2And O, stripping.
And centrifuging the suspension at the rotating speed of 1000r/min for 3 hours to obtain an upper suspension, namely the successfully stripped vanadium oxide nanosheet (HVO-NS), which accounts for 75-85% of the total mass of the vanadium oxide. While the bottom precipitate is the multilayer or bulk vanadium oxide V which is not successfully stripped5O12·nH2O, accounting for about 15-25% of the total mass, and the process also proves that the in-situ liquid phase growth ultrasonic stripping is a very efficient means for stripping vanadium oxide.
Step D: freeze-drying the product;
and D, quickly freezing the upper suspension obtained in the step C by using liquid nitrogen, and then putting the upper suspension into a freeze dryer for drying for 72 hours to obtain fluffy yellow-green flocculent vanadium oxide nanosheets, wherein the vanadium oxide nanosheets obtained in the embodiment are used as samples 1-1.
A preparation method of a two-dimensional composite material of vanadium oxide nanosheets and MXene takes the vanadium oxide nanosheets prepared in the step D as a raw material in the step E.
Step E: carrying out positive electricity pretreatment on the vanadium oxide nano sheet;
vanadium oxide nanosheets (HVO-NS) were pretreated with poly (vinylpropyldimethylammonium chloride) (PDDA), with reference to the following steps:
weighing 45mg of vanadium oxide nanosheet (HVO-NS) obtained in the step D and 46.5316mg of 35% polyvinyl propyl dimethyl ammonium chloride solution (PDDA) in a molar ratio of 1:1, adding the mixture into 30mL of deionized water, mixing (the concentration is about 3g/L), stirring for 1 hour at room temperature to enable the mixture to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheet.
Step F: self-assembly compounding of positively charged vanadium oxide nanosheets and negatively charged MXene nanosheets;
and E, adding 45mg of positively charged vanadium oxide nanosheets and 15mg of negatively charged MXene nanosheets prepared in the step E into 30mL of deionized water (the concentration is 2g/L) according to the mass ratio of 3:1, and slowly stirring for 10 hours at the stirring speed of 150r/min to form a composite material suspension combined in a face-to-face mode.
Step G: centrifugal washing and freeze-drying;
f, centrifugally washing the composite material suspension prepared in the step F by using deionized water; then freeze-drying for 72 hours to obtain the powdery vanadium oxide nano sheet and MXene two-dimensional composite material (V)5O12·nH2O @ MXene), two-dimensional composite (V) of the vanadium oxide nanosheet and MXene obtained in this example5O12·nH2O @ MXene) as sample 1-2.
Example 2
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V2O5The deionized water added is 250mL, and V with the mol concentration of 0.047mol/L is finally formed2O5A suspension; adding 190mL of hydrogen peroxide in volume; 12 drops of ethylene glycol (measured at about 0.6mL) was added; and (3) performing constant-temperature magnetic stirring for 3 hours at the temperature of 50 ℃ in a water bath kettle to uniformly disperse the vanadium source.
And C, heating the water bath in the step B at 50 ℃, and preserving the heat for 20 hours.
The temperature for heat preservation in the step C is 50 ℃; the time of constant temperature ultrasound is 1 hour; the suspension centrifugation index is: the rotating speed is 3000r/min, and the time is 0.5 hour.
Similarly, the obtained upper suspension is vanadium oxide nanosheet (HVO-NS) which is successfully stripped, and accounts for about 75-85% of the total mass of the vanadium oxide. While the bottom precipitate is the multilayer or bulk vanadium oxide V which is not successfully stripped5O12nH2O, representing about 15-25% of the total mass.
And D, rapidly freezing by using liquid nitrogen, and putting the vanadium oxide nanosheet into a freeze dryer to be dried for 84 hours to obtain a vanadium oxide nanosheet as a sample 2-1.
Step E vanadium oxide nanosheets (HVO-NS) are treated with ammonium dihydrogen phosphate (NH)4H2PO4) The pretreatment is carried out by the following specific steps:
weighing 45mg of vanadium oxide nanosheet (HVO-NS) obtained in the step D and 11.588mg of ammonium dihydrogen phosphate (NH)4H2PO4) Adding the mixture into 30mL of deionized water according to the molar ratio of 1:1, mixing (the concentration is about 1.89g/L), stirring for 1 hour at room temperature to enable the mixture to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets.
In the step F, 15mg of MXene nanosheets with negative charges and 45mg of vanadium oxide nanosheets obtained in the step D are weighed and dispersed in 40mL of deionized water (the concentration is about 1.5g/L), the mass ratio is 3:1, and the stirring indexes are as follows: 100r/min, 24 hours.
The lyophilization time in step G was 48 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nanosheet and MXene5O12·nH2O @ MXene) as sample 2-2.
Example 3
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V2O5The deionized water added is 450mL, and V with the molar concentration of 0.026mol/L is finally formed2O5A suspension; adding 90mL of hydrogen peroxide; add 9 drops of ethylene glycol (measured at about 0.5 mL); in thatAnd (3) in a water bath kettle, carrying out constant-temperature magnetic stirring for 3.5 hours at the temperature of 50 ℃ to uniformly disperse the vanadium source.
And C, heating the water bath in the step B at 50 ℃, and preserving heat for 30 hours.
The temperature for heat preservation in the step C is 50 ℃; the time of constant temperature ultrasound is 3 hours; the suspension centrifugation index is: the rotating speed is 1500r/min, and the time is 1 hour.
Similarly, the obtained upper suspension is vanadium oxide nanosheet (HVO-NS) which is successfully stripped, and accounts for about 75-85% of the total mass of the vanadium oxide. While the bottom precipitate is the multilayer or bulk vanadium oxide V which is not successfully stripped5O12·nH2O, accounting for about 15-25% of the total mass.
And D, rapidly freezing by using liquid nitrogen, and putting the liquid nitrogen into a freeze dryer to dry for 96 hours to obtain vanadium oxide nanosheets serving as the samples 3-1.
Step E vanadium oxide nanosheets (HVO-NS) are treated with ammonium dihydrogen phosphate (NH)4H2PO4) The pretreatment is carried out by the following specific steps:
weighing 30mg of vanadium oxide nanosheet (HVO-NS) obtained in the step D and 7.725mg of ammonium dihydrogen phosphate (NH)4H2PO4) Adding the mixture into 35mL of deionized water according to the molar ratio of 1:1, mixing ((the concentration is 1g/L)), stirring for 1 hour at room temperature to enable the mixture to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets.
In the step F, 30mg of negatively charged MXene nanosheets and 30mg of vanadium oxide nanosheets obtained in the step D are weighed and dispersed in 30mL of deionized water ((with the concentration of 2g/L)), the mass ratio is 1:1, and the stirring indexes are as follows: 300r/min, 16 hours.
The freeze-drying time in step G was 56 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nanosheet and MXene5O12·nH2O @ MXene) as sample 3-2.
Example 4.
The difference from example 1 is that:
the vanadium source weighed in the step A is 2.133V of g2O5350mL of deionized water was added to finally form V with a molar concentration of 0.035mol/L2O5A suspension; the volume of the added hydrogen peroxide is 35 mL; adding 10 drops of ethylene glycol; and (3) performing constant-temperature magnetic stirring for 2.5 hours at the temperature of 50 ℃ in a water bath kettle to uniformly disperse the vanadium source.
In the step B, the temperature of water bath heating is 50 ℃, and the temperature is kept for 30 hours; .
The temperature for heat preservation in the step C is 50 ℃; the time of constant temperature ultrasound is 5 hours; the suspension centrifugation index is: the rotating speed is 2000r/min, and the time is 1.5 hours.
Similarly, the obtained upper suspension is vanadium oxide nanosheet (HVO-NS) which is successfully stripped, and accounts for about 75-85% of the total mass of the vanadium oxide. While the bottom precipitate is the multilayer or bulk vanadium oxide V which is not successfully stripped5O12·nH2O, accounting for about 15-25% of the total mass.
And D, rapidly freezing by using liquid nitrogen, and putting the liquid nitrogen into a freeze dryer to dry for 110 hours to obtain vanadium oxide nanosheets serving as samples 4-1.
Step E vanadium oxide nanosheets (HVO-NS) are treated with ammonium dihydrogen phosphate (NH)4H2PO4) The pretreatment is carried out by the following specific steps:
weighing 50mg of vanadium oxide nanosheet (HVO-NS) obtained in the step D and 12.87mg of ammonium dihydrogen phosphate (NH)4H2PO4) Adding the mixture into 50mL of deionized water according to the molar ratio of 1:1, mixing ((the concentration is about 1.26g/L)), stirring for 1 hour at room temperature to enable the mixture to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets.
In the step F, 10mg of negatively charged MXene nanosheets and 50mg of vanadium oxide nanosheets obtained in the step D are weighed and dispersed in 60mL of deionized water (with the concentration of 1g/L), the mass ratio is 5:1, and the stirring indexes are as follows: 200r/min, 19 hours.
And G, freeze-drying for 64 hours to finally obtain the vanadium oxide nanosheet and MXene two-dimensional composite material (V)5O12·nH2O @ MXene) asSample 4-2.
Example 5
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V2O5Adding 450mL of deionized water to finally form a V2O5 suspension with the molar concentration of 0.026 mol/L; the volume of the added hydrogen peroxide is 90 mL; adding 9 drops of ethylene glycol; (measured at about 0.5 mL); and (3) performing constant-temperature magnetic stirring for 3.5 hours at the temperature of 30 ℃ in a water bath kettle to uniformly disperse the vanadium source.
And C, heating the water bath in the step B at the temperature of 30 ℃ for 30 hours.
The temperature for heat preservation in the step C is 30 ℃; the time of constant temperature ultrasound is 7 hours; the suspension centrifugation index is: the rotating speed is 2500r/min, and the time is 2 hours.
Similarly, the obtained upper suspension is vanadium oxide nanosheet (HVO-NS) which is successfully stripped, and accounts for about 75-85% of the total mass of the vanadium oxide. While the bottom precipitate is the multilayer or bulk vanadium oxide V which is not successfully stripped5O12nH2O, representing about 15-25% of the total mass.
And D, rapidly freezing by using liquid nitrogen, and putting the sample into a freeze dryer to dry for 120 hours to obtain vanadium oxide nanosheets serving as samples 5-1.
Step E vanadium oxide nanosheets (HVO-NS) are treated with ammonium dihydrogen phosphate (NH)4H2PO4) The pretreatment is carried out by the following specific steps:
namely weighing 60mg of vanadium oxide nanosheet (HVO-NS) obtained in the step D and 15.45mg of ammonium dihydrogen phosphate (NH)4H2PO4) Adding the mixture into 60mL of deionized water according to the molar ratio of 1:1, mixing (the concentration is about 1.258g/L), stirring for 1 hour at room temperature to enable the mixture to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets.
In the step F, 3mg of MXene nanosheets with negative charges and 60mg of vanadium oxide nanosheets obtained in the step D are weighed and dispersed in 45mL of deionized water (the concentration is about 1.4g/L), the mass ratio is 20:1, and the stirring indexes are as follows: 180r/min, 21 hours.
The freeze-drying time in step G was 68 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nanosheet and MXene5O12·nH2O @ MXene) as sample 5-2.
Verification test 1
Samples 1-1, 2-1, 3-1, 4-1, and 5-1 prepared in examples 1 to 5, respectively, were mixed to form a new sample 1.
Sample 1 was tested by SEM (scanning electron microscope) to obtain figure 1;
sample 1 was tested by TEM (transmission electron microscope) and SAED (selected area electron diffraction) to give figure 2;
XRD testing of sample 1 gave FIG. 3;
XRD test analysis can confirm that the sample 1 is V5O12·nH2O, V is obtained from the 2 theta angle of the crystal plane of the main peak (001)5O12·nH2Interlayer spacing of O of
Figure BDA0003315517330000121
Meanwhile, the transverse size of the nano sheet is 10-30 mu m according to TEM and SEM.
Samples 1-2, 2-2, 3-2, 4-2, and 5-2 prepared in examples 1-5, respectively, were mixed to form a new sample 2.
Sample 2 was tested by SEM (scanning electron microscope) to obtain figure 4;
sample 2 was tested by TEM (transmission electron microscope) and SAED (selected area electron diffraction) to give figure 5;
sample 2 was EDS tested to give FIG. 6;
it was confirmed that sample 2 was V5O12·nH2Two-dimensional composite material (V) of O nanosheet and MXene5O12·nH2O @ MXene), and V5O12·nH2The O nano-sheet and the MXene nano-sheet are compounded in a face-to-face mode.
Verification test 2
V obtained in example 15O12·nH2The mass ratio of the O nano-sheet to the MXene nano-sheet is 3:1A radical V5O12·nH2The O @ MXene composite material is used as an AZIBs positive electrode, the performance of the O @ MXene composite material is tested to obtain a figure 7, and the actual capacity shown by the composite material is calculated and verified to be higher than V5O12·nH2The theoretical capacity of O proceeds as follows.
1. And (3) calculating: (V)5O12·nH2O is as V5O12Calculating)
V exists in the electrode material during discharging/charging5+→V4+、V4+→V3+/V3+→V4+、V4+→V5+So that V is assumed without taking into account the bulk expansion of the material and the hindrance of the migration barrier caused by intercalation of the intercalating ions5O12Can be converted into V2O3Then, there are:
Figure BDA0003315517330000131
i.e. each V5O12The molecule involves the transfer of 9 electrons; and V5O12Relative molecular mass M ofwIs 446.71 g.mol-1According to a theoretical capacity calculation formula:
Figure BDA0003315517330000132
wherein F is the Faraday constant 96485.34 C.mol-1And n is the number of charge transfers involved in the reaction.
Thus a simple V5O12The theoretical specific mass capacity of the electrode is as follows:
Figure BDA0003315517330000133
however, since the simple MXene electrode has no Faraday activity in AZIBs, does not provide capacity, and V compounded in a mass ratio of 3:15O12·nH2O@MXene composite material electrode V5O12Is 75% by mass, so V5O12·nH2The theoretical mass specific capacity of the O @ MXene composite material electrode is as follows:
CTHVOM＝75％×CTHVO＝404.98mAh·g-1 (4)
in the graph of FIG. 7 for multiplying power performance comparison, V5O12·nH2O @ MXene electrode at 0.2A · g-1Has a current density of 461.20mAh g-1The actual specific mass capacity of (A) is clearly seen in V combined with a mass ratio of 3:15O12·nH2The actual capacity of the O @ MXene composite material electrode exceeds the theoretical capacity C of the electrodeTHVOM。
At the same time, it can be found that: pure HVO (V)5O12·nH2O) electrode showed only 420.40mAh g-1The actual specific capacity of the material is not only lower than the theoretical specific capacity CTHVO(539.98mAh·g-1) And is lower than V5O12·nH2Actual capacity of O @ MXene composite.
Thus, the two-dimensional composite material V of the vanadium oxide nanosheet and MXene prepared by the invention is shown5O12·nH2O @ MXene activates the Faraday activity of MXene through an interface effect generated by a composite heterostructure, so that MXene participates in redox reaction and provides additional active sites for the storage of intercalation ions, and therefore the actual capacity exceeding the theoretical capacity is shown.

Claims (3)

1. A preparation method of a vanadium oxide nanosheet is characterized by comprising the following steps: the method comprises the following steps:
step A, dispersing a vanadium source;
dispersing vanadium oxide serving as a vanadium source into deionized water at a molar concentration of 0.022-0.047mol/L, then adding hydrogen peroxide with a molar concentration of 10-40 times that of the vanadium oxide and 8-12 drops of ethylene glycol (about 0.4-0.6mL), then transferring the mixed solution into a water bath, and carrying out constant-temperature magnetic stirring at 30-60 ℃ for 2-3.5 hours to uniformly disperse the vanadium source;
b, growing vanadium oxide nucleation;
taking out magnetons, preserving the heat of the dispersed clear yellow solution at 30-60 ℃ for 10-30 hours, and taking out the dark green suspension from the water bath after the vanadium oxide forms nuclei and grows;
step C, preparation of vanadium oxide (V)5O12·nH2O) nanoflakes;
transferring the dark green suspension to an ultrasonic cleaner, and ultrasonically treating at 30-60 deg.C for 1-10 hr to remove V5O12·nH2Stripping O;
centrifuging the suspension at the rotating speed of 1000-3000r/min for 0.5-3 hours to obtain an upper layer suspension which is the vanadium oxide (V) successfully stripped5O12·nH2O) nanoflakes;
step D: freeze-drying the product;
and D, quickly freezing the upper suspension obtained in the step C, and then putting the upper suspension into a freeze dryer to dry for 72-120 hours to obtain fluffy yellow-green flocculent vanadium oxide nanosheets.
2. A method of preparing vanadium oxide nanoplates as in claim 1, wherein: the vanadium oxide used as the vanadium source in the step A is V2O5Or V2O5·nH2O。
3. A preparation method of a two-dimensional composite material of a vanadium oxide nanosheet and MXene is characterized by comprising the following steps: the method is based on the preparation method of any one of the vanadium oxide nano sheets in claims 1 to 3, and further comprises the following steps:
step E: carrying out positive electricity pretreatment on the vanadium oxide nano sheet;
vanadium oxide nanosheet (HVO-NS) treated with ammonium dihydrogen phosphate (NH)4H2PO4) Or performing pretreatment on polyvinyl propyl dimethyl ammonium chloride (PDDA), and referring to the following specific steps: namely vanadium oxide nanosheet (HVO-NS) and ammonium dihydrogen phosphate (NH)4H2PO4) Or adding vanadium oxide nanosheets (HVO-NS) and polyvinyl propyl dimethyl ammonium chloride (PDDA) into deionized water according to the molar ratio of 1:1 to form suspension with the concentration of 1-3g/L, stirring for 1 hour at room temperature to enable the suspension to be positively charged, then centrifugally washing for 3 times by using the deionized water, and collecting precipitates to obtain the positively charged vanadium oxide nanosheets;
step F: self-assembly compounding of positively charged vanadium oxide nanosheets and negatively charged MXene nanosheets;
adding the positively charged vanadium oxide nanosheet and the negatively charged MXene nanosheet prepared in the step E into deionized water according to the mass ratio of 1:1-20:1 to form suspension with the concentration of 1-2g/L, and slowly stirring for 10-24 hours at the stirring speed of 100-300r/min to form composite suspension combined in a face-to-face manner;
step G: centrifugal washing and freeze-drying;
and F, centrifugally washing the composite material suspension prepared in the step F by using deionized water, and freeze-drying for 48-72 hours to obtain the powdery two-dimensional composite material (V) of the vanadium oxide nanosheet and MXene5O12·nH2O@MXene)。
CN202111229654.8A 2021-10-21 2021-10-21 Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene Active CN114162866B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111229654.8A CN114162866B (en) 2021-10-21 2021-10-21 Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111229654.8A CN114162866B (en) 2021-10-21 2021-10-21 Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene

Publications (2)

Publication Number Publication Date
CN114162866A true CN114162866A (en) 2022-03-11
CN114162866B CN114162866B (en) 2023-08-29

Family

ID=80477284

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111229654.8A Active CN114162866B (en) 2021-10-21 2021-10-21 Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene

Country Status (1)

Country Link
CN (1) CN114162866B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784455A (en) * 2022-04-06 2022-07-22 山东大学 Diaphragm, preparation method thereof and battery application
CN115207493A (en) * 2022-07-12 2022-10-18 西安交通大学 High-performance vanadium-based water-based zinc ion battery and preparation method thereof
CN116130608A (en) * 2023-04-04 2023-05-16 山东科技大学 Method for preparing titanium oxide film flexible electrode by self-assembly technology
CN116282156A (en) * 2023-04-13 2023-06-23 重庆大学 Magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111056571A (en) * 2020-01-19 2020-04-24 兰州大学 Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof
WO2021072150A1 (en) * 2019-10-11 2021-04-15 Drexel University Mxene compositions featuring five atomic layers
CN113120958A (en) * 2021-04-29 2021-07-16 东南大学 Preparation method of lamellar porous nano vanadium oxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021072150A1 (en) * 2019-10-11 2021-04-15 Drexel University Mxene compositions featuring five atomic layers
CN111056571A (en) * 2020-01-19 2020-04-24 兰州大学 Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof
CN113120958A (en) * 2021-04-29 2021-07-16 东南大学 Preparation method of lamellar porous nano vanadium oxide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUANGSHENG XU ET AL.: "Three-dimensional hydrated vanadium pentoxide/MXene composite for high-rate zinc-ion batteries", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 593, pages 417 - 423 *
HANGDA CHEN ET AL.: "Interlayer Modification of Pseudocapacitive Vanadium Oxide and Zn(H2O)n 2+ Migration Regulation for Ultrahigh Rate and Durable Aqueous Zinc-Ion Batteries", ADV. SCI., vol. 8, pages 2004924 *
段永胜;杨修春;: "钒氧化物纳米带的合成及其去除水中Cu~(2+)离子的研究", 陶瓷学报, vol. 39, no. 01, pages 33 - 37 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784455A (en) * 2022-04-06 2022-07-22 山东大学 Diaphragm, preparation method thereof and battery application
CN115207493A (en) * 2022-07-12 2022-10-18 西安交通大学 High-performance vanadium-based water-based zinc ion battery and preparation method thereof
CN116130608A (en) * 2023-04-04 2023-05-16 山东科技大学 Method for preparing titanium oxide film flexible electrode by self-assembly technology
CN116282156A (en) * 2023-04-13 2023-06-23 重庆大学 Magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, preparation method and application

Also Published As

Publication number Publication date
CN114162866B (en) 2023-08-29

Similar Documents

Publication Publication Date Title
CN114162866B (en) Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene
EP4079685A1 (en) Method for preparing lithium iron manganese phosphate precursor and method for preparing lithium iron manganese phosphate
Lu et al. Graphene nanosheets encapsulated α-MoO 3 nanoribbons with ultrahigh lithium ion storage properties
JP6123839B2 (en) Carbon particle for negative electrode of lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery
CN102394287B (en) Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
CN108147464B (en) Rice-shaped manganese dioxide/titanium carbide composite material and preparation method thereof
KR102178900B1 (en) Silicon composite materials for anode active material of lithium secondary battery, and manufacturing method of the composite material
WO2024026984A1 (en) Preparation method for and use of positive electrode material
CN102013477A (en) Method for preparing lithium iron phosphate/carbon composite material of lithium ion battery
CN113363483A (en) Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery
CN102376944A (en) Method for preparing silicon carbide alloy negative electrode material for lithium ion battery
CN108389732A (en) A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material
WO2023092894A1 (en) Hard carbon composite material, and preparation method therefor and use thereof
CN106784616B (en) The self-assembly preparation method thereof and positive electrode composition of spherical manganese silicate of lithium composite material
CN109103440B (en) Lithium ion battery cathode material, preparation method and lithium ion battery
WO2016110108A1 (en) Method of preparing plasma spraying for nanoscale lithium-ion composite positive electrode
CN111048764A (en) Silicon-carbon composite material and preparation method and application thereof
CN111640917A (en) Composite, SiOC structure, method for producing same, negative electrode, composition, and secondary battery
CN108190962A (en) A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof
CN110010877B (en) Surface-coated high-nickel ternary material and preparation method and application thereof
Yang et al. Synthesis of nano-sized urchin-shaped LiFePO 4 for lithium ion batteries
CN113690429A (en) Carbon-coated graphene/metal oxide composite material and preparation method thereof
CN108364802A (en) A kind of manganese dioxide nanowire/titanium carbide composite material and preparation method
CN106602008B (en) The self-assembly preparation method thereof and manganese-lithium phosphate anode material of manganese-lithium phosphate anode material
CN115101739A (en) Preparation method of multifunctional silicon carbide carbon negative electrode material and silicon carbon negative electrode material

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