CN107934965B - Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material - Google Patents

Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material Download PDF

Info

Publication number
CN107934965B
CN107934965B CN201711350994.XA CN201711350994A CN107934965B CN 107934965 B CN107934965 B CN 107934965B CN 201711350994 A CN201711350994 A CN 201711350994A CN 107934965 B CN107934965 B CN 107934965B
Authority
CN
China
Prior art keywords
alc
ceramic powder
powder
electrode
hours
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
CN201711350994.XA
Other languages
Chinese (zh)
Other versions
CN107934965A (en
Inventor
武文玲
卫丹
朱建锋
崔云
方园
王芬
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and 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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201711350994.XA priority Critical patent/CN107934965B/en
Publication of CN107934965A publication Critical patent/CN107934965A/en
Application granted granted Critical
Publication of CN107934965B publication Critical patent/CN107934965B/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
    • C01G51/00—Compounds of cobalt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
    • C04B35/5618—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides based on titanium aluminium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • 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
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

一种Ti3C2‑Co(OH)(CO3)0.5纳米复合材料的制备方法，首先，在浓度为40wt％的HF溶液中选择性腐蚀掉三元Ti3AlC2陶瓷粉体的Al层，形成二维层状Ti3C2纳米材料；然后，以二维Ti3C2纳米材料为基体，以Co(NO3)2·6H2O为钴源，CO(NH2)2为沉淀剂均匀搅拌后，将混合液通过水热法在80‑85℃原位生长成功制备得到形貌多样的Ti3C2@Co(OH)(CO3)0.5纳米复合材料；并将其组装成三电极体系的超级电容器，Ti3C2‑Co(OH)(CO3)0.5表现了良好的电化学性能；这种方法实验过程简单、成本低、环保、Co(OH)(CO3)0.5形貌利于控制，为Ti3C2‑Co(OH)(CO3)0.5在超级电容器、锂离子电池方面的应用奠定了基础。A method for preparing a Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite material. First, the Al layer of the ternary Ti 3 AlC 2 ceramic powder is selectively etched away in a HF solution with a concentration of 40 wt %. , forming a two-dimensional layered Ti 3 C 2 nanomaterial; then, using the two-dimensional Ti 3 C 2 nanomaterial as the matrix, Co(NO 3 ) 2 ·6H 2 O as the cobalt source, and CO(NH 2 ) 2 as the precipitation After the mixture was evenly stirred, the mixed solution was successfully prepared by in-situ growth at 80‑85℃ by hydrothermal method to obtain Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 nanocomposites with various morphologies; The supercapacitor of the three-electrode system, Ti 3 C 2 ‑Co(OH)(CO 3 ) 0.5 , showed good electrochemical performance; this method has simple experimental process, low cost, environmental protection, and Co(OH)(CO 3 ) 0.5 The morphology is easy to control, which lays a foundation for the application of Ti 3 C 2 ‑Co(OH)(CO 3 ) 0.5 in supercapacitors and lithium-ion batteries.

Description

Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material
Technical Field
The invention belongs to the technical field of preparation of nano functional materials and electrochemical energy storage materials, and particularly relates to Ti3C2-Co(OH)(CO3)0.5A method for preparing a nanocomposite.
Background
Novel two-dimensional material MXene is transition gold with graphene-like structureOf carbonitrides or carbides, e.g. Ti3C2、Ti2C and the like. Ti3C2Removal of MAX phase Ti from nano material by HF selective etching3AlC2The Al layer element in the MAX structure is prepared and can be kept unchanged. Two-dimensional carbide Ti3C2Good stability, larger specific surface area, high bending strength and elastic modulus, and excellent electrical property and conductivity, which indicates that the material can be used as an ideal matrix of a composite material, and has wide application prospects in the fields of electrochemistry, composite material reinforcement and the like.
Naguib et al acid etch Ti3AlC2And after the aluminum alloy is completely soaked in hydrofluoric acid for a certain time at room temperature, the Al atomic layer is completely stripped.
Maria et al press on Ti3C2: conductive agent: the mass ratio of the adhesive is 85 percent to 10 percent to 5 percent, and Ti is treated by adopting a three-electrode asymmetric system in KOH solution3C2The electrochemical performance of (2) is characterized. The experimental result shows that Ti3C2The specific volume capacity of the catalyst can reach 340F/cm in KOH solution3And the interlayer spacing increases.
Sun et al general description of Ti3C2As a lithium ion electrode cathode material, a test result shows that the capacity of the lithium ion battery can reach 123.6mAh/g under the multiplying power of 1C, and the coulombic efficiency is about 47%. However, Ti3C2The theoretical specific capacity is small, so that the electrochemical performance of the lithium ion battery is poor, and the application of MXene group in the energy storage fields of super capacitors, lithium ion batteries and the like is yet to be further researched.
Basic cobalt carbonate Co (OH) (CO)3)0.5Is to prepare nano Co3O4Good precursors for materials have therefore gained much attention in recent years. Basic cobalt carbonate is easy to decompose by heating, but the decomposition product has few impurities, so the basic cobalt carbonate is very suitable for processing and manufacturing various cobalt materials and is commonly used as an additive of electronic materials and magnetic materials. In recent years, research on the crystal structure, thermal stability, surface properties and the like of the basic carbonate has been advanced. However, studies on their electrochemical propertiesIt has not yet been matured.
Zhou W.J. et al electrochemically deposit Co (OH) as an active material2Directly deposited on a substrate and tested as a working electrode of a super capacitor, and the specific capacitance is up to 1084F/g.
Searching the literature, and finding that Co (OH) (CO) has not been utilized to date3)0.5To improve Ti3C2The electrochemical performance of (2). The invention uses two-dimensional Ti with good conductivity and stable structure3C2Ceramic powder as matrix and Co (NO)3)2·6H2O is a source of cobalt, CO (NH)2)2Is a precipitator, PVP is used as a structure directing agent, Ti is successfully prepared by in-situ growth at 80-85 ℃ by a hydrothermal method3C2@Co(OH)(CO3)0.5A nanocomposite material. And assembling it into a supercapacitor of three-electrode system, Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the experimental process is simple, the product appearance is controllable, the method is safe and environment-friendly, and a foundation is laid for the application of the method in the energy storage fields of lithium ion batteries, super capacitors and the like.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, the present invention is directed to providing a Ti3C2-Co(OH)(CO3)0.5The preparation method of the nano composite material utilizes a hydrothermal method to grow Co (OH) (CO) in situ3)0.5Preparing Ti with various shapes3C2-Co(OH)(CO3)0.5The method has simple experimental process, low cost, environmental protection, and high performance of Co (OH) (CO)3)0.5The shape is easy to control, and Ti is enlarged3C2The specific surface area of the electrode improves the electrode material of the super capacitor.
In order to achieve the purpose, the invention adopts the technical scheme that:
ti3C2-Co(OH)(CO3)0.5A method for preparing a nanocomposite comprising the steps of:
step (ii) ofFirstly, preparing ternary Ti3AlC2Ceramic powder;
step two, preparing two-dimensional layered Ti3C2A nanomaterial;
step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 145.5-1164mg of Co (NO)3)2·6H2O and the two-dimensional layered Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 100-800mg of CO (NH) under magnetic stirring2)2And 200 and 1600g PVP are continuously stirred for 0.5 to 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 80-85 ℃, and preserving the heat for 6-12 h; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying in a vacuum drying oven at 40 ℃ for 12-24h to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2A rectangle with a size of 160-200mg of active substances, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 20-30mg of conductive acetylene black and 1-10mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel for 12-24h in a vacuum drying oven at the temperature of 60-80 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15-20Mpa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
The first step is to prepare the ternary layered Ti3AlC2The ceramic powder specifically comprises: first, according to the molar ratio Ti: al: 1.0 of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain ternary Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two is to prepare two-dimensional layered Ti3C2The nano material specifically comprises: taking 5g of Ti obtained in the step (one)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by deionized water until the pH value of a supernatant is about 5-6, centrifuging the corrosion product by absolute ethyl alcohol for 4 times, and finally vacuum drying black precipitate at 40 ℃ for 24 hours to obtain the two-dimensional layered Ti3C2And (3) nano powder.
And (3) product verification:
using a three-electrode system with Ti3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance. Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the CV curve graph is close to a regular rectangle, and the symmetry is good; circulation curveThe formed area increases with the increase of the scanning rate, but the rough shape of the pattern is basically unchanged, and good rate performance is shown.
The invention has the beneficial effects that:
1. the invention first selectively etches off ternary Ti in HF solution with concentration of 40 wt%3AlC2Al layer of ceramic powder to form two-dimensional layered Ti3C2And (3) nano materials. Then, with two-dimensional Ti3C2Nano material as matrix and Co (NO)3)2·6H2O is a source of cobalt, CO (NH)2)2Uniformly stirring the precipitator, and then carrying out in-situ growth on the mixed solution at 80-85 ℃ by a hydrothermal method to successfully prepare Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. And the three-electrode super capacitor is assembled by using 6M KOH solution as electrolyte and Ti3C2-Co(OH)(CO3)0.5As a working electrode, a platinum electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode to perform cyclic voltammetry, and Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the experimental process is simple, the product appearance is controllable, the method is safe and environment-friendly, and a foundation is laid for the application of the method in the energy storage fields of lithium ion batteries, super capacitors and the like.
2. The prepared Ti with various shapes3C2-Co(OH)(CO3)0.5The nanocomposite serving as an active electrode of a supercapacitor is tested on a CHI660E electrochemical workstation, and shows good electrochemical performance, namely Ti3C2-Co(OH)(CO3)0.5Lays a foundation for the application of super capacitors and lithium ion batteries.
Drawings
FIG. 1 is Ti3C2-Co(OH)(CO3)0.5The XRD patterns of the nano composite material are shown in the following four curves of a, b, c and d, which are the XRD patterns of the first, second, third and fourth examples.
FIG. 2 is Ti3C2-Co(OH)(CO3)0.5SEM images of the nanocomposite, wherein a, b, c, d are SEM images of examples one, two, three, and four, respectively.
FIG. 3 shows example III3C2-Co(OH)(CO3)0.5Cyclic voltammograms of nanocomposites at different scan rates under a three-electrode system.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example one
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 1164mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and adding 800mg of CO (NH) in sequence under magnetic stirring2)2Continuously stirring the mixed solution and 1600mg of PVP for 2h to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the curve a in fig. 1, in addition to the characteristic peaks of Ti3C2 corresponding to the (111), (200), (220) crystal planes at 2 θ 36 °, 42 °, 62 °, CO (oh) (CO) at 48-0083 in the PDF standard card at 2 θ 18 °, 25 °, 34 °, 18 °, 25 °, 36 °3)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from the a diagram of FIG. 2, Co (OH) (CO) is present in the reaction system due to too much loading3)0.5At Ti3C2The surface of the material is provided with a thicker coating layer, Co (OH) (CO)3)0.5Is in a nano sheet shape and self-assembled into a flower-shaped image.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 20mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
Example two
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 727.6mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 500mg of CO (NH) under magnetic stirring2)2Continuously stirring the mixed solution and 1000mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the curve b in fig. 1, in addition to the characteristic peaks of Ti3C2 corresponding to the (111), (200) and (220) crystal planes at 2 θ 36 °, 42 ° and 62 °, CO (oh) (CO) with PDF standard card number 48-0083 at 2 θ 18 °, 25 ° and 34 ° are shown3)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from the b-diagram of FIG. 2, Co (OH) (CO) was still supported in the reaction system in a large amount3)0.5At Ti3C2The surface of the material is provided with a thicker coating layer, Co (OH) (CO)3)0.5Is in a nanowire shape.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode was used as the working electrode, the platinum sheet as the counter electrode, the silver/silver chloride as the reference electrode, and Ti was tested using the Shanghai Hua CHI660E electrochemical workstation in 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
EXAMPLE III
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materialsCombining; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 291.0mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving nanometer powder 200mg in ultrapure water, adding CO (NH) 200mg under magnetic stirring2)2Continuously stirring the mixed solution and 400mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75 percent into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, and lifting the assembled hydrothermal reaction kettleHeating to 82 ℃ and preserving the temperature for 8 h; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the c-curve of fig. 1, when 2 θ is 36 °, 42 °, 62 ° respectively corresponds to Ti of the (111), (200), (220) crystal planes3C2In addition to the characteristic peaks, the peaks are also Co (OH) (CO) with 2 theta being 18 degrees, 25 degrees and 34 degrees corresponding to PDF standard card numbers of 48-00833)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. Ti is clearly seen from the c diagram of FIG. 23C2Concertina structure of Co (OH) (CO)3)0.5The shape of the nano-wire is changed into a honeycomb shape and finally changed into nano-particles distributed on Ti3C2The sheet surface and the layers. Ti is obtained from FIG. 33C2-Co(OH)(CO3)0.5The electrochemical performance is good, the CV curve graph is close to a regular rectangle, and the symmetry is good; the area formed by the cyclic curve increases with the increase of the scanning speed, but the approximate shape of the graph is basically unchanged, and good rate performance is shown.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
Example four
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2The ceramic powder is slowly immersed in 100mL of 40 wt% hydrofluoric acid solutionAnd magnetically stirring at room temperature for 48h at the rotation speed of 1200r/min until no air bubbles are generated, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging for 4 times by using absolute ethyl alcohol. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 145.5mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 100mg of CO (NH) under magnetic stirring2)2Continuously stirring the mixed solution and 200mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the d-curve of fig. 1, when 2 θ is 36 °, 42 °, 62 ° respectively corresponds to Ti of the (111), (200), (220) crystal planes3C2In addition to the characteristic peaks, the peaks are also Co (OH) (CO) with 2 theta being 18 degrees, 25 degrees and 34 degrees corresponding to PDF standard card numbers of 48-00833)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from plot d of FIG. 2, Co (OH) (CO)3)0.5Is uniformly distributed in Ti3C2The interlayer content is high, and no agglomeration occurs.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2A rectangle with a size of 200mg is sequentially weighed, namely step threeObtained Ti3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.

Claims (4)

1.一种基于Ti3C2-Co(OH)(CO3)0.5纳米复合材料的电极制备方法，其特征在于，包括下述步骤：1. an electrode preparation method based on Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite material, is characterized in that, comprises the following steps: 步骤一，制备三元Ti3AlC2陶瓷粉体；Step 1, prepare ternary Ti 3 AlC 2 ceramic powder; 步骤二，制备二维层状Ti3C2纳米材料；Step 2, preparing two-dimensional layered Ti 3 C 2 nanomaterials; 步骤三，一种Ti3C2-Co(OH)(CO3)0.5纳米复合材料的制备；Step 3, preparation of a Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite; 首先，将145.5-1164mg Co(NO3)2·6H2O和步骤(2)所得的二维层状Ti3C2纳米粉体200mg溶于超纯水中，在磁力搅拌下先后加入100-800mg CO(NH2)2和200-1600g PVP持续搅拌0.5-2h得到混合液；其次，将体积分数为75％混合液转移到100ml的水热反应釜聚四氟乙烯内衬中，将组装好的水热反应釜升温至80-85℃保温6-12h；然后，将自然冷却至室温的产物依次用超纯水和无水乙醇分别离心分离清洗3次，每次4000-6000r/min离心3-5min；最后，于真空干燥箱中40℃干燥12-24h后得到所需Ti3C2@Co(OH)(CO3)0.5纳米复合材料；First, 145.5-1164 mg of Co(NO 3 ) 2 ·6H 2 O and 200 mg of the two-dimensional layered Ti 3 C 2 nano-powder obtained in step (2) were dissolved in ultrapure water, and 100- 800mg CO(NH 2 ) 2 and 200-1600g PVP were continuously stirred for 0.5-2h to obtain a mixed solution; secondly, the mixed solution with a volume fraction of 75% was transferred to a 100ml hydrothermal reaction kettle polytetrafluoroethylene lining, and the assembled The hydrothermal reaction kettle was heated to 80-85°C and kept for 6-12h; then, the products that had been naturally cooled to room temperature were centrifuged and washed 3 times with ultrapure water and absolute ethanol, respectively, at 4000-6000r/min for 3 times each time. -5min; finally, the desired Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 nanocomposite was obtained after drying in a vacuum drying oven at 40°C for 12-24 hours; 步骤四，Ti3C2-Co(OH)(CO3)0.5电极的制备；Step 4, preparation of Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 electrode; 首先，将泡沫镍裁剪成1×2cm大小的长方形，依次称取160-200mg的活性物质即步骤三所得Ti3C2@Co(OH)(CO3)0.5纳米粉体，20-30mg的导电乙炔黑，1-10mg的聚偏二氟乙烯，在玛瑙研钵中研磨1-2h；其次，用移液枪吸取300μL的NMP研磨均匀后，浆料平均滴加在裁剪好的泡沫镍上，并将滴加好的泡沫镍在真空干燥箱中60-80℃干燥12-24h；再次，将制好的电极片在压片机下15-20Mpa保压1min既得Ti3C2@Co(OH)(CO3)0.5电极。First, cut the nickel foam into a rectangle with a size of 1 × 2 cm, and sequentially weigh 160-200 mg of the active material, that is, the Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 nanometer powder obtained in step 3, and 20-30 mg of conductive material. Acetylene black, 1-10 mg of polyvinylidene fluoride, ground in an agate mortar for 1-2 hours; secondly, after sucking 300 μL of NMP with a pipette and grinding evenly, the slurry is evenly added dropwise on the cut nickel foam. The dripped nickel foam was dried in a vacuum drying oven at 60-80°C for 12-24h; again, the prepared electrode sheet was kept under a tablet press at 15-20Mpa for 1min to obtain Ti 3 C 2 @Co(OH )(CO 3 ) 0.5 electrode. 2.根据权利要求1所述的一种基于Ti3C2-Co(OH)(CO3)0.5纳米复合材料的电极制备方法，其特征在于，所述的步骤一制备三元层状Ti3AlC2陶瓷粉体，具体为：首先，根据摩尔比为Ti：Al：TiC＝1.0：1.2：2.0的比例将三种原料混合；其次，将三种原料置于球磨罐内，以氧化铝球作为研磨介质，无水乙醇作为球磨助剂，球磨机转速为900转/分钟，按照质量比为球：料：乙醇＝3.0：1.0：1.0的比例，普通球磨1h获得均匀粉末，并在40℃恒温干燥烘箱将其烘干；然后，将干燥好的混料置于刚玉坩埚内，采用真空无压烧结的方法，以8℃/min的升温速率加热至1350℃，保温1h，随炉冷却至室温得到高纯Ti3AlC2陶瓷粉料；最后，对Ti3AlC2陶瓷粉料进行湿法高能球磨3h，每30分钟一次，转速400r/min，钢球和陶瓷粉料的质量比为10:1，将磨细的粉体过筛，即得到粒径小于38μm的三元Ti3AlC2陶瓷粉体。2 . The method for preparing an electrode based on Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite material according to claim 1 , wherein the step 1 prepares ternary layered Ti 3 AlC 2 ceramic powder, specifically: firstly, according to the molar ratio of Ti:Al:TiC=1.0:1.2:2.0, mix the three raw materials; As the grinding medium, anhydrous ethanol is used as a ball milling aid. The ball mill rotates at 900 rpm. According to the mass ratio, the ratio of ball: material: ethanol = 3.0: 1.0: 1.0, ordinary ball milling for 1 hour to obtain uniform powder, and the temperature is kept at 40 °C. Dry it in a drying oven; then, place the dried mixture in a corundum crucible, use vacuum pressureless sintering, heat it to 1350°C at a heating rate of 8°C/min, keep it for 1 hour, and cool it to room temperature with the furnace Obtain high-purity Ti 3 AlC 2 ceramic powder; finally, carry out wet high-energy ball milling for Ti 3 AlC 2 ceramic powder for 3h, once every 30 minutes, rotating speed 400r/min, the mass ratio of steel ball and ceramic powder is 10: 1. Sieve the ground powder to obtain a ternary Ti 3 AlC 2 ceramic powder with a particle size of less than 38 μm. 3.根据权利要求1所述的一种基于Ti3C2-Co(OH)(CO3)0.5纳米复合材料的电极制备方法，其特征在于，所述的步骤二制备二维层状Ti3C2纳米材料，具体为：取5g步骤(一)中所得Ti3AlC2陶瓷粉体缓缓浸没在100mL 40wt％氢氟酸溶液中，至不在冒气泡后将其室温下磁力搅拌48h，转速为1200r/min，将腐蚀产物用去离子水离心清洗至上清液pH值为5-6时，再用无水乙醇离心4次，最后将黑色沉淀于40℃真空干燥24h，即得到二维层状Ti3C2纳米粉体。3 . The method for preparing an electrode based on Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite material according to claim 1 , wherein the step 2 prepares two-dimensional layered Ti 3 . C 2 nanomaterials, specifically: take 5 g of the Ti 3 AlC 2 ceramic powder obtained in step (1) and slowly immerse it in 100 mL of a 40wt% hydrofluoric acid solution, and magnetically stir it at room temperature for 48 h at room temperature until no bubbles are formed. At 1200 r/min, the corrosion product was centrifuged with deionized water until the pH value of the supernatant was 5-6, and then centrifuged with absolute ethanol for 4 times. Finally, the black precipitate was vacuum-dried at 40 °C for 24 h to obtain a two-dimensional layer. Shaped Ti 3 C 2 nano-powder. 4.根据权利要求1所述的一种基于Ti3C2-Co(OH)(CO3)0.5纳米复合材料的电极制备方法，其特征在于，4 . The method for preparing an electrode based on Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite material according to claim 1 , wherein, 步骤一，三元Ti3AlC2陶瓷粉体的制备；Step 1, preparation of ternary Ti 3 AlC 2 ceramic powder; 首先，根据摩尔比为Ti：Al：TiC＝1.0：1.2：2.0的比例将三种原料混合；其次，将三种原料置于球磨罐内，以氧化铝球作为研磨介质，无水乙醇作为球磨助剂，球磨机转速为900转/分钟，按照质量比为球：料：乙醇＝3.0：1.0：1.0的比例，普通球磨1h获得均匀粉末，并在40℃恒温干燥烘箱将其烘干；然后，将干燥好的混料置于刚玉坩埚内，采用真空无压烧结的方法，以8℃/min的升温速率加热至1350℃，保温1h，随炉冷却至室温得到高纯Ti3AlC2陶瓷粉料；First, the three raw materials were mixed according to the molar ratio of Ti:Al:TiC=1.0:1.2:2.0; secondly, the three raw materials were placed in a ball mill, with alumina balls as the grinding medium and absolute ethanol as the ball mill Auxiliary, the ball mill speed is 900 rpm, according to the mass ratio of ball: material: ethanol = 3.0: 1.0: 1.0, ordinary ball milling for 1 hour to obtain uniform powder, and drying it in a constant temperature drying oven at 40 °C; then, The dried mixture was placed in a corundum crucible, heated to 1350°C at a heating rate of 8°C/min by vacuum pressureless sintering, kept for 1 hour, and cooled to room temperature with the furnace to obtain high-purity Ti 3 AlC 2 ceramic powder material; 最后，对Ti3AlC2陶瓷粉料进行湿法高能球磨3h，每30分钟一次，转速400r/min，钢球和陶瓷粉料的质量比为10:1，将磨细的粉体过筛，即得到粒径小于38μm的Ti3AlC2陶瓷粉体；Finally, the Ti 3 AlC 2 ceramic powder was subjected to wet high-energy ball milling for 3 hours, once every 30 minutes, at a speed of 400 r/min, and the mass ratio of steel balls and ceramic powder was 10:1, and the finely ground powder was sieved. That is to obtain Ti 3 AlC 2 ceramic powder with a particle size of less than 38 μm; 步骤二，二维层状Ti3C2纳米材料的制备；Step 2, preparation of two-dimensional layered Ti 3 C 2 nanomaterials; 取5g步骤(一)中所得Ti3AlC2陶瓷粉体缓缓浸没在100mL40wt％氢氟酸溶液中，至不在冒气泡后将其室温下磁力搅拌48h，转速为1200r/min，将腐蚀产物用去离子水离心清洗至上清液pH值为5-6时，再用无水乙醇离心4次；最后将黑色沉淀于40℃真空干燥24h，即得到二维层状Ti3C2纳米粉体；Take 5 g of the Ti 3 AlC 2 ceramic powder obtained in step (1) and slowly immerse it in 100 mL of a 40 wt% hydrofluoric acid solution, and then stir it magnetically at room temperature for 48 hours at room temperature for 48 hours, and the speed is 1200 r/min. Deionized water was centrifuged and washed until the pH value of the supernatant was 5-6, and then centrifuged for 4 times with absolute ethanol; finally, the black precipitate was vacuum-dried at 40°C for 24 hours, to obtain two-dimensional layered Ti 3 C 2 nano-powder; 步骤三，一种Ti3C2-Co(OH)(CO3)0.5纳米复合材料的制备；Step 3, preparation of a Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 nanocomposite; 首先，将291.0mg Co(NO3)2·6H2O和步骤(2)所得的Ti3C2纳米粉体200mg溶于超纯水中，在磁力搅拌下先后加入200mg CO(NH2)2和400mg PVP持续搅拌2h得到混合液；其次，将体积分数为75％混合液转移到100ml的水热反应釜聚四氟乙烯内衬中，将组装好的水热反应釜升温至82℃保温8h；然后，将自然冷却至室温的产物依次用超纯水和无水乙醇分别离心分离清洗3次，每次4000-6000r/min离心3-5min；最后，于真空干燥箱中40℃干燥24h后得到所需Ti3C2@Co(OH)(CO3)0.5纳米复合材料；First, 291.0 mg of Co(NO 3 ) 2 ·6H 2 O and 200 mg of Ti 3 C 2 nano-powder obtained in step (2) were dissolved in ultrapure water, and 200 mg of CO(NH 2 ) 2 were added successively under magnetic stirring. and 400mg PVP were continuously stirred for 2h to obtain a mixed solution; secondly, the volume fraction of 75% of the mixed solution was transferred to a 100ml PTFE lining of the hydrothermal reactor, and the assembled hydrothermal reactor was heated to 82°C and kept for 8h ; Then, the product that was naturally cooled to room temperature was centrifuged and washed 3 times with ultrapure water and absolute ethanol in turn, and centrifuged at 4000-6000 r/min for 3-5 min each time; finally, dried in a vacuum drying box at 40 °C for 24 h. Obtain the desired Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 nanocomposite; 步骤四，Ti3C2-Co(OH)(CO3)0.5电极的制备；Step 4, preparation of Ti 3 C 2 -Co(OH)(CO 3 ) 0.5 electrode; 首先，将泡沫镍裁剪成1×2cm大小的长方形，依次称取200mg的活性物质即步骤三所得Ti3C2@Co(OH)(CO3)0.5纳米粉体，2mg的导电乙炔黑，1mg的聚偏二氟乙烯，在玛瑙研钵中研磨1-2h；其次，用移液枪吸取300μL的NMP研磨均匀后，浆料平均滴加在裁剪好的泡沫镍上，并将滴加好的泡沫镍在真空干燥箱中60℃干燥24h；再次，将制好的电极片在压片机下15Mpa保压1min既得Ti3C2@Co(OH)(CO3)0.5电极。First, cut the nickel foam into a rectangle with a size of 1 × 2 cm, and sequentially weigh 200 mg of active material, namely Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 nanometer powder obtained in step 3, 2 mg of conductive acetylene black, 1 mg The polyvinylidene fluoride was ground in an agate mortar for 1-2 hours; secondly, after sucking 300 μL of NMP with a pipette and grinding evenly, the slurry was evenly added dropwise on the cut nickel foam, and the dropwise added The nickel foam was dried in a vacuum drying oven at 60°C for 24h; again, the prepared electrode sheet was kept under a tablet press at 15Mpa for 1min to obtain a Ti 3 C 2 @Co(OH)(CO 3 ) 0.5 electrode.
CN201711350994.XA 2017-12-15 2017-12-15 Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material Active CN107934965B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711350994.XA CN107934965B (en) 2017-12-15 2017-12-15 Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711350994.XA CN107934965B (en) 2017-12-15 2017-12-15 Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material

Publications (2)

Publication Number Publication Date
CN107934965A CN107934965A (en) 2018-04-20
CN107934965B true CN107934965B (en) 2021-02-02

Family

ID=61944447

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711350994.XA Active CN107934965B (en) 2017-12-15 2017-12-15 Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material

Country Status (1)

Country Link
CN (1) CN107934965B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108735522B (en) * 2018-05-25 2020-01-03 西南大学 CoNiO2/MXene composite material and preparation method and application thereof
CN108987126B (en) * 2018-09-28 2019-12-17 大连理工大学 A kind of Ti3C2/Ni composite electrode material and preparation method thereof
CN110040787A (en) * 2019-04-22 2019-07-23 陕西科技大学 A kind of nano whiskers FeCo2O4The preparation method and application of electrode material
CN111994965B (en) * 2019-05-27 2022-08-19 湖北万润新能源科技股份有限公司 Preparation method of precursor of LTH-structure ternary cathode material
CN110323081B (en) * 2019-06-14 2021-02-05 电子科技大学 Method for preparing nickel hydroxide/basic cobaltous carbonate composite material on current collector
CN111627720B (en) * 2020-06-19 2021-10-01 太原理工大学 A kind of Ni-doped composite electrode material and preparation method thereof
CN113213552A (en) * 2021-03-20 2021-08-06 长沙理工大学 Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof
CN115043436B (en) * 2022-06-23 2025-02-25 齐齐哈尔大学 A preparation method and application of Co3O4 nanocage

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103464189B (en) * 2013-09-13 2015-12-09 哈尔滨工程大学 The H of the coated titanium carbide Supported Co of carbon and cobaltosic oxide 2o 2the preparation method of electroreduction catalysis material
CN105986139B (en) * 2015-03-04 2018-02-09 海南大学 A kind of titanium carbide ceramic and preparation method thereof
KR20170106857A (en) * 2016-03-14 2017-09-22 한국에너지기술연구원 Preparing method of the 3D porous structured graphene/Mxene composite by ice-templating method and 3D porous structured graphene/Mxene composite by the same method
CN106976917B (en) * 2017-03-03 2018-06-01 陕西科技大学 Sheet cobalt black-two-dimensional layer carbonization titanium composite material and its two-step preparation
CN106971854A (en) * 2017-04-18 2017-07-21 西安交通大学 The two-dimensional layer Ti of transition metal oxide nano particle doping3C2Film nano composite material and preparation method thereof

Also Published As

Publication number Publication date
CN107934965A (en) 2018-04-20

Similar Documents

Publication Publication Date Title
CN107934965B (en) Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material
Yao et al. Nanostructured transition metal vanadates as electrodes for pseudo-supercapacitors: a review
CN109167066A (en) A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material
CN106698430B (en) A kind of poly-dopamine is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof
CN108147464B (en) A kind of rice granular manganese dioxide/titanium carbide composite material and its preparation method
CN106783230B (en) A kind of titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof
CN105870447B (en) Sodium-ion battery N doping rutile TiO2The preparation method of/C negative materials
Jia et al. Synthesis of porous Co3O4/Reduced graphene oxide by a two-step method for supercapacitors with excellent electrochemical performance
CN104556018A (en) Preparation method of high quality graphene conductive film
CN112233912A (en) A kind of preparation method and application of foam nickel-supported MnCo2O4.5/MXene composite nanomaterial
CN108389732A (en) A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material
CN103227317A (en) V2O5 quantum dot/graphene composite material and its preparation method and application
CN106299271A (en) Nano nickel cobaltate/graphene composite material and preparation method thereof
CN106784706A (en) A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof
CN109941997B (en) A kind of preparation method and application of hemoglobin-like Co3O4/Ti3C2 nanocomposite material
CN110156081A (en) A kind of preparation method of porous sheet-like TiNb2O7 nanocrystal for negative electrode of lithium ion battery
CN106505185A (en) A kind of antimony/nitrogen doped carbon compound and its preparation method and application
CN107611359A (en) The preparation method of lithium ion battery Ni NiO/ graphene composite negative poles
CN111217361B (en) Method for preparing graphene nanosheet through electrochemical cathode stripping
CN107464924A (en) A kind of sheet oxygen defect lithium vanadate anode material and preparation method thereof
CN103943379A (en) Preparation method for graphene load flower-shaped porous nickel oxide composite materials
CN112786865A (en) MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material
Li et al. Controllable synthesis of 3D hierarchical cactus-like ZnCo2O4 films on nickel foam for high-performance asymmetric supercapacitors
CN113690429A (en) Carbon-coated graphene/metal oxide composite material and preparation method thereof
Niu et al. High-rate lithium storage of TiNb2O7/reduced graphene oxide

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