CN112717843A - Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof - Google Patents
Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112717843A CN112717843A CN202011431270.XA CN202011431270A CN112717843A CN 112717843 A CN112717843 A CN 112717843A CN 202011431270 A CN202011431270 A CN 202011431270A CN 112717843 A CN112717843 A CN 112717843A
- Authority
- CN
- China
- Prior art keywords
- tin dioxide
- composite material
- dioxide quantum
- quantum dot
- sulfur
- 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
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material and a preparation method and application thereof, wherein the carbon nano tube with tin dioxide quantum dots growing on the surface is dispersed in a polyvinyl alcohol solution to form a capsule internal phase; the ETPTA, the photoinitiator and the silicon dioxide nanospheres are uniformly stirred to form an outer phase of the capsule; the tin dioxide quantum dot/carbon nano tube/microcapsule composite material is prepared by a micro-fluidic technology, silicon dioxide nanospheres and sulfur are etched after high-temperature carbonization, and sulfur particles are loaded on the tube wall of the nano tube in the microcapsule and in the inner wall and the shell of the microcapsule to form the tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material. The abundant gap structure in the anode can buffer the volume change, greatly improve the structural integrity of the sulfur particles and the stannic oxide quantum dots/carbon nano tubes, reduce the active mass loss in the charging/discharging process and further improve the electrochemical performance of the anode.
Description
Technical Field
The invention belongs to the technical field of battery composite materials, and particularly relates to a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared by a microfluidic technology, a preparation method thereof, and a lithium-sulfur battery anode and a lithium-sulfur battery prepared by using the same.
Background
Since the 21 st century, global energy crisis and environmental problems have become more serious, and human beings need to reduce dependence on fossil fuels, so that the vigorous development of new environmentally friendly energy sources and efficient energy storage systems is urgent. With the increase of energy consumption and global warming, a novel energy storage system, namely a lithium ion secondary battery, with high energy density, low cost, no pollution and long service life is produced. At present, the actual specific capacity of commercial lithium ion batteries is less than 200m Ah/g, the specific energy is less than 300Wh/kg, the development of industries such as electric automobiles, electronic products, smart grids and the like is severely restricted, and researchers are promoted to develop more reasonable and effective battery energy systems.
The lithium-sulfur battery (Li-S battery) has high theoretical specific energy (2600 W.h/kg) and high theoretical specific capacity (1675 mA.h/g), and the sulfur element has the advantages of rich content in the earth crust, low price, no toxicity, no pollution and the like, so the Li-S battery is considered to be one of novel energy storage batteries with the greatest prospect of improving the energy density.
The most commonly used positive electrode material in Li-S batteries is elemental sulfur, which is mainly cyclic S in nature8The molecule is present. Different from the lithium intercalation and deintercalation reaction of the traditional lithium ion battery, the lithium sulfur battery adopts sulfur or a sulfur-containing compound as a positive electrode and lithium as a negative electrode, and is realized by the fracture generation of a sulfur-sulfur bondThe electric energy and the chemical energy are mutually converted. During discharge, lithium ions migrate from the negative electrode to the positive electrode, and the positive electrode active material is broken in a sulfur-sulfur bond and combined with lithium ions to produce Li2S; upon charging, Li2And S is electrolyzed, and the released lithium ions return to the negative electrode again to be deposited as metal lithium or inserted into the negative electrode material. The chemical process of sulfur is complex and there is a series of reversible reactions and disproportionation reactions. During the discharge, the S-S bond starts to break and continues to react with Li+Combined, successively reduced to Li2S8、Li2S6、Li2S4Long-chain polysulfides that are equally soluble in organic electrolytes; as the reaction proceeds, these long-chain polysulfides are further reduced to short-chain polysulfides Li which are insoluble in the electrolyte2S2And Li2S, depositing on the surface of the positive electrode and precipitating in a solid form. When Li is present2When S covers the entire electrode, the voltage drops rapidly, resulting in termination of the discharge. During this kinetic process, a series of soluble polysulfide intermediates, LiS, are producedx(x>2)。
Although the lithium-sulfur battery has extremely high theoretical specific capacity and energy density, the utilization rate of active substances is low, the capacity attenuation is rapid, the cycle life is short, and a certain gap is left between the capacity theoretical value and the capacity theoretical value. The specific reasons are as follows: (1) during discharge, sulfur reacts with metallic lithium to form lithium polysulfide Li which is readily soluble in the electrolyte2Sx(2<x<8) And insoluble Li2S2With Li2And S. The dissolved lithium polysulfide generates redox shuttle reaction between the anode and the cathode to cause overcharge and corrosion and pulverization of the lithium cathode, so that the coulombic efficiency is low and the lithium loss is serious in the circulating process; insoluble Li2S2And Li2S is unevenly covered on the sulfur anode, so that the conductivity of the anode is deteriorated, and finally, the service life of the battery is reduced; (2) elemental sulfur and its final product have very poor conductivity. Elemental sulfur is an electronic and ionic insulator at room temperature and has a conductivity of only 5X 10-30S/cm, when used as an electrode material, the activated carbon is difficult to activate and the utilization rate is low; (3) volume expansion and contraction in the process of charging and discharging, volume expansion after complete lithiationAbout 80%, resulting in separation of sulfur from the conductive skeleton, severe destruction of the battery structure, and severe capacity fading; (4) the SEI layer is repeatedly formed-cracked, and the metallic lithium and the electrolyte are continuously consumed; (5) the unevenness of the surface of the negative metal lithium may cause lithium dendrites to pierce through the diaphragm, causing short circuit failure inside the battery and bringing serious potential safety hazard.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material, which is characterized in that a microcapsule wrapping the tin dioxide quantum dot/carbon nano tube is synthesized by utilizing a microfluidic technology, then the tin dioxide quantum dot/carbon nano tube porous microcapsule is obtained by carbonization and etching, so that the tin dioxide quantum dot/carbon nano tube porous microcapsule has rich pores and larger specific surface area in the interior, and then the tin dioxide quantum dot/carbon nano tube porous microcapsule is subjected to sulfuration to obtain the tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material, so that the tin dioxide quantum dot/carbon nano tube composite material with sulfur particles attached in the interior of the capsule is obtained.
The invention also aims to provide a tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material.
The last purpose of the invention is to provide the application of the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material for manufacturing the lithium-sulfur battery. The lithium-sulfur battery anode is prepared by taking the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material as an active material, and the lithium-sulfur battery is assembled by the lithium-sulfur battery anode.
The specific technical scheme of the invention is as follows:
a preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1) dispersing carbon nano tubes in a tin dioxide quantum dot solution, carrying out hydrothermal reaction, centrifuging, cleaning, drying and calcining a product to obtain tin dioxide quantum dots/carbon nano tubes;
2) dispersing the tin dioxide quantum dots/carbon nano tubes in a polyvinyl alcohol solution to form a phase solution A in the capsule;
3) adding 2-hydroxy-2-methyl propiophenone and silicon dioxide nanospheres into trimethylolpropane ethoxy triacrylate, and uniformly stirring to form an out-capsule phase solution B;
4) synthesizing the solution A prepared in the step 2), the solution B prepared in the step 3) and a polyvinyl alcohol aqueous solution by a micro-fluidic technology, and filtering, cleaning and drying a product to obtain tin dioxide quantum dots/carbon nano tubes/microcapsules;
5) calcining the tin dioxide quantum dots/the carbon nano tubes/the microcapsules to obtain carbonized microcapsules;
6) etching the silicon dioxide nanospheres of the carbonized capsule, filtering, cleaning and drying to obtain the tin dioxide quantum dots/carbon nano tubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/the carbon nano tubes/the porous microcapsules to obtain the tin dioxide quantum dots/the carbon nano tubes/the sulfur particle porous microcapsule composite material.
In the step 1), the mass ratio of the tin dioxide quantum dot solution to the carbon nano tube is 7.5: 0.005-0.2 mL/g; the hydrothermal reaction condition is 170-180 ℃ for 9-12 hours.
In the step 1), the preparation method of the tin dioxide quantum dot solution comprises the following steps: 0.677 g SnCl2·2H2O, 0.226 g of thiourea and 30 ml of water, and stirring for 36 hours by magnetic force to obtain the compound.
In the step 1), the drying temperature is 50-80 ℃, and the drying time is 10-12 hours.
In the step 1), the calcination temperature is 300-350 ℃, and the calcination time is 2 hours.
In step 1), the calcination is preferably carried out in a nitrogen atmosphere.
In the step 2), the mass concentration of the polyvinyl alcohol solution is 2-20%, and the dosage ratio of the tin dioxide quantum dots/carbon nano tubes to the polyvinyl alcohol solution is 0.25-0.5: 4 g/mL.
In the step 3), the mass ratio of the trimethylolpropane ethoxyacrylate triacrylate to the 2-hydroxy-2-methyl propiophenone to the silicon dioxide nanospheres is 10: (0.2-1.0): (0.1-0.5). Trimethyl propane ethoxy ester triacrylate as the outer phase material of the capsule; 2-hydroxy-2-methyl propiophenone is used as a photocuring material, so that the capsule is solidified and is not easy to break; the silicon dioxide is etched back to form the porosity of the capsule.
The step 4) is specifically as follows: mixing the solution A, the solution B and the polyvinyl alcohol aqueous solution according to the volume ratio of (1-5): (1-5): (100-200) are respectively placed in a needle tube to be used as an internal phase, an external phase and a driving phase, a micro-flow control technology is utilized, the flow rate of an internal phase pump is 3-10mL/h, the flow rate of an external phase pump is 4-10mL/h, the flow rate of an outermost layer driving phase pump is 800-800 mL/h, products are collected and repeatedly washed by deionized water, the products are kept stand in the deionized water for 2-3 days, after filtration, the products are placed in a 60 ℃ oven to be dried for 10-12h overnight, and the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained.
The preparation method of the polyvinyl alcohol aqueous solution in the step 4) comprises the following steps: dispersing polyvinyl alcohol in deionized water, placing the mixture in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution with the mass concentration of 0.02-0.04 g/ml;
the calcining temperature in the step 5) is 520 ℃, and the calcining time is 2 hours. Preferably, the calcination is carried out in an argon atmosphere. The calcining carbonization makes the organic matters of the capsule shell, namely the trimethylolpropane ethoxy triacrylate and the 2-hydroxy-2-methyl propiophenone, become inorganic carbon, and increases the conductivity.
Step 6), placing the carbonized capsule in a hydrofluoric acid solution to soak and etch away the silicon dioxide nanospheres; the mass concentration of the hydrofluoric acid solution is 10-40%, and the soaking time at normal temperature is 10-30 minutes.
In the step 7), the vulcanization temperature is 155 ℃, and the vulcanization time is 15-48 hours.
The tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material provided by the invention is prepared by adopting the method. The tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, and the tin dioxide quantum dot/carbon nanotube composite material is wrapped inside the spherical capsule and is loaded with sulfur particles.
The invention provides application of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material in preparation of a lithium-sulfur battery. The method specifically comprises the following steps: the anode of the lithium-sulfur battery is prepared by using the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material, so that the lithium-sulfur battery is prepared, the cycling stability is good, and the battery capacity is still stabilized to be more than 596mAh/g after 100 cycles.
In the preparation method of the tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material, firstly, the carbon nano tube with the tin dioxide quantum dot growing on the surface is ultrasonically dispersed in a polyvinyl alcohol solution to form a capsule internal phase; then, uniformly stirring trimethylolpropane ethoxy triacrylate ETPTA, a 2-hydroxy-2-methyl propiophenone photoinitiator and silicon dioxide nanospheres to form an outer phase of the capsule; preparing a tin dioxide quantum dot/carbon nano tube/microcapsule composite material under the action of polyvinyl alcohol driving liquid by a micro-fluidic technology; carrying out high-temperature carbonization on the microcapsules wrapped with the tin dioxide quantum dots/the carbon nano tubes under the protection of argon; the obtained stannic oxide quantum dot/carbon nano tube microcapsule composite material is soaked in hydrofluoric acid solution to etch away silicon dioxide nanospheres in the microcapsule shell, and then sulfur particles are loaded on the tube wall of the nano tube in the microcapsule and in the inner wall and the shell of the microcapsule after a sulfur fumigating step is carried out, so that the stannic oxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material is formed.
The tin dioxide quantum dot/carbon nano tube/sulfur particle porous microcapsule composite material provided by the invention has a larger specific surface area due to the fact that a large amount of tin dioxide quantum dots/carbon nano tubes are wrapped, the improvement of sulfur loading capacity and the acceleration of electron transmission are facilitated, meanwhile, the porous microcapsule structure of the tin dioxide quantum dot/carbon nano tube/sulfur particle composite material plays a role in slowing down the shuttle effect of polysulfide, the loss of active substances in the charging and discharging process is reduced, and the electrochemical performance of a positive electrode material is improved. Meanwhile, the capsule structure can well accommodate the volume change of sulfur particles in the charging and discharging processes, the structural integrity of sulfur is greatly improved, and the material is used as the positive electrode of the lithium-sulfur battery and has the characteristics of high capacity and stable cycle performance.
Compared with the prior art, the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared by the micro-fluidic technology has good controllability; simple experimental process and high yield.
Drawings
FIG. 1 is a TEM image of tin dioxide quantum dots grown on the surface of a carbon nanotube;
FIG. 2 is an HRTEM image of tin dioxide quantum dots grown on the surface of a carbon nanotube;
FIG. 3 is an optical picture of the tin dioxide quantum dot/carbon nanotube/microcapsule composite material prepared in step 4) of example 1;
FIG. 4 is an SEM image of the tin dioxide quantum dot/carbon nanotube/microcapsule composite material prepared in step 4) of example 1;
FIG. 5 is an SEM image (enlarged view) of the tin dioxide quantum dot/carbon nanotube/microcapsule composite material prepared in step 4) of example 1;
FIG. 6 is an SEM image of a calcined tin dioxide quantum dot/carbon nanotube/microcapsule composite material prepared in step 5) of example 1;
FIG. 7 is an SEM image of the composite material of tin dioxide quantum dots/carbon nanotubes/porous microcapsules prepared in step 6) of example 1, in which silicon dioxide is etched away after calcination;
FIG. 8 is an XRD pattern of the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared in step 7) of example 1;
fig. 9 is a charge/discharge capacity measurement test of a lithium-sulfur battery assembled by a positive electrode of the lithium-sulfur battery prepared from the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared in example 3 at a current density of 0.1C;
fig. 10 is a charge-discharge curve test chart of the lithium-sulfur battery assembled by the positive electrode of the lithium-sulfur battery prepared from the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared in example 3 at a current density of 0.1C.
Detailed Description
The present invention will be described in detail with reference to examples.
The construction of the microfluidic device is carried out by referring to the content in Chinese patent CN 206935332U: utilize welding technique to obtain coaxial syringe needle, interior syringe needle inlays inside the outer syringe needle, constitutes the shell with transparent organic glass pipe, and coaxial syringe needle passes through the cork and fixes in the organic glass shell to align with the aperture (its diameter is 0.3mm) on the glass board of bottom, adjust the distance between the aperture bottom the bottom of interior syringe needle and glass board bottom to 0.8 mm. And three injection pumps are used for controlling the flow of the inner phase, the outer phase and the driving phase respectively. The present invention will be described in detail with reference to examples.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test materials and reagents used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1)0.677 g SnCl2·2H2O, 0.226 g thiourea and 30 ml water, magnetically stirring for 36 hoursObtaining a stannic oxide quantum dot solution; ultrasonically dispersing 0.005 g of carbon nano tube in 7.5 ml of stannic oxide quantum dot solution, and reacting for 10 hours under the hydrothermal reaction condition of 180 ℃; then centrifugally cleaning, calcining in a 60 ℃ oven for 10 hours in a nitrogen atmosphere at 350 ℃ for 2 hours to obtain the tin dioxide quantum dot/carbon nanotube composite material;
2) ultrasonically dispersing 0.25g of tin dioxide quantum dots/carbon nano tubes in 4mL of 2% polyvinyl alcohol solution to obtain a mixed solution A;
3) uniformly stirring and mixing 0.2mL of 2-hydroxy-2-methyl propiophenone, 10g of ETPTA and 0.25g of silicon dioxide to obtain a mixed solution B;
4) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution which is a mixed solution C; mixing the mixed solution A, the mixed solution B and the mixed solution C according to a volume ratio of 1: 1: 120 are respectively placed in a needle tube to be respectively used as an inner phase, an outer phase and a driving phase, the micro-fluidic technology is utilized, the flow rate of an inner phase pump is 4mL/h, the flow rate of an outer phase pump is 5mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, a product is collected and repeatedly washed by deionized water, the product is kept stand in the deionized water for 2 days, and after filtration, the product is placed in a 60 ℃ oven to be dried overnight for 12 hours, so that the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained;
5) calcining the obtained microcapsule in argon atmosphere at 520 ℃ for 2 hours to obtain a carbonized capsule;
6) soaking the carbonized capsule in 10% hydrofluoric acid solution for 30 min at normal temperature to etch away the silicon dioxide nanospheres, filtering, cleaning, and drying to obtain tin dioxide quantum dots/carbon nanotubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/carbon nano tubes/porous microcapsules at 155 ℃ for 24 hours to obtain the tin dioxide quantum dots/carbon nano tubes/sulfur particle porous microcapsule composite material.
The prepared stannic oxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, the stannic oxide quantum dot/carbon nanotube composite material is wrapped inside the spherical capsule, and sulfur particles are loaded.
Example 2
A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1)0.677 g SnCl2·2H2O, 0.226 g of thiourea and 30 ml of water, and stirring for 36 hours by magnetic force to obtain a tin dioxide quantum dot solution; ultrasonically dispersing 0.005 g of carbon nano tube in 7.5 ml of stannic oxide quantum dot solution, and reacting for 10 hours under the hydrothermal reaction condition of 180 ℃; then centrifugally cleaning, drying in a 60 ℃ oven for 10 hours, calcining in a nitrogen atmosphere at 300 ℃ for 2 hours to obtain the tin dioxide quantum dot/carbon nanotube composite material;
2) ultrasonically dispersing 0.25g of tin dioxide quantum dots/carbon nano tubes in 4mL of 2% polyvinyl alcohol solution to obtain a mixed solution A;
3) uniformly stirring and mixing 0.2mL of 2-hydroxy-2-methyl propiophenone, 10g of ETPTA and 0.25g of silicon dioxide to obtain a mixed solution B;
4) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution which is a mixed solution C; mixing the mixed solution A, the mixed solution B and the mixed solution C according to a volume ratio of 1: 1: 160 are respectively placed in a needle tube to be respectively used as an inner phase, an outer phase and a driving phase, the micro-fluidic technology is utilized, the flow rate of an inner phase pump is 4mL/h, the flow rate of an outer phase pump is 5mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, a product is collected and repeatedly washed by deionized water, the product is kept stand in the deionized water for 3 days, and after filtration, the product is placed in a 60 ℃ oven to be dried overnight for 12 hours, so that the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained.
5) Calcining the obtained microcapsule at 520 ℃ for 2 hours in an argon atmosphere;
6) soaking the carbonized capsule in 10% hydrofluoric acid solution for 30 min to etch away the silicon dioxide nanospheres, filtering, cleaning, and drying to obtain tin dioxide quantum dots/carbon nanotubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/carbon nano tubes/porous microcapsules at 155 ℃ for 24 hours to obtain the tin dioxide quantum dots/carbon nano tubes/sulfur particle porous microcapsule composite material.
The prepared tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is characterized in that the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, the tin dioxide quantum dot/carbon nanotube composite material is wrapped in the spherical capsule, and sulfur particles are loaded on the spherical capsule.
Example 3
A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1)0.677 g SnCl2·2H2O, 0.226 g of thiourea and 30 ml of water, and stirring for 36 hours by magnetic force to obtain a tin dioxide quantum dot solution; ultrasonically dispersing 0.01 g of carbon nano tube in 7.5 ml of stannic oxide quantum dot solution, and reacting for 10 hours under the hydrothermal reaction condition of 180 ℃; then centrifugally cleaning, drying in a 60 ℃ oven for 10 hours, calcining in a nitrogen atmosphere at 350 ℃ for 2 hours to obtain the tin dioxide quantum dot/carbon nanotube composite material;
2) ultrasonically dispersing 0.25g of tin dioxide quantum dots/carbon nano tubes in 4mL of 10% polyvinyl alcohol solution to obtain a mixed solution A;
3) uniformly stirring and mixing 0.2mL of 2-hydroxy-2-methyl propiophenone, 10g of ETPTA and 0.25g of silicon dioxide to obtain a mixed solution B;
4) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution, thus obtaining a mixed solution C; mixing the mixed solution A, the mixed solution B and the mixed solution C according to a volume ratio of 1: 1: 180 are respectively arranged in a needle tube to be respectively used as an inner phase, an outer phase and a driving phase, the micro-fluidic technology is utilized, the flow rate of an inner phase pump is 5mL/h, the flow rate of an outer phase pump is 6mL/h, the flow rate of an outermost layer driving phase pump is 800mL/h, a product is collected and repeatedly washed by deionized water, the product is kept stand in the deionized water for 3 days, and after filtration, the product is placed in a 60 ℃ oven to be dried overnight for 12 hours, so that the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained.
5) Calcining the obtained microcapsule at 520 ℃ for 2 hours in an argon atmosphere;
6) soaking the carbonized capsule in 10% hydrofluoric acid solution for 30 min to etch away the silicon dioxide nanospheres, filtering, cleaning, and drying to obtain tin dioxide quantum dots/carbon nanotubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/carbon nano tubes/porous microcapsules at 155 ℃ for 24 hours to obtain the tin dioxide quantum dots/carbon nano tubes/sulfur particle porous microcapsule composite material.
The prepared tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is characterized in that the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, the tin dioxide quantum dot/carbon nanotube composite material is wrapped in the spherical capsule, and sulfur particles are loaded on the spherical capsule.
Example 4
A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1)0.677 g SnCl2·2H2O, 0.226 g of thiourea and 30 ml of water, and stirring for 36 hours by magnetic force to obtain a tin dioxide quantum dot solution; ultrasonically dispersing 0.01 g of carbon nano tube in 7.5 ml of stannic oxide quantum dot solution, and reacting for 10 hours under the hydrothermal reaction condition of 180 ℃; then centrifugally cleaning, drying in a 60 ℃ oven for 10 hours, calcining in a nitrogen atmosphere at 300 ℃ for 2 hours to obtain the tin dioxide quantum dot/carbon nanotube composite material;
2) ultrasonically dispersing 0.25g of tin dioxide quantum dots/carbon nano tubes in 4mL of 10% polyvinyl alcohol solution to obtain a mixed solution A;
3) uniformly stirring and mixing 0.2mL of 2-hydroxy-2-methyl propiophenone, 10g of ETPTA and 0.25g of silicon dioxide to obtain a mixed solution B;
4) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution, and mixing the solution C; mixing the mixed solution A, the mixed solution B and the mixed solution C according to a volume ratio of 1: 1: 200 are respectively placed in a needle tube to be used as an internal phase, an external phase and a driving phase, the micro-fluidic technology is utilized, the flow rate of an internal phase pump is 5mL/h, the flow rate of an external phase pump is 8mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, a product is collected and repeatedly washed by deionized water, the product is kept stand in the deionized water for 3 days, and after filtration, the product is placed in a 60 ℃ oven to be dried overnight, and the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained.
5) Calcining the microcapsule obtained in the step 4) at 520 ℃ for 2 hours in an argon atmosphere;
6) soaking the carbonized capsule in 10% hydrofluoric acid solution for 30 min to etch away the silicon dioxide nanospheres, filtering, cleaning, and drying to obtain tin dioxide quantum dots/carbon nanotubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/carbon nano tubes/porous microcapsules at 155 ℃ for 24 hours to obtain the tin dioxide quantum dots/carbon nano tubes/sulfur particle porous microcapsule composite material.
The prepared tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is characterized in that the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, the tin dioxide quantum dot/carbon nanotube composite material is wrapped in the spherical capsule, and sulfur particles are loaded on the spherical capsule.
Example 5
A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material comprises the following steps:
1)0.677 g SnCl2·2H2O, 0.226 g of thiourea and 30 ml of water, and stirring for 36 hours by magnetic force to obtain a tin dioxide quantum dot solution; 0.01 g of carbon nano tube is added into the reactorThe mixture is dispersed in 7.5 ml of stannic oxide quantum dot solution by sound, and the hydrothermal reaction condition is that the mixture reacts for 10 hours at 180 ℃; then centrifugally cleaning, drying in a 60 ℃ oven for 10 hours, calcining in a nitrogen atmosphere at 330 ℃ for 2 hours to obtain the tin dioxide quantum dot/carbon nanotube composite material;
2) ultrasonically dispersing 0.25g of tin dioxide quantum dots/carbon nano tubes in 4mL of 5% polyvinyl alcohol solution to obtain a mixed solution A;
3) uniformly stirring and mixing 0.2mL of 2-hydroxy-2-methyl propiophenone, 10g of ETPTA and 0.23g of silicon dioxide to obtain a mixed solution B;
4) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution, and mixing the solution C; mixing the mixed solution A, the mixed solution B and the mixed solution C according to a volume ratio of 1: 1: 160 are respectively placed in a needle tube to be used as an internal phase, an external phase and a driving phase, the micro-fluidic technology is utilized, the flow rate of an internal phase pump is 4mL/h, the flow rate of an external phase pump is 5mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, a product is collected and repeatedly washed by deionized water, the product is kept stand in the deionized water for 3 days, and after filtration, the product is placed in a 60 ℃ oven to be dried overnight for 10 hours, so that the tin dioxide quantum dot/carbon nano tube/microcapsule composite material can be obtained.
5) Calcining the capsule obtained in the step 4) at 520 ℃ for 2 hours in an argon atmosphere;
6) soaking the carbonized capsule in 10% hydrofluoric acid solution for 30 min to etch away the silicon dioxide nanospheres, filtering, cleaning, and drying to obtain tin dioxide quantum dots/carbon nanotubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/carbon nano tubes/porous microcapsules at 155 ℃ for 24 hours to obtain the tin dioxide quantum dots/carbon nano tubes/sulfur particle porous microcapsule composite material.
The prepared tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is characterized in that the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with the average diameter of 45-60 mu m, the tin dioxide quantum dot/carbon nanotube composite material is wrapped in the spherical capsule, and sulfur particles are loaded on the spherical capsule.
Example 6
A lithium-sulfur battery is prepared by adopting the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared in the embodiment 3 to prepare a lithium-sulfur battery positive electrode, and the positive electrode is used as a positive electrode to be assembled to obtain the lithium-sulfur battery.
The preparation method comprises the following steps:
taking the final product tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material obtained in the embodiment 3 as a positive electrode active material of a lithium-sulfur battery, and mixing the obtained active material with superconducting carbon black and PVDF in a proportion of 70: 20: 10, preparing the mixture into uniform slurry by using an N-methyl pyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, uniformly coating the uniform slurry into a film sheet by using a scraper, and uniformly adhering the film sheet to the surface of the aluminum foil. Then the prepared coating is put in a drying oven and dried for 12 hours at the temperature of 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃; and cutting an electrode plate of the dried composite material coating by adopting a mechanical cutting machine, taking a lithium plate as a counter electrode, and assembling the electrolyte which is a commercially available 1mol/L LiTFSI/DME + DOL solution to obtain the lithium-sulfur battery.
The lithium-sulfur battery obtained by assembling is tested for charge and discharge performance by using a battery tester, and the result of the cycling stability test under the current density of 0.1C is shown in figures 9 and 10, so that the cycling stability of the battery is good, and the battery capacity is still stabilized to be more than 596mAh/g after 100 times of cycling.
The above detailed description of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material, a preparation method thereof, a lithium sulfur battery positive electrode and a lithium sulfur battery, which refer to the examples, is illustrative and not restrictive, and several examples can be cited according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is characterized by comprising the following steps:
1) dispersing carbon nano tubes in a tin dioxide quantum dot solution, carrying out hydrothermal reaction, centrifuging, cleaning, drying and calcining a product to obtain tin dioxide quantum dots/carbon nano tubes;
2) dispersing the tin dioxide quantum dots/carbon nanotubes in a polyvinyl alcohol solution to form an inner phase solution A of the capsule;
3) adding 2-hydroxy-2-methyl propiophenone and the silicon dioxide nanospheres into trimethylolpropane ethoxy triacrylate, and uniformly stirring to form a capsule external phase solution B;
4) synthesizing the solution A prepared in the step 2), the solution B prepared in the step 3) and a polyvinyl alcohol aqueous solution by a micro-fluidic technology, and filtering, cleaning and drying a product to obtain tin dioxide quantum dots/carbon nano tubes/microcapsules;
5) calcining the tin dioxide quantum dots/the carbon nano tubes/the microcapsules to obtain carbonized microcapsules;
6) etching the silicon dioxide nanospheres of the carbonized capsule, filtering, cleaning and drying to obtain the tin dioxide quantum dots/carbon nano tubes/porous microcapsules;
7) and vulcanizing the tin dioxide quantum dots/the carbon nano tubes/the porous microcapsules to obtain the tin dioxide quantum dots/the carbon nano tubes/the sulfur particle porous microcapsule composite material.
2. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the tin dioxide quantum dots to the carbon nanotubes is 7.5: 0.005-0.2 mL/g.
3. The method as claimed in claim 1, wherein the hydrothermal reaction is carried out at 180 ℃ for 9-12 hours under 170 ℃ in step 1).
4. The method as claimed in claim 1, wherein the calcination temperature in step 1) is 300-350 ℃ and the calcination time is 2 hours.
5. The preparation method according to claim 1, wherein in the step 2), the ratio of the tin dioxide quantum dots/carbon nanotubes dispersed in the polyvinyl alcohol solution is 0.25-0.5: 4 g/mL.
6. The preparation method according to claim 1, wherein in the step 3), the weight ratio of the trimethylolpropane ethoxytriacrylate, the 2-hydroxy-2-methyl propiophenone and the silica nanospheres is 10: (0.2-1.0): (0.1-0.5).
7. The method according to claim 1, wherein the calcination temperature in step 5) is 520 ℃ and the calcination time is 2 hours.
8. The preparation method according to claim 1, wherein in step 5), the carbonized capsule is placed in a hydrofluoric acid solution to be soaked and etched to remove the silicon dioxide nanospheres; the mass concentration of the hydrofluoric acid solution is 10-40%, and the soaking time is 10-30 minutes.
9. The tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared by the preparation method of any one of claims 1 to 8, wherein the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material is spherical with an average diameter of 45 to 60 μm, the tin dioxide quantum dot/carbon nanotube composite material is wrapped in the spherical capsule, and sulfur particles are loaded on the spherical capsule.
10. Use of the tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material prepared by the preparation method according to any one of claims 1 to 8 for preparing a lithium-sulfur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011431270.XA CN112717843B (en) | 2020-12-07 | 2020-12-07 | Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011431270.XA CN112717843B (en) | 2020-12-07 | 2020-12-07 | Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112717843A true CN112717843A (en) | 2021-04-30 |
| CN112717843B CN112717843B (en) | 2022-06-21 |
Family
ID=75598700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011431270.XA Active CN112717843B (en) | 2020-12-07 | 2020-12-07 | Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112717843B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406018A (en) * | 2021-06-17 | 2021-09-17 | 大连海事大学 | Detector and detection method for sulfur content of marine fuel oil |
| CN113603132A (en) * | 2021-08-02 | 2021-11-05 | 郑州航空工业管理学院 | Carbon nano composite material and application thereof in battery |
| CN113788493A (en) * | 2021-09-18 | 2021-12-14 | 安徽师范大学 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
| CN114804190A (en) * | 2022-04-21 | 2022-07-29 | 贵州梅岭电源有限公司 | SnO (stannic oxide) 2 /SnS 2 Method for homogenizing size of flower-ball-shaped micron-sized particles |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140264193A1 (en) * | 2013-03-15 | 2014-09-18 | Nanoco Technologies, Ltd. | Preparation of Quantum Dot Beads Having a Silyl Surface Shell |
| CN104091934A (en) * | 2014-07-17 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Multi-component composite negative electrode material, preparation method of multi-component composite negative electrode material and lithium ion battery comprising multi-component composite negative electrode material |
| CN105047866A (en) * | 2015-06-15 | 2015-11-11 | 西北师范大学 | Preparation method of carbon-coating sulfur micron material doped with graphene quantum dots |
| CN105375070A (en) * | 2011-08-23 | 2016-03-02 | 株式会社日本触媒 | Gel electrolyte and cell using same |
| KR20170142344A (en) * | 2016-06-17 | 2017-12-28 | 서울대학교산학협력단 | Electrode composite and preparing method thereof |
| CN107638851A (en) * | 2017-08-31 | 2018-01-30 | 西北工业大学 | One kind is rung a bell shape Fe3O4@void@SiO2Nano chain and preparation method |
| CN111146429A (en) * | 2020-01-10 | 2020-05-12 | 安徽师范大学 | Preparation method of graphene oxide/sulfur microcapsule composite material, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| WO2020098276A1 (en) * | 2018-11-14 | 2020-05-22 | 五邑大学 | Preparation method of carbon nanotube/manganese dioxide composite electrode |
-
2020
- 2020-12-07 CN CN202011431270.XA patent/CN112717843B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105375070A (en) * | 2011-08-23 | 2016-03-02 | 株式会社日本触媒 | Gel electrolyte and cell using same |
| US20140264193A1 (en) * | 2013-03-15 | 2014-09-18 | Nanoco Technologies, Ltd. | Preparation of Quantum Dot Beads Having a Silyl Surface Shell |
| CN104091934A (en) * | 2014-07-17 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Multi-component composite negative electrode material, preparation method of multi-component composite negative electrode material and lithium ion battery comprising multi-component composite negative electrode material |
| CN105047866A (en) * | 2015-06-15 | 2015-11-11 | 西北师范大学 | Preparation method of carbon-coating sulfur micron material doped with graphene quantum dots |
| KR20170142344A (en) * | 2016-06-17 | 2017-12-28 | 서울대학교산학협력단 | Electrode composite and preparing method thereof |
| CN107638851A (en) * | 2017-08-31 | 2018-01-30 | 西北工业大学 | One kind is rung a bell shape Fe3O4@void@SiO2Nano chain and preparation method |
| WO2020098276A1 (en) * | 2018-11-14 | 2020-05-22 | 五邑大学 | Preparation method of carbon nanotube/manganese dioxide composite electrode |
| CN111146429A (en) * | 2020-01-10 | 2020-05-12 | 安徽师范大学 | Preparation method of graphene oxide/sulfur microcapsule composite material, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Non-Patent Citations (4)
| Title |
|---|
| YAOHONG ZHANG: "Surface-Modified Graphene Oxide/Lead Sulfide Hybrid Film-Forming Ink for High-Efficiency Bulk Nano-Heterojunction Colloidal Quantum Dot Solar Cells", 《NANO-MICRO LETTERS》 * |
| YONG WU: "A novel silicon nanoparticles-infilled capsule prepared by an oil-in-water emulsion strategy for high-performance Li-ion battery anodes", 《NANOTECHNOLOGY》 * |
| 张俊等: "混合动力汽车用二氧化锡填充碳纳米管复合材料的制备及储锂性能研究", 《绝缘材料》 * |
| 郭庆生: "基于量子点的荧光传感器用于生物分析研究", 《中国博士学位论文全文数据库》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113406018A (en) * | 2021-06-17 | 2021-09-17 | 大连海事大学 | Detector and detection method for sulfur content of marine fuel oil |
| CN113406018B (en) * | 2021-06-17 | 2024-02-09 | 大连海事大学 | Marine fuel oil sulfur content detector and detection method |
| CN113603132A (en) * | 2021-08-02 | 2021-11-05 | 郑州航空工业管理学院 | Carbon nano composite material and application thereof in battery |
| CN113788493A (en) * | 2021-09-18 | 2021-12-14 | 安徽师范大学 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
| CN113788493B (en) * | 2021-09-18 | 2023-09-01 | 乌海瑞森新能源材料有限公司 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
| CN114804190A (en) * | 2022-04-21 | 2022-07-29 | 贵州梅岭电源有限公司 | SnO (stannic oxide) 2 /SnS 2 Method for homogenizing size of flower-ball-shaped micron-sized particles |
| CN114804190B (en) * | 2022-04-21 | 2023-07-28 | 贵州梅岭电源有限公司 | SnO (tin oxide) 2 /SnS 2 Method for homogenizing sizes of flower-sphere micron-sized particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112717843B (en) | 2022-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112717843B (en) | Tin dioxide quantum dot/carbon nanotube/sulfur particle porous microcapsule composite material and preparation method and application thereof | |
| CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN107256956B (en) | Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof | |
| CN108539171B (en) | Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery | |
| CN103441247B (en) | A kind of high performance silicon/graphene oxide negative material constructed based on chemical bond and preparation method thereof | |
| CN102593418A (en) | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material | |
| CN113594415B (en) | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof | |
| CN110931753B (en) | Silicon negative electrode material and preparation method thereof | |
| CN109103424B (en) | Carbon-sulfur composite positive electrode material, preparation method thereof, positive electrode and lithium-sulfur battery | |
| CN109360939A (en) | A kind of flexibility of lithium ion battery is without collector thin film pole piece preparation method | |
| CN108923045A (en) | Improve the method for electrochemical performances of lithium iron phosphate using copper ion/graphene | |
| WO2021004259A1 (en) | Symmetrical aqueous sodium-ion battery | |
| CN104282894A (en) | Preparation method of porous Si/C composite microsphere | |
| CN112242570B (en) | Application of mixture of carbon material and ionic bromide and aqueous zinc-bromine double-ion battery | |
| CN108539160B (en) | CoO/rGO compound and preparation method and application thereof | |
| CN108666533B (en) | Preparation method and application of sulfur electrode of lithium-sulfur battery | |
| CN111554905B (en) | Preparation method, product and application of zinc oxide-based carbon composite nano material | |
| CN110611068B (en) | Preparation method of novel lithium-sulfur battery diaphragm material | |
| CN112980436A (en) | Carbon quantum dot derived carbon nanosheet composite silicon dioxide cathode material and preparation method thereof | |
| CN114094063B (en) | Method for preparing battery anode material by combining cavity precursor and ZIF derivative | |
| CN105633391A (en) | Preparation method of metal manganese/reduced-oxidized graphene/lithium iron phosphate composite material | |
| CN109698333A (en) | A kind of Lithium-sulphur battery anode material and its preparation method and application | |
| CN109346726A (en) | A kind of high temperature modification manganese systems lithium battery anode | |
| CN113788493B (en) | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN114751395A (en) | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |