CN105390677A - Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof - Google Patents
Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof Download PDFInfo
- Publication number
- CN105390677A CN105390677A CN201510726289.XA CN201510726289A CN105390677A CN 105390677 A CN105390677 A CN 105390677A CN 201510726289 A CN201510726289 A CN 201510726289A CN 105390677 A CN105390677 A CN 105390677A
- Authority
- CN
- China
- Prior art keywords
- carbon
- metal oxide
- composite material
- graphene composite
- oxide semiconductor
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and an application thereof, and belongs to the technical field of lithium ion batteries. The material serving as a negative electrode of a lithium ion battery can show excellent electrochemical performance, so that the material can be applied to the field of new energy. According to the material, a metal organic nanosheet precursor is synthesized with a solvothermal synthesis method and perpendicularly grows on a graphene substrate at first, and then heat treatment is performed in a mixed atmosphere of hydrogen and argon to obtain the carbon self-coated semiconductor metal oxide nanosheet and graphene composite material; and importantly, a carbon source does not need to be additionally added in the process, an organic part in the metal organic precursor is directly thermally decomposed, carbonized and self-applied to the surface of a metal oxide nanoparticle, and the metal oxide nanoparticle is obtained by thermal decomposition transformation of a metal part in the precursor. The material serving as the negative electrode of the lithium ion battery shows excellent electrochemical performance.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of carbon from coated metal oxide semiconductor nanometer sheet and graphene composite material and application thereof, this material can show excellent chemical property as the negative pole of lithium ion battery, and it can be applied in new energy field.
Background technology
Rechargeable lithium ion batteries as a kind of energy storage facilities gradually studied personnel paid close attention to because it has many excellent features, such as high energy density, high voltage, long cycle life, self-discharge phenomenon that quality is light and low etc.Current business negative material used mainly based on graphite, although the cost of graphite is low, its theoretical capacity (372mAhg
-1) lower, and security performance is low etc., and problem makes application be restricted.Metal oxide semiconductor material is a kind of high performance lithium ionic cell cathode material with the characteristic such as long circulation life, safety and environmental protection.Compared with material with carbon element, it has, and intercalation potential is high, chemical stability good, fail safe advantages of higher.Metal oxide nano-sheet makes it have larger specific area, pore-size distribution and pore volume, stronger adsorption capacity due to the special construction with two dimension in addition, is expected to improve storage lithium performance greatly.Two-dimensional sheet structure as the evolving path of the shortening lithium ion of electrode energy high degree, and then promotes the high rate performance of battery, but itself electron conduction is poor, has restriction to the performance of its performance.Carbon is coated is a kind of method of raising material conductivity the most common, and it not only can improve the conductivity of material, and can the volumetric expansion that causes in embedding lithium process of limiting material, and then improves the chemical property of material.
In addition, Graphene is a kind of carbon monoatomic layer structure of two dimension, and owing to having ultra-thin thickness, larger specific area, the advantages such as high conductance, make it be widely used in the field such as electronic technology, energy storage.Therefore, in order to improve the conductivity of semi-conducting material, together with being compound to semi-conducting material nanometer sheet by Graphene, the combination property of material can be improved greatly.Up to the present, semi-conducting material nanometer length of a film is remained on Graphene an important brainstorm subject.Chinese patent CN102185143A by being dissolved in by slaine in the organic solvent containing surfactant, then adding hydrazine hydrate and reduces, and then uses alkaline conditioner adjust ph, obtains transition metal oxide/graphene composite material.Metal salt solution and carbon source mix by Chinese patent CN104269535A, and then have synthesized carbon-clad metal oxide-graphene combination electrode material through high-temperature roasting.Chinese patent CN104815637A is for medium with the mixed solvent of low-carbon (LC) alcohol and water, take surfactant as dressing agent, first by graphene oxide functional modification, then mix with the acid solution of titanium salt, after hydrothermal crystallizing, obtain the composite material of graphene-supported flower-shaped titanium dioxide.These synthetic method more complicated, synthesis cost is higher, and the raw material type used is also more, for extremely unfavorable large-scale production.In order to overcome these shortcomings, we adopt the method one-step synthesis of simple solvent heat to go out the electrode material of carbon from coated metal oxide semiconductor nanometer sheet and Graphene compound, and this material shows excellent chemical property as the negative pole of lithium ion battery.
Summary of the invention
The present invention adopts the synthetic method of solvent heat first to synthesize the vertical growth of metal organic nano sheet presoma in the substrate of Graphene, then under hydrogen and argon gas mixed atmosphere, heat treatment obtains the composite material of carbon from coated metal oxide semiconductor nanometer sheet and Graphene, importantly do not need in this process additionally to add carbon source again, by the direct thermal decomposition carbonization of the organic moiety in metal organic precursor from being coated on the surface of metal oxide nanoparticles, and this metal oxide nanoparticles is that in presoma, the thermal decomposition of metallic member is transformed.
Carbon of the present invention is from coated metal oxide semiconductor nanometer sheet and graphene composite material, and it is prepared (all raw materials all can obtain from conven-tional channels) by following steps:
(1) by the ultrasonic process 30 ~ 120 minutes in 20 ~ 40 milliliters of solvents of 20 ~ 100 milligrams of graphene oxides, graphene oxide dispersion is obtained;
(2) 0.3 ~ 1.5 gram of slaine is joined in the dispersion liquid of step (1), stir 10 ~ 60 minutes;
(3) solution step (2) obtained loads in reactor, thermostatic crystallization at autogenous pressures after airtight, treat centrifugal treating after crystallization, solid product with absolute ethyl alcohol supersound washing repeatedly, then 60 ~ 120 DEG C of air dryings 12 ~ 48 hours, metal organic nano sheet presoma and the former powder of graphene composite material is obtained;
(4) by the roasting in the mixed atmosphere of argon gas and hydrogen of above-mentioned former powder, carbon is obtained from coated metal oxide semiconductor nanometer sheet and graphene composite material.
Solvent in step (1) described above is one or more the mixing in glacial acetic acid, formic acid or benzoic acid;
Slaine in step (2) described above is one or more the mixing in butyl titanate, titanium tetraisopropylate, titanium tetrachloride, manganese acetate, cobalt acetate, nickel acetate, Schweinfurt green, zinc acetate;
The rotating speed stirred in step (2) is 500 ~ 900 revs/min;
Crystallization temperature in step (3) is 130 ~ 160 DEG C, and crystallization time is 12 ~ 24 hours;
In in step (3) argon gas and hydrogen mixed atmosphere in, the volumn concentration of hydrogen is 5 ~ 10%;
In step (3), the temperature of roasting is 450 ~ 550 DEG C, and roasting time is 2 ~ 10 hours.
The metal oxide semiconductor material that this synthesis step can synthesize comprises titanium dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, cobaltosic oxide, nickel oxide, zinc oxide, cupric oxide, cobalt acid zinc, cobalt acid nickel and cobalt acid manganese etc., and the metal oxide semiconductor material of other metallic elements synthesized as used this method also belongs to the protection range of this patent.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of the carbon prepared of the embodiment of the present invention 2 from the composite material of coated titanium dioxide nanoplate and Graphene.
Fig. 2 is that the embodiment of the present invention 2 prepares the scanned picture of carbon from the composite material of coated titanium dioxide nanoplate and Graphene.
Fig. 3 is that the embodiment of the present invention 2 prepares carbon oxygen element, titanium elements and carbon distribution map in the composite material of coated titanium dioxide nanoplate and Graphene.
Fig. 4 is that the carbon prepared of the embodiment of the present invention 2 is from coated titanium dioxide nanoplate and the graphene composite material high rate performance as cathode of lithium battery.
Embodiment
The metal oxide semiconductor material related to due to this patent is more, carries out detailed description the present invention below to synthesize carbon from the composite material of coated titanic oxide material nanometer sheet and Graphene by embodiment, but has more than and be limited to these examples.
Embodiment 1
(1) graphene oxide of 20 milligrams is dispersed in the glacial acetic acid of 20 milliliters, ultrasonic 30 minutes, obtains graphene oxide solution A liquid;
(2) butyl titanate of 0.3 gram is added in A liquid, stir 10 minutes;
(3) load in reactor by aforesaid liquid, crystallization 24 hours at 130 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 80 DEG C of air dryings 24 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 450 DEG C of roastings 10 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 5%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 80 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample by scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene, known by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Embodiment 2
(1) graphene oxide of 20 milligrams is dispersed in the glacial acetic acid of 30 milliliters, ultrasonic 120 minutes, obtains graphene oxide solution A liquid;
(2) butyl titanate of 0.5 gram is added in A liquid, stir 10 minutes;
(3) load in reactor by aforesaid liquid, crystallization 12 hours at 150 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 60 DEG C of air dryings 12 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 500 DEG C of roastings 2 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 5%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 120 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample by scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene, known by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Embodiment 3
(1) graphene oxide of 50 milligrams is dispersed in the glacial acetic acid of 30 milliliters, ultrasonic 30 minutes, obtains graphene oxide solution A liquid;
(2) butyl titanate of 1.0 grams is added in A liquid, stir 30 minutes;
(3) load in reactor by aforesaid liquid, crystallization 24 hours at 140 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 120 DEG C of air dryings 12 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 550 DEG C of roastings 2 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 10%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 200 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample by scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene, known by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Embodiment 4
(1) graphene oxide of 80 milligrams is dispersed in the glacial acetic acid of 40 milliliters, ultrasonic 120 minutes, obtains graphene oxide solution A liquid;
(2) butyl titanate of 1.2 grams is added in A liquid, stir 60 minutes;
(3) load in reactor by aforesaid liquid, crystallization 12 hours at 150 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 100 DEG C of air dryings 48 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 500 DEG C of roastings 5 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 10%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 313 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample by scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene, known by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Embodiment 5
(1) graphene oxide of 100 milligrams is dispersed in the glacial acetic acid of 40 milliliters, ultrasonic 120 minutes, obtains graphene oxide solution A liquid;
(2) butyl titanate of 1.5 grams is added in A liquid, stir 60 minutes;
(3) load in reactor by aforesaid liquid, crystallization 24 hours at 160 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 80 DEG C of air dryings 24 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 450 DEG C of roastings 10 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 10%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 406 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample from scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Embodiment 6
(1) graphene oxide of 20 milligrams is dispersed in the benzoic acid of 30 milliliters, ultrasonic 120 minutes, obtains graphene oxide solution A liquid;
(2) titanium tetraisopropylate of 0.5 gram is added in A liquid, stir 10 minutes;
(3) load in reactor by aforesaid liquid, crystallization 12 hours at 150 DEG C at autogenous pressures after airtight, after treating crystallization, solid product is through centrifugal, with absolute ethanol washing repeatedly, then 60 DEG C of air dryings 12 hours, obtain organic titanium nanometer sheet and the former powder of graphene composite material;
(4) by the 500 DEG C of roastings 2 hours in the mixed atmosphere of argon gas and hydrogen (hydrogen volume mark is 10%) of above-mentioned former powder, obtain carbon from coated titanium dioxide nanoplate and graphene composite material, product quality is 109 milligrams.By XRD characterize find obtain sample structure be Anatase (PDF21-1272) in titanium dioxide and TiO
2(B) phase (PDF35-0088), the pattern that can obtain sample by scanned picture be carbon from the uniform vertical-growth of coated titanium dioxide nanoplate on the surface of Graphene, known by Elemental redistribution scanned picture, oxygen element, titanium elements and carbon are evenly distributed on whole sample topography, can prove that carbon has been coated on the surface of titanium dioxide nanoplate simultaneously.
Carbon of the present invention is tested (preparation of electrode and test condition) from the performance of lithium ion battery of coated metal oxide semiconductor material nano sheet and graphene composite material:
The carbon that above-described embodiment 2 is obtained from coated metal oxide semiconductor material nano sheet and graphene composite material as active material, acetylene black is conductive agent, polytetrafluoroethylene is binding agent, be the ratio of 80:10:10 in mass ratio by it, with METHYLPYRROLIDONE as solvent, mix the negative pole be coated on as battery in copper foil current collector, positive pole uses simple substance lithium paper tinsel, add electrolyte and be assembled into battery, charge-discharge test is carried out, discharge and recharge window 3 ~ 0.01V (vsLi/Li with battery test system
+).
Claims (9)
1. carbon is from coated metal oxide semiconductor nanometer sheet and a graphene composite material, and it is prepared by following steps:
(1) by the ultrasonic process 30 ~ 120 minutes in 20 ~ 40 milliliters of solvents of 20 ~ 100 milligrams of graphene oxides, graphene oxide dispersion is obtained;
(2) 0.3 ~ 1.5 gram of slaine is joined in the dispersion liquid of step (1), stir 10 ~ 60 minutes;
(3) solution step (2) obtained loads in reactor, thermostatic crystallization at autogenous pressures after airtight, treat centrifugal treating after crystallization, solid product with absolute ethyl alcohol supersound washing repeatedly, then 60 ~ 120 DEG C of air dryings 12 ~ 48 hours, metal organic nano sheet presoma and the former powder of graphene composite material is obtained;
(4) by the roasting in the mixed atmosphere of argon gas and hydrogen of above-mentioned former powder, carbon is obtained from coated metal oxide semiconductor nanometer sheet and graphene composite material.
2. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: the solvent in step (1) is one or more the mixing in glacial acetic acid, formic acid or benzoic acid.
3. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: the slaine in step (2) is one or more the mixing in butyl titanate, titanium tetraisopropylate, titanium tetrachloride, manganese acetate, cobalt acetate, nickel acetate, Schweinfurt green, zinc acetate.
4. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: the rotating speed stirred in step (2) is 500 ~ 900 revs/min.
5. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: the crystallization temperature in step (3) is 130 ~ 160 DEG C, and crystallization time is 12 ~ 24 hours.
6. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: in step (3) argon gas and hydrogen mixed atmosphere in, the volumn concentration of hydrogen is 5 ~ 10%.
7. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: in step (3), the temperature of roasting is 450 ~ 550 DEG C, and roasting time is 2 ~ 10 hours.
8. a kind of carbon as claimed in claim 1 is from coated metal oxide semiconductor nanometer sheet and graphene composite material, it is characterized in that: the metal oxide semiconductor in step (4) is titanium dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, cobaltosic oxide, nickel oxide, zinc oxide, cupric oxide, cobalt acid zinc, cobalt acid nickel or cobalt acid manganese.
9. a kind of carbon of claim 1-8 described in any one from coated metal oxide semiconductor nanometer sheet and graphene composite material as the application in lithium ion battery negative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510726289.XA CN105390677A (en) | 2015-11-02 | 2015-11-02 | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510726289.XA CN105390677A (en) | 2015-11-02 | 2015-11-02 | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105390677A true CN105390677A (en) | 2016-03-09 |
Family
ID=55422718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510726289.XA Pending CN105390677A (en) | 2015-11-02 | 2015-11-02 | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105390677A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328392A (en) * | 2016-09-23 | 2017-01-11 | 安徽师范大学 | Mesoporous ZnCo2O4 nanosheet@NiCo2O4 nanosheet composite material, preparation method and application |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN106531988A (en) * | 2016-10-21 | 2017-03-22 | 吉林大学 | N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof |
| CN107359350A (en) * | 2017-04-26 | 2017-11-17 | 沈阳工业大学 | Preparation method with excellent electrochemical performance iron Zn complex and its derivative |
| CN107381656A (en) * | 2017-06-23 | 2017-11-24 | 上海电力学院 | A kind of preparation method of lithium ion battery negative material |
| CN111554517A (en) * | 2020-05-12 | 2020-08-18 | 邓李金 | Nitrogen-doped porous carbon-coated nano NiCo2O4Electrode active material and method for producing the same |
| CN111599995A (en) * | 2020-04-28 | 2020-08-28 | 惠州锂威新能源科技有限公司 | Cathode material, preparation method thereof and high-voltage lithium ion battery |
| CN113816468A (en) * | 2021-09-13 | 2021-12-21 | 华南理工大学 | DSA electrode and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185143A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Transition metal oxide/ graphene composite material and preparation method thereof |
| CN104269535A (en) * | 2014-09-15 | 2015-01-07 | 南京工业大学 | Preparation method of carbon-coated metal oxide-graphene composite electrode material |
| CN104310468A (en) * | 2014-10-14 | 2015-01-28 | 吉林大学 | Method for preparing monodisperse titanium dioxide (B) nano particles |
| CN104386743A (en) * | 2014-11-26 | 2015-03-04 | 上海大学 | Solvothermal preparation method of anatase type TiO2 nanometer tube |
-
2015
- 2015-11-02 CN CN201510726289.XA patent/CN105390677A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185143A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Transition metal oxide/ graphene composite material and preparation method thereof |
| CN104269535A (en) * | 2014-09-15 | 2015-01-07 | 南京工业大学 | Preparation method of carbon-coated metal oxide-graphene composite electrode material |
| CN104310468A (en) * | 2014-10-14 | 2015-01-28 | 吉林大学 | Method for preparing monodisperse titanium dioxide (B) nano particles |
| CN104386743A (en) * | 2014-11-26 | 2015-03-04 | 上海大学 | Solvothermal preparation method of anatase type TiO2 nanometer tube |
Non-Patent Citations (1)
| Title |
|---|
| SHANG JIANG，ET AL: ""Assembling porous carbon-coated TiO2(B)/anatase nanosheets on reduced graphene oxide for high performance lithium-ion batteries"", 《ELECTROCHIMICA ACTA》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328392A (en) * | 2016-09-23 | 2017-01-11 | 安徽师范大学 | Mesoporous ZnCo2O4 nanosheet@NiCo2O4 nanosheet composite material, preparation method and application |
| CN106328392B (en) * | 2016-09-23 | 2018-05-08 | 安徽师范大学 | A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanosheet composite material, preparation method and application |
| CN106531988A (en) * | 2016-10-21 | 2017-03-22 | 吉林大学 | N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN106410203B (en) * | 2016-11-11 | 2019-07-12 | 南京理工大学 | A method of using metal alkoxide as precursor preparation spherical shape cobalt acid zinc/carbon composite |
| CN107359350A (en) * | 2017-04-26 | 2017-11-17 | 沈阳工业大学 | Preparation method with excellent electrochemical performance iron Zn complex and its derivative |
| CN107381656A (en) * | 2017-06-23 | 2017-11-24 | 上海电力学院 | A kind of preparation method of lithium ion battery negative material |
| CN111599995A (en) * | 2020-04-28 | 2020-08-28 | 惠州锂威新能源科技有限公司 | Cathode material, preparation method thereof and high-voltage lithium ion battery |
| CN111554517A (en) * | 2020-05-12 | 2020-08-18 | 邓李金 | Nitrogen-doped porous carbon-coated nano NiCo2O4Electrode active material and method for producing the same |
| CN113816468A (en) * | 2021-09-13 | 2021-12-21 | 华南理工大学 | DSA electrode and preparation method and application thereof |
| CN113816468B (en) * | 2021-09-13 | 2022-08-12 | 华南理工大学 | DSA electrode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Graphite-based lithium ion battery with ultrafast charging and discharging and excellent low temperature performance | |
| Tang et al. | High‐Density Microporous Li4Ti5O12 Microbars with Superior Rate Performance for Lithium‐Ion Batteries | |
| Chen et al. | Uniform and porous Mn-doped Co3O4 microspheres: Solvothermal synthesis and their superior supercapacitor performances | |
| Zhu et al. | Synthesis of MnO/C composites derived from pollen template for advanced lithium-ion batteries | |
| Long et al. | Synthesis of a nanowire self-assembled hierarchical ZnCo 2 O 4 shell/Ni current collector core as binder-free anodes for high-performance Li-ion batteries | |
| CN105390677A (en) | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof | |
| Sha et al. | Hierarchical carbon-coated acanthosphere-like Li4Ti5O12 microspheres for high-power lithium-ion batteries | |
| CN103367719B (en) | The preparation method of Yolk-shell structure tin dioxide-nitrogen-dopcarbon carbon material | |
| CN103219168B (en) | A kind of Li 4ti 5o 12/ graphene combination electrode material and preparation method thereof | |
| CN103000906B (en) | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery | |
| CN108598444B (en) | Vanadium trioxide/graphene composite negative electrode material of lithium ion battery and preparation method | |
| CN102376937A (en) | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof | |
| CN104868112A (en) | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof | |
| Ling et al. | Double-shelled hollow Na 2 FePO 4 F/C spheres cathode for high-performance sodium-ion batteries | |
| CN103682296A (en) | Preparation method for nanoscale lithium titanate material with high specific capacity | |
| Zheng et al. | Zn-MOFs derived porous carbon nanofiber for high performance lithium-ion batteries | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN104810515A (en) | Preparation method of doped Li4Ti5O12 anode material | |
| Chen et al. | MOF-derived bimetal oxides NiO/NiCo 2 O 4 with different morphologies as anodes for high-performance lithium-ion battery | |
| Shi et al. | Nb2O5 nanospheres/surface-modified graphene composites as superior anode materials in lithium ion batteries | |
| CN103545518A (en) | Lithium vanadium phosphate/carbon heterogeneous mesoporous nanowire material and preparation method and application thereof | |
| Li et al. | Synthesis and electrochemical performance of Li4Ti5O12/Ag composite prepared by electroless plating | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode | |
| CN104393275A (en) | Preparation method of carbon-coated lithium titanate battery material | |
| CN106374086A (en) | Nano lithium titanate-graphene composite material and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160309 |