CN105161721B - The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation - Google Patents
The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation Download PDFInfo
- Publication number
- CN105161721B CN105161721B CN201510469973.4A CN201510469973A CN105161721B CN 105161721 B CN105161721 B CN 105161721B CN 201510469973 A CN201510469973 A CN 201510469973A CN 105161721 B CN105161721 B CN 105161721B
- Authority
- CN
- China
- Prior art keywords
- dimensional grapheme
- carbon coating
- composite material
- tin
- carbon
- 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.)
- Expired - Fee Related
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si 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
- H01M4/36—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
- H01M4/387—Tin or alloys based on tin
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the composite materials and preparation method of a kind of three-dimensional grapheme interlayer filling carbon coating tin particles.The material is uniformly filled into graphene sheet layer by carbon covered stannum rice grain, forms three-dimensional sandwich-like structure.Its preparation process is as follows：Using NaCl as dispersant and template, it with source metal and carbon source is fully dissolved and is mixed, is freeze-dried and finely ground, obtains mixture；Mixture is put into tube furnace, lower calcining is protected in argon gas, obtains calcined product；Calcined product is washed, is mixed with DEXTROSE ANHYDROUS and carries out hydro-thermal cladding, hydrothermal product is subjected to hydrogen catalytic calcining again, obtains the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles.The invention has the advantages that safe preparation process is harmless, easy to operate, the composite material of prepared three-dimensional grapheme interlayer filling carbon coating tin particles has high reversible capacity, strong cyclical stability and excellent high rate performance as lithium ion battery negative material.
Description
Technical field
The present invention relates to the composite materials and preparation method of a kind of three-dimensional grapheme interlayer filling carbon coating tin particles, belong to
Electrode material of secondary lithium ion battery field.
Background technology
The fuel such as traditional coal, oil consume always as the main energy sources of the mankind as it is a large amount of, not only cause
Energy crisis also seriously polluted air, and the haze weather moment growed in intensity is reminding people that searching Novel clean is renewable
The energy has been extremely urgent.In recent years, it is all obtained as industries such as novel energy, water energy, wind energy, solar energy, battery, capacitors
It is fast-developing.Wherein, lithium rechargeable battery is because with energy density is big, working range is wide, discharge voltage is high, dirty without environment
It the advantages that dye, memory-less effect, receives significant attention, and be widely used to mobile phone, video camera, camera, notebook
In the portable devices such as computer, more in hybrid vehicle of new generation（HEV）And pure electric automobile（EV）In serve as important energy source,
Soon it will also be applied in the military fields such as satellite and space flight.
Good lithium ion battery negative material should have a high conductivity, high-specific surface area, and active material stability is good
The advantages that, graphene just meets this requirement, and three-dimensional grapheme is due to the connection between graphene film so that overall structure group
Three-dimensional conductive network is built up, and tap density greatly improved, there is the property better than conventional graphite alkene.Three-dimensional stone is prepared at present
The method of black alkene mainly has：Redox graphene stack process and foam metal CVD growth method, cut both ways, for reduction
Graphene oxide stack process, prepared graphene are easily reunited, and are restored not exclusively, this has resulted in graphene and has compared table
The shortcomings of area is low, poorly conductive；For foam metal CVD growth method, the graphene quality prepared is fine, but due to its production
Measure extremely limited, and production cost is high, hardly results in application.
Sandwich structure is all seen as the ideal structure of lithium ion battery negative material, so-called sandwich knot all the time
Structure is exactly generally by crust of the carbon material as sandwich, and heart of the active metal material as sandwich is formed
Sandwich.This structure not only can make it avoid being in direct contact with electrolyte, so as to reduce two with protection activity metal material
Side reaction at boundary, and volume expansion of the active metal material in charge and discharge can be alleviated, reduce its broken, dusting
Probability.There are mainly two types of ways for conventional graphite alkenes sandwich structure：One be using its lamella during redox graphene it
Between stacking, active metal particles is made to sandwich in graphene sheet layer, so as to obtain Sanming City of graphene-active metal-graphene
Control structure；Two, first active metal material to be caused to be supported on graphene sheet layer, then carry out carbon coating, make its outermost coat again
Last layer carbon, so as to obtain graphene-active metal-amorphous carbon structure, and the sandwich structure of three-dimensional grapheme is due to preparing
Difficulty is larger, rare report.
Invention content
Composite material and preparation the object of the present invention is to provide a kind of three-dimensional grapheme interlayer filling carbon coating tin particles
Method.The composite material has good charge-discharge performance, high rate performance and stabilization as lithium ion battery negative material
Property, it has a extensive future.Preparation method process is simple, suitable for batch production.
The present invention is to be realized by the following technical programs, and a kind of three-dimensional grapheme interlayer fills carbon coating tin
The composite material of particle, which is characterized in that the composite material by upper and lower three-dimensional grapheme layer and this upper and lower three
Tie up graphene layer between carbon coating tin nano-particle layer form, wherein, three-dimensional grapheme layer thickness be 1-10nm, three-dimensional graphite
Alkene network radius is 1-10um；Carbon covered stannum rice grain grain size is 5-30nm, and carbon coating layer thickness is 1-4nm；It is compound at this
The mass percent of tin and total carbon in material is：(0.4-0.7):(0.6-0.3).
The preparation method of the composite material of the three-dimensional grapheme interlayer filling carbon coating tin particles of above structure, feature exist
In including the following steps：
(1) is using glucose as carbon source, using stannous chloride as tin source, by the molar ratio of the tin in the carbon and tin source in carbon source
For（50~10）：1, and using the tin in tin source and the mass ratio of sodium chloride as（0.01~0.1）：1 meter, by carbon source, tin source and chlorination
Sodium, which is added in deionized water, to be dissolved, and stirs wiring solution-forming, ultrasonic mixing is uniformly placed in refrigerator and freezes, and treats solution freeze over
It is placed in freeze drier and is dried in vacuo in -50 DEG C, obtain mixture；
(2) mixture grind into powder made from step (1) is laid in Noah's ark, is placed in tube furnace flat-temperature zone and is forged by
It burns：Using Ar as inert gas source, inert gas is first passed through as 200 ~ 400ml/min using flow and excludes air within 10 ~ 30 minutes；Again
Using Ar as protection gas, protection air-flow amount is fixed as 50 ~ 200ml/min, 300 are warming up to the heating rate of 1 ~ 10 DEG C/min
~ 450 DEG C, heat preservation 1-2h is carbonized, and is cooled to room temperature after reaction, obtains calcined product A；
(3) calcined product A made from collection steps (2), it is finely ground, it is washed to until there is no sodium chloride in calcined product A,
It is dried at being 60-120 DEG C in temperature；It is again (5- by the mass ratio of DEXTROSE ANHYDROUS and the calcined product A for drying non-sodium chloride
10):1 meter, by DEXTROSE ANHYDROUS and drying non-sodium chloride calcined product A be separately added into deionized water and absolute ethyl alcohol in,
Two kinds of solution are made, then two kinds of solution are transferred in hydrothermal reaction kettle through ultrasonic disperse respectively, are reacted at being 180 DEG C in temperature
Products therefrom is washed with deionized until solution is in neutrality 10h, in 80 DEG C of dryings, obtains product B；
(4) product B grind into powder made from step (3) is laid on Noah's ark, is placed in quartz ampoule, using Ar as inertia by
Gas source is first passed through inert gas 10 ~ 20 minutes to exclude air using flow as 200-400ml/min；Again with H2As carrier gas,
Gas flow is fixed as 50 ~ 200ml/min, is catalyzed within 1-2 hours with 5-10 DEG C/min heating tube furnaces to 750 DEG C of heat preservations
Reaction is collected calcined product C, is washed through deionized water, in 80 DEG C of drying, obtains three-dimensional grapheme interlayer filling carbon coating tin
The composite material of grain.
The present invention has the following advantages：The present invention prepares three-dimensional grapheme interlayer filling carbon packet using raw material cheap and easy to get
The composite material of tin particles is covered, manufacturing cost is cheap, and reaction process is simple, and controllability is strong, carbon covered stannum rice grain grain size is small,
Uniformly, good dispersion, folder are attached between graphene layer, and integral composite is in sandwich-like, it is negative electrode of lithium ion battery material
A kind of ideal structure of material.This material, which is used as lithium ion battery negative material, has height ratio capacity, excellent cycle performance and Zhuo
High rate performance more recycles 500 times under the electric current of 2A/g, remains to keep the specific capacity of more than 600mAh/g.
Description of the drawings
Fig. 1 is the SEM for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Photo.It will become apparent from three-dimensional grapheme and the compound pattern of carbon coating tin particles from figure.
Fig. 2 is the TEM for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Photo.Will become apparent from that metallic particles is well dispersed, and uniform particle diameter, graphene film is very thin from figure, carbon coating tin particles grain size compared with
It is small.
Fig. 3 is the TEM for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Photo.Carbon coating tin particles are will become apparent from from figure to be sandwiched between graphene.
Fig. 4 is the TEM for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Photo.Will become apparent from carbon coating tin particles surface from figure has carbon-coating cladding.
Fig. 5 is the XRD for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Collection of illustrative plates.
Fig. 6 is the drawing for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Graceful collection of illustrative plates.
Fig. 7 is the nitrogen for the composite material that three-dimensional grapheme interlayer made from the embodiment of the present invention 1 fills carbon coating tin particles
Gas constant temperature adsorption desorption collection of illustrative plates.
Fig. 8 is the composite material that carbon coating tin particles are filled using three-dimensional grapheme interlayer made from the embodiment of the present invention 1
The charge-discharge performance figure of negative electrode of lithium ion battery obtained.
Fig. 9 is the composite material that carbon coating tin particles are filled using three-dimensional grapheme interlayer made from the embodiment of the present invention 1
The charge-discharge magnification performance map of negative electrode of lithium ion battery obtained.
Specific embodiment
The particular content of the present invention is described as follows with reference to specific embodiment：
Embodiment 1：
2.5g citric acids, 0.384g stannous chlorides and 9.8gNaCl are weighed, mixture is dissolved in the deionized water of 50ml,
With the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then the ultrasonic device again using power as 400W surpass
Sound 15min is uniformly mixed.The solution mixed is put into refrigerator overnight to freeze, is placed on -50 DEG C of vacuum in freeze drier
It is dry, until drying obtains mixture.Milled mixtures take 10g to be placed in Noah's ark, and Noah's ark is put into tube furnace, are passed through
The Ar inert gases 10min of 200ml/min excludes air, then with the Ar inert gases of 200ml/min and with the liter of 10 DEG C/min
Warm speed is warming up to 400 DEG C of temperature, and heat preservation 1h carries out carburizing reagent, is cooled to room temperature under Ar atmosphere protections after reaction,
Obtain calcined product A.Calcined product A is collected, it is finely ground, it is washed to until there is no NaCl in product, dries, weigh at 80 DEG C
The anhydrous glucose sugar of calcined product As and 0.5g of the 0.1g without NaCl, is dissolved separately in 10ml absolute ethyl alcohols and 30ml deionized waters,
Ultrasonic dissolution is mixed and is transferred in the hydrothermal reaction kettle of 50ml, and 10h is reacted at 180 DEG C, collects hydrothermal product, is washed, and is dried
It is dry, product B is obtained, product B is placed in Noah's ark, is put into tube furnace, the Ar inert gases 10min for being passed through 200ml/min is excluded
Air, then the H with 200ml/min2Gas is simultaneously warming up to 750 DEG C of temperature with the heating rate of 10 DEG C/min, and heat preservation 2h is urged
Change reaction, obtain the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles, wherein carbon covered stannum rice grain grain size
In 20nm or so, carbon coating layer thickness is 1nm, and three-dimensional grapheme thickness is 3nm.
With obtained material, PVDF, conductive carbon black mass ratio is 8:1:1 meter is applied to copper sheet as battery cathode, with 1M
LiPF6As electrolyte, using lithium piece as anode, half-cell is made, is recycled under the current density of 200mA/g
100 specific capacities for still keeping more than 900mAh/g, as shown in Figure 1, and with excellent high rate performance, in the electricity of 10A/g
Still there is the specific capacity of more than 200mA/g, as shown in Figure 2 under current density.
Embodiment 2：
2.5g citric acids, 0.576g stannous chlorides and 14.7gNaCl are weighed, mixture is dissolved in the deionized water of 50ml
In, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again using power as the ultrasonic device of 400W
Ultrasonic 15min is uniformly mixed.The solution mixed is put into refrigerator overnight to freeze, be placed in freeze drier -50 DEG C it is true
Sky is dry, until drying obtains mixture.Milled mixtures, take the mixed-powder of 10g to be placed in Noah's ark, and Noah's ark is put into tubular type
In stove, the Ar inert gases 10min for being passed through 200ml/min excludes air, then with the Ar inert gases of 200ml/min and with 10
DEG C/heating rate of min is warming up to 400 DEG C of temperature, heat preservation 1h carries out carburizing reagent, cold under Ar atmosphere protections after reaction
But to room temperature, calcined product A is obtained.Calcined product A is collected, it is finely ground, it is washed to until there is no NaCl in product, is dried at 80 DEG C
It is dry, weigh the anhydrous glucose sugar of calcined product As and 0.7g of the 0.1g without NaCl, be dissolved separately in 10ml absolute ethyl alcohols and 30ml go from
In sub- water, ultrasonic dissolution is mixed and is transferred in the hydrothermal reaction kettle of 50ml, and 10h is reacted at 180 DEG C, collects hydrothermal product,
Washing, drying, obtains product B, product B is placed in Noah's ark, is put into tube furnace, be passed through the Ar inert gases of 200ml/min
10min excludes air, then the H with 200ml/min2Gas is simultaneously warming up to 750 DEG C of temperature with the heating rate of 10 DEG C/min, protects
Warm 1h carries out catalysis reaction, obtains the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles.
Embodiment 3：
2.5g citric acids, 0.576g stannous chlorides and 29.4gNaCl are weighed, mixture is dissolved in the deionized water of 50ml
In, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again using power as the ultrasonic device of 400W
Ultrasonic 15min is uniformly mixed.The solution mixed is put into refrigerator overnight to freeze, be placed in freeze drier -50 DEG C it is true
Sky is dry, until drying obtains mixture.Milled mixtures, take the mixed-powder of 10g to be placed in Noah's ark, and Noah's ark is put into tubular type
In stove, the Ar inert gases 10min for being passed through 200ml/min excludes air, then with the Ar inert gases of 200ml/min and with 10
DEG C/heating rate of min is warming up to 300 DEG C of temperature, heat preservation 2h carries out carburizing reagent, cold under Ar atmosphere protections after reaction
But to room temperature, calcined product A is obtained.Calcined product A is collected, it is finely ground, it is washed to until there is no NaCl in product, is dried at 80 DEG C
It is dry, weigh the anhydrous glucose sugar of calcined product As and 0.7g of the 0.1g without NaCl, be dissolved separately in 10ml absolute ethyl alcohols and 30ml go from
In sub- water, ultrasonic dissolution is mixed and is transferred in the hydrothermal reaction kettle of 50ml, and 10h is reacted at 180 DEG C, collects hydrothermal product,
Washing, drying, obtains product B, product B is placed in Noah's ark, is put into tube furnace, be passed through the Ar inert gases of 200ml/min
10min excludes air, then the H with 200ml/min2Gas is simultaneously warming up to 750 DEG C of temperature with the heating rate of 10 DEG C/min, protects
Warm 2h carries out catalysis reaction, obtains the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles.
Embodiment 4：
2.5g citric acids, 0.768g stannous chlorides and 29.4gNaCl are weighed, mixture is dissolved in the deionized water of 50ml
In, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again using power as the ultrasonic device of 400W
Ultrasonic 15min is uniformly mixed.The solution mixed is put into refrigerator overnight to freeze, be placed in freeze drier -50 DEG C it is true
Sky is dry, until drying obtains mixture.Milled mixtures, take the mixed-powder of 10g to be placed in Noah's ark, and Noah's ark is put into tubular type
In stove, the Ar inert gases 10min for being passed through 200ml/min excludes air, then with the Ar inert gases of 200ml/min and with 10
DEG C/heating rate of min is warming up to 450 DEG C of temperature, heat preservation 1h carries out carburizing reagent, cold under Ar atmosphere protections after reaction
But to room temperature, calcined product A is obtained.Calcined product A is collected, it is finely ground, it is washed to until there is no NaCl in product, is dried at 80 DEG C
It is dry, the anhydrous glucose sugar of calcined product As and 1g of the 0.1g without NaCl is weighed, is dissolved separately in 10ml absolute ethyl alcohols and 30ml deionizations
In water, ultrasonic dissolution is mixed and is transferred in the hydrothermal reaction kettle of 50ml, and 10h is reacted at 180 DEG C, collects hydrothermal product, water
It washes, dries, obtain product B, product B is placed in Noah's ark, is put into tube furnace, be passed through the Ar inert gases 10min of 200ml/min
Exclude air, then the H with 200ml/min2Gas is simultaneously warming up to 750 DEG C of temperature with the heating rate of 10 DEG C/min, heat preservation 2h into
Row catalysis reaction, obtains the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles.
Claims (1)
1. a kind of preparation method of the composite material of three-dimensional grapheme interlayer filling carbon coating tin particles, the composite material by it is upper,
Lower three-dimensional grapheme layer and the upper and lower three-dimensional grapheme interlayer carbon coating tin nano-particle layer form, wherein, three-dimensional stone
Black alkene layer thickness is 1-10nm, and three-dimensional grapheme network radius is 1-10um；Carbon covered stannum rice grain grain size be 5-30nm, carbon
Coating thickness is 1-4nm；The mass percent of tin and total carbon in the composite material is：(0.4-0.7):(0.6-
0.3)；Including the step of：
1) using glucose as carbon source, using stannous chloride as tin source, by the molar ratio of the tin in the carbon and tin source in carbon source for 50 ~
10：1, and using the tin in tin source and the mass ratio of sodium chloride as 0.01 ~ 0.1：1 meter, by carbon source, tin source and sodium chloride addition go from
It is dissolved in sub- water, stirs wiring solution-forming, ultrasonic mixing is uniformly placed in refrigerator and freezes, and treats that solution freeze over is placed on freezing
It is dried in vacuo in drying machine in -50 DEG C, obtains mixture；It is characterized in that：
2) it by mixture grind into powder made from step 1), is laid in Noah's ark, is placed in tube furnace flat-temperature zone and is calcined：With Ar
As inert gas source, inert gas is first passed through as 200 ~ 400ml/min using flow and excludes air within 10 ~ 30 minutes；Made again with Ar
To protect gas, protection air-flow amount is fixed as 50 ~ 200ml/min, 300 ~ 450 are warming up to the heating rate of 1 ~ 10 DEG C/min
DEG C, heat preservation 1-2h is carbonized, and is cooled to room temperature after reaction, obtains calcined product A；
3) collection step 2) made from calcined product A, it is finely ground, be washed to until there is no sodium chloride in calcined product A, be in temperature
It is dried at 60-120 DEG C；It is again 5-10 by the mass ratio of DEXTROSE ANHYDROUS and the calcined product A for drying non-sodium chloride:1 meter, by nothing
Water glucose is added in deionized water, and the calcined product A for drying non-sodium chloride is added in absolute ethyl alcohol, respectively through ultrasonic disperse system
Two kinds of solution are obtained, then two kinds of solution are transferred in hydrothermal reaction kettle, 10h is reacted at being 180 DEG C in temperature, products therefrom is used
Deionized water is washed until solution is in neutrality, and in 80 DEG C of dryings, obtains product B；
4) by product B grind into powder made from step 3), Noah's ark is laid on, is placed in quartz ampoule, using Ar as inert gas source,
First inert gas is passed through 10 ~ 20 minutes to exclude air using flow as 200-400ml/min；Again with H2As carrier gas, by gas
Flow is fixed as 50 ~ 200ml/min, and catalysis reaction is carried out within 1-2 hours with 5-10 DEG C/min heating tube furnaces to 750 DEG C of heat preservations,
Calcined product C is collected, is washed through deionized water, in 80 DEG C of drying, obtains three-dimensional grapheme interlayer filling carbon coating tin particles
Composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510469973.4A CN105161721B (en) | 2015-08-04 | 2015-08-04 | The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510469973.4A CN105161721B (en) | 2015-08-04 | 2015-08-04 | The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105161721A CN105161721A (en) | 2015-12-16 |
| CN105161721B true CN105161721B (en) | 2018-07-06 |
Family
ID=54802528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510469973.4A Expired - Fee Related CN105161721B (en) | 2015-08-04 | 2015-08-04 | The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105161721B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299270B (en) * | 2016-08-22 | 2018-11-27 | 天津大学 | The preparation and application of three-dimensional grapheme reticular structure carrying tin oxide nano particle and molybdenum disulfide nano sheet material |
| CN106784736A (en) * | 2017-02-08 | 2017-05-31 | 大连理工大学 | A kind of sodium-ion battery negative pole coats the preparation method and application of tin particles nanometer sheet with coal tar pitch resin base amorphous carbon |
| CN107732245B (en) * | 2017-10-20 | 2018-08-28 | 江苏舜天高新炭材有限公司 | A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery |
| CN110224115B (en) * | 2018-03-02 | 2020-12-22 | 华南理工大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN109904433A (en) * | 2019-03-18 | 2019-06-18 | 山东星火科学技术研究院 | Large capacity fast charging and discharging graphene lithium ion battery and its synthesis technology |
| CN110237835B (en) * | 2019-06-12 | 2020-06-19 | 西安交通大学 | Titanium dioxide-tin dioxide-graphene composite photocatalyst and preparation method thereof |
| CN110391408B (en) * | 2019-07-24 | 2021-03-16 | 东北大学秦皇岛分校 | Tin-based oxide embedded pyrolytic carbon battery negative electrode material and preparation method thereof |
| CN110391412A (en) * | 2019-08-22 | 2019-10-29 | 广东工业大学 | A kind of negative electrode material and preparation method thereof and lithium ion battery |
| CN110518228B (en) * | 2019-09-17 | 2023-06-20 | 安徽大学 | Inorganic nanoparticle embedded three-dimensional grapheme carbon nanocomposite and application thereof |
| CN112234196B (en) * | 2020-09-04 | 2022-11-08 | 陕西科技大学 | Sn nano half-moon tooth particle-2 DLMG composite material synthesized by organic molecule constrained reaction and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715430A (en) * | 2013-12-23 | 2014-04-09 | 天津大学 | Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof |
-
2015
- 2015-08-04 CN CN201510469973.4A patent/CN105161721B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715430A (en) * | 2013-12-23 | 2014-04-09 | 天津大学 | Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Design and synthesis of porous nano-sized Sn@C/graphene electrode material with 3D carbon network for high-performance lithium-ion batteries;Peichao Lian等;《Journal of Alloys and Compounds》;20140401;第604卷;第188-195页 * |
| Graphene Networks Anchored with Sn@Graphene as Lithium Ion Battery Anode;Jian Qin等;《ACSNANO》;20140108;第8卷(第2期);第1728-1738页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105161721A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105161721B (en) | The composite material of three-dimensional grapheme interlayer filling carbon coating tin particles and preparation | |
| CN103715430B (en) | Three-dimensional grapheme network structure load carbon covered stannum rice material and preparation and application | |
| CN106299270B (en) | The preparation and application of three-dimensional grapheme reticular structure carrying tin oxide nano particle and molybdenum disulfide nano sheet material | |
| CN104409702B (en) | A kind of nitrogen-doped graphene wraps up the preparation method of micron silicon composite | |
| CN109244391B (en) | Nitrogen-doped carbon-coated lithium manganese iron phosphate material and preparation method thereof | |
| CN106410150A (en) | MoO2-MoS2 negative electrode material of sodium-ion battery with core-shell structure and preparation method of MoO2-MoS2 negative electrode material | |
| CN104966812A (en) | Three-dimensional porous quasi-graphene loaded molybdenum disulfide composite and preparation method thereof | |
| CN105870417B (en) | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN107732205B (en) | Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material | |
| CN102544459A (en) | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere | |
| CN104638219A (en) | Composite diaphragm for lithium-selenium battery and preparation method of composite diaphragm | |
| CN104733695A (en) | Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN103456929A (en) | Anode material of lithium-sulfur battery and preparation method thereof | |
| CN106450219B (en) | A kind of three-dimensional vanadium trioxide/carbon composite nano-material and its preparation method and application of various dimensions assembling | |
| CN109860526B (en) | Preparation method of graphite material doped with metal oxalate lithium battery composite negative electrode material | |
| CN102148371A (en) | Graphene/phosphoric acid iron-lithium composite material with sandwich structure and preparation method thereof | |
| CN103594707A (en) | High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2 | |
| Butt et al. | Microwave-assisted synthesis of functional electrode materials for energy applications | |
| Fu et al. | Synthesis of carbon coated nanoporous microcomposite and its rate capability for lithium ion battery | |
| CN105552369B (en) | The method for preparing three-dimensional porous niobic acid titanium oxide using template and its application in lithium ion battery | |
| CN103078087A (en) | Preparation method of lithium titanate/carbon nano tube composite cathode material | |
| CN101540393B (en) | Method for preparing lithium-manganese silicate of lithium-ion battery cathode material | |
| CN103682277B (en) | Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180706 Termination date: 20200804 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |