CN105161721A - Three-dimensional composite material formed by filling carbon-encapsulated tin granules into graphene interlaminations and by filling graphene layers with carbon-encapsulated tin granules and preparation method for three-dimensional composite material - Google Patents
Three-dimensional composite material formed by filling carbon-encapsulated tin granules into graphene interlaminations and by filling graphene layers with carbon-encapsulated tin granules and preparation method for three-dimensional composite material Download PDFInfo
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
Abstract
The invention discloses a three-dimensional composite material formed by filling graphene layers with carbon-encapsulated tin granules and a preparation method for the three-dimensional composite material. The material is formed by uniformly filling the graphene layers with the carbon-encapsulated tin granules to form a three-dimensional sandwich-shaped structure; the preparation process is as follows: taking NaCl as a dispersing agent and a template, fully dissolving and mixing the NaCl with a metal source and a carbon source, freezing, drying and porphyrizing to obtain a mixture; putting the mixture into a tube furnace, and calcining under the argon protection to obtain a calcined product; and washing the calcined product, then mixing with glucosum anhydricum for hydrothermal cladding, and catalyzing the hydrothermal product by hydrogen and calcining to obtain the three-dimensional composite material formedby filling the graphene layers with the carbon-encapsulated tin granules. The advantages of the three-dimensional composite material and the preparation method are that: the preparation process is safe and harmless, and simple in operation; the prepared three-dimensional composite material formed by filling the graphene layers with the carbon-encapsulated tin granules is high in reversible capacity, high in cycling stability, and excellent in rate capacity when the three-dimensional composite material is used as the cathode material of lithium ion batteries.
Description
Technical field
The present invention relates to composite material and preparation method that a kind of three-dimensional grapheme interlayer fills the coated tin particles of carbon, belong to electrode material of secondary lithium ion battery field.
Background technology
Tradition coal; the fuel such as oil always as the main energy sources of the mankind, but along with it consumes in a large number, not only cause energy crisis; also severe contamination air, is engraved in during the haze weather growed in intensity that to remind people to find Novel clean regenerative resource be extremely urgent.In recent years, as novel energy, water energy, wind energy, solar energy, battery, the industries such as capacitor are all rapidly developed.Wherein, lithium rechargeable battery is the advantage such as energy density is large, working range is wide, discharge voltage is high, non-environmental-pollution, memory-less effect because having, be subject to extensive concern, and be widely used in the portable sets such as mobile phone, video camera, camera, notebook computer, more in hybrid vehicle of new generation (HEV) and pure electric automobile (EV), serve as important energy source, also will be applied in the military field such as satellite and space flight soon.
Good lithium ion battery negative material should possess high conductivity, high-specific surface area, the advantages such as active material good stability, Graphene just meets this requirement, and three-dimensional grapheme is due to the connection between graphene film, make overall structure set up into three-dimensional conductive network, and significantly improve tap density, there is the character being better than conventional graphite alkene.The method preparing three-dimensional grapheme at present mainly contains: redox graphene stack process and foam metal CVD growth method, it cuts both ways, for redox graphene stack process, prepared Graphene is very easily reunited, and reduction not exclusively, it is low that this just causes Graphene specific area, the shortcomings such as poorly conductive; For foam metal CVD growth method, the Graphene quality prepared is fine, but due to its output extremely limited, and production cost is high, is difficult to be applied.
Sandwich structure is all seen as the ideal structure of lithium ion battery negative material all the time, so-called sandwich structure, is exactly generally by the crust of material with carbon element as sandwich, active metal material as the heart of sandwich, the sandwich formed.This structure not only can prolection metal material, makes it avoid directly contacting with electrolyte, thus reduces the side reaction at two-phase interface place, and can alleviate the volumetric expansion of active metal material when discharge and recharge, reduces that it is broken, the probability of efflorescence.Conventional graphite alkene class sandwich structure mainly contains two kinds of ways: one for utilizing redox graphene time its lamella between stacking, active metal particles is sandwiched in graphene sheet layer, thus obtains the sandwich structure of Graphene-active metal-Graphene; Two for first to make active metal material load on graphene sheet layer, carry out carbon more coated, make its outermost coated last layer carbon again, thus obtain Graphene-active metal-amorphous carbon structure, and the sandwich structure of three-dimensional grapheme is comparatively large owing to preparing difficulty, rare report.
Summary of the invention
The object of this invention is to provide composite material and preparation method that a kind of three-dimensional grapheme interlayer fills the coated tin particles of carbon.This composite material has good charge-discharge performance, high rate performance and stability as lithium ion battery negative material, has a extensive future.Its preparation method process is simple, is suitable for batch production.
The present invention is realized by the following technical programs, and a kind of three-dimensional grapheme interlayer fills the coated tin of carbon
The composite material of particle, it is characterized in that, this composite material is formed by upper and lower three-dimensional grapheme layer and at the nano-particle layer of the coated tin of carbon of this upper and lower three-dimensional grapheme interlayer, wherein, three-dimensional grapheme layer thickness is 1-10nm, and three-dimensional grapheme network radius is 1-10um; Carbon covered stannum rice grain particle diameter is 5-30nm, and carbon coating layer thickness is 1-4nm; Tin in this composite material and the mass percent of total carbon are: (0.4-0.7): (0.6-0.3).
The three-dimensional grapheme interlayer of said structure fills the preparation method of the composite material of the coated tin particles of carbon, it is characterized in that comprising the following steps:
(1). take glucose as carbon source, take stannous chloride as Xi Yuan, be (50 ~ 10) by the mol ratio of the tin in the carbon in carbon source and tin source: 1, and be (0.01 ~ 0.1) in the mass ratio of the tin in tin source and sodium chloride: 1, by carbon source, Xi Yuan and sodium chloride add in deionized water and dissolve, stir wiring solution-forming, ultrasonic mixing is placed in refrigerator freezing, treats that solution freeze over is placed in freeze drier and carries out vacuumize in-50 DEG C, obtain mixture;
(2). the mixture grind into powder obtained by step (1), be laid in Noah's ark, be placed in tube furnace flat-temperature zone to calcine: using Ar as inert gas source, first is that 200 ~ 400ml/min passes into inert gas 10 ~ 30 minutes deaerations with flow; Again using Ar as protection gas, shielding gas flow amount is fixed as 50 ~ 200ml/min, is warming up to 300 ~ 450 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 1-2h carries out carbonization, is cooled to room temperature, obtains calcined product A after reaction terminates;
(3). collect the calcined product A that step (2) is obtained, porphyrize, is washed to till not having sodium chloride in calcined product A, dries at temperature is 60-120 DEG C; Pressing DEXTROSE ANHYDROUS again with the mass ratio of the calcined product A of drying non-sodium chloride is (5-10): 1, the calcined product A of DEXTROSE ANHYDROUS and oven dry non-sodium chloride is added in deionized water respectively with in absolute ethyl alcohol, respectively through the obtained two kinds of solution of ultrasonic disperse, again two kinds of solution are transferred in hydrothermal reaction kettle, 10h is reacted at temperature is 180 DEG C, products therefrom is spent deionized water to solution is neutrality, in 80 DEG C of dryings, obtain product B;
(4). by product B grind into powder obtained for step (3), being laid on Noah's ark, being placed in quartz ampoule, using Ar as inert gas source, is first that 200-400ml/min passes into inert gas 10 ~ 20 minutes with deaeration with flow; Again with H
2as carrier gas, gas flow is fixed as 50 ~ 200ml/min, within 1-2 hour, carries out catalytic reaction with DEG C insulation of 5-10 DEG C/min intensification tube furnace to 750, collect calcined product C, through deionized water washing, in 80 DEG C of oven dry, obtain the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon.
The present invention has the following advantages: the present invention utilizes raw material cheap and easy to get to prepare the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon, preparation cost is cheap, course of reaction is simple, controllability is strong, carbon covered stannum rice grain particle diameter is little, even, good dispersion, and folder is attached between graphene layer, integral composite is sandwich-like, and it is a kind of ideal structure of lithium ion battery negative material.This material is used as lithium ion battery negative material and has height ratio capacity, and excellent cycle performance and remarkable high rate performance, circulate 500 times, still can keep the specific capacity of more than 600mAh/g under the electric current of 2A/g.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.The pattern of three-dimensional grapheme and the coated tin particles compound of carbon is obviously found out from figure.
Fig. 2 is the TEM photo of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.From figure, obviously find out metallic particles good dispersion, uniform particle diameter, graphene film is very thin, and carbon coated tin particles particle diameter is less.
Fig. 3 is the TEM photo of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.From figure, obviously find out that the coated tin particles of carbon is sandwiched between Graphene.
Fig. 4 is the TEM photo of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.From figure, obviously find out that carbon coated tin particles surface has carbon-coating coated.
Fig. 5 is the XRD collection of illustrative plates of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.
Fig. 6 is the Raman collection of illustrative plates of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.
Fig. 7 is the nitrogen constant temperature adsorption desorption collection of illustrative plates of the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon that the embodiment of the present invention 1 obtains.
Fig. 8 is the charge-discharge performance figure of the lithium ion battery negative that the composite material adopting the obtained three-dimensional grapheme interlayer of the embodiment of the present invention 1 to fill the coated tin particles of carbon obtains.
Fig. 9 is the charge-discharge magnification performance map of the lithium ion battery negative that the composite material adopting the obtained three-dimensional grapheme interlayer of the embodiment of the present invention 1 to fill the coated tin particles of carbon obtains.
Embodiment
Below in conjunction with specific embodiment, particular content of the present invention is described as follows:
Embodiment 1:
Take 2.5g citric acid, 0.384g stannous chloride and 9.8gNaCl, 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, and then take power as the ultrasonic 15min of ultrasonic device of 400W, mix.The solution mixed is put into refrigerator overnight freeze, be placed on-50 DEG C of vacuumizes in freeze drier, obtain mixture until dry.Milled mixtures; get 10g and be placed in Noah's ark; Noah's ark is put into tube furnace; pass into the Ar inert gas 10min deaeration of 200ml/min; temperature 400 DEG C is warming up to the programming rate of 10 DEG C/min again with the Ar inert gas of 200ml/min; insulation 1h carries out carburizing reagent, is cooled to room temperature, obtains calcined product A after reaction terminates under Ar atmosphere protection.Collect calcined product A, porphyrize, be washed to till there is no NaCl in product, dry at 80 DEG C, take calcined product A and the 0.5g anhydrous glucose sugar of 0.1g without NaCl, be dissolved in 10ml absolute ethyl alcohol and 30ml deionized water respectively, ultrasonic dissolution, mix and transfer in the hydrothermal reaction kettle of 50ml, at 180 DEG C, react 10h, collect hydrothermal product, washing, dry, obtain product B, product B is placed in Noah's ark, put into tube furnace, pass into the Ar inert gas 10min deaeration of 200ml/min, then with the H of 200ml/min
2gas is also warming up to temperature 750 DEG C with the programming rate of 10 DEG C/min, insulation 2h carries out catalytic reaction, obtain the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon, wherein carbon covered stannum rice grain particle diameter is at about 20nm, carbon coating layer thickness is 1nm, and three-dimensional grapheme thickness is 3nm.
With obtained material, PVDF, conductive carbon black mass ratio is that 8:1:1 meter is applied to copper sheet as battery cathode, with the LiPF of 1M
6as electrolyte, using lithium sheet as anode, obtained half-cell, it circulates and still keeps the specific capacity of more than 900mAh/g for 100 times under the current density of 200mA/g, as shown in Figure 1, and there is excellent high rate performance, still there is the specific capacity of more than 200mA/g under the current density of 10A/g, as shown in Figure 2.
Embodiment 2:
Take 2.5g citric acid, 0.576g stannous chloride and 14.7gNaCl, 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, and then take power as the ultrasonic 15min of ultrasonic device of 400W, mix.The solution mixed is put into refrigerator overnight freeze, be placed on-50 DEG C of vacuumizes in freeze drier, obtain mixture until dry.Milled mixtures; the mixed-powder getting 10g is placed in Noah's ark; Noah's ark is put into tube furnace; pass into the Ar inert gas 10min deaeration of 200ml/min; temperature 400 DEG C is warming up to the programming rate of 10 DEG C/min again with the Ar inert gas of 200ml/min; insulation 1h carries out carburizing reagent, is cooled to room temperature, obtains calcined product A after reaction terminates under Ar atmosphere protection.Collect calcined product A, porphyrize, be washed to till there is no NaCl in product, dry at 80 DEG C, take calcined product A and the 0.7g anhydrous glucose sugar of 0.1g without NaCl, be dissolved in 10ml absolute ethyl alcohol and 30ml deionized water respectively, ultrasonic dissolution, mix and transfer in the hydrothermal reaction kettle of 50ml, at 180 DEG C, react 10h, collect hydrothermal product, washing, dry, obtain product B, product B is placed in Noah's ark, put into tube furnace, pass into the Ar inert gas 10min deaeration of 200ml/min, then with the H of 200ml/min
2gas is also warming up to temperature 750 DEG C with the programming rate of 10 DEG C/min, and insulation 1h carries out catalytic reaction, obtains the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon.
Embodiment 3:
Take 2.5g citric acid, 0.576g stannous chloride and 29.4gNaCl, 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, and then take power as the ultrasonic 15min of ultrasonic device of 400W, mix.The solution mixed is put into refrigerator overnight freeze, be placed on-50 DEG C of vacuumizes in freeze drier, obtain mixture until dry.Milled mixtures; the mixed-powder getting 10g is placed in Noah's ark; Noah's ark is put into tube furnace; pass into the Ar inert gas 10min deaeration of 200ml/min; temperature 300 DEG C is warming up to the programming rate of 10 DEG C/min again with the Ar inert gas of 200ml/min; insulation 2h carries out carburizing reagent, is cooled to room temperature, obtains calcined product A after reaction terminates under Ar atmosphere protection.Collect calcined product A, porphyrize, be washed to till there is no NaCl in product, dry at 80 DEG C, take calcined product A and the 0.7g anhydrous glucose sugar of 0.1g without NaCl, be dissolved in 10ml absolute ethyl alcohol and 30ml deionized water respectively, ultrasonic dissolution, mix and transfer in the hydrothermal reaction kettle of 50ml, at 180 DEG C, react 10h, collect hydrothermal product, washing, dry, obtain product B, product B is placed in Noah's ark, put into tube furnace, pass into the Ar inert gas 10min deaeration of 200ml/min, then with the H of 200ml/min
2gas is also warming up to temperature 750 DEG C with the programming rate of 10 DEG C/min, and insulation 2h carries out catalytic reaction, obtains the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon.
Embodiment 4:
Take 2.5g citric acid, 0.768g stannous chloride and 29.4gNaCl, 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, and then take power as the ultrasonic 15min of ultrasonic device of 400W, mix.The solution mixed is put into refrigerator overnight freeze, be placed on-50 DEG C of vacuumizes in freeze drier, obtain mixture until dry.Milled mixtures; the mixed-powder getting 10g is placed in Noah's ark; Noah's ark is put into tube furnace; pass into the Ar inert gas 10min deaeration of 200ml/min; temperature 450 DEG C is warming up to the programming rate of 10 DEG C/min again with the Ar inert gas of 200ml/min; insulation 1h carries out carburizing reagent, is cooled to room temperature, obtains calcined product A after reaction terminates under Ar atmosphere protection.Collect calcined product A, porphyrize, be washed to till there is no NaCl in product, dry at 80 DEG C, take calcined product A and the 1g anhydrous glucose sugar of 0.1g without NaCl, be dissolved in 10ml absolute ethyl alcohol and 30ml deionized water respectively, ultrasonic dissolution, mix and transfer in the hydrothermal reaction kettle of 50ml, at 180 DEG C, react 10h, collect hydrothermal product, washing, dry, obtain product B, product B is placed in Noah's ark, put into tube furnace, pass into the Ar inert gas 10min deaeration of 200ml/min, then with the H of 200ml/min
2gas is also warming up to temperature 750 DEG C with the programming rate of 10 DEG C/min, and insulation 2h carries out catalytic reaction, obtains the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon.
Claims (2)
1. the composite material of the coated tin particles of three-dimensional grapheme interlayer filling carbon, it is characterized in that, this composite material is formed by upper and lower three-dimensional grapheme layer and at the nano-particle layer of the coated tin of carbon of this upper and lower three-dimensional grapheme interlayer, wherein, three-dimensional grapheme layer thickness is 1-10nm, and three-dimensional grapheme network radius is 1-10um; Carbon covered stannum rice grain particle diameter is 5-30nm, and carbon coating layer thickness is 1-4nm; Tin in this composite material and the mass percent of total carbon are: (0.4-0.7): (0.6-0.3).
2., by a preparation method for the composite material of the three-dimensional grapheme interlayer filling carbon coated tin particles of claim 1 institute, it is characterized in that comprising the following steps:
(1). take glucose as carbon source, take stannous chloride as Xi Yuan, be (50 ~ 10) by the mol ratio of the tin in the carbon in carbon source and tin source: 1, and be (0.01 ~ 0.1) in the mass ratio of the tin in tin source and sodium chloride: 1, by carbon source, Xi Yuan and sodium chloride add in deionized water and dissolve, stir wiring solution-forming, ultrasonic mixing is placed in refrigerator freezing, treats that solution freeze over is placed in freeze drier and carries out vacuumize in-50 DEG C, obtain mixture;
(2). the mixture grind into powder obtained by step (1), be laid in Noah's ark, be placed in tube furnace flat-temperature zone to calcine: using Ar as inert gas source, first is that 200 ~ 400ml/min passes into inert gas 10 ~ 30 minutes deaerations with flow; Again using Ar as protection gas, shielding gas flow amount is fixed as 50 ~ 200ml/min, is warming up to 300 ~ 450 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 1-2h carries out carbonization, is cooled to room temperature, obtains calcined product A after reaction terminates;
(3). collect the calcined product A that step (2) is obtained, porphyrize, is washed to till not having sodium chloride in calcined product A, dries at temperature is 60-120 DEG C; Pressing DEXTROSE ANHYDROUS again with the mass ratio of the calcined product A of drying non-sodium chloride is (5-10): 1, the calcined product A of DEXTROSE ANHYDROUS and oven dry non-sodium chloride is added in deionized water respectively with in absolute ethyl alcohol, respectively through the obtained two kinds of solution of ultrasonic disperse, again two kinds of solution are transferred in hydrothermal reaction kettle, 10h is reacted at temperature is 180 DEG C, products therefrom is spent deionized water to solution is neutrality, in 80 DEG C of dryings, obtain product B;
(4). by product B grind into powder obtained for step (3), being laid on Noah's ark, being placed in quartz ampoule, using Ar as inert gas source, is first that 200-400ml/min passes into inert gas 10 ~ 20 minutes with deaeration with flow; Again with H
2as carrier gas, gas flow is fixed as 50 ~ 200ml/min, within 1-2 hour, carries out catalytic reaction with DEG C insulation of 5-10 DEG C/min intensification tube furnace to 750, collect calcined product C, through deionized water washing, in 80 DEG C of oven dry, obtain the composite material that three-dimensional grapheme interlayer fills the coated tin particles of carbon.
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