CN105742635A - Stannic oxide/graphene/carbon composite material and preparation method thereof - Google Patents
Stannic oxide/graphene/carbon composite material and preparation method thereof Download PDFInfo
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- CN105742635A CN105742635A CN201610002361.9A CN201610002361A CN105742635A CN 105742635 A CN105742635 A CN 105742635A CN 201610002361 A CN201610002361 A CN 201610002361A CN 105742635 A CN105742635 A CN 105742635A
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/362—Composites
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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
- H01M4/48—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
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- 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
Abstract
The invention discloses a stannic oxide/graphene/carbon composite material and a preparation method thereof, and belongs to the fields of electrochemistry and new energy materials. The method comprises the following steps: oxidizing graphite into a graphite oxide with an oxidant in preparation and then ultrasonically stripping the graphite oxide into a graphite oxide material; mixing a tin source and an organic carbon source with a graphite oxide solution evenly according to different ratios, and preparing a stannic oxide/graphene/carbon liquid gel composite material from the mixed solution through hydrothermal reaction, wherein the hydrothermal reaction temperature is 120-250 DEG C; and the hydrothermal reaction time is 1-48 hours; and carrying out freeze drying and heating treatment on the prepared stannic oxide/graphene/carbon liquid gel composite material to obtain a three-dimensional stannic oxide/graphene/carbon foam composite material. The material disclosed by the invention has good flexibility, is suitable for manufacturing of a flexible electrode, does not need to be added with any assistant when taken as an anode material for a lithium-ion battery, does not need to utilize a metal substrate and demonstrates good cycling stability and relatively high specific capacity.
Description
Technical field
The invention discloses a kind of tin ash/graphene/carbon composite material and preparation method thereof, belong to electrochemistry and new energy materials field.
Background technology
The flexible electronic device of the flexible folding demand in recent years strongly increases, and flexible lithium ion battery is the core component of flexible electronic device.Active material, conductive agent, binding agent mixing are mainly coated in metal collector by traditional lithium ion battery, form through drying roll-in.The addition of binding agent reduces the electronic conductivity of electrode material, hinders lithium ion and spreads in electrode material, adds the polarization of electrode material.And conductive agent contributes capacity hardly, so the existence of conductive agent and binding agent can reduce the energy density of battery；Metal collector can dramatically increase electrode material and the weight of whole battery, and binder free, self-supporting flexible electrode material without conductive agent, without metal collector can significantly improve the energy density of electrode.
Graphene, as a kind of novel carbonaceous material, has the ionic conductivity of excellence, good mechanical flexibility energy and excellent chemical stability.Grapheme foam becomes the focus of research due to the three-dimensional porous structure of its uniqueness.Grapheme foam can directly obtain graphene film through simple mechanical compaction.Graphene film has excellent mechanical flexibility energy, simultaneously because its internal loose structure is conducive to the infiltration of electrolyte, demonstrates preferable high rate performance.But graphene film has, as lithium ion battery flexibility negative material, the problem that efficiency first is low, reversible specific capacity is low.In order to improve the reversible capacity of graphene-based negative material, it is prepared as combination electrode material by compound to Graphene and other high-capacity electrode material (such as silica-based, tinbase etc.), is remarkably improved the specific capacity of negative material.Due to Graphene there is good electronic conductivity and stable circulation performance can improve stability and the multiplying power property of high-capacity electrode material.The foamed composite that Graphene and tin-based material such as tin ash is compounded to form has been in the news, and this foamed composite significantly improves the specific capacity of Graphene, improves the stable circulation performance of tin ash sill.In the Graphene/tin ash foamed composite of report, Graphene and tin ash are typically by mechanical bond effect, and after repeatedly circulation, Graphene is often separated from each other mutually with tin ash activity, affects structural stability and the chemical property of material.In order to improve the adhesion between Graphene and tin ash, Cong et al. uses the grapheme material of N doping to improve combination (the Cong H P between Graphene and tin ash, et al, Nano energy2015,13,482-490), after 1000 circulations, capacity can also be maintained at 1029mAhg-1。
Summary of the invention
It is an object of the invention to be tin ash/graphene/carbon composite material that a kind of three-dimensional foam structure is provided and preparation method thereof.The method is by butter of tin, glucose and graphene oxide ultrasonic disperse, subsequently by hydro-thermal reaction, mixed solution being prepared tin ash/graphene/carbon lyogel composite, further lyophilization and heat treated obtain three-dimensional tin ash/graphene/carbon foamed composite.Tin ash in the raw material of this composite, Graphene, carbon account for the mass fraction of composite and are respectively 20%-50%, 30%-60%, 5%-30%.More preferably tin ash, Graphene, carbon account for the mass fraction of composite and are respectively 45%, 45%, 10%.
The object of the present invention is achieved like this: the preparation method of the tin ash of a kind of three-dimensional foam structure/graphene/carbon composite negative pole material, its processing step:
(1) with oxidant, graphite oxidation is become graphite oxide, then peel off into graphene oxide composite material by ultrasonic for graphite oxide；
(2) Xi Yuan and organic carbon source are mixed according to different ratio uniform from graphene oxide solution, mixed solution is prepared tin ash/graphene/carbon lyogel composite by hydro-thermal reaction；The temperature of hydro-thermal reaction is 120-250 DEG C, and the time of hydro-thermal reaction is 1-48 hour.
(3) prepared tin ash/graphene/carbon lyogel composite lyophilization and heat treated are obtained three-dimensional tin ash/graphene/carbon foamed composite.Heat treatment temperature is 500-1000 DEG C, and heat treatment time is 1-12 hour.
Described organic carbon source includes any one in glucose, carbamide, citric acid, polyvinyl alcohol.Described oxidant includes any one in concentrated sulphuric acid, concentrated nitric acid, potassium permanganate, hydrogen peroxide.
The present invention by described tin ash/graphene/carbon composite material in the application prepared on lithium ion battery negative material.
The present invention is with concentrated sulphuric acid, concentrated nitric acid, potassium permanganate and hydrogen peroxide as oxidant, graphite powder is oxidized to graphite oxide, graphite oxide is peeled off into graphene oxide by the method using ultrasonic stripping, graphene oxide is mixed with butter of tin, glucose, preparing tin ash/graphene/carbon lyogel composite by hydro-thermal reaction, further lyophilization and heat treated obtain three-dimensional tin ash/graphene/carbon foamed composite.Electro-chemical test shows: three-dimensional tin ash/graphene/carbon foam prepared by the method has higher specific capacity and good stable circulation performance, is a kind of preferably flexible lithium ion battery negative material.
Butter of tin, organic carbon source and graphene oxide are carried out ultrasonic disperse by the present invention, prepare tin ash/graphene/carbon lyogel composite by hydro-thermal reaction, its further lyophilization and heat treated are obtained three-dimensional tin ash/graphene/carbon foamed composite.Hydro-thermal method easily prepares Graphene lyogel, but nano material easily causes caving in of lyogel structure after being combined with it, it is difficult to prepare Graphene/other nano material complex liquid gel, the present invention is simultaneously introduced organic carbon source and butter of tin in water-heat process, the amorphous carbon formed after organic carbon source hydro-thermal and heat treatment can strengthen the combination of graphene nanometer sheet and tin oxide nano particles, separate between tin oxide nano particles with graphene nanometer sheet after stoping repeatedly circulation, keep the Stability Analysis of Structures performance of composite foam.This composite foam is a kind of flexility and the good lithium ion battery negative material of chemical property, and this method there is not yet document and patent report.
The preparation method of combination electrode material that the present invention provides, possesses following beneficial effect:
(1) electrode material prepared by has 3-D solid structure, can be lithium ion and the three-dimensional transport path of electronics offer, be effectively improved the cyclical stability of battery.
(2) flexible electrode material prepared by need not the additive such as metal collector and conductive carbon, is conducive to improving energy density and power density.
Accompanying drawing explanation
Fig. 1 is the photo of the three-dimensional tin ash/graphene/carbon foam of the embodiment of the present invention 1 preparation.
Fig. 2 is the X-ray diffracting spectrum of the three-dimensional tin ash/graphene/carbon foamed composite of the embodiment of the present invention 1 preparation.
Fig. 3 is the stereoscan photograph of the three-dimensional tin ash/graphene/carbon foamed composite of the embodiment of the present invention 1 preparation.
Fig. 4 is the three-dimensional tin ash/graphene/carbon foamed composite first three charging and discharging curve as lithium ion battery negative material of the embodiment of the present invention 1 preparation.
Fig. 5 is that the three-dimensional tin ash/graphene/carbon foamed composite of the embodiment of the present invention 1 preparation is as the cycle performance curve of lithium ion battery negative material and coulombic efficiency curve.
Fig. 6 is the three-dimensional tin ash/graphene/carbon foamed composite hydrophobicity picture of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is further described.
Embodiment 1: three-dimensional tin ash/graphene/carbon foam combination electrode material I
Concentrated sulphuric acid is cooled to 0 DEG C, is subsequently adding graphite and sodium nitrate, is stirred until homogeneous, gradually continuous print adds potassium permanganate, stirs 3 hours, temperature rises to 35 DEG C, continuing stirring 0.5h, the most gradually continuous print adds deionized water, and temperature rises to 98 DEG C, react 15min at this temperature, move to room temperature, add the hydrogen peroxide of 10%, stir 1 hour, being subsequently adding the stirring of 1M mixed in hydrochloric acid, products therefrom deionized water water cleans to neutral, obtains graphite oxide.Graphite oxide is disperseed in deionized water with the concentration of 4mg/mL, ultrasonic stripping, obtain graphene oxide composite material.The ratio of graphene oxide, butter of tin, glucose 1:5:1 in mass ratio is mixed, after ultrasonic disperse is uniform, mixed solution is transferred in teflon-lined autoclave, the hydro-thermal reaction 24 hours when 200 DEG C, obtains tin ash/graphene/carbon lyogel composite.By the tin ash/graphene/carbon lyogel composite lyophilization of preparation, obtain three-dimensional tin ash/graphene/carbon foamed composite at 500 DEG C of heat treatment 2h subsequently.Fig. 1 is the X-ray diffracting spectrum of prepared three-dimensional tin ash/graphene/carbon foam combination electrode material I, wherein it can be clearly seen that tin ash and the diffraction maximum of Graphene, this explanation tin ash is embedded in Graphene and graphene oxide is heat reduced to Graphene.Fig. 2 is the stereoscan photograph of prepared three-dimensional tin ash/graphene/carbon foam combination electrode material I, can be seen that tin ash is coated with wherein by amorphous carbon and Graphene, with the structural stability of reinforcing material and electric conductivity, and then the cyclical stability of material can be improved.Using this electrode material as working electrode, lithium sheet is for assisting and reference electrode, and electrolyte is general lithium-ion battery electrolytes, such as 1.1M LiPF6/ DMC:EC:DEC=1:1:1, prepares 2025 type button cells, with the electric current density discharge and recharge of 100mA/g.This electrode material charging and discharging curve 3 times is as it is shown on figure 3, the charge and discharge platform of tin ash can be found out clearly.The cycle performance curve of this electrode material and coulombic efficiency curve are as shown in Figure 4, it can be seen that this composite discharge capacity first is up to 2500mAh/g, and the discharge capacity after 100 circulations is 750mAh/g.This composite is the most irreversible relatively big, and coulombic efficiency is relatively low first, but along with the increase of cycle-index, coulombic efficiency significantly improves.
Three-dimensional tin ash/graphene/carbon foam the combination electrode material II of embodiment 2
Graphene oxide composite material is prepared described in embodiment 1, the ratio of graphene oxide, butter of tin, glucose 1:10:1 in mass ratio is mixed, after ultrasonic disperse is uniform, mixed solution is transferred in teflon-lined autoclave, the hydro-thermal reaction 32 hours when 220 DEG C, obtains tin ash/graphene/carbon lyogel composite.By the tin ash/graphene/carbon lyogel composite lyophilization of preparation, obtain three-dimensional tin ash/graphene/carbon foamed composite at 750 DEG C of heat treatment 2h subsequently.As described in example 1 above, with the electric current density discharge and recharge of 100mA/g, discharge capacity also has 550mAh/g up to 1800mAh/g, the capacity after secondary circulation to this electrode material test condition first.
Three-dimensional tin ash/graphene/carbon foam the combination electrode material III of embodiment 3
Described in embodiment 1, prepare graphene oxide composite material, the ratio of graphene oxide, butter of tin, glucose 1:20:1 in mass ratio mixed, after ultrasonic disperse is uniform, mixed solution is transferred in teflon-lined autoclave,
The hydro-thermal reaction 48 hours when 240 DEG C, obtains tin ash/graphene/carbon lyogel composite.By the tin ash/graphene/carbon lyogel composite lyophilization of preparation, obtain three-dimensional tin ash/graphene/carbon foamed composite at 1000 DEG C of heat treatment 2h subsequently.As described in example 1 above, with the electric current density discharge and recharge of 100mA/g, discharge capacity also has 630mAh/g up to 2000mAh/g, the capacity after secondary circulation to this electrode material test condition first.
Deionized water, according to the three-dimensional tin ash/graphene/carbon foamed composite of preparation described in embodiment 1, is dropped in foam surface by embodiment 4, and water droplet does not the most infiltrate this foam, and foam demonstrates good hydrophobicity.Being placed on by this foam in the mixing liquid of water and oil, this foam can quickly blot the oil in mixing liquid, demonstrates good lipophile.
Claims (8)
1. tin ash/graphene/carbon composite material, it is characterised in that this composite is 3 D stereo foaming structure,
Tin ash in the raw material of this composite, Graphene, carbon account for the mass fraction of composite be respectively 20%-50%, 30%-60%,
5%-30%.
2. tin ash/the graphene/carbon composite material described in claim 1, it is characterised in that tin ash, Graphene,
Carbon accounts for the mass fraction of composite and is respectively 45%, 45%, 10%.
3. the preparation method of the tin ash/graphene/carbon composite material described in claim 1, it is characterised in that include as follows
Step:
(1) with oxidant, graphite oxidation is become graphite oxide, then peel off into graphene oxide composite material by ultrasonic for graphite oxide；
(2) Xi Yuan and organic carbon source are mixed according to different ratio uniform from graphene oxide solution, mixed solution is passed through water
Thermal response prepares tin ash/graphene/carbon lyogel composite；
(3) prepared tin ash/graphene/carbon lyogel composite lyophilization and heat treated are obtained three-dimensional titanium dioxide
Stannum/graphene/carbon foamed composite.
4. the preparation method of the tin ash/graphene/carbon composite material described in claim 3, it is characterised in that organic carbon source bag
Include in glucose, carbamide, citric acid, polyvinyl alcohol any one.
5. the preparation method of the tin ash/graphene/carbon composite material described in claim 3, it is characterised in that described oxidation
Agent includes any one in concentrated sulphuric acid, concentrated nitric acid, potassium permanganate, hydrogen peroxide.
6. the preparation method of the tin ash/graphene/carbon composite material described in claim 3, it is characterised in that hydro-thermal reaction
Temperature is 120-250 DEG C, and the time of hydro-thermal reaction is 1-48 hour.
7. the preparation method of the tin ash/graphene/carbon composite material described in claim 3, it is characterised in that heat treatment temperature
For 500-1000 DEG C, heat treatment time is 1-12 hour.
8. tin ash/the graphene/carbon composite material described in any one of claim 1-7 is being prepared on lithium ion battery negative material
Application.
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| CN106129389A (en) * | 2016-09-29 | 2016-11-16 | 柳州申通汽车科技有限公司 | The preparation method of new energy car battery pole piece |
| CN106159245A (en) * | 2016-09-29 | 2016-11-23 | 柳州申通汽车科技有限公司 | A kind of preparation method of graphene battery negative plate |
| CN106207141A (en) * | 2016-09-29 | 2016-12-07 | 柳州申通汽车科技有限公司 | The preparation method of new energy car battery negative material |
| CN106219521A (en) * | 2016-07-12 | 2016-12-14 | 昆明理工大学 | A kind of preparation method of three-dimensional foam Graphene |
| CN106229494A (en) * | 2016-09-29 | 2016-12-14 | 柳州申通汽车科技有限公司 | A kind of preparation method of automobile batteries |
| CN106299313A (en) * | 2016-10-15 | 2017-01-04 | 成都育芽科技有限公司 | A kind of li-ion electrode composite nano materials and preparation method thereof |
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| CN107069004A (en) * | 2017-04-11 | 2017-08-18 | 东南大学 | A kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure |
| CN108199014A (en) * | 2017-12-07 | 2018-06-22 | 银隆新能源股份有限公司 | A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications |
| CN108598405A (en) * | 2018-04-17 | 2018-09-28 | 河南师范大学 | A kind of preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials |
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| CN108987796A (en) * | 2018-09-10 | 2018-12-11 | 江西克莱威纳米碳材料有限公司 | A kind of flexible lithium ion battery and preparation method thereof |
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| CN106219521B (en) * | 2016-07-12 | 2018-08-31 | 昆明理工大学 | A kind of preparation method of three-dimensional foam graphene |
| CN106129389A (en) * | 2016-09-29 | 2016-11-16 | 柳州申通汽车科技有限公司 | The preparation method of new energy car battery pole piece |
| CN106159245A (en) * | 2016-09-29 | 2016-11-23 | 柳州申通汽车科技有限公司 | A kind of preparation method of graphene battery negative plate |
| CN106229494A (en) * | 2016-09-29 | 2016-12-14 | 柳州申通汽车科技有限公司 | A kind of preparation method of automobile batteries |
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