CN104953101B - The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene - Google Patents
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene Download PDFInfo
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- CN104953101B CN104953101B CN201510354726.XA CN201510354726A CN104953101B CN 104953101 B CN104953101 B CN 104953101B CN 201510354726 A CN201510354726 A CN 201510354726A CN 104953101 B CN104953101 B CN 104953101B
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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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
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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 present invention relates to the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, graphene oxide water solution and tin ash ethanol solution, L ascorbic acid are mixed in proportion, then 4~6 hours are heated at a temperature of 75 DEG C, taking-up is washed, and is freeze-dried；It is subsequently placed under inert gas and is heat-treated, graphene aerogel load stannic oxide electrode material is prepared.Compared with prior art, the product that the present invention is prepared has larger specific surface area and porosity, and cost of manufacture is cheap, saves the energy, production safety.
Description
Technical field
The present invention relates to a kind of electrode material preparation method, more particularly, to a kind of heat-treated graphite alkene aerogel carried two
The preparation method of tin oxide electrode materials.
Background technology
Graphene since the advent of the world, the extensive concern of people is just received with its unique property.It has many excellent
Performance, such as good electric conductivity, higher Young's modulus, huge surface area.Graphene is as a kind of lithium ion battery
Negative material also shows excellent chemical property, compared to common carbon-based material, its have higher specific capacity and
More preferable cycle performance.Flower-shaped graphene platelet is synthesized as lithium ion battery negative material using chemical method, it stores up lithium and held
Measure (650mAh/g) remote high and graphite cathode (372mAh/g).This is due to its unique two-dimensional structure and special performance, it
With electric conductivity more more preferable than other carbon-based materials, ionic mobility, mechanical strength etc..
Graphene composite material also goes out more excellent performance as negative material than single raw material electrode common manifestation.
This is due to:First, the introducing of graphene, it is swollen can effectively to alleviate negative material volume serious during removal lithium embedded
It is swollen, extend the service life of electrode；Second, graphene can produce cooperative effect, particularly metal oxide with Cucumber
Such as SnO2,Fe2O3Deng realizing the specific capacity higher than primary electrode and more preferable cycle performance；3rd, some element (N, B, S
Deng) addition can prevent the inactivation of graphenic surface.So graphene-based composite is a kind of excellent lithium ion battery
Negative material.
Chinese patent CN 104143631A disclose a kind of preparation of graphene aerogel load tin dioxide composite material
Method.Belong to technical field of lithium ion battery electrode, main process and step are as follows：It is 2 by mass ratio:1~1:3 oxidation stones
Black alkene and the stirring of water-soluble pink salt, ultrasound, add 0.1~2mL Amine Solutions and are transferred to water heating kettle, 6 are kept at 80 DEG C~180 DEG C
~24h, then take out cylindric product, freeze-drying obtain graphene aerogel load tin dioxide composite material, wherein
Thin graphene is cross-linked, and forms micron order duct, surface 3~6nm of uniform load of graphene stannic oxide particle.Should
Patent due to reproduction aeroge during apply hydro-thermal method, temperature is higher, and the reaction time is longer, be not suitable for actual production in
Application.And the patent, without the process of heat treatment, this also results in its specific capacity has certain gap compared with our patent.
The content of the invention
There is larger ratio it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
Surface area and porosity, cost of manufacture are cheap, save the energy, the aerogel carried tin ash of heat-treated graphite alkene of production safety
The preparation method of electrode material.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, using following steps：
(1) graphene oxide water solution and tin ash ethanol solution, L-AA are mixed in proportion, then
Heated at a temperature of 75 DEG C 4~6 hours, taking-up is washed, and is freeze-dried；
(2) product after freeze-drying is placed under inert gas and be heat-treated, graphene aerogel is prepared and bears
Carry stannic oxide electrode material.
The mass ratio of graphene oxide and tin ash is 2:1~1:3.
The mass ratio of graphene oxide and L-AA is 1:2~1:3.
Tin ash ethanol solution be by the aqueous solution of butter of tin at a temperature of 160 DEG C in ptfe autoclave
Middle reaction 16h, then by centrifuging and being dissolved in ethanol.
Described inert gas is argon gas.
The treatment temperature of described heat treatment is 400-600 DEG C, handles 1-4h, and heating rate is 10 DEG C/min, cooling speed
Rate is 5 DEG C/min.
Compared with prior art, the present invention utilizes the aerogel carried tin ash combination electrode material of heat-treated graphite alkene,
So as to have larger specific surface area and porosity, specific surface area also has been improved compared with prior art, and cost of manufacture is cheap,
Do not utilize hydro-thermal method during load, save the energy, production safety, and in high current and the process of low current discharge and recharge
In all there is relatively good effect, and there is very long cycle life and charging and discharging capacity.The addition of graphene can be very
Weaken the attenuation effect of tin ash capacity in big degree, there is great application value.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of the aerogel carried tin ash combination electrode material of heat-treated graphite alkene.
Fig. 2 is the scanning electron microscopic picture of the aerogel carried tin ash combination electrode material of heat-treated graphite alkene.
Fig. 3 is the aerogel carried tin ash combination electrode material charge and discharge under 200mA/g electric current of heat-treated graphite alkene
Electric cycle performance.
Fig. 4 is the aerogel carried tin ash combination electrode material charge and discharge under 1000mA/g electric current of heat-treated graphite alkene
Electric cycle performance.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, using following steps：
Take 1gSnCl4·5H2O is dissolved in about 50ml deionized water, then transfers the solution into 2 50ml polytetrafluoro
In the stainless steel cauldron of ethene liner, reacted at a temperature of 160 DEG C 16 hours, after reaction terminates, naturally cool to room
Temperature, the solution that reaction is completed is taken out, then by milky white nano SnO2Solution centrifugal, 10000 rpms of centrifugal speed, centrifugation
Time 5min, supernatant liquid is removed, solid matter below is dissolved among 50ml industrial alcohol, ultrasonic disperse to no solid
Untill, obtain nano SnO2Alcoholic solution (about 10mg/ml).The graphene oxide solution prepared is configured to concentration
For 2mg/ml, 25ml solution (containing about graphene oxide 50mg) is then taken, progress magnetic force stirs among being added to 100ml beaker
Mix, then add the SnO prepared2Nanoparticles solution, 2 hours of stir about, then ultrasound is 1 under 300W power
Individual hour, uniform brown yellow solution is obtained, then add 100mg L-AA, continued stirring 30 minutes, be subsequently poured into
Among the 25ml vial with lid, 10 hours of heating among 75 DEG C of baking oven are put into, are naturally cooled to after taking-up
Room temperature, black cylinder solid body is obtained, here it is be loaded with nano SnO2The graphene hydrogel of particle.Hydrogel is oozed
Enter and carry out changing clothes 2 days in deionized water, every 12 hours change a water.Then add to freeze-dryer, be freeze-dried
36 hours so that hydrogel is completely dried, and is taken out out of freeze-drying the phase, here it is be loaded with nano SnO2The graphite of particle
Alkene aeroge.Then nano SnO will be loaded with2The graphene aerogel of particle is heat-treated 2 small under the atmosphere of 550 DEG C of argon gas
When, heating rate is 10 DEG C/min, is cooled as furnace cooling.The graphene aerogel load tin ash compound electric being prepared
The scanning electron microscope (SEM) photograph of pole material with 200mA/g electric current as shown in figure 1, carry out charge and discharge cycles test.After 50 circulations
Still there is 850mAh/g specific capacity, as shown in Figure 3.
Embodiment 2
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, its process are basic with embodiment 1
Identical, difference is, heat treatment temperature is changed into 500 DEG C, and the time is 3 hours, and heating rate is 10 DEG C/min, cooling
Scanning electron microscope (SEM) photograph such as Fig. 2 institutes of tin ash combination electrode material are loaded for the graphene aerogel that furnace cooling is prepared
Show.Charge and discharge cycles test is carried out with 1000mA/g electric current, still with 515mAh/g, as shown in Figure 4.
Embodiment 3
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, using following steps：
(1) aqueous solution of butter of tin is reacted into 16h at a temperature of 160 DEG C in ptfe autoclave, then
By centrifuging and being dissolved in ethanol, tin ash ethanol solution is obtained；
(2) graphene oxide water solution is well mixed with tin ash ethanol solution, L-AA, wherein, oxidation
The mass ratio of graphene and tin ash is 2:1, the mass ratio of graphene oxide and L-AA is 1:2, then at 75 DEG C
At a temperature of heat 4 hours, taking-up is washed, and is freeze-dried；
(3) product after freeze-drying is placed under argon gas atmosphere and be heat-treated, the treatment temperature of heat treatment is 400
DEG C, 4h is handled, heating rate therein is 10 DEG C/min, and rate of temperature fall is 5 DEG C/min, and graphene aerogel load is prepared
Stannic oxide electrode material.
Embodiment 4
The preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, using following steps：
(1) aqueous solution of butter of tin is reacted into 16h at a temperature of 160 DEG C in ptfe autoclave, then
By centrifuging and being dissolved in ethanol, tin ash ethanol solution is obtained；
(2) graphene oxide water solution is well mixed with tin ash ethanol solution, L-AA, wherein, oxidation
The mass ratio of graphene and tin ash is 1:3, the mass ratio of graphene oxide and L-AA is 1:3, then at 75 DEG C
At a temperature of heat 6 hours, taking-up is washed, and is freeze-dried；
(3) product after freeze-drying is placed under argon gas atmosphere and be heat-treated, the treatment temperature of heat treatment is 600
DEG C, 1h is handled, heating rate therein is 10 DEG C/min, and rate of temperature fall is 5 DEG C/min, and graphene aerogel load is prepared
Stannic oxide electrode material.
Claims (6)
1. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene, it is characterised in that this method uses
Following steps：
(1) graphene oxide water solution and tin ash ethanol solution, L-AA are mixed in proportion, then 75
Heated at a temperature of DEG C 4~6 hours, taking-up is washed, and is freeze-dried；
(2) product after freeze-drying is placed under inert gas and be heat-treated, the treatment temperature of heat treatment is 400-600
DEG C, 1-4h is handled, graphene aerogel load stannic oxide electrode material is prepared.
2. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene according to claim 1, its
It is characterised by, the mass ratio of graphene oxide and tin ash is 2:1~1:3.
3. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene according to claim 1, its
It is characterised by, the mass ratio of graphene oxide and L-AA is 1:2~1:3.
4. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene according to claim 1, its
It is characterised by, tin ash ethanol solution is to react the aqueous solution of butter of tin in a kettle at a temperature of 160 DEG C
16h, then by centrifuging and being dissolved in ethanol.
5. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene according to claim 1, its
It is characterised by, described inert gas is argon gas.
6. the preparation method of the aerogel carried stannic oxide electrode material of heat-treated graphite alkene according to claim 1, its
It is characterised by, the heating rate of described heat treatment is 10 DEG C/min, and rate of temperature fall is 5 DEG C/min.
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| CN105355877B (en) * | 2015-11-06 | 2017-07-11 | 盐城工学院 | A kind of graphene metal oxide composite cathode material and preparation method thereof |
| CN108328596B (en) * | 2017-01-20 | 2020-05-26 | 中国科学院物理研究所 | Carbon sponge, preparation method thereof and pressure sensor |
| CN107394153A (en) * | 2017-07-18 | 2017-11-24 | 福州大学 | A kind of lithium ion battery negative material |
| CN108390063A (en) * | 2018-01-19 | 2018-08-10 | 同济大学 | Graphene prepares the method and electrode of flexible self-supporting electrode as conductive adhesive |
| CN108735983B (en) * | 2018-04-04 | 2021-05-11 | 广东工业大学 | Graphene hydrogel composite material loaded with metal nanoparticles as well as preparation method and application of graphene hydrogel composite material |
| CN113735102B (en) * | 2021-08-16 | 2023-07-14 | 中钢集团南京新材料研究院有限公司 | Graphene aerogel carrying metal oxide and preparation method and application thereof |
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| KR101406371B1 (en) * | 2012-11-29 | 2014-06-16 | 연세대학교 산학협력단 | Metal or Metal oxide/Graphene self-assembly Nanocomposite of Three-dimensional structure and Method of preparing the same |
| CN104143631B (en) * | 2014-05-12 | 2016-12-07 | 上海大学 | A kind of preparation method of graphene aerogel load tin dioxide composite material |
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