CN106129343B - A kind of preparation method of graphene-titanium dioxide microballoon sphere - Google Patents
A kind of preparation method of graphene-titanium dioxide microballoon sphere Download PDFInfo
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- CN106129343B CN106129343B CN201610351307.5A CN201610351307A CN106129343B CN 106129343 B CN106129343 B CN 106129343B CN 201610351307 A CN201610351307 A CN 201610351307A CN 106129343 B CN106129343 B CN 106129343B
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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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- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention discloses a kind of preparation method of graphene-titanium dioxide microballoon sphere, it comprises the following steps that the pre-treatment of 1) graphite: graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, ultrasonic agitation processing, the product of acquisition is washed, filter, dry be placed in Muffle furnace is handled, and it is spare to obtain expanded graphite product；2) graphene-titanium dioxide microballoon sphere preparation: step 1) products therefrom expanded graphite is dissolved in deionized water; surfactant is added; ultrasonic agitation; it is gradually added into appropriate titanium source in the solution; the spray-dried processing of gained mixed solution, products therefrom are placed in the Muffle furnace high temperature processing under special atmosphere protection, and products therefrom is after diluted acid or diluted alkaline and deionized water solution repeatedly wash; it is dry in vacuum drying oven, both obtain graphene-titanium dioxide microballoon sphere.This method well combines graphene and grapheme material, improves the electronic conductance of material；In addition this method carries out secondary granulation to precursor using spray drying process, substantially increases the tap density of product.
Description
Technical field
The present invention relates to field of graphene technologies, are especially to provide a kind of preparation method of graphene-titanium dioxide microballoon sphere.
Background technique
Lithium ion battery has monopolized mobile electronic device market, and lithium ion battery is still secondary electricity in the coming years
The main growth factor in pond market.In terms of lithium ion battery negative material, graphite-like carbon-based material is steady due to its good circulation
Qualitative and ideal charge and discharge platform is still the preferred negative electrode material of lithium ion battery in following a period of time.But with lithium electricity
Utilization of the pond in terms of power battery, the charging and discharging capacity of traditional carbon material is lower, can no longer meet high-capacity lithium battery
The demand of negative electrode material.Therefore many R&D teams are developing novel anode material, want to meet to cell high-capacity
It asks.In the research of the negative electrode material of novel non-carbon, metal oxide is attracted attention due to high specific capacity.But metal oxygen
For compound material during duplicate lithium ion removal lithium embedded, there are serious volume change effects, cause the stable circulation of electrode
Property sharp fall.
But there is this low fatal weakness of conductivity as semiconductor material titanium dioxide, so that it is as electrode material
The application of material is restricted.As lithium ion battery is using more and more extensive, especially in hybrid-power electric vehicle, pure electricity
Motor-car and in smart grid equal fields application, requirement of the people to the circulation of lithium ion battery and high rate performance is also increasingly
Height, and the current chemical property of titanium dioxide is not met by these requirements.Therefore, it prepares with more high-tap density, more
The titanium dioxide electrodes material of big reversible specific capacity and superior circulation and high rate performance is extremely urgent.
Summary of the invention
In view of this, the present invention is in view of the existing deficiencies of the prior art, the purpose of the present invention is to provide a kind of graphenes-
The preparation method of titanium dioxide microballoon sphere, this method well combine graphene and grapheme material, improve the electricity of material
Sub- conductance；In addition this method carries out secondary granulation to precursor using spray drying process, substantially increases the tap density of product.
To achieve the above object, the present invention is using following technical solution: a kind of preparation of graphene-titanium dioxide microballoon sphere
Method comprises the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, ultrasonic agitation is handled at 20 ~ 60 DEG C
0.5 ~ 5h, the product of acquisition is washed, filtering, drying are placed in Muffle furnace, in nitrogen atmosphere and 600 ~ 1200 DEG C of high temperature
0.1 ~ 6h of lower processing, it is spare to obtain expanded graphite product；
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 0.1 ~ 5wt%, ultrasound is added
After stirring 0.1 ~ 2h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 0.1 ~ 20:
1；Ammonium hydroxide is added after 0.5 ~ 4h of ultrasonic agitation, the molar ratio of the ammonium hydroxide and titanium source is 1 ~ 10:1, continues 0.5 ~ 4h of ultrasonic agitation, institute
The spray-dried processing of mixed solution is obtained, products therefrom is placed in the Muffle furnace under special atmosphere protection, in 600 ~ 1200 DEG C of height
Temperature is lower to handle 0.1 ~ 6h, and products therefrom is after diluted acid or diluted alkaline and deionized water solution repeatedly wash, in vacuum drying oven
Dry 0.5 ~ 8h, both obtains graphene-titanium dioxide microballoon sphere.
As a preferred embodiment, the surfactant be CTAB, neopelex, polyethylene glycol (PEG),
One of polyvinylpyrrolidone.
As a preferred embodiment, the special atmosphere is one of argon gas, nitrogen.
As a preferred embodiment, the titanium source is butyl titanate, titanium propanolate, titanium chloride, titanium sulfate, titanium dioxide
One of.
As a preferred embodiment, the quality (g) of the step graphite: the volume (L) of the concentrated sulfuric acid: the quality of potassium permanganate
(g)=1:0.05-0.1:0.1-0.5.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically:
1, graphene-titanium dioxide microballoon sphere tap density with higher (> 1.8g/cm3) that the method for the present invention is prepared
2, graphene made from the method and titanium dioxide can be very good to be combined with each other, and can be good at two kinds comprehensive
The advantages of material, improve its as lithium ion battery specific capacity (> 300mAh/g) and cycle performance (500 weeks circulation after capacity
90% or more conservation rate)；
3, the method for the present invention simple process, abundant raw material, easy to operate, production equipment is few, thus further reduce the cost,
It is easy to promote and utilize, it is suitable for large-scale production.
Specific embodiment
Embodiment 1
A kind of preparation method of graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, ultrasonic agitation processing 5h, is obtained at 20 DEG C
The product obtained is washed, filter, drying is placed in Muffle furnace, handles 0.1h in nitrogen atmosphere and under 1200 DEG C of high temperature, obtains
It is spare to expanded graphite product；The quality (g) of the step graphite: the volume (L) of the concentrated sulfuric acid: quality (g)=1 of potassium permanganate:
0.05:0.1。
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 5wt% is added, is stirred by ultrasonic
After 0.1h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 20:1；Ultrasonic agitation
Ammonium hydroxide is added after 4h, the molar ratio of the ammonium hydroxide and titanium source is 10:1, continues that 0.5h is stirred by ultrasonic, gained mixed solution is through spraying dry
Dry processing, products therefrom are placed in the Muffle furnace under special atmosphere protection, 6h are handled under 600 DEG C of high temperature, products therefrom is through dilute
After acid or diluted alkaline and deionized water solution repeatedly wash, it is micro- both to have obtained graphene-titanium dioxide by the dry 8h in vacuum drying oven
Ball.
The surfactant is CTAB；The special atmosphere is argon gas；The titanium source is butyl titanate.
Embodiment 2
A kind of preparation method of graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, the ultrasonic agitation processing 0.5h at 60 DEG C,
The product of acquisition is washed, filter, drying is placed in Muffle furnace, handles 6h in nitrogen atmosphere and under 600 DEG C of high temperature, obtains
Expanded graphite product is spare；The quality (g) of the step graphite: the volume (L) of the concentrated sulfuric acid: quality (g)=1 of potassium permanganate:
0.1:0.1。
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 0.1wt% is added, ultrasound is stirred
After mixing 2h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 0.1:1；Ultrasound is stirred
Ammonium hydroxide is added after mixing 0.5h, the molar ratio of the ammonium hydroxide and titanium source is 1:1, continues that 0.5h is stirred by ultrasonic, gained mixed solution is through spraying
Mist is dried, and products therefrom is placed in the Muffle furnace under special atmosphere protection, and 0.1h is handled under 1200 DEG C of high temperature, and gained produces
Object is after diluted acid or diluted alkaline and deionized water solution repeatedly wash, and dry 0.5h, both obtains graphene-two in vacuum drying oven
Titania microsphere.
The surfactant is neopelex；The special atmosphere is nitrogen；The titanium source is titanium dioxide
In titanium.
Embodiment 3
A kind of preparation method of graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, the ultrasonic agitation processing 3.5h at 40 DEG C,
The product of acquisition is washed, filter, drying is placed in Muffle furnace, handles 3h in nitrogen atmosphere and under 800 DEG C of high temperature, obtains
Expanded graphite product is spare；The quality (g) of the step graphite: the volume (L) of the concentrated sulfuric acid: quality (g)=1 of potassium permanganate:
0.07:0.3。
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 3wt% is added, is stirred by ultrasonic
After 1h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 10:1；3h is stirred by ultrasonic
After ammonium hydroxide is added, the molar ratio of the ammonium hydroxide and titanium source is 6:1, continues that 3h, the spray-dried place of gained mixed solution is stirred by ultrasonic
Reason, products therefrom are placed in the Muffle furnace under special atmosphere protection, handle 3h under 1000 DEG C of high temperature, products therefrom through diluted acid or
After diluted alkaline and deionized water solution repeatedly wash, dry 3h, both obtains graphene-titanium dioxide microballoon sphere in vacuum drying oven.
The surfactant is polyethylene glycol (PEG)；The special atmosphere is argon gas；The titanium source is titanium propanolate.
Embodiment 4
A kind of preparation method of graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, ultrasonic agitation processing 2h, is obtained at 40 DEG C
The product obtained is washed, filter, drying is placed in Muffle furnace, handles 4h in nitrogen atmosphere and under 900 DEG C of high temperature, obtains swollen
Swollen graphite product is spare；The quality (g) of the step graphite: the volume (L) of the concentrated sulfuric acid: quality (g)=1 of potassium permanganate:
0.08:0.4。
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 3wt% is added, is stirred by ultrasonic
After 1h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 10:1；3h is stirred by ultrasonic
After ammonium hydroxide is added, the molar ratio of the ammonium hydroxide and titanium source is 5:1, continues that 2h, the spray-dried place of gained mixed solution is stirred by ultrasonic
Reason, products therefrom are placed in the Muffle furnace under special atmosphere protection, handle 4h under 900 DEG C of high temperature, products therefrom through diluted acid or
After diluted alkaline and deionized water solution repeatedly wash, dry 4h, both obtains graphene-titanium dioxide microballoon sphere in vacuum drying oven.
The surfactant is polyethylene glycol (PEG), and the special atmosphere is argon gas, and the titanium source is four fourth of metatitanic acid
Ester.
Comparative example 1,
It is in mass ratio 80:10:10 by active material, acetylene black and Kynoar (PVDF) mixed grinding, is added dropwise suitable
N-Methyl pyrrolidone (NMP) solution of amount, agitation and dilution is homogeneous paste, is coated in nickel foam, and negative electrode tab is formed.Pole piece
It is placed in 80 DEG C of vacuum oven drying, tabletting is carried out with the pressure of 10MPa on tablet press machine, then pole piece is put into 120 DEG C
Dry 12h in vacuum oven.Pole piece after drying is transferred in glove box, using metal lithium sheet as to electrode, is done being full of
Simulation button cell is assembled into the glove box of dry argon gas.Diaphragm is porous polypropylene film, and electrolyte is that the LiPF6 of 1mol/L is molten
Liquid, wherein electrolyte solvent is the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC).
The charge-discharge performance at different conditions of battery is tested by Land cell tester.Charging/discharging voltage tests model
Enclose 1 ~ 3V, cycle-index 500 circulations.
Obtained battery performance is compared as follows:
| Embodiment/right Ratio | System | 0.1C specific capacity for the first time (mAh/g) | 0.1C is imitated for the first time Rate (%) | 10C compares for the first time Capacity | 10C100 capacity retention ratio (%) | 1 circulation volume of C 500 times is protected Holdup (%) | Tap density (g/cm3) |
| Embodiment 1 | Titanium dioxide-graphene (0.1:1) | 317 | 94 | 281 | 94 | 94 | 1.53 |
| Embodiment 2 | Titanium dioxide-graphene (1:1) | 301 | 90 | 265 | 93 | 93 | 1.67 |
| Embodiment 3 | Titanium dioxide-graphene (10:1) | 297 | 87 | 247 | 92 | 92 | 1.74 |
| Embodiment 4 | Titanium dioxide-graphene (20:1) | 282 | 85 | 232 | 91 | 91 | 1.81 |
| Comparative example 1 | Commercially available nano-titanium dioxide | 257 | 80 | 228 | 37 | 64 | 1.23 |
As seen from the above table, the advantages of can integrating two kinds of materials by this kind of process, improves it as lithium-ion electric
The specific capacity (> 300mAh/g) in pond, cycle performance (90% or more capacity retention ratio after 500 weeks circulations) and high rate performance (circulation
100 weeks 90% or more capacity retention ratios)；And the tap density of material is also improved, optimal reachable 1.8g/cm3 with
On, can be used as negative electrode material extensively should be in lithium ion battery.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (1)
1. a kind of preparation method of graphene-titanium dioxide microballoon sphere, it is characterised in that: comprise the following steps that
1) pre-treatment of graphite:
Graphite is placed in the mixed solution being made of the concentrated sulfuric acid, potassium permanganate, at 20 ~ 60 DEG C ultrasonic agitation processing 0.5 ~
5h, the product of acquisition is washed, filter, drying is placed in Muffle furnace, in nitrogen atmosphere and under 600 ~ 1200 DEG C of high temperature
0.1 ~ 6h is handled, it is spare to obtain expanded graphite product；
2) graphene-titanium dioxide microballoon sphere preparation:
Step 1) products therefrom expanded graphite is dissolved in deionized water, the surfactant of 0.1 ~ 5wt% is added, ultrasound is stirred
After mixing 0.1 ~ 2h, it is gradually added into appropriate titanium source in the solution, the mass ratio of the titanium source and expanded graphite presoma is 0.1 ~
20:1；Ammonium hydroxide is added after 0.5 ~ 4h of ultrasonic agitation, the molar ratio of the ammonium hydroxide and titanium source is 1 ~ 10:1, continues to be stirred by ultrasonic
0.5 ~ 4h, the spray-dried processing of gained mixed solution, products therefrom are placed in the Muffle furnace under special atmosphere protection, in
Under 600 ~ 1200 DEG C of high temperature handle 0.1 ~ 6h, products therefrom after diluted acid or diluted alkaline and deionized water solution repeatedly wash,
For dry 0.5 ~ 8h to get graphene-titanium dioxide microballoon sphere, the surfactant is CTAB, ten in vacuum drying oven
One of dialkyl benzene sulfonic acids sodium, polyethylene glycol (PEG), polyvinylpyrrolidone, the special atmosphere are argon gas, in nitrogen
One kind, the titanium source be one of butyl titanate, titanium propanolate, titanium chloride, titanium sulfate, titanium dioxide, the step
The quality (g) of graphite: the volume (L) of the concentrated sulfuric acid: the quality (g) of potassium permanganate=1:0.05-0.1:0.1-0.5.
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| CN109107558A (en) * | 2018-09-07 | 2019-01-01 | 宁波米瑞科技有限公司 | Catalysis material and preparation method thereof, fabric |
| CN111554934B (en) * | 2020-05-14 | 2021-09-07 | 陕西科技大学 | Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof |
| CN113582220A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | TiO 22Preparation method of/carbon composite interlayer |
| CN113421780A (en) * | 2021-06-24 | 2021-09-21 | 浙江工业大学 | graphene/TiO for supercapacitor2Preparation method of NPs composite electrode material |
| CN113948691B (en) * | 2021-10-15 | 2023-03-10 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
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| CN102683657A (en) * | 2012-05-11 | 2012-09-19 | 常州第六元素材料科技股份有限公司 | Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
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| CN102683657A (en) * | 2012-05-11 | 2012-09-19 | 常州第六元素材料科技股份有限公司 | Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
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