CN106129343A - 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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- CN106129343A CN106129343A CN201610351307.5A CN201610351307A CN106129343A CN 106129343 A CN106129343 A CN 106129343A CN 201610351307 A CN201610351307 A CN 201610351307A CN 106129343 A CN106129343 A CN 106129343A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- 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 discloses the preparation method of a kind of Graphene titanium dioxide microballoon sphere, comprise the following steps that 1) pre-treatment of graphite: graphite is placed in the mixed solution being made up of concentrated sulphuric acid, potassium permanganate, ultrasonic agitation processes, the product obtained is scrubbed, filter, be placed in Muffle furnace process after drying, obtains expanded graphite product standby；2) preparation of Graphene titanium dioxide microballoon sphere: step 1) products therefrom expanded graphite is dissolved in deionized water; add surfactant; ultrasonic agitation; it is gradually added into appropriate titanium source in the solution; the spray-dried process of gained mixed solution, products therefrom is placed in high-temperature process in the Muffle furnace under special atmosphere protection, and products therefrom is after diluted acid or diluted alkaline and deionized water solution repeatedly wash; it is dried in vacuum drying oven, has both obtained Graphene titanium dioxide microballoon sphere.Graphene and grapheme material are well combined by the method, improve the electronic conductance of material；Additionally the method utilizes spray drying method that precursor is carried out secondary granulation, substantially increases the tap density of product.
Description
Technical field
The present invention relates to field of graphene technology, the preparation method of a kind of Graphene-titanium dioxide microballoon sphere is particularly provided.
Background technology
Lithium ion battery has monopolized mobile electronic device market, and in the coming years, lithium ion battery is still secondary electricity
The main growth factor in market, pond.In terms of lithium ion battery negative material, graphite-like carbon-based material is steady due to its good circulation
Qualitative and preferable charge and discharge platform, is still the first-selected negative material of lithium ion battery in following a period of time.But along with lithium electricity
Pond utilization in terms of electrokinetic cell, the charging and discharging capacity of conventional carbon material is relatively low, cannot meet high-capacity lithium battery
The demand of negative material.Therefore many R&D teams are developing Novel anode material, meet and want cell high-capacity
Ask.In the research of the negative material of novel non-carbon, metal-oxide is attracted attention because having high specific capacity.But metal oxygen
During the lithium ion removal lithium embedded repeated, there is serious change in volume effect, cause the stable circulation of electrode in compound material
Property significantly declines.
But as semi-conducting material titanium dioxide, there is electrical conductivity this fatal weakness low so that it is as electrode material
The application of material is restricted.Along with the application of lithium ion battery is more and more extensive, particularly at hybrid-power electric vehicle, pure electricity
Motor-car and the application in the first-class field of intelligent grid, people are to the requirement of the circulation of lithium ion battery and high rate performance the most increasingly
Height, and the current chemical property of titanium dioxide is not met by these requirements.Therefore, preparation has more high-tap density, more
The titanium dioxide electrodes material of big reversible specific capacity and more excellent circulation and high rate performance is extremely urgent.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, it is an object of the invention to provide a kind of Graphene-
The preparation method of titanium dioxide microballoon sphere, Graphene and grapheme material are well combined by the method, improve the electricity of material
Sub-conductance；Additionally the method utilizes spray drying method that precursor is carried out secondary granulation, substantially increases the tap density of product.
For achieving the above object, the present invention uses such as purgation technical scheme: the preparation of a kind 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 up of concentrated sulphuric acid, potassium permanganate, at 20 ~ 60 DEG C ultrasonic agitation process 0.5 ~
5h, it is thus achieved that product scrubbed, filter, be placed in Muffle furnace after drying, in nitrogen atmosphere and under 600 ~ 1200 DEG C of high temperature locate
Reason 0.1 ~ 6h, obtains expanded graphite product standby；
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 0.1 ~ 5wt%, ultrasonic agitation
After 0.1 ~ 2h, being gradually added into appropriate titanium source in the solution, this titanium source is 0.1 ~ 20:1 with the mass ratio of expanded graphite presoma；Super
Adding ammonia after sound stirring 0.5 ~ 4h, this ammonia is 1 ~ 10:1 with the mol ratio in titanium source, continues ultrasonic agitation 0.5 ~ 4h, and gained mixes
Closing the spray-dried process of solution, products therefrom is placed in the Muffle furnace under special atmosphere protection, under 600 ~ 1200 DEG C of high temperature
Processing 0.1 ~ 6h, products therefrom, after diluted acid or diluted alkaline and deionized water solution repeatedly wash, is dried in vacuum drying oven
0.5 ~ 8h, had both obtained Graphene-titanium dioxide microballoon sphere.
As a kind of preferred version, described surfactant is CTAB, dodecylbenzene sodium sulfonate, Polyethylene Glycol (PEG),
One in polyvinylpyrrolidone.
As a kind of preferred version, described special atmosphere is the one in argon, nitrogen.
As a kind of preferred version, described titanium source is butyl titanate, titanium propanolate, titanium chloride, titanium sulfate, titanium dioxide
In one.
As a kind of preferred version, the quality (g) of described step graphite: the volume (L) of concentrated sulphuric acid: the quality of potassium permanganate
(g)=1:0.05-0.1:0.1-0.5.
The present invention compared with prior art has clear advantage and beneficial effect, particularly as follows:
1, Graphene-titanium dioxide microballoon sphere that the inventive method is prepared has higher tap density (> 1.8g/cm3)
2, the method prepares Graphene and titanium dioxide can well be combined with each other, it is possible to the most comprehensive bi-material
Advantage, improve its specific capacity (> 300mAh/g as lithium ion battery) and cycle performance (500 weeks circulation after capacity keep
Rate more than 90%)；
3, the inventive method technique is simple, abundant raw material, easy to operate, produces equipment few, thus reduces cost further, it is simple to
Popularization and application, are suitable to large-scale production.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of Graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Being placed in by graphite in the mixed solution being made up of concentrated sulphuric acid, potassium permanganate, at 20 DEG C, ultrasonic agitation processes 5h, it is thus achieved that
Product is scrubbed, filter, be placed in Muffle furnace after drying, processes 0.1h, obtain swollen in nitrogen atmosphere and under 1200 DEG C of high temperature
Swollen graphite product is standby；The quality (g) of described step graphite: the volume (L) of concentrated sulphuric acid: quality (g)=1 of potassium permanganate:
0.05:0.1。
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 5wt%, ultrasonic agitation 0.1h
After, it being gradually added into appropriate titanium source in the solution, this titanium source is 20:1 with the mass ratio of expanded graphite presoma；After ultrasonic agitation 4h
Adding ammonia, this ammonia is 10:1 with the mol ratio in titanium source, continues ultrasonic agitation 0.5h, the spray-dried place of gained mixed solution
Reason, products therefrom is placed in the Muffle furnace that special atmosphere protection is lower, process 6h under 600 DEG C of high temperature, products therefrom through diluted acid or
After diluted alkaline and deionized water solution repeatedly wash, in vacuum drying oven, it is dried 8h, had both obtained Graphene-titanium dioxide microballoon sphere.
Described surfactant is CTAB；Described special atmosphere is argon；Described titanium source is butyl titanate.
Embodiment 2
The preparation method of a kind of Graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Being placed in by graphite in the mixed solution being made up of concentrated sulphuric acid, potassium permanganate, at 60 DEG C, ultrasonic agitation processes 0.5h, it is thus achieved that
Product scrubbed, filter, be placed in Muffle furnace after drying, in nitrogen atmosphere and under 600 DEG C of high temperature process 6h, expanded
Graphite product is standby；The quality (g) of described step graphite: the volume (L) of concentrated sulphuric acid: the quality (g) of potassium permanganate=1:0.1:
0.1。
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 0.1wt%, ultrasonic agitation 2h
After, it being gradually added into appropriate titanium source in the solution, this titanium source is 0.1:1 with the mass ratio of expanded graphite presoma；Ultrasonic agitation
Adding ammonia after 0.5h, this ammonia is 1:1 with the mol ratio in titanium source, continues ultrasonic agitation 0.5h, and gained mixed solution is through spraying
Dried, products therefrom is placed in the Muffle furnace under special atmosphere protection, processes 0.1h, products therefrom under 1200 DEG C of high temperature
After diluted acid or diluted alkaline and deionized water solution repeatedly wash, in vacuum drying oven, be dried 0.5h, both Graphene-dioxy
Change titanium microsphere.
Described surfactant is dodecylbenzene sodium sulfonate；Described special atmosphere is nitrogen；Described titanium source is titanium dioxide
In titanium.
Embodiment 3
The preparation method of a kind of Graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Being placed in by graphite in the mixed solution being made up of concentrated sulphuric acid, potassium permanganate, at 40 DEG C, ultrasonic agitation processes 3.5h, it is thus achieved that
Product scrubbed, filter, be placed in Muffle furnace after drying, in nitrogen atmosphere and under 800 DEG C of high temperature process 3h, expanded
Graphite product is standby；The quality (g) of described step graphite: the volume (L) of concentrated sulphuric acid: the quality (g) of potassium permanganate=1:0.07:
0.3。
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 3wt%, after ultrasonic agitation 1h,
Being gradually added into appropriate titanium source in the solution, this titanium source is 10:1 with the mass ratio of expanded graphite presoma；Add after ultrasonic agitation 3h
Entering ammonia, this ammonia is 6:1 with the mol ratio in titanium source, continues ultrasonic agitation 3h, the spray-dried process of gained mixed solution, institute
Obtaining product to be placed in the Muffle furnace under special atmosphere protection, process 3h under 1000 DEG C of high temperature, products therefrom is through diluted acid or diluted alkaline
And after deionized water solution repeatedly washs, in vacuum drying oven, be dried 3h, both obtained Graphene-titanium dioxide microballoon sphere.
Described surfactant is Polyethylene Glycol (PEG)；Described special atmosphere is argon；Described titanium source is titanium propanolate.
Embodiment 4
The preparation method of a kind of Graphene-titanium dioxide microballoon sphere, comprises the following steps that
1) pre-treatment of graphite:
Being placed in by graphite in the mixed solution being made up of concentrated sulphuric acid, potassium permanganate, at 40 DEG C, ultrasonic agitation processes 2h, it is thus achieved that
Product is scrubbed, filter, be placed in Muffle furnace after drying, processes 4h, obtain expanding stone in nitrogen atmosphere and under 900 DEG C of high temperature
Ink product is standby；The quality (g) of described step graphite: the volume (L) of concentrated sulphuric acid: the quality (g) of potassium permanganate=1:0.08:
0.4。
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 3wt%, after ultrasonic agitation 1h,
Being gradually added into appropriate titanium source in the solution, this titanium source is 10:1 with the mass ratio of expanded graphite presoma；Add after ultrasonic agitation 3h
Entering ammonia, this ammonia is 5:1 with the mol ratio in titanium source, continues ultrasonic agitation 2h, the spray-dried process of gained mixed solution, institute
Product is placed in the Muffle furnace that special atmosphere protection is lower, process 4h under 900 DEG C of high temperature, products therefrom through diluted acid or diluted alkaline and
After deionized water solution repeatedly washs, in vacuum drying oven, it is dried 4h, had both obtained Graphene-titanium dioxide microballoon sphere.
Described surfactant is Polyethylene Glycol (PEG), and described special atmosphere is argon, and described titanium source is metatitanic acid four fourth
Ester.
Comparative example 1,
Be in mass ratio 80:10:10 by active substance, acetylene black and Kynoar (PVDF) mixed grinding, drip appropriate
N-Methyl pyrrolidone (NMP) solution, agitation and dilution is homogeneous paste, is coated in nickel foam, forms negative plate.Pole piece is placed in
The vacuum drying oven of 80 DEG C is dried, on tablet machine, carries out tabletting with the pressure of 10MPa, then pole piece is put into 120 DEG C of vacuum
Drying baker is dried 12h.Dried pole piece is transferred in glove box, using metal lithium sheet as to electrode, is dried argon being full of
The glove box of gas is assembled into simulation button cell.Barrier film is porous polypropylene film, and electrolyte is the LiPF6 solution of 1mol/L,
Wherein electrolyte solvent is ethylene carbonate (EC) and the mixed solvent of diethyl carbonate (DEC).
Charge-discharge performance at different conditions by Land cell tester test battery.Charging/discharging voltage test model
Enclose 1 ~ 3V, cycle-index 500 circulation.
Obtained battery performance is compared as follows:
| Embodiment/right Ratio | System | 0.1C specific volume first Amount (mAh/g) | 0.1C is imitated first Rate (%) | 10C first than Capacity | 10C100 time capacity keeps Rate (%) | 1 C 500 times circulation volume 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 oxide | 257 | 80 | 228 | 37 | 64 | 1.23 |
As seen from the above table, by this kind of process can the advantage of comprehensive bi-material, improve it as lithium ion battery
Specific capacity (> 300mAh/g), cycle performance (capability retention more than 90% after circulation in 500 weeks) and high rate performance (circulate 100 weeks
Capability retention more than 90%)；And the tap density of material is also improved, optimum up to more than 1.8g/cm3, permissible
Extensively should be in lithium ion battery as negative material.
The above, be only presently preferred embodiments of the present invention, not impose any restrictions the technical scope of the present invention,
Therefore every technical spirit according to the present invention is to any trickle amendment made for any of the above embodiments, equivalent variations and modification, the most still
Belong in the range of technical solution of the present invention.
Claims (5)
1. the 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 up of concentrated sulphuric acid, potassium permanganate, at 20 ~ 60 DEG C ultrasonic agitation process 0.5 ~
5h, it is thus achieved that product scrubbed, filter, be placed in Muffle furnace after drying, in nitrogen atmosphere and under 600 ~ 1200 DEG C of high temperature locate
Reason 0.1 ~ 6h, obtains expanded graphite product standby；
2) preparation of Graphene-titanium dioxide microballoon sphere:
Step 1) products therefrom expanded graphite is dissolved in deionized water, adds the surfactant of 0.1 ~ 5wt%, ultrasonic agitation
After 0.1 ~ 2h, being gradually added into appropriate titanium source in the solution, this titanium source is 0.1 ~ 20:1 with the mass ratio of expanded graphite presoma；Super
Adding ammonia after sound stirring 0.5 ~ 4h, this ammonia is 1 ~ 10:1 with the mol ratio in titanium source, continues ultrasonic agitation 0.5 ~ 4h, and gained mixes
Closing the spray-dried process of solution, products therefrom is placed in the Muffle furnace under special atmosphere protection, under 600 ~ 1200 DEG C of high temperature
Processing 0.1 ~ 6h, products therefrom, after diluted acid or diluted alkaline and deionized water solution repeatedly wash, is dried in vacuum drying oven
0.5 ~ 8h, had both obtained Graphene-titanium dioxide microballoon sphere.
A kind of preparation method of Graphene-titanium dioxide microballoon sphere, it is characterised in that: described surface
Activating agent is CTAB, one in dodecylbenzene sodium sulfonate, Polyethylene Glycol (PEG), polyvinylpyrrolidone.
A kind of preparation method of Graphene-titanium dioxide microballoon sphere, it is characterised in that: described special
Atmosphere is the one in argon, nitrogen.
A kind of preparation method of Graphene-titanium dioxide microballoon sphere, it is characterised in that: described titanium source
For the one in butyl titanate, titanium propanolate, titanium chloride, titanium sulfate, titanium dioxide.
A kind of preparation method of Graphene-titanium dioxide microballoon sphere, it is characterised in that: described step
The quality (g) of graphite: the volume (L) of concentrated sulphuric acid: the quality (g) of potassium permanganate=1:0.05-0.1:0.1-0.5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN111554934A (en) * | 2020-05-14 | 2020-08-18 | 陕西科技大学 | Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof |
| CN113421780A (en) * | 2021-06-24 | 2021-09-21 | 浙江工业大学 | graphene/TiO for supercapacitor2Preparation method of NPs composite electrode material |
| CN113582220A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | TiO 22Preparation method of/carbon composite interlayer |
| CN113948691A (en) * | 2021-10-15 | 2022-01-18 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN111554934A (en) * | 2020-05-14 | 2020-08-18 | 陕西科技大学 | Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof |
| 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 |
| CN113948691A (en) * | 2021-10-15 | 2022-01-18 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage 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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