CN106829931A - A kind of three-dimensional structure graphene aerogel and its preparation method and application - Google Patents
A kind of three-dimensional structure graphene aerogel and its preparation method and application Download PDFInfo
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- CN106829931A CN106829931A CN201710119449.3A CN201710119449A CN106829931A CN 106829931 A CN106829931 A CN 106829931A CN 201710119449 A CN201710119449 A CN 201710119449A CN 106829931 A CN106829931 A CN 106829931A
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- dimensional structure
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- structure graphene
- graphene aerogel
- aerogel
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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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 a kind of three-dimensional structure graphene aerogel and its preparation method and application.It is that, with graphene oxide as raw material, with water as solvent, with thiocarbamide as reducing agent and binding agent, under room temperature condition, reaction is obtained three-dimensional structure Graphene hydrogel, in vacuum drying, the target product for obtaining.There is level loose structure in the three-dimensional structure graphene aerogel being prepared from by the method for the present invention, on the premise of conductive agent good characteristic is kept, conductive agent electric conductivity is more improve relative to acetylene black, solve material and be difficult the problems such as being compacted, significantly, the addition of Graphene can significantly improve the accounting of active material, contact with active material is that a point face contacts, lift the level density of lithium ion battery, the maximized effect for playing conductive agent, reduce the consumption of conductive agent, improve the level density of lithium ion battery, and then improve the chemical property of material.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of graphene aerogel with three-dimensional structure is made
The application for being conductive additive in lithium ion battery, to effectively improve conductive agent electric conductivity, solve material be difficult compacting and
The problems such as material usage is excessive.
Background technology
Positive and negative electrode in lithium ion battery is all made up of active material (Lithium storage materials), binding agent and conductive agent.
In order to ensure that electrode has good charge-discharge performance, a certain amount of conductive materials are usually added into when pole piece makes, in activity
Play a part of to collect micro-current between material, between active material and collector, to reduce the contact resistance of electrode, accelerate electricity
The rate travel of son, while migration rate of the lithium ion in electrode material can be also effectively improved, so as to improve filling for electrode
Discharging efficiency.
The conventional conductive agent of lithium ion battery is generally nanometer conductive material, there is acetylene black, gas-phase growth of carbon fibre and carbon
Nanotube etc..The species of conductive agent is larger to the Electrochemical Performances of electrode, due to acetylene black granularity very little and isotropism,
Lattice low degree, insertion is more or less the same lithium ion with the Gibbs free energy of deintercalation wherein, and resistance heat release is smaller, therefore its
Influence the degree of battery security smaller, therefore always all using acetylene black as leading in the positive and negative electrode of lithium ion battery
Electric agent.Acetylene black is used as conventional conductive agent, and its volume is fluffy, and the compacting influence on material is larger；Surface area enriches, and is unfavorable for shape
Into conductive network, polarization of electrode is serious.Thus study a kind of good conductivity, be easy to be compacted and can avoid or reduce electrode
The conductive agent of polarization phenomena turns into the study hotspot of various equivalent modifications.
The content of the invention
It is an object of the invention to provide a kind of three-dimensional structure graphene aerogel and utilize it as conductive additive should
In for lithium ion battery, to effectively improve conductive agent electric conductivity, solve that material is difficult compacting and material usage is excessive etc. asks
Topic.
The technical solution adopted by the present invention is：A kind of three-dimensional structure graphene aerogel, be with graphene oxide as raw material,
With water as solvent, with thiocarbamide as reducing agent and binding agent, under room temperature condition, reaction is obtained three-dimensional structure Graphene hydrogel,
In vacuum drying, the target product for obtaining.
A kind of preparation method of three-dimensional structure graphene aerogel, comprises the following steps：
1) it is graphene oxide is soluble in water, obtain graphene oxide water solution；
In order to ensure obtained aeroge can be loose structure, so as to increase the specific surface area of material, material is improved
Chemical property, it is preferred that the concentration of graphene oxide solution be 1-3mg/ml.
2) under room temperature condition, thiocarbamide is placed in graphene oxide water solution, is dissolved, be sufficiently stirred for 1-2h, must reacted molten
Liquid；
Preferably, in mass ratio, graphene oxide:Thiocarbamide=1:0.25-0.5.
3) reaction solution is transferred in reactor, hydro-thermal reaction, obtains three-dimensional structure Graphene hydrogel；
Preferably, hydro-thermal reaction is at 170-180 DEG C, to react 12-13h.
4) three-dimensional structure Graphene hydrogel is washed with deionized, 6-8h is vacuum dried in 70-80 DEG C, obtain target
Product graphene aerogel.
Application of the above-mentioned three-dimensional structure graphene aerogel as conductive additive in lithium ion battery.Method is such as
Under：Li is taken respectively4Ti5O12, above-mentioned three-dimensional structure graphene aerogel and Kynoar (PVDF), be well mixed, as
Battery conductive agent, lithium piece, with 1-METHYLPYRROLIDONE (NMP) as solvent, is assembled into button cell as to electrode.
Preferably, in mass ratio, Li4Ti5O12:Three-dimensional structure graphene aerogel:PVDF=8:1:1.
The beneficial effects of the invention are as follows：The present invention, in order to really enable raw material graphene oxide well-bonded, as technology
The improvement of scheme, using thiocarbamide as reducing agent and binding agent.The three-dimensional structure Graphene being prepared from by the method for the present invention
There is level loose structure in aeroge, on the premise of conductive agent good characteristic is kept, is more improve relative to acetylene black and led
Electric agent electric conductivity, solves material and is difficult the problems such as being compacted, particular, it is important that the addition of Graphene can significantly improve work
Property material accounting, contact with active material contacts for point-face, lifts the level density of lithium ion battery, maximized hair
The effect of conductive agent is waved, the consumption of conductive agent is reduced, the level density of lithium ion battery is improved, and then improves the electrification of material
Learn performance.
Brief description of the drawings
Fig. 1 is the XRD of graphene aerogel and GO；
Wherein, a, graphene aerogel；b、GO.
Fig. 2 is the photomacrograph of graphene aerogel.
Fig. 3 schemes for the SEM of graphene aerogel.
Specific embodiment
The present invention is further expalined with reference to specific embodiment, but be not intended to limit the invention
Protection domain.
The three-dimensional structure graphene aerogel of embodiment 1
(1) preparation method is as follows：
1) it is graphene oxide (GO) is soluble in water, obtain the graphene oxide water solution that concentration is 2mg/ml；
2) under room temperature condition, 0.015g thiocarbamides are placed in 20mL graphene oxide water solutions, are dissolved, under drying condition,
1h is sufficiently stirred for and mixed, sepia reaction solution is obtained；
3) sepia reaction solution is transferred in reactor, 170-180 DEG C of reaction 12h obtains three-dimensional structure Graphene
Hydrogel；
4) above-mentioned gained three-dimensional structure Graphene hydrogel deionized water is fully cleaned up, in 70-80 DEG C of vacuum
6-8h is dried, target product three-dimensional structure graphene aerogel is obtained.
(2) detect
The three-dimensional structure graphene aerogel of preparation is carried out into XRD and SEM detections, as a result as shown in figures 1 and 3, graphite
The three-dimensional macro morphology of alkene aeroge is as shown in Figure 2.
As seen from Figure 1, by contrasting GO with the three-dimensional structure graphene aerogel for obtaining it can be found that graphene aerogel
It is that the Graphene reduced by GO is constituted, because the unordered disorderly three-D pore structure of its internal structure causes the strong of Graphene characteristic peak
Degree is greatly reduced.The XRD spectra for observing graphene aerogel finds, rapid in the characteristic diffraction peak intensity of 12.1 ° of GO in script
Subtract, and a peak occur at 26.5 °.This explanation has the process that GO is reduced in aeroge forming process.With in GO
The disengaging of oxygen-containing functional group so that diffraction peak intensities of the GO at 12.1 ° is decayed rapidly, while functional group departs from lamellar structure
So that the graphite flake layer exposure of script, thus a peak is can detect at 26.5 °.
From Figure 2 it can be seen that the graphene aerogel for obtaining has rich obvious 3-D solid structure, surface is macroscopically presented
Rich hole.
As seen from Figure 3, the graphene aerogel of acquisition, it can be seen that the distinctive spun silk shape lines of Graphene and its obvious
The three-dimensional porous network structure being cross-linked with each other, the hole wall of aeroge is all to be stacked along direction in face by Graphene on chip, taken
Connect and form, here it is apparent that the vestige of fold.
Complex chart 1, Fig. 2, Fig. 3 can be obtained, and resulting materials of the present invention are redox graphene, in the process that aeroge is formed
In, GO is reduced.And three-dimensional structure graphene aerogel has abundant multidimensional network structure and huge specific surface area, carries
For bigger active material accounting.
Application of the three-dimensional structure graphene aerogel of embodiment 2 in lithium ion battery
Buy acetylene black-materials for three-dimensional structure graphene aerogel of the invention and common market, using its as
Battery conductive additive, lithium piece is assembled into button cell as to electrode, and electrochemical property test is carried out to it
1st, the lithium ion battery with three-dimensional structure graphene aerogel as conductive additive
Preparation method：By negative active core-shell material Li4Ti5O12(LTO), three-dimensional structure Graphene airsetting prepared by embodiment 1
Glue, Kynoar (PVDF), according to mass ratio (LTO:Graphene aerogel:PVDF=8:1:1) material is weighed, mixing is equal
Even, used as battery conductive agent, using coating method, lithium piece, with NMP as solvent, is assembled into button cell as to electrode, and it is entered
Row electrochemical property test.Result such as table 1.
2nd, the lithium ion battery with acetylene black as conductive additive
Preparation method：By negative active core-shell material Li4Ti5O12(LTO), acetylene black purchased in market, Kynoar (PVDF), according to
Mass ratio (LTO:Acetylene black:PVDF=8:1:1) material is weighed, is well mixed, as battery conductive agent, using coating method, lithium
Piece, with NMP as solvent, is assembled into button cell as to electrode, and electrochemical property test is carried out to it.Result such as table 1.
The variety classes conductive agent charge-discharge performance of table 1 compares (charge-discharge magnification 1C)
From table 1, compared to addition acetylene black as conductive agent LTO materials, the graphite of method of the present invention synthesis
The chemical property of alkene aeroge is improved significantly, and not only realizes that solving the conductive agents such as acetylene black is difficult compacting and consumption mistake
Many problems, and due to its level vesicular texture, the specific surface area of material is further increased, electrical conductivity is improve, enter
And improve the chemical property of material.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for those skilled in the art
For member, the present invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of three-dimensional structure graphene aerogel, it is characterised in that be with graphene oxide as raw material, with water as solvent, with
Thiocarbamide is reducing agent and binding agent, and under room temperature condition, reaction is obtained three-dimensional structure Graphene hydrogel, in vacuum drying, obtains
The target product for arriving.
2. a kind of preparation method of three-dimensional structure graphene aerogel, it is characterised in that comprise the following steps：
1) it is graphene oxide is soluble in water, obtain graphene oxide water solution；
2) under room temperature condition, thiocarbamide is placed in graphene oxide water solution, is dissolved, be sufficiently stirred for 1-2h, obtain reaction solution；
3) reaction solution is transferred in reactor, hydro-thermal reaction, obtains three-dimensional structure Graphene hydrogel；
4) three-dimensional structure Graphene hydrogel is washed with deionized, 6-8h is vacuum dried in 70-80 DEG C, obtain target product
Graphene aerogel.
3. according to a kind of preparation method of the three-dimensional structure graphene aerogel described in claim 2, it is characterised in that step 1)
In, the concentration of graphene oxide water solution is 1-3mg/ml.
4. according to a kind of preparation method of the three-dimensional structure graphene aerogel described in claim 2, it is characterised in that by quality
Than graphene oxide:Thiocarbamide=1:0.25-0.5.
5. according to a kind of preparation method of the three-dimensional structure graphene aerogel described in claim 2, it is characterised in that step 3)
In, hydro-thermal reaction is at 170-180 DEG C, to react 12-13h.
6. application of the three-dimensional structure graphene aerogel described in claim 1 as conductive additive in lithium ion battery.
7. according to the application described in claim 6, it is characterised in that take Li respectively4Ti5O12, three-dimensional knot described in claim 1
Structure graphene aerogel and PVDF, are well mixed, and used as battery conductive agent, lithium piece, with NMP as solvent, is assembled as to electrode
Into button cell.
8. according to the application described in claim 7, it is characterised in that in mass ratio, Li4Ti5O12:Three-dimensional structure Graphene airsetting
Glue:PVDF=8:1:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439376A (en) * | 2018-03-21 | 2018-08-24 | 大连理工大学 | A kind of preparation method of the graphene aerogel composite material of carried magnetic nano particle |
| JP2019046584A (en) * | 2017-08-30 | 2019-03-22 | 旭化成株式会社 | Secondary battery inorganic particle binder material, and secondary battery separator and secondary battery using the same |
| CN109638268A (en) * | 2018-12-26 | 2019-04-16 | 赵宏伟 | A kind of bismuth phosphate/cerous phosphate composite lithium ion battery positive electrode and preparation method |
| CN109659437A (en) * | 2018-11-23 | 2019-04-19 | 上海工程技术大学 | Based on the perovskite solar battery of low temperature graphene aerogel and its preparation |
| CN111554869A (en) * | 2020-04-09 | 2020-08-18 | 上海应用技术大学 | Efficient heteroatom doping method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019046584A (en) * | 2017-08-30 | 2019-03-22 | 旭化成株式会社 | Secondary battery inorganic particle binder material, and secondary battery separator and secondary battery using the same |
| JP6998155B2 (en) | 2017-08-30 | 2022-01-18 | 旭化成株式会社 | Inorganic particle binder for secondary battery, separator for secondary battery and secondary battery using this |
| CN108439376A (en) * | 2018-03-21 | 2018-08-24 | 大连理工大学 | A kind of preparation method of the graphene aerogel composite material of carried magnetic nano particle |
| CN109659437A (en) * | 2018-11-23 | 2019-04-19 | 上海工程技术大学 | Based on the perovskite solar battery of low temperature graphene aerogel and its preparation |
| CN109638268A (en) * | 2018-12-26 | 2019-04-16 | 赵宏伟 | A kind of bismuth phosphate/cerous phosphate composite lithium ion battery positive electrode and preparation method |
| CN109638268B (en) * | 2018-12-26 | 2020-11-13 | 泰州新滨江环保科技有限公司 | Bismuth phosphate/cerium phosphate composite lithium battery positive electrode material and preparation method thereof |
| CN111554869A (en) * | 2020-04-09 | 2020-08-18 | 上海应用技术大学 | Efficient heteroatom doping method |
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Application publication date: 20170613 |