CN103833010A - Graphene, and preparation method and application thereof - Google Patents
Graphene, and preparation method and application thereof Download PDFInfo
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- CN103833010A CN103833010A CN201210480794.7A CN201210480794A CN103833010A CN 103833010 A CN103833010 A CN 103833010A CN 201210480794 A CN201210480794 A CN 201210480794A CN 103833010 A CN103833010 A CN 103833010A
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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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention belongs to the electrochemical field, and discloses a graphene, a preparation method thereof, an electrode slice and a supercapacitor. The preparation method of the graphene comprises the following steps: preparing a graphene oxide suspension; preparing a NaOH and graphene oxide mixed solution; and preparing the graphene. Graphene prepared through the graphene preparation method has the advantages of high specific surface area, high conductivity and high specific capacity, and has the advantages of operation step simplification, and substantial reduction of the production cost.
Description
Technical field
The present invention relates to Graphene field, relate in particular to a kind of Graphene and its preparation method and application.
Background technology
Ultracapacitor (Supercapacitors) claims again electrochemical capacitor (Electrochemical Capacitors) or double layer capacitor (Electric Double Layer Capacitors), it is a kind of novel energy-storing element between traditional capacitor and battery, there is more high-specific capacitance super and energy density compared with traditional capacitor, there is higher power density compared with battery; Because ultracapacitor has that the speed of discharging and recharging is fast, environmentally safe and the advantage such as have extended cycle life, promise to be novel green energy resource in this century.Electrode materials is the important component part of ultracapacitor, be affect ultracapacitor capacitive character can and the key factor of production cost, therefore research and develop high-performance, electrode materials is the important content of ultracapacitor research work cheaply.The electrode materials of the ultracapacitor of research mainly contains Carbon Materials, metal oxide and hydrate electrode materials thereof and conductive polymer electrodes material at present.
At present the electrode materials of double electric layers supercapacitor is mainly carbon material, has good heat conduction and conductivity, higher specific surface area, is widely used in electrochemical field and makes electrode materials, and carbon material is the most successfully one of electrode materials of current industrialization.At present, the research of carbon-based electrode material mainly concentrates on research and development and has the research of the aspects such as porous carbon materials that high-specific surface area, internal resistance are less.Graphene has high specific surface area, fabulous electroconductibility, good thermal conductivity, and the cost performance of the Graphene obtaining by graphite oxide reduction method is higher, and good stability, is the ideal electrode material of ultracapacitor.The ultracapacitor that use Graphene produces will be all higher than the energy storage density of at present all ultracapacitors.But the actual Graphene electrodes material preparing is due to reasons such as reunions, capacity is on the low side, in water system, capacity is 135F/g, organic system capacity 99F/g, Distance Theory capacity (550F/g) differs far away, at present to the improvement of Graphene electric capacity mainly on specific discharge capacity, also the few start to pay close attention to the volumetric capacitance of Graphene.
Graphene has higher quality than electric capacity, lower resistivity, but its volumetric capacitance is not significantly improved.The volumetric capacitance that improves at present Graphene becomes the key factor that improves super capacitor energy density, and quality is the principal element that determines ultracapacitor volumetric capacitance than electric capacity and tap density, thereby how to improve its tap density under than the prerequisite of electric capacity Graphene obtaining better quality, become the key that improves its volumetric capacitance.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of preparation method of the Graphene higher than electric capacity.
Technical scheme of the present invention is as follows:
A preparation method for Graphene, comprises the steps:
By the graphite oxide ultrasonic dispersion treatment that is added to the water, obtaining concentration is the graphene oxide suspension of 1～20mg/ml;
The NaOH solution that is 1～500g/L by concentration joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of NaOH and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening is carried out to drying treatment, more dried screening is put into retort furnace and under inert atmosphere, carry out high-temperature calcination, cooling after, washing, filter, dry, obtain described Graphene.
Preferably, the preparation method of described Graphene, wherein, the described ultrasonic dispersion treatment time is 1～5h.
Preferably, the preparation method of described Graphene, wherein, in the mixing solutions of described NaOH and graphene oxide, the mass ratio of NaOH and graphene oxide is 1～50: 1.
Preferably, the preparation method of described Graphene, wherein, in described drying treatment process, drying treatment temperature is 60～80 ℃, the drying treatment time is 24～48h.
Preferably, the preparation method of described Graphene, wherein, when described high-temperature calcination, temperature is 800～1200 ℃, calcination time is 1～5h.
The present invention also provides a kind of Graphene, and this Graphene adopts above-mentioned preparation method to make.
The present invention also provides a kind of electrode slice, comprises collector, and is coated in the active material of described collection liquid surface; This active material comprises the above-mentioned Graphene making, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor; The mass ratio of Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor is 88: 10: 2.
The present invention also provides a kind of ultracapacitor, and its electrode adopts above-mentioned electrode slice.
The preparation method of Graphene provided by the invention, adopts NaOH to activate the Graphene obtaining, and micropore size distribution is concentrated, pore structure is controlled, tap density is large; After NaOH activation, the specific surface area of Graphene can reach 1000～1500m
2/ g, is greater than the specific surface area～900m of general thermal reduction Graphene
2/ g; Made Graphene, as electrode material for electric double layer capacitor, has excellent volumetric capacitance.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of Graphene of the present invention.
Embodiment
The preparation method of Graphene provided by the invention, as shown in Figure 1, its process flow steps is as follows:
S1, by the graphite oxide ultrasonic dispersion 1～5h that is added to the water, obtaining concentration is the graphene oxide suspension of 1～20mg/ml;
S2, the NaOH solution that is 1～500g/L by concentration join in described graphene oxide suspension, stir 1～5h, obtain the mixing solutions of NaOH and graphene oxide; Wherein, in the mixing solutions of described NaOH and graphene oxide, the mass ratio of NaOH and graphene oxide is 1～50: 1;
S3, the mixing solutions that step S2 is obtained filter, screening is placed in 60～80 ℃ of drying treatment 24～48h, again dried screening is put into retort furnace, and under inert atmosphere (preferably argon atmosphere), in 800～1200 ℃ high-temperature calcination 1～5h, cooling after, washing, filter, the dry Graphene that obtains.
The preparation method of Graphene provided by the invention, adopts NaOH to activate the Graphene obtaining, and micropore size distribution is concentrated, pore structure is controlled, tap density is large; After NaOH activation, the specific surface area of Graphene can reach 1000～1500m
2/ g, is greater than the specific surface area～900m of general thermal reduction Graphene
2/ g; Made Graphene, as electrode material for electric double layer capacitor, has excellent volumetric capacitance.
Below the making method of ultracapacitor:
1, prepare electrode slice
First, the ratio that is 88: 10: 2 according to mass ratio, selects the above-mentioned Graphene making, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor to mix, and obtains gel slurry;
Secondly, by gel slurry be coated in collector (as, aluminium foil, nickel foil, nickel screen, Copper Foil, preferably aluminium foil) upper, drying, roll film, trimming processing, make electrode slice.
2, prepare ultracapacitor
Select two of the above-mentioned electrode slices making, respectively as positive plate and negative plate; Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses battery housing seal battery core, injects electrolytic solution subsequently by the spout being arranged on battery container in battery container, and sealing spout, obtains ultracapacitor;
Wherein, electrolytic solution adopts BMIMBF
4, EMIMTFSI plasma liquid, also can adopt conventional electrolytic solution TEABF
4/ AN.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
(1) 1g graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1h, forming concentration is 1mg/ml graphene oxide suspension,
(2) the NaOH solution that compound concentration is 1g/L, joins NaOH solution in above-mentioned graphene oxide suspension, stirs 1h, obtains the mixing solutions of NaOH and graphene oxide, and wherein the mass ratio of NaOH and graphene oxide is 1: 1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 60 ℃ of dry 48h, again dried screening is put into retort furnace, 800 ℃ of reaction 5h, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 2
(1) 20g graphite oxide is added to the water to formation suspension, ultrasonic dispersion 5h, forming concentration is 20mg/ml graphene oxide suspension,
(2) the NaOH solution that compound concentration is 500g/L, joins NaOH solution in above-mentioned graphene oxide suspension, stirs 5h, obtains the mixing solutions of NaOH and graphene oxide, and wherein the mass ratio of NaOH and graphene oxide is 50: 1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 80 ℃ of dry 24h, again dried screening is put into retort furnace, 1200 ℃ of reaction 1h, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 3
(1) 10g graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1h, forming concentration is 10mg/ml graphene oxide suspension,
(2) the NaOH solution that compound concentration is 100g/L, joins NaOH solution in above-mentioned graphene oxide suspension, stirs 2h, obtains the mixing solutions of NaOH and graphene oxide, and wherein the mass ratio of NaOH and graphene oxide is 10: 1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 70 ℃ of dry 36h, again dried screening is put into retort furnace, 900 ℃ of reaction 4h, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 4
(1) 5g graphite oxide is added to the water to formation suspension, ultrasonic dispersion 2h, forming concentration is 5mg/ml graphene oxide suspension,
(2) the NaOH solution that compound concentration is 300g/L, joins NaOH solution in above-mentioned graphene oxide suspension, stirs 3h, obtains the mixing solutions of NaOH and graphene oxide, and wherein the mass ratio of NaOH and graphene oxide is 30: 1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 75 ℃ of dry 30h, again dried screening is put into retort furnace, 1000 ℃ of reaction 3h, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
The Graphene of embodiment 1～4 preparation is tested to the specific surface area obtaining by BET as shown in table 1:
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The specific surface area m of Graphene 2/g | 1000 | 1500 | 1400 | 1300 |
Graphene specific surface area prepared by conventional thermal reduction method is～900m
2/ g, as shown in Table 1, the present invention obtains Graphene specific surface area and has substantially exceeded ordinary method.
Embodiment 5～8th, the Graphene of preparing using embodiment 1～4 is respectively as the application of the active material of super capacitor electrode slice.
Embodiment 5
1, prepare super capacitor electrode slice
First, select Graphene prepared by embodiment 1 active material as electrode slice;
Secondly, the ratio that is 88: 10: 2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor are mixed, obtain slurry;
Finally, slurry is coated on aluminium foil, drying, roll film, trimming processing, make the pole piece of ultracapacitor.
2, the assembling of ultracapacitor
Get above-mentioned two plate electrode sheets, respectively as positive, negative electrode plate, dress up battery core according to the order stack of laminations of pole piece, barrier film, negative plate, then use battery housing seal battery core, in battery container, inject BMIMBF by the spout being arranged on battery container subsequently
4il electrolyte, sealing spout, obtains ultracapacitor.
Embodiment 6
1, prepare super capacitor electrode slice
First, select Graphene prepared by embodiment 2 active material as electrode slice;
Secondly, the ratio that is 88: 10: 2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor are mixed, obtain slurry;
Finally, slurry is coated on aluminium foil, drying, roll film, trimming processing, make the pole piece of ultracapacitor.
2, the assembling of ultracapacitor
Get above-mentioned two plate electrode sheets, respectively as positive, negative electrode plate, order stack of laminations according to pole piece, barrier film, negative plate is dressed up battery core, use again battery housing seal battery core, in battery container, inject EMIMTFSI il electrolyte by the spout being arranged on battery container subsequently, sealing spout, obtains ultracapacitor.
Embodiment 7
1, prepare super capacitor electrode slice
First, select Graphene prepared by embodiment 3 active material as electrode slice;
Secondly, the ratio that is 88: 10: 2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor are mixed, obtain slurry;
Finally, slurry is coated on aluminium foil, drying, roll film, trimming processing, make the pole piece of ultracapacitor.
2, the assembling of ultracapacitor
Get above-mentioned two plate electrode sheets, respectively as positive, negative electrode plate, dress up battery core according to the order stack of laminations of pole piece, barrier film, negative plate, then use battery housing seal battery core, in battery container, inject TEABF by the spout being arranged on battery container subsequently
4/ AN electrolytic solution, sealing spout, obtains ultracapacitor.
Embodiment 8
1, prepare super capacitor electrode slice
First, select Graphene prepared by embodiment 4 active material as electrode slice;
Secondly, the ratio that is 88: 10: 2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor are mixed, obtain slurry;
Finally, slurry is coated on aluminium foil, drying, roll film, trimming processing, make the pole piece of ultracapacitor.
2, the assembling of ultracapacitor
Get above-mentioned two plate electrode sheets, respectively as positive, negative electrode plate, dress up battery core according to the order stack of laminations of pole piece, barrier film, negative plate, then use battery housing seal battery core, in battery container, inject TEABF by the spout being arranged on battery container subsequently
4/ AN electrolytic solution, sealing spout, obtains ultracapacitor.
The charge-discharge test volumetric capacitance that embodiment 5～8 is made to ultracapacitor, result is as shown in table 2:
Table 2
| ? | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Volumetric capacitance F/cm 3 | 91 | 108 | 95 | 99 |
The Graphene capacity activating with KOH is separately at 60F/cm
3left and right; As shown in Table 2, the Graphene volumetric capacitance that prepared by the present invention exceedes 90F/cm
3, capacity has had large increase.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for Graphene, is characterized in that, comprises the steps:
By the graphite oxide ultrasonic dispersion treatment that is added to the water, obtaining concentration is the graphene oxide suspension of 1～20mg/ml;
The NaOH solution that is 1～500g/L by concentration joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of NaOH and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening is carried out to drying treatment, more dried screening is put into retort furnace and under inert atmosphere, carry out high-temperature calcination, cooling after, washing, filter, dry, obtain described Graphene.
2. the preparation method of Graphene according to claim 1, is characterized in that, the described ultrasonic dispersion treatment time is 1～5h.
3. the preparation method of Graphene according to claim 1, is characterized in that, in the mixing solutions of described NaOH and graphene oxide, the mass ratio of NaOH and graphene oxide is 1～50: 1.
4. the preparation method of Graphene according to claim 1, is characterized in that, in described drying treatment process, drying treatment temperature is 60～80 ℃, and the drying treatment time is 24～48h.
5. the preparation method of Graphene according to claim 1, is characterized in that, when described high-temperature calcination, temperature is 800～1200 ℃, and calcination time is 1～5h.
6. a Graphene, is characterized in that, this Graphene adopts the arbitrary described preparation method of claim 1～5 to make.
7. an electrode slice, comprises collector, and is coated in the active material of described collection liquid surface; It is characterized in that, described active material comprises Graphene claimed in claim 6, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor; The mass ratio of described Graphene, polyvinylidene difluoride (PVDF) binding agent and acetylene black conductor is 88: 10: 2.
8. a ultracapacitor, is characterized in that, comprises electrode slice claimed in claim 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105869924A (en) * | 2016-05-06 | 2016-08-17 | 清华大学深圳研究生院 | Preparation method of graphene-based thick and dense electrode |
| CN107244668A (en) * | 2017-05-31 | 2017-10-13 | 武汉大学 | A kind of high density high electrochemical specific volume graphene and its preparation method and application |
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| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| CN102509639A (en) * | 2011-11-28 | 2012-06-20 | 深圳市贝特瑞纳米科技有限公司 | Super-capacitor |
| CN102723211A (en) * | 2012-05-08 | 2012-10-10 | 海博瑞恩电子科技无锡有限公司 | High performance super capacitor and manufacturing process thereof |
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2012
- 2012-11-23 CN CN201210480794.7A patent/CN103833010A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102509639A (en) * | 2011-11-28 | 2012-06-20 | 深圳市贝特瑞纳米科技有限公司 | Super-capacitor |
| CN102723211A (en) * | 2012-05-08 | 2012-10-10 | 海博瑞恩电子科技无锡有限公司 | High performance super capacitor and manufacturing process thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105869924A (en) * | 2016-05-06 | 2016-08-17 | 清华大学深圳研究生院 | Preparation method of graphene-based thick and dense electrode |
| CN107244668A (en) * | 2017-05-31 | 2017-10-13 | 武汉大学 | A kind of high density high electrochemical specific volume graphene and its preparation method and application |
| CN107244668B (en) * | 2017-05-31 | 2019-04-12 | 武汉大学 | A kind of high density high electrochemical specific volume graphene and its preparation method and application |
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