CN104882297B - Process for preparing stretchable supercapacitor based on highly conductive graphene/nickel particle mixed structure - Google Patents

Process for preparing stretchable supercapacitor based on highly conductive graphene/nickel particle mixed structure Download PDF

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Publication number
CN104882297B
CN104882297B CN201510165881.7A CN201510165881A CN104882297B CN 104882297 B CN104882297 B CN 104882297B CN 201510165881 A CN201510165881 A CN 201510165881A CN 104882297 B CN104882297 B CN 104882297B
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graphene
mixed structure
particle mixed
nickel particle
stretchable
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CN104882297A (en
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杨诚
毕懿卿
路婧
张超
满宝元
姜守振
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Shandong Normal University
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Shandong Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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

Abstract

The invention relates to a process for preparing a stretchable supercapacitor based on a highly conductive graphene/nickel particle mixed structure. Firstly, a chemical vapor deposition method is used for preparing spongy graphene material on a nickel foam, and the prepared graphene/nickel foam are immersed in an etching solution for slow reaction so that most of the nickel metal can be chemically displaced into various small nickel particles; secondly, the spongy graphene/nickel particle mixed structure is fished out from the etching solution by using a seal-type fishing method, cleaned and dried, and a pre-stretched elastic substrate slowly returns back to the original length or area; and thirdly, the prepared stretchable graphene/nickel particle mixed structure is used as electrode material, and an all-solid-state stretchable supercapacitor is prepared according to the elastomer/electrode/solid electrolyte/electrode/elastomer structure. According to the invention, the capacitance of a conventional capacitor is increased, contact resistance is reduced, the stretching stability, frequency and performance are excellent, the cost is low, and the method is controllable and suitable for mass production.

Description

A kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure The preparation method of device
Technical field
The present invention relates to a kind of preparation method of stretchable capacitor, and in particular to a kind of high connductivity spongy graphene/ The preparation method of the stretchable ultracapacitor of nickel particle mixing nanostructured, belongs to capacitor technology field.
Background technology
Used as current new electronic equipment, stretchable electronic installation still is able in the case where larger mechanical stress is born Represent good electric property, at aspects such as human body implanted device, flexible portable's equipment, wearable device, wire-less inductive devices Tool has been widely used.To realize its independent driving force, develop the energy storage device (such as ultracapacitor) of tensility particularly It is important.However, the progress of correlation is more slow, main cause is the stretchable electrode material of excellent electricity and chemical property Preparing for material is relatively difficult.
Three-dimensional sponge shape Graphene has the excellent electrical properties of two-dimensional graphene, at the same have bigger specific surface area and More excellent pliability, the distortion of general level does not interfere with the property and characteristic of material, is conducive to preparing energy storage greatly, surely Qualitative good flexible super capacitor.Flexible 3 D spongy graphene is transferred in the elastic substrate of pre-stretching, is formed soft The self-assembled structures of property, in stretching-contraction process, its basic structure will not be destroyed, and make it have Ultra-Drawing performance, phase More common Graphene, it is flexible more preferably, and elasticity is bigger, and its electricity and chemical property are held essentially constant afterwards before the stretching, This is of great significance to preparing stretchable conductive material and its ultracapacitor tool.
On the other hand, the resistance between external conductor and active electrode material has a strong impact on the performance and reality of ultracapacitor Apply on border.Because Activated Graphite alkene electrode material is larger with the contact resistance of external conductor, single three-dimensional sponge shape Graphene There is defect as compliant conductive electrode.This project studies the flexible electrode of new three-dimensional grapheme/nickel particle mixed structure Material, itself had both played active electrode material effect, flexible current-collecting body was played a part of again, the contact resistance with external conductor It is smaller.Importantly, due to the flexibility and foldability of three-dimensional grapheme, flexible graphene/nickel particle mixed structure can To be transformed into the stretchable electrode material of periodicity gauffer, so as to have Ultra-Drawing performance.This can draw for it in high-performance A new path is opened in the application for stretching ultracapacitor, to promoting the further development of stretchable ultracapacitor and extensively should With with important effect.
This problem is conceived to the practical application of the aspects such as flexible portable's equipment, stretchable electronic installation, new by preparing The flexible electrode material of three-dimensional grapheme/nickel particle foaming structure realize the preparation and application of stretchable ultracapacitor. The research of this problem can not only realize the preparation of stretchable ultracapacitor, more can be that the preparation of other stretchable devices is carried It is that the research and development of the new stretchable electronic product of China contribute for a kind of method.
The preparation research of high performance graphene-based active electrode and its stretchable ultracapacitor also has two to need solution badly Problem certainly：1. the preparation process of stretchable graphene-based active material is complicated, and preparation cost is also higher.Most of preparation method Be required for the multi step strategy under the conditions of higher temperature, higher vacuum etc., it is necessary to preparation time it is more long, much also need to utilize Complicated wet method or dry method transfer process；2. the contact resistance of independent Graphene and external wire is too big, influences ultracapacitor Performance.Under normal circumstances, in order to preferably derive the electric current of active electrode, during ultracapacitor is prepared, also Need one layer of collector (nickel foam is a kind of collector of conventional ultracapacitor).However, nickel foam can not be stretched, nothing Method is directly applied in stretchable ultracapacitor.If not using collector, due to Graphene and the external conductor of derived current Contact resistance it is larger, influence the performance of stretchable ultracapacitor.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, and provides a kind of mixed based on high connductivity graphene/nickel particle Close the preparation method of the stretchable ultracapacitor of structure.
The technical scheme that the present invention takes is：
A kind of preparation method of the stretchable ultracapacitor based on high connductivity graphene/nickel particle mixed structure, including Step is as follows：
(1) chemical gaseous phase depositing process prepares spongy graphene material in nickel foam
Nickel foam is put into vacuum reaction stove heating region, is vacuumized, while heating, by hydrogen injection vacuum reaction stove In, then annealed within constant temperature 10-30 minutes after being heated to 100-500 DEG C of predetermined temperature, it is heated to predetermined temperature 900- After 1100 DEG C, carbon source is passed through vacuum reaction stove, while keeping hydrogen flowing quantity constant, growth closes gas simultaneously after 5-180 minutes It is down to the substrate that room temperature can obtain Direct precipitation Graphene, i.e. graphene/nickel；
(2) preparation and its transfer of stretchable graphene/nickel particle mixed structure
Graphene/the nickel foam of preparation is immersed in etching solution, slow reaction, most of nickel foam is put by chemistry Change, nickel foam is transformed into metallic particles small one by one, then by spongy graphene/nickel particle mixed structure from etching Pulled out with the seal style method of dragging in solution, respectively in acetone, alcohol and deionized water clean, after pre-stretched elastic substrate is sticked On hollow stent, drag for method with same seal style and shift on pre-stretched elastic substrate, dry naturally, substrate pre-stretching is edge One direction is stretched to 1.5 to 4 times of original length, or is stretched to 2 to 10 times of original area along two orthogonal directions； Then the pre-stretched elastic substrate of covering Flexible graphene/nickel particle mixed structure is allowed slowly to return to the original length or face Product, prepares a kind of stretchable graphene/nickel particle mixed structure of self assembly gauffer；
(3) preparation of all solid state stretchable ultracapacitor
By the use of prepare stretchable graphene/nickel particle mixed structure as electrode material, Gu according to elastomer/electrode/ The structure of body electrolyte/electrode/elastomer prepares all solid state stretchable ultracapacitor.
In above-mentioned preparation method,
The size of nickel foam described in step (1) is 1cm × 1cm-30cm × 30cm.The carbon source be methane, acetylene, One or several in ethene.In 1-300sccm, purity is higher than 99.99% for the flow control of the carbon source；The hydrogen In 1-100sccm, purity is higher than 99.99% for flow control.The vacuum reaction stove evacuation degree is 3 × 10-3-3×10- 6Torr, to remove the active gases in furnace chamber, keeps the growing environment of cleaning.Described annealing refers to dispelling substrate surface Except the process of the magazines such as oxide.After obtaining the substrate of Direct precipitation Graphene, carbon-source gas valve is closed, keep hydrogen flowing quantity Constant cooling, takes out the Graphene of deposition afterwards.
The method for taking out backing material is to wait after vacuum reaction furnace temperature drops to room temperature, closes hydrogen gas valve, true Empty pump, an atmospheric pressure state is filled to air by furnace cavity is reacted, and then takes out backing material.The Graphene of preparation/ The number of plies of Graphene is 1-10 layers in foam metal.
Etching solution described in step (2) is iron chloride or iron nitrate solution, and the solution concentration is 0.5-5mol/ L；The elastic substrate is the elastic substrates such as PMMA, PDFS；The chemical replacement reaction time is 15-1000 minutes, reaction temperature Spend is 10-50 degrees Celsius；
The seal style method of dragging for is specially：Spongy graphene/metallic particles mixed structure is covered in flexible substrate On, then light pressure 10-30 seconds is slowly gently lifted from a side of substrate, is connect using small between Graphene and substrate Touch, graphene substrate is pulled out.
Elastomer described in step (3) is the elastomers such as PMMA, PDFS；The solid electrolyte be PVA- acid, alkali or in Property electrolyte；The nickel particle size is 10-500nm；The nickel particle content ratio is 0%-50%.
Using the degree of electrochemical workstation test pre-stretching, the number of repetition of stretching-contraction and speed to super electricity The influence of container relevant nature (capacitance, capacitor cycle life-span, electrical impedance etc.)；Different graphene/nickel particles are prepared to contain The stretchable conductive film of amount ratio, and it is assembled into all solid state stretchable ultracapacitor.
Elastomer/electrode/solid electrolyte/electrode/elastomer structure (Gu i.e. elastomer/graphene-based active material/ The structure of body electrolyte/graphene-based active material/elastomer) preparation method include step it is as follows：
1) electrode, referred to as A ends are prepared in one end of two graphene/nickel particle mixed structures respectively；
2) each its one end for not preparing electrode of graphene/nickel particle mixed structure coat large area PVA- acid, alkali or Neutral electrolyte, referred to as B ends；
3) two B ends of graphene/nickel particle mixed structure are overlapped into covering, connects the part large area for scribbling electrolyte Touch, it is pasted together；
4) clinged using PMMA or PDFS.
Wherein, step 1) method for preparing electrode has two kinds：First, directly using adhesive tape or glue by stretchable conduction The disconnected periphery for sticking at graphene/nickel particle mixed structure of material；
Described stretchable conductive material includes stretchable conductive carbon fibre, conductive carbon nanotube fiber, conductive graphene The stretchable fiber electrode such as fiber；Notice that electrode material is not connected with PVA- acid, alkali or neutral electrolyte.
The second is not connected in one end deposition of stretchable graphene/nickel particle mixed structure directly using depositing device Electrode material, specifically include following preparation process：
(1) graphene/nickel particle mixed structure is put into low temperature depositing system；
(2) preparing two ends has the shutter of rectangle sky bar, is placed in the top of graphene/nickel particle mixed structure, notes Mixed structure can not be contacted, in order to avoid damage the gas sensitive for preparing；
(3) disconnected metal electrode is deposited at graphene/nickel particle mixed structure two ends using depositing device；Note electricity Pole material is not connected with PVA- acid, alkali or neutral electrolyte.
The depositing device low temperature depositing system such as including magnetron sputtering deposition system, evaporator, impulse laser deposition system System；
The electrode material metal material such as including copper, iron, silver, platinum.
The present invention utilizes the collector-nickel foam of ultracapacitor, it is proposed that a kind of novel flexible three-dimensional sponge shape graphite The preparation method of the electrode material of alkene/nickel particle mixed structure；Using a kind of Ultra-Drawing performance (tensile elongation is more than 300%) Electrode preparation method, prepare it is stretchable have concurrently active electrode and collector effect mixed structure；Using electrode/electro solution The sandwich structure of matter/electrode, the excellent all solid state stretchable ultracapacitor of processability.
The beneficial effects of the invention are as follows：
1) spongy graphene growth temperature precise control；
2) the Graphene defect peak of growth is low, with high crystal mass；
3) the graphene/nickel particle of growth has fabulous electrical conductivity；
4) the Graphene size of growth is only limited by CVD cavitys, is capable of achieving the large area deposition of Graphene；
5) PMMA glue need not be used in wet method transfer process, it is time saving and energy saving；
6) transfer process is shifted using seal style, and Graphene will not any drift in the solution, it is to avoid stone in transfer process Black alkene
Damage, process is simple and easy to apply.
7) with low cost, method is simply controllable, is suitable to produce in enormous quantities, and application value is high.
Brief description of the drawings
Fig. 1 is the syntheti c route figure of stretchable graphene/nickel particle mixed electrode；
Fig. 2 is the SEM patterns of stretchable electrode；(correspondence embodiment 1)
Fig. 3 is the C-V cyclic curves for preparing stretchable ultracapacitor.(correspondence embodiment 1)
Specific embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing.
Embodiment 1
1. size is taken for 8cm × 8cm nickel foams are placed in tube furnace；
2. open vavuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
3. vacuum state 3 × 10 is kept-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
5. after tubular type furnace temperature is warmed up to 300 DEG C, constant temperature is annealed for 20 minutes；
6. after tubular type furnace temperature is warmed up to 1000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as 200sccm, stop is grown for 30 minutes；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with the speed of 50 DEG C/min；
8. hydrogen flowmeter and vavuum pump are closed；
9. valve is opened, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. quartz ampoule vacuum interface is opened, the nickel foam of deposited graphite alkene is taken out；
11. by FeCl3Dissolved in adding deionized water according to certain mass, prepare certain density etching solution FeCl3 (4.5mol/L)；
12. Graphene/the nickel foams for preparing are immersed in 20 DEG C of FeCl3140 minutes in (4.5mol/L) solution；
The pattern of 13. observation Graphene/nickel foams, until its structure becomes Flexible graphene/nickel particle mixed structure；
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface by 14., light pressure 25 seconds；
15. slowly gently lift from substrate side, using the small contact force between Graphene and substrate, by stone Black alkene nickel particle mixed structure is pulled out；
16. are respectively washed spongy graphene acetone, ethanol and deionized water 3 minutes；
17. 1.5 to 4 times that PDFS elastic substrates are stretched to original length in one direction, or it is orthogonal along two Direction is stretched to 2 to 10 times of original area；
18. will paste on empty support in a circle in the elastic substrate after stretching；
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface by 19., gently presses 20 Second；
20. slowly gently lift from substrate side, using between Graphene nickel particle mixed structure and substrate Small contact force, graphene/nickel particle mixed structure is pulled out；
21. dry in the air 3 hours in vacuum drying chamber；
22. elastic substrates that graphene/nickel particle mixed structure is will be covered with from hollow circle or square set take Under, side is sticked on support；
23. in vacuum drying chamber clear-cutting forestland 5 hours, it is returned to original size, it is a kind of from group to prepare according to this Fill the stretchable graphene/nickel particle mixed structure of gauffer.
24. are sticked at stretchable conductive carbon fibre is disconnected two graphene/nickel particles and mixed respectively with adhesive tape or glue Close one end of structure；
25. coat the PVA- acid of large area in its one end for not pasting stretchable conductive carbon fibre, note PVA- acid and lead Electric fiber is not connected；
26. by two graphene/nickel particle mixed structures scribble PVA- acid one end overlap covering, make its be in contact so as to Paste together；
27. are clinged contact jaw using PMMA or PDFS.
Embodiment 2
Graphene/nickel particle mixed structure in nickel foam Grown Graphene and is finally grown, so as to prepare to draw Stretch capacitor, including following preparation process
1. size is taken for 8cm × 9cm nickel foams are placed in tube furnace；
2. open vavuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
3. vacuum state 3 × 10 is kept-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
5. after tubular type furnace temperature is warmed up to 300 DEG C, constant temperature is annealed for 20 minutes；
6. after tubular type furnace temperature is warmed up to 1000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as 200sccm, stop is grown for 40 minutes；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with the speed of 60 DEG C/min；
8. hydrogen flowmeter and vavuum pump are closed；
9. valve is opened, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. quartz ampoule vacuum interface is opened, the nickel foam of deposited graphite alkene is taken out；
11. by FeCl3Dissolved in adding deionized water according to certain mass, prepare certain density etching solution FeCl3 (0.5mol/L)；
12. Graphene/the nickel foams for preparing are immersed in 40 DEG C of FeCl3150 minutes in (0.5mol/L) solution；
The pattern of 13. observation Graphene/nickel foams, until its structure becomes Flexible graphene/nickel particle mixed structure；
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface by 14., light pressure 15 seconds；
15. slowly gently lift from substrate side, using the small contact force between Graphene and substrate, by stone Black alkene nickel particle mixed structure is pulled out；
16. are respectively washed spongy graphene acetone, ethanol and deionized water 3 minutes；
17. 5 times that PDFS elastic substrates are stretched to original area along two orthogonal directions；
18. will paste on hollow square support in the elastic substrate after stretching；
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface by 19., gently presses 30 Second；
20. slowly gently lift from substrate side, using between Graphene nickel particle mixed structure and substrate Small contact force, graphene/nickel particle mixed structure is pulled out；
21. dry in the air 3 hours in vacuum drying chamber；
22. elastic substrates that graphene/nickel particle mixed structure is will be covered with from square set are removed, and side sticks at branch On frame；
23. clear-cutting forestland 3-5 hours in vacuum drying chamber, it is returned to original size, according to this come prepare it is a kind of from Assemble the stretchable graphene/nickel particle mixed structure of gauffer.
24. are put into low temperature depositing system graphene/nickel particle mixed structure；
There is the shutter of rectangle sky bar at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, gauffer Stretchable graphene/nickel particle mixed structure.
26. copper electrodes for depositing not UNICOM two one end of graphene/nickel particle mixed structure respectively using evaporator.
27. coat the PVA- acid of large area in one end of its non-depositing electrode, notice that PVA- acid is not connected with copper electrode；
28. by two graphene/nickel particle mixed structures scribble PVA- acid one end overlap covering, make its be in contact so as to Paste together；
29. are clinged overlapping part using PMMA.
Embodiment 3
Graphene/nickel particle mixed structure is grown in nickel foam Grown Graphene and finally, preparing high connductivity can Stretching capacitor, including following preparation process：
1. size is taken for 5cm × 9cm nickel foams are placed in tube furnace；
2. open vavuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
3. vacuum state 3 × 10 is kept-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
5. after tubular type furnace temperature is warmed up to 300 DEG C, constant temperature is annealed for 20 minutes；
6. after tubular type furnace temperature is warmed up to 1000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as 200sccm, stop is grown for 40 minutes；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with the speed of 30-60 DEG C/min；
8. hydrogen flowmeter and vavuum pump are closed；
9. valve is opened, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. quartz ampoule vacuum interface is opened, the nickel foam of deposited graphite alkene is taken out；
11. by FeCl3Dissolved in adding deionized water according to certain mass, prepare certain density etching solution FeCl3 (4mol/L)；
12. Graphene/the nickel foams for preparing are immersed in 27 DEG C of FeCl3150 minutes in (4mol/L) solution；
The pattern of 13. observation Graphene/nickel foams, until its structure becomes Flexible graphene/nickel particle mixed structure；
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface by 14., light pressure 15 seconds；
15. slowly gently lift from substrate side, using the small contact force between Graphene and substrate, by stone Black alkene nickel particle mixed structure is pulled out；
16. are respectively washed spongy graphene acetone, ethanol and deionized water 3 minutes；
17. 8 times that PMMA elastic substrates are stretched to original area along two orthogonal directions；
18. will paste on hollow square support in the elastic substrate after stretching；
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface by 19., gently presses 30 Second；
20. slowly gently lift from substrate side, using between Graphene nickel particle mixed structure and substrate Small contact force, graphene/nickel particle mixed structure is pulled out；
21. dry in the air 3 hours in vacuum drying chamber；
22. elastic substrates that graphene/nickel particle mixed structure is will be covered with from square set are removed, and side sticks at branch On frame；
23. clear-cutting forestland 3-5 hours in vacuum drying chamber, it is returned to original size, according to this come prepare it is a kind of from Assemble the stretchable graphene/nickel particle mixed structure of gauffer.
24. are put into low temperature depositing system graphene/nickel particle mixed structure；
There is the shutter of rectangle sky bar at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, but not Mixed structure can be contacted, in order to avoid damage the gas sensitive for preparing；
26. finally using impulse laser deposition system respectively in two one end depositions of graphene/nickel particle mixed structure The not silver electrode of UNICOM.
27. coat the PVA- alkali of large area in the one end for not depositing silver electrode, notice that PVA- alkali is not connected with silver electrode；
28. by two graphene/nickel particle mixed structures scribble PVA- alkali one end overlap covering, make its be in contact so as to Paste together；
29. are clinged lap using glue.
Embodiment 4
Graphene/nickel particle mixed structure in nickel foam Grown Graphene and is finally grown, so as to prepare to draw Stretching ultracapacitor includes following preparation process：
1. size is taken for 7cm × 7cm nickel foams are placed in tube furnace；
2. open vavuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
3. vacuum state 3 × 10 is kept-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
5. after tubular type furnace temperature is warmed up to 300 DEG C, constant temperature is annealed for 20 minutes；
6. after tubular type furnace temperature is warmed up to 1000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as 200sccm, stop is grown for 35 minutes；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with the speed of 30-60 DEG C/min；
8. hydrogen flowmeter and vavuum pump are closed；
9. valve is opened, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. quartz ampoule vacuum interface is opened, the nickel foam of deposited graphite alkene is taken out；
11. by FeCl3Dissolved in adding deionized water according to certain mass, prepare certain density etching solution FeCl3 (1mol/L)；
12. Graphene/the nickel foams for preparing are immersed in 35 DEG C of FeCl3190 minutes in (1mol/L) solution；
The pattern of 13. observation Graphene/nickel foams, until its structure becomes Flexible graphene/nickel particle mixed structure；
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface by 14., light pressure 15 seconds；
15. slowly gently lift from substrate side, using the small contact force between Graphene and substrate, by stone Black alkene nickel particle mixed structure is pulled out；
16. are respectively washed spongy graphene acetone, ethanol and deionized water 3 minutes；
17. 2.5 times that PMMA elastic substrates are stretched to original length in one direction；
18. will paste on hollow circular support in the elastic substrate after stretching；
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface by 19., gently presses 30 Second；
20. slowly gently lift from substrate side, using between Graphene nickel particle mixed structure and substrate Small contact force, graphene/nickel particle mixed structure is pulled out；
21. dry in the air 3 hours in vacuum drying chamber；
22. elastic substrates that graphene/nickel particle mixed structure is will be covered with from hollow circle are removed, and side sticks at On support；
23. clear-cutting forestland 3-5 hours in vacuum drying chamber, it is returned to original size, according to this come prepare it is a kind of from Assemble the stretchable graphene/nickel particle mixed structure of gauffer.
24. are put into low temperature depositing system graphene/nickel particle mixed structure；
There is the shutter of rectangle sky bar at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, but not Mixed structure can be contacted, in order to avoid damage the stretchable graphene/nickel particle mixed structure of gauffer.
26. are not joined in one end deposition of two graphene/nickel particle mixed structures respectively using magnetron sputtering deposition system Logical platinum electrode；
27. coat the PVA- alkali of large area in one end of non-depositing electrode, notice that PVA- alkali is not connected with platinum electrode；
28. by two graphene/nickel particle mixed structures scribble PVA- alkali one end overlap covering, make its be in contact so as to Paste together；
29. are clinged using PMMA.
Embodiment 5
In nickel foam Grown Graphene and graphene/nickel particle mixed structure is grown, can so as to prepare high connductivity Stretching ultracapacitor, including following preparation process
1. size is taken for 6cm × 8cm nickel foams are placed in tube furnace；
2. open vavuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
3. vacuum state 3 × 10 is kept-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
5. after tubular type furnace temperature is warmed up to 300 DEG C, constant temperature is annealed for 20 minutes；
6. after tubular type furnace temperature is warmed up to 1000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as 200sccm, stop is grown for 30 minutes；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with the speed of 30-60 DEG C/min；
8. hydrogen flowmeter and vavuum pump are closed；
9. valve is opened, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. quartz ampoule vacuum interface is opened, the nickel foam of deposited graphite alkene is taken out；
11. by FeCl3Dissolved in adding deionized water according to certain mass, prepare certain density etching solution FeCl3 (3mol/L)；
12. Graphene/the nickel foams for preparing are immersed in 30 DEG C of FeCl3150 minutes in (3mol/L) solution；
The pattern of 13. observation Graphene/nickel foams, until its structure becomes Flexible graphene/nickel particle mixed structure；
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface by 14., light pressure 20 seconds；
15. slowly gently lift from substrate side, using the small contact force between Graphene and substrate, by stone Black alkene nickel particle mixed structure is pulled out；
16. are respectively washed spongy graphene acetone, ethanol and deionized water 4 minutes；
17. 1.5 to 4 times that PDFS elastic substrates are stretched to original length in one direction, or it is orthogonal along two Direction is stretched to 2 to 10 times of original area；
18. will paste on hollow stent in the elastic substrate after stretching；
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface by 19., gently presses 20 Second；
20. slowly gently lift from substrate side, using between Graphene nickel particle mixed structure and substrate Small contact force, graphene/nickel particle mixed structure is pulled out；
21. dry in the air 3 hours in vacuum drying chamber；
22. elastic substrates that graphene/nickel particle mixed structure is will be covered with from hollow circle or square set take Under, side is sticked on support；
23. in vacuum drying chamber clear-cutting forestland 4 hours, it is returned to original size, it is a kind of from group to prepare according to this Fill the stretchable graphene/nickel particle mixed structure of gauffer.
24. stick at two graphene/nickels by stretchable conductive graphene fiber is disconnected respectively with adhesive tape or glue One end of grain mixed structure.
25. coat the PVA- alkali of large area in the one end for not pasting graphene fiber, notice that PVA- alkali is fine with graphene Dimension is not connected；
26. by two graphene/nickel particle mixed structures scribble PVA- alkali one end overlap covering, make its be in contact so as to Paste together；
27. are clinged overlapping ends using glue.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this hair is not limited to Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it is still Technical scheme described in previous embodiment can be modified, or equivalent is carried out to which part.It is all in this hair Within bright spirit and principle, any modification, equivalent substitution and improvements made etc. should be included in protection scope of the present invention Within.

Claims (11)

1. a kind of preparation method of the stretchable ultracapacitor based on high connductivity graphene/nickel particle mixed structure, its feature It is, including step is as follows：
（One）Chemical gaseous phase depositing process prepares spongy graphene material in nickel foam：Nickel foam is put into vacuum reaction stove In heating region, vacuumize, while heating, by hydrogen injection vacuum reaction stove, is heated to constant temperature after 100-500 DEG C of predetermined temperature Then annealed within 10-30 minutes, after being heated to 900-1100 DEG C of predetermined temperature, carbon source is passed through vacuum reaction stove, while Keep hydrogen flowing quantity constant, growth is closed gas and is down to the bubble that room temperature can obtain Direct precipitation Graphene after 5-180 minutes Foam nickel, i.e. Graphene/nickel foam；
（Two）The preparation and its transfer of stretchable graphene/nickel particle mixed structure：Graphene/the nickel foam of preparation is immersed in In etching solution, slow reaction makes most of nickel foam be fallen by chemical replacement, is transformed into the nickel foam for having neither part nor lot in displacement reaction Small metallic particles, then drags for method from etching solution by spongy graphene/nickel particle mixed structure with seal style one by one Pull out, cleaned in acetone, alcohol and deionized water respectively, after pre-stretched elastic substrate is sticked on hollow stent, will be described Spongy graphene/nickel particle mixed structure after cleaning drags for method and shifts on pre-stretched elastic substrate with same seal style, Naturally dry, substrate pre-stretching is be stretched to original length in one direction 1.5 to 4 times, or along two orthogonal sides To being stretched to 2 to 10 times of original area；Then the pre-stretched elastic substrate of covering Flexible graphene/nickel particle mixed structure is allowed The original length or area are slowly returned to, a kind of stretchable graphene/nickel particle mixed structure of self assembly gauffer is prepared；
The seal style method of dragging for is specially：It is covered on spongy graphene/metallic particles mixed structure with flexible substrate, gently Pressure 10-30 seconds, then slowly gently lifts from a side of substrate, using the small contact force between Graphene and substrate, Graphene/nickel particle mixed structure is pulled out；
（Three）The preparation of all solid state stretchable ultracapacitor：Made using the stretchable graphene/nickel particle mixed structure for preparing It is electrode material, all solid state stretchable super electricity is prepared according to the structure of elastomer/electrode/solid electrolyte/electrode/elastomer Container.
2. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（One）Described in carbon source be methane, acetylene, ethene in one or several.
3. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（One）Described in carbon source flow control in 1-300sccm, purity is higher than 99.99%； In 1-100sccm, purity is higher than 99.99% for the flow control of the hydrogen.
4. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（One）Described in vacuum reaction stove evacuation degree be 3 × 10-3-3×10-6Torr。
5. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（Two）Described in etching solution be iron chloride or iron nitrate solution, the solution is dense It is 0.5-5mol/L to spend.
6. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（Two）The chemical replacement reaction time is 15-1000 minutes, and reaction temperature is 10- 50 degrees Celsius.
7. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（Three）Described in elastomer be polymer elastomer；The solid electrolyte is PVA- Acid, alkali or neutral electrolyte.
8. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（Three）Described in nickel particle size be 10-500nm；The nickel particle content ratio It is 0%-50%.
9. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1 The preparation method of device, it is characterized in that, step（Three）It is prepared by the structure of elastomer/electrode/solid electrolyte/electrode/elastomer Method includes that step is as follows：
1) electrode, referred to as A ends are prepared in one end of two graphene/nickel particle mixed structures respectively；
2) large area PVA- acid, alkali or neutrality are coated in each its one end for not preparing electrode of graphene/nickel particle mixed structure Electrolyte, referred to as B ends；
3) two B ends of graphene/nickel particle mixed structure are overlapped into covering, make to scribble the part bump contact of electrolyte, It is set to paste together；
4) clinged using PMMA or PDFS elastomers.
10. a kind of stretchable super capacitor based on high connductivity graphene/nickel particle mixed structure according to claim 9 The preparation method of device, it is characterized in that, step 1）The method for preparing electrode has two kinds：First, directly use adhesive tape or glue will The disconnected two ends for sticking at graphene/nickel particle mixed structure periphery substrate of stretchable conductive material；It is described stretchable to lead Electric material is stretchable conductive carbon fibre, and electrode material is not connected with PVA- acid, alkali or neutral electrolyte；The second is using heavy The direct disconnected metal electrode material in one end deposition of stretchable graphene/nickel particle mixed structure of product equipment.
A kind of 11. stretchable super electricity based on high connductivity graphene/nickel particle mixed structure according to claim 10 The preparation method of container, it is characterized in that：The stretchable conductive carbon fibre is that conductive carbon nanotube fiber or conductive graphene are fine Dimension.
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CN105783695A (en) * 2016-04-22 2016-07-20 武汉大学深圳研究院 Graphene composite nano gold thin film flexible strain sensor manufacturing method and strain sensor thereof
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CN106546720B (en) * 2016-10-31 2020-05-05 山东师范大学 Preparation method of three-dimensional graphene/silver nanoflower stretchable biosensor material
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103545121A (en) * 2013-10-23 2014-01-29 南京大学 Supercapacitor electrode material preparation method based on three-dimensional graphene
CN103680974A (en) * 2012-09-14 2014-03-26 海洋王照明科技股份有限公司 Graphene/nickel composite material, preparation method thereof, electrode plate and capacitor
CN103903880A (en) * 2014-03-03 2014-07-02 广东工业大学 Method for in-situ preparation of graphene supercapacitor electrode based on nickel foam

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102093441B1 (en) * 2013-03-11 2020-03-25 삼성전자주식회사 A method for preparing grapheme

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103680974A (en) * 2012-09-14 2014-03-26 海洋王照明科技股份有限公司 Graphene/nickel composite material, preparation method thereof, electrode plate and capacitor
CN103545121A (en) * 2013-10-23 2014-01-29 南京大学 Supercapacitor electrode material preparation method based on three-dimensional graphene
CN103903880A (en) * 2014-03-03 2014-07-02 广东工业大学 Method for in-situ preparation of graphene supercapacitor electrode based on nickel foam

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