CN104882297A - 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 PDFInfo
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- CN104882297A CN104882297A CN201510165881.7A CN201510165881A CN104882297A CN 104882297 A CN104882297 A CN 104882297A CN 201510165881 A CN201510165881 A CN 201510165881A CN 104882297 A CN104882297 A CN 104882297A
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- particle mixed
- mixed structure
- nickel
- nickel particle
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 315
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 173
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 158
- 239000002245 particle Substances 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 239000006260 foam Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007772 electrode material Substances 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000806 elastomer Substances 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 239000013528 metallic particle Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 239000003708 ampul Substances 0.000 description 20
- 239000010453 quartz Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- -1 Activated Graphite alkene Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
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
Technical field
The present invention relates to a kind of preparation method of the capacitor that stretches, be specifically related to the preparation method of the stretched ultracapacitor of a kind of high connductivity spongy graphene/nickel particle mixing nanostructure, belong to capacitor technology field.
Background technology
As electronic equipment novel now, the electronic installation that can stretch still can represent good electric property when bearing larger mechanical stress, and in human body implanted device, flexible portable's equipment, wearable device, wire-less inductive devices etc., tool has been widely used.For realizing its drive ability, the energy storage device (as ultracapacitor) of development tensility is particularly important.But relevant progress is comparatively slow, and main cause is that the preparation of the stretched electrode material of excellent electricity and chemical property is more difficult.
Three-dimensional sponge shape Graphene has the electrical properties of two-dimensional graphene excellence, there are larger specific area and more excellent pliability simultaneously, the distortion of general degree can not have influence on character and the characteristic of material, is conducive to preparing that energy storage is large, the flexible super capacitor of good stability.Flexible 3 D spongy graphene is transferred in the elastic substrate of pre-stretching, form flexible self-assembled structures, in stretching-contraction process, its basic structure can not be destroyed, and makes it have Ultra-Drawing performance, compares common Graphene, it is flexible better, elasticity is larger, its electricity and chemical property before the stretching after substantially remain unchanged, this is of great significance can stretch electric conducting material and ultracapacitor tool thereof of preparation.
On the other hand, the resistance between external conductor and active electrode material has a strong impact on performance and the practical application of ultracapacitor.Because the contact resistance of Activated Graphite alkene electrode material and external conductor is comparatively large, independent three-dimensional sponge shape Graphene has defect as compliant conductive electrode.This project studies the flexible electrode material of novel three-dimensional grapheme/nickel particle mixed structure, and itself had both played active electrode material effect, played again the effect of flexible current-collecting body, less with the contact resistance of external conductor.The more important thing is, due to flexibility and the foldability of three-dimensional grapheme, flexible graphene/nickel particle mixed structure can be transformed into the stretched electrode material of periodically gauffer, thus has Ultra-Drawing performance.This opens a new path for it in can the stretch application of ultracapacitor of high-performance, to the ultracapacitor that promotes to stretch further developing and extensive use has important effect.
This problem is conceived to the practical application of flexible portable's equipment, the aspects such as electronic installation that can stretch, by preparing the flexible electrode material of novel three-dimensional grapheme/nickel particle foam structure, and the Synthesis and applications of the ultracapacitor that realizes stretching.The research of this problem can not only realize stretching the preparation of ultracapacitor, more the preparation of tensile means can provide a kind of method, for the research and development of the new stretchable electronic product of China contribute for other.
The preparation research of high performance graphene-based active electrode and the ultracapacitor that can stretch thereof also has two problems needing solution badly: 1. the preparation process of the graphene-based active material that can stretch is complicated, and preparation cost is also higher.Major part preparation method needs multi step strategy under the condition such as higher temperature, higher vacuum, and the preparation time of needs is longer, much also needs to utilize complicated wet method or dry method transfer process; 2. the contact resistance of Graphene and external wire is too large separately, affects the performance of ultracapacitor.Under normal circumstances, in order to better, the electric current of active electrode is derived, in the process preparing ultracapacitor, also need one deck collector (nickel foam is a kind of collector of conventional ultracapacitor).But nickel foam can not be stretched, directly cannot be applied in and can stretch in ultracapacitor.If do not use collector, because the contact resistance of the external conductor of Graphene and derived current is comparatively large, impact can stretch the performance of ultracapacitor.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and a kind of preparation method of the stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure is provided.
The technical scheme that the present invention takes is:
Based on a preparation method for the stretched ultracapacitor of high connductivity graphene/nickel particle mixed structure, comprise step 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, vacuumize, heat simultaneously, hydrogen is injected vacuum reaction stove, after being heated to predetermined temperature 100-500 DEG C, then constant temperature 10-30 minute anneals, then after being heated to predetermined temperature 900-1100 DEG C, carbon source is passed into vacuum reaction stove, keep hydrogen flowing quantity constant simultaneously, grow and close gas after 5-180 minute and be down to the substrate that room temperature can obtain Direct precipitation Graphene, i.e. graphene/nickel;
(2) can stretch the preparation of graphene/nickel particle mixed structure and transfer thereof
Graphene/the nickel foam of preparation is immersed in etching solution, slow reaction, most of nickel foam is fallen by chemical replacement, nickel foam is made to be transformed into metallic particles little one by one, then spongy graphene/nickel particle mixed structure is pulled out by the seal style method of dragging for from etching solution, respectively at acetone, clean in alcohol and deionized water, after pre-stretched elastic substrate is sticked on hollow stent, method transfer is dragged on pre-stretched elastic substrate with same seal style, naturally dry, this substrate pre-stretching is be stretched to original length along a direction 1.5 to 4 times, or 2 to 10 times of original area are stretched to along two orthogonal directions, then allow the pre-stretched elastic substrate of covering Flexible graphene/nickel particle mixed structure slowly return to the original length or area, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer,
(3) preparation of all solid state ultracapacitor that stretches
Utilize the stretched graphene/nickel particle mixed structure of preparation as electrode material, prepare all solid state ultracapacitor that stretches according to elastomer/electrode/solid electrolyte/electrode/elastomeric structure.
In above-mentioned preparation method,
Described in step (), nickel foam is of a size of 1cm × 1cm-30cm × 30cm.Described carbon source is one or several in methane, acetylene, ethene.The flow control of described carbon source is at 1-300sccm, and purity is higher than 99.99%; The flow control of described hydrogen is at 1-100sccm, and purity is higher than 99.99%.Described vacuum reaction stove evacuation degree is 3 × 10
-3-3 × 10
-6torr, to remove the active gases in furnace chamber, keeps clean growing environment.Described annealing refers to process substrate surface being dispelled to the magazines such as oxide.After obtaining the substrate of Direct precipitation Graphene, close carbon-source gas valve, keep the constant cooling of hydrogen flowing quantity, take out the Graphene of deposition afterwards.
The method of taking out backing material is closed hydrogen gas valve, vacuum pump, with air, reacting furnace cavity is filled to an atmospheric pressure state, is then taken out by backing material after being to wait vacuum reaction furnace temperature to drop to room temperature.In the Graphene/foam metal of preparation, the number of plies of Graphene is 1-10 layer.
Etching solution described in step (two) is iron chloride or iron nitrate solution, and described solution concentration is 0.5-5mol/L; Described elastic substrate is the elastic substrate such as PMMA, PDFS; The described chemical replacement reaction time is 15-1000 minute, and reaction temperature is 10-50 degree Celsius;
The described seal style method of dragging for is specially: cover on spongy graphene/metallic particles mixed structure with flexible substrate; light pressure 10-30 second; then slowly lift gently from a side of substrate, utilize the little contact force between Graphene and substrate, graphene substrate is pulled out.
Described in step (three), elastomer is the elastomers such as PMMA, PDFS; Described solid electrolyte is PVA-acid, alkali or neutral electrolyte; Described nickel granular size is 10-500nm; Described nickel granule content ratio is 0%-50%.
Electrochemical workstation can be utilized to test the degree of pre-stretching, the number of repetition of stretching-contraction and speed to the impact of ultracapacitor relevant nature (capacitance, capacitor cycle life-span, electrical impedance etc.); Prepare the stretched conductive film of different graphene/nickel granule content ratios, and be assembled into all solid state ultracapacitor that stretches.
It is as follows that elastomer/electrode/solid electrolyte/electrode/elastomeric structure (i.e. elastomer/graphene-based active material/solid electrolyte/graphene-based active material/elastomeric structure) preparation method comprises step:
1) prepare electrode in one end of two graphene/nickel particle mixed structures respectively, be called that A holds;
2) coat large area PVA-acid, alkali or neutral electrolyte in each its one end of not preparing electrode of graphene/nickel particle mixed structure, be called that B holds;
3) B of two graphene/nickel particle mixed structures is held overlapping covering, make to scribble electrolytical part bump contact, make it paste together;
4) PMMA or PDFS is used to be clinged.
Wherein, step 1) the described method preparing electrode has two kinds: one, directly can to stretch the disconnected periphery sticking at graphene/nickel particle mixed structure of electric conducting material with adhesive tape or glue;
Described stretched electric conducting material comprises the conductive carbon fibre that can stretch, conductive carbon nanotube fiber, conductive graphene fiber etc. can drawing of fiber electrode; Notice that electrode material is not communicated with PVA-acid, alkali or neutral electrolyte.
Its two be utilize depositing device directly the one end of the graphene/nickel particle mixed structure that can stretch deposition on disconnected electrode material, specifically comprise following preparation process:
(1) graphene/nickel particle mixed structure is put into low temperature depositing system;
(2) prepare the shutter that there is the empty bar of rectangle at two ends, be placed in the top of graphene/nickel particle mixed structure, attention can not contact mixed structure, in order to avoid damage the gas sensitive of preparation;
(3) depositing device is utilized to deposit disconnected metal electrode at graphene/nickel particle mixed structure two ends; Notice that electrode material is not communicated with PVA-acid, alkali or neutral electrolyte.
Described depositing device comprises the low temperature depositing systems such as magnetron sputtering deposition system, evaporator, impulse laser deposition system;
Described electrode material comprises the metal materials such as copper, iron, silver, platinum.
The present invention utilizes the collector-nickel foam of ultracapacitor, proposes a kind of preparation method of electrode material of novel flexible three-dimensional sponge shape graphene/nickel particle mixed structure; Utilize a kind of electrode preparation method of Ultra-Drawing performance (tensile elongation is greater than 300%), prepare the stretchable mixed structure having active electrode and collector effect concurrently; Utilize the sandwich structure of electrode/electrolyte/electrode, all solid state ultracapacitor that stretches of processability excellence.
The invention has the beneficial effects as follows:
1) spongy graphene growth temperature accurately controls;
2) the Graphene defect peak grown is low, has high crystal mass;
3) the graphene/nickel particle grown has fabulous conductivity;
4) the Graphene size grown only by the restriction of CVD cavity, can realize the large area deposition of Graphene;
5) do not need in wet method transfer process to use PMMA glue, time saving and energy saving;
6) transfer process adopts seal style transfer, and Graphene can not arbitrarily drift in the solution, avoids Graphene in transfer process
Damage, process is simple.
7) with low cost, method is simply controlled, is suitable for producing in enormous quantities, and using value is high.
Accompanying drawing explanation
Fig. 1 is the syntheti c route figure of graphene/nickel particle mixed electrode of can stretching;
Fig. 2 is the SEM pattern of electrode of can stretching; (corresponding embodiment 1)
Fig. 3 is the C-V cyclic curve preparing the ultracapacitor that can stretch.(corresponding embodiment 1)
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described.
Embodiment 1
1. get and be of a size of 8cm × 8cm nickel foam and be placed in tube furnace;
2. open vacuum pump and the air pressure of tube furnace is evacuated to ultimate vacuum state 3 × 10
-6holder (Torr);
3. keep vacuum state 3 × 10
-6torr is (the vacuum effect of 15 minutes is the impurity, air etc. of dispelling quartz ampoule inside, guarantees that reaction chamber is clean) after 15 minutes, and the air pressure of quartz ampoule 3 is raised to 3 × 10
-3torr;
4. hydrogen flowmeter is set as 100sccm, and hydrogen is injected vacuum chamber;
5. tube furnace temperature is to after 300 DEG C, and constant temperature is annealed for 20 minutes;
6. tube furnace temperature is to after 1000 DEG C, and methane is injected vacuum chamber, and gas flowmeter is set as 200sccm, stops and grows for 30 minutes;
7. close methane gas flowmeter and tube furnace temperature is down to room temperature fast with the speed of 50 DEG C/min;
8. close hydrogen flowmeter and vacuum pump;
9. open valve, with air, quartz ampoule air pressure is filled to an atmospheric pressure state;
10. open quartz ampoule vacuum interface, take out the nickel foam of deposited graphite alkene;
11. by FeCl
3add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl
3(4.5mol/L);
Graphene/the nickel foam of 12. preparations is immersed in the FeCl of 20 DEG C
3(4.5mol/L) in solution 140 minutes;
The pattern of 13. observation Graphene/nickel foam, until its structure becomes Flexible graphene/nickel particle mixed structure;
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 25 seconds by 14.;
15. slowly lift gently from substrate side, utilize the little contact force between Graphene and substrate, are pulled out by Graphene nickel particle mixed structure;
Spongy graphene acetone, ethanol and deionized water are cleaned 3 minutes by 16. respectively;
PDFS elastic substrate to be stretched to 1.5 to 4 times of original length by 17. along a direction, or is stretched to 2 to 10 times of original area along two orthogonal directions;
18. will the elastic substrate after stretching be pasted in a circle on empty support;
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 20 seconds by 19.;
20. slowly lift gently from substrate side, utilize the little contact force between Graphene nickel particle mixed structure and substrate, are pulled out by graphene/nickel particle mixed structure;
21. dry in the air 3 hours in vacuum drying chamber;
The elastic substrate being coated with graphene/nickel particle mixed structure is taken off by 22. from the circle or square set of hollow, and side sticks on support;
23. in vacuum drying chamber clear-cutting forestland 5 hours, make it return to original size, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer according to this.
24. can to stretch the disconnected one end sticking at two graphene/nickel particle mixed structures respectively of conductive carbon fibre with adhesive tape or glue;
25. coat large-area PVA-acid in one end that it does not paste the conductive carbon fibre that can stretch, and notice that PVA-acid is not communicated with conductive fiber;
The 26. one end overlaps two graphene/nickel particle mixed structures being scribbled PVA-acid cover, and make it contact thus paste together;
27. use PMMA or PDFS to be clinged by contact jaw.
Embodiment 2
At nickel foam Grown Graphene also final growing graphene/nickel particle mixed structure, the capacitor thus preparation can stretch, comprises following preparation process
1. get and be of a size of 8cm × 9cm nickel foam and be placed in tube furnace;
2. open vacuum pump and the air pressure of tube furnace is evacuated to ultimate vacuum state 3 × 10
-6holder (Torr);
3. keep vacuum state 3 × 10
-6torr is (the vacuum effect of 15 minutes is the impurity, air etc. of dispelling quartz ampoule inside, guarantees that reaction chamber is clean) after 15 minutes, and the air pressure of quartz ampoule 3 is raised to 3 × 10
-3torr;
4. hydrogen flowmeter is set as 100sccm, and hydrogen is injected vacuum chamber;
5. tube furnace temperature is to after 300 DEG C, and constant temperature is annealed for 20 minutes;
6. tube furnace temperature is to after 1000 DEG C, and methane is injected vacuum chamber, gas flowmeter is set as 200sccm, stops and grows for 40 minutes;
7. close methane gas flowmeter and tube furnace temperature is down to room temperature fast with the speed of 60 DEG C/min;
8. close hydrogen flowmeter and vacuum pump;
9. open valve, with air, quartz ampoule air pressure is filled to an atmospheric pressure state;
10. open quartz ampoule vacuum interface, take out the nickel foam of deposited graphite alkene;
11. by FeCl
3add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl
3(0.5mol/L);
Graphene/the nickel foam of 12. preparations is immersed in the FeCl of 40 DEG C
3(0.5mol/L) in solution 150 minutes;
The pattern of 13. observation Graphene/nickel foam, until its structure becomes Flexible graphene/nickel particle mixed structure;
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 15 seconds by 14.;
15. slowly lift gently from substrate side, utilize the little contact force between Graphene and substrate, are pulled out by Graphene nickel particle mixed structure;
Spongy graphene acetone, ethanol and deionized water are cleaned 3 minutes by 16. respectively;
PDFS elastic substrate to be stretched to 5 times of original area by 17. along two orthogonal directions;
18. will the elastic substrate after stretching be pasted on hollow square support;
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 30 seconds by 19.;
20. slowly lift gently from substrate side, utilize the little contact force between Graphene nickel particle mixed structure and substrate, are pulled out by graphene/nickel particle mixed structure;
21. dry in the air 3 hours in vacuum drying chamber;
The elastic substrate being coated with graphene/nickel particle mixed structure is taken off by 22. from square set, and side sticks on support;
23. in vacuum drying chamber clear-cutting forestland 3-5 hour, make it return to original size, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer according to this.
Graphene/nickel particle mixed structure is put into low temperature depositing system by 24.;
There is the shutter of the empty bar of rectangle at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, the stretched graphene/nickel particle mixed structure of gauffer.
26. utilize evaporator to deposit the copper electrode of not UNICOM respectively in one end of two graphene/nickel particle mixed structures.
27. coat large-area PVA-acid in one end of its non-depositing electrode, notice that PVA-acid is not communicated with copper electrode;
The 28. one end overlaps two graphene/nickel particle mixed structures being scribbled PVA-acid cover, and make it contact thus paste together;
29. use PMMA to be clinged by overlapping part.
Embodiment 3
At nickel foam Grown Graphene and final growing graphene/nickel particle mixed structure, prepare high connductivity and can to stretch capacitor, comprise following preparation process:
1. get and be of a size of 5cm × 9cm nickel foam and be placed in tube furnace;
2. open vacuum pump and the air pressure of tube furnace is evacuated to ultimate vacuum state 3 × 10
-6holder (Torr);
3. keep vacuum state 3 × 10
-6torr is (the vacuum effect of 15 minutes is the impurity, air etc. of dispelling quartz ampoule inside, guarantees that reaction chamber is clean) after 15 minutes, and the air pressure of quartz ampoule 3 is raised to 3 × 10
-3torr;
4. hydrogen flowmeter is set as 100sccm, and hydrogen is injected vacuum chamber;
5. tube furnace temperature is to after 300 DEG C, and constant temperature is annealed for 20 minutes;
6. tube furnace temperature is to after 1000 DEG C, and methane is injected vacuum chamber, gas flowmeter is set as 200sccm, stops and grows for 40 minutes;
7. close methane gas flowmeter and tube furnace temperature is down to room temperature fast with the speed of 30-60 DEG C/min;
8. close hydrogen flowmeter and vacuum pump;
9. open valve, with air, quartz ampoule air pressure is filled to an atmospheric pressure state;
10. open quartz ampoule vacuum interface, take out the nickel foam of deposited graphite alkene;
11. by FeCl
3add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl
3(4mol/L);
Graphene/the nickel foam of 12. preparations is immersed in the FeCl of 27 DEG C
3(4mol/L) in solution 150 minutes;
The pattern of 13. observation Graphene/nickel foam, until its structure becomes Flexible graphene/nickel particle mixed structure;
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 15 seconds by 14.;
15. slowly lift gently from substrate side, utilize the little contact force between Graphene and substrate, are pulled out by Graphene nickel particle mixed structure;
Spongy graphene acetone, ethanol and deionized water are cleaned 3 minutes by 16. respectively;
PMMA elastic substrate to be stretched to 8 times of original area by 17. along two orthogonal directions;
18. will the elastic substrate after stretching be pasted on hollow square support;
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 30 seconds by 19.;
20. slowly lift gently from substrate side, utilize the little contact force between Graphene nickel particle mixed structure and substrate, are pulled out by graphene/nickel particle mixed structure;
21. dry in the air 3 hours in vacuum drying chamber;
The elastic substrate being coated with graphene/nickel particle mixed structure is taken off by 22. from square set, and side sticks on support;
23. in vacuum drying chamber clear-cutting forestland 3-5 hour, make it return to original size, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer according to this.
Graphene/nickel particle mixed structure is put into low temperature depositing system by 24.;
There is the shutter of the empty bar of rectangle at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, but can not contact mixed structure, in order to avoid damage the gas sensitive of preparation;
26. finally utilize impulse laser deposition system to deposit the silver electrode of not UNICOM respectively in one end of two graphene/nickel particle mixed structures.
27. coat large-area PVA-alkali in one end of non-depositing silver electrode, notice that PVA-alkali is not communicated with silver electrode;
The 28. one end overlaps two graphene/nickel particle mixed structures being scribbled PVA-alkali cover, and make it contact thus paste together;
29. use glue to be clinged by lap.
Embodiment 4
At nickel foam Grown Graphene also final growing graphene/nickel particle mixed structure, thus preparation can stretch, ultracapacitor comprises following preparation process:
1. get and be of a size of 7cm × 7cm nickel foam and be placed in tube furnace;
2. open vacuum pump and the air pressure of tube furnace is evacuated to ultimate vacuum state 3 × 10
-6holder (Torr);
3. keep vacuum state 3 × 10
-6torr is (the vacuum effect of 15 minutes is the impurity, air etc. of dispelling quartz ampoule inside, guarantees that reaction chamber is clean) after 15 minutes, and the air pressure of quartz ampoule 3 is raised to 3 × 10
-3torr;
4. hydrogen flowmeter is set as 100sccm, and hydrogen is injected vacuum chamber;
5. tube furnace temperature is to after 300 DEG C, and constant temperature is annealed for 20 minutes;
6. tube furnace temperature is to after 1000 DEG C, and methane is injected vacuum chamber, gas flowmeter is set as 200sccm, stops and grows for 35 minutes;
7. close methane gas flowmeter and tube furnace temperature is down to room temperature fast with the speed of 30-60 DEG C/min;
8. close hydrogen flowmeter and vacuum pump;
9. open valve, with air, quartz ampoule air pressure is filled to an atmospheric pressure state;
10. open quartz ampoule vacuum interface, take out the nickel foam of deposited graphite alkene;
11. by FeCl
3add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl
3(1mol/L);
Graphene/the nickel foam of 12. preparations is immersed in the FeCl of 35 DEG C
3(1mol/L) in solution 190 minutes;
The pattern of 13. observation Graphene/nickel foam, until its structure becomes Flexible graphene/nickel particle mixed structure;
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 15 seconds by 14.;
15. slowly lift gently from substrate side, utilize the little contact force between Graphene and substrate, are pulled out by Graphene nickel particle mixed structure;
Spongy graphene acetone, ethanol and deionized water are cleaned 3 minutes by 16. respectively;
PMMA elastic substrate to be stretched to 2.5 times of original length by 17. along a direction;
18. will the elastic substrate after stretching be pasted on hollow circular support;
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 30 seconds by 19.;
20. slowly lift gently from substrate side, utilize the little contact force between Graphene nickel particle mixed structure and substrate, are pulled out by graphene/nickel particle mixed structure;
21. dry in the air 3 hours in vacuum drying chamber;
The elastic substrate being coated with graphene/nickel particle mixed structure is taken off by 22. the circle of hollow, and side sticks on support;
23. in vacuum drying chamber clear-cutting forestland 3-5 hour, make it return to original size, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer according to this.
Graphene/nickel particle mixed structure is put into low temperature depositing system by 24.;
There is the shutter of the empty bar of rectangle at 25. preparation two ends, are placed in the top of graphene/nickel particle mixed structure, but can not contact mixed structure, in order to avoid damage the stretched graphene/nickel particle mixed structure of gauffer.
26. utilize magnetron sputtering deposition system to deposit the platinum electrode of not UNICOM respectively in one end of two graphene/nickel particle mixed structures;
27. coat large-area PVA-alkali in one end of non-depositing electrode, notice that PVA-alkali is not communicated with platinum electrode;
The 28. one end overlaps two graphene/nickel particle mixed structures being scribbled PVA-alkali cover, and make it contact thus paste together;
29. use PMMA to be clinged.
Embodiment 5
At nickel foam Grown Graphene and growing graphene/nickel particle mixed structure, thus prepare high connductivity and can to stretch ultracapacitor, comprise following preparation process
1. get and be of a size of 6cm × 8cm nickel foam and be placed in tube furnace;
2. open vacuum pump and the air pressure of tube furnace is evacuated to ultimate vacuum state 3 × 10
-6holder (Torr);
3. keep vacuum state 3 × 10
-6torr is (the vacuum effect of 15 minutes is the impurity, air etc. of dispelling quartz ampoule inside, guarantees that reaction chamber is clean) after 15 minutes, and the air pressure of quartz ampoule 3 is raised to 3 × 10
-3torr;
4. hydrogen flowmeter is set as 100sccm, and hydrogen is injected vacuum chamber;
5. tube furnace temperature is to after 300 DEG C, and constant temperature is annealed for 20 minutes;
6. tube furnace temperature is to after 1000 DEG C, and methane is injected vacuum chamber, and gas flowmeter is set as 200sccm, stops and grows for 30 minutes;
7. close methane gas flowmeter and tube furnace temperature is down to room temperature fast with the speed of 30-60 DEG C/min;
8. close hydrogen flowmeter and vacuum pump;
9. open valve, with air, quartz ampoule air pressure is filled to an atmospheric pressure state;
10. open quartz ampoule vacuum interface, take out the nickel foam of deposited graphite alkene;
11. by FeCl
3add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl
3(3mol/L);
Graphene/the nickel foam of 12. preparations is immersed in the FeCl of 30 DEG C
3(3mol/L) in solution 150 minutes;
The pattern of 13. observation Graphene/nickel foam, until its structure becomes Flexible graphene/nickel particle mixed structure;
Flexible substrate is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 20 seconds by 14.;
15. slowly lift gently from substrate side, utilize the little contact force between Graphene and substrate, are pulled out by Graphene nickel particle mixed structure;
Spongy graphene acetone, ethanol and deionized water are cleaned 4 minutes by 16. respectively;
PDFS elastic substrate to be stretched to 1.5 to 4 times of original length by 17. along a direction, or is stretched to 2 to 10 times of original area along two orthogonal directions;
18. will the elastic substrate after stretching be pasted on hollow stent;
Elastic substrate one side on support is pressed on Flexible graphene/nickel particle mixed structure surface, light pressure 20 seconds by 19.;
20. slowly lift gently from substrate side, utilize the little contact force between Graphene nickel particle mixed structure and substrate, are pulled out by graphene/nickel particle mixed structure;
21. dry in the air 3 hours in vacuum drying chamber;
The elastic substrate being coated with graphene/nickel particle mixed structure is taken off by 22. from the circle or square set of hollow, and side sticks on support;
23. in vacuum drying chamber clear-cutting forestland 4 hours, make it return to original size, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer according to this.
24. can to stretch conductive graphene fiber disconnected one end sticking at two graphene/nickel particle mixed structures respectively with adhesive tape or glue.
25. coat large-area PVA-alkali in the one end of not pasting graphene fiber, notice that PVA-alkali is not communicated with graphene fiber;
The 26. one end overlaps two graphene/nickel particle mixed structures being scribbled PVA-alkali cover, and make it contact thus paste together;
27. use glue to be clinged by overlapping ends.
Finally should be noted that, the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in previous embodiment, or to wherein partly carrying out equivalent replacement.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1., based on a preparation method for the stretched ultracapacitor of high connductivity graphene/nickel particle mixed structure, it is characterized in that, comprise step 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, vacuumize, heat simultaneously, hydrogen is injected vacuum reaction stove, after being heated to predetermined temperature 100-500 DEG C, then constant temperature 10-30 minute anneals, then after being heated to predetermined temperature 900-1100 DEG C, carbon source is passed into vacuum reaction stove, keep hydrogen flowing quantity constant simultaneously, grow and close gas after 5-180 minute and be down to the substrate that room temperature can obtain Direct precipitation Graphene, i.e. graphene/nickel;
(2) can stretch the preparation of graphene/nickel particle mixed structure and transfer thereof
Graphene/the nickel foam of preparation is immersed in etching solution, slow reaction, most of nickel foam is fallen by chemical replacement, nickel foam is made to be transformed into metallic particles little one by one, then spongy graphene/nickel particle mixed structure is pulled out by the seal style method of dragging for from etching solution, respectively at acetone, clean in alcohol and deionized water, after pre-stretched elastic substrate is sticked on hollow stent, method transfer is dragged on pre-stretched elastic substrate with same seal style, naturally dry, this substrate pre-stretching is be stretched to original length along a direction 1.5 to 4 times, or 2 to 10 times of original area are stretched to along two orthogonal directions, then allow the pre-stretched elastic substrate of covering Flexible graphene/nickel particle mixed structure slowly return to the original length or area, prepare a kind of stretched graphene/nickel particle mixed structure of self assembly gauffer,
(3) preparation of all solid state ultracapacitor that stretches
Utilize the stretched graphene/nickel particle mixed structure of preparation as electrode material, prepare all solid state ultracapacitor that stretches according to elastomer/graphene-based active material/solid electrolyte/graphene-based active material/elastomeric structure.
2. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1, it is characterized in that, carbon source described in step () is one or several in methane, acetylene, ethene.
3. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1, it is characterized in that, described in step (), the flow control of carbon source is at 1-300sccm, and purity is higher than 99.99%; The flow control of described hydrogen is at 1-100sccm, and purity is higher than 99.99%.
4. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1, it is characterized in that, described in step (), vacuum reaction stove evacuation degree is 3 × 10
-3-3 × 10
-6torr.
5. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1; it is characterized in that; etching solution described in step (two) is iron chloride or iron nitrate solution, and described solution concentration is 0.5-5mol/L.
6. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1; it is characterized in that; step (two) the described chemical replacement reaction time is 15-1000 minute, and reaction temperature is 10-50 degree Celsius.
7. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1, it is characterized in that, described in step (three), elastomer is polymer elastomer; Described solid electrolyte is PVA-acid, alkali or neutral electrolyte.
8. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1, it is characterized in that, described in step (three), nickel granular size is 10-500nm; Described nickel granule content ratio is 0%-50%.
9. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 1; it is characterized in that, that elastomer/electrode/solid electrolyte/electrode/elastomeric structure preparation method comprises step to step (three) is as follows:
1) prepare electrode in one end of two graphene/nickel particle mixed structures respectively, be called that A holds;
2) coat large area PVA-acid, alkali or neutral electrolyte in each its one end of not preparing electrode of graphene/nickel particle mixed structure, be called that B holds;
3) B of two graphene/nickel particle mixed structures is held overlapping covering, make to scribble electrolytical part bump contact, make it paste together;
4) PMMA or PDFS elastomer is used to be clinged.
10. the preparation method of a kind of stretched ultracapacitor based on high connductivity graphene/nickel particle mixed structure according to claim 9, it is characterized in that, step 1) the described method preparing electrode has two kinds: one, directly can to stretch the disconnected two ends sticking at graphene/nickel particle mixed structure periphery substrate of electric conducting material with adhesive tape or glue; Described stretched electric conducting material comprises the conductive carbon fibre that can stretch, conductive carbon nanotube fiber, conductive graphene fiber etc. can drawing of fiber electrode, and electrode material is not communicated with PVA-acid, alkali or neutral electrolyte;
Its two be utilize depositing device directly the one end of the graphene/nickel particle mixed structure that can stretch deposition on disconnected metal electrode material.
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| CN106129536A (en) * | 2016-08-12 | 2016-11-16 | 复旦大学 | A kind of stretchable lithium-air battery and preparation method thereof |
| CN106546720A (en) * | 2016-10-31 | 2017-03-29 | 山东师范大学 | A kind of preparation method of the stretchable biosensor material of three-dimensional grapheme/silver nano flower-like |
| CN106653158A (en) * | 2016-12-26 | 2017-05-10 | 哈尔滨工业大学 | High-elasticity conductive film material and preparation method thereof |
| CN108155387A (en) * | 2016-12-06 | 2018-06-12 | 华为技术有限公司 | A kind of elastic collector and preparation method thereof, cell electrode piece and flexible lithium ion battery |
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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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| CN106653158B (en) * | 2016-12-26 | 2018-07-17 | 哈尔滨工业大学 | A kind of high resiliency conducting membrane material and preparation method thereof |
| CN111807416A (en) * | 2020-07-22 | 2020-10-23 | 哈尔滨工业大学 | Preparation method of hollow tubular structure FeOOH @ rGO lithium ion battery anode material |
| CN111807416B (en) * | 2020-07-22 | 2022-10-04 | 哈尔滨工业大学 | Preparation method of hollow tubular structure FeOOH @ rGO lithium ion battery anode material |
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