CN104616908A - Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material - Google Patents
Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material Download PDFInfo
- Publication number
- CN104616908A CN104616908A CN201510045280.2A CN201510045280A CN104616908A CN 104616908 A CN104616908 A CN 104616908A CN 201510045280 A CN201510045280 A CN 201510045280A CN 104616908 A CN104616908 A CN 104616908A
- Authority
- CN
- China
- Prior art keywords
- nickel
- graphite
- graphene
- electrode
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 130
- 239000010439 graphite Substances 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 45
- 238000000034 method Methods 0.000 claims abstract description 56
- 230000008569 process Effects 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 174
- 229910052759 nickel Inorganic materials 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000006260 foam Substances 0.000 claims description 46
- 238000002484 cyclic voltammetry Methods 0.000 claims description 41
- 239000000725 suspension Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 29
- 230000004913 activation Effects 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 24
- 238000004070 electrodeposition Methods 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 17
- 230000010355 oscillation Effects 0.000 claims description 17
- 229920000557 Nafion® Polymers 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 15
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 abstract 3
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 239000002245 particle Substances 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 18
- 239000002105 nanoparticle Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 238000000151 deposition Methods 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000004062 sedimentation Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000005611 electricity Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001652 electrophoretic deposition Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Carbon And Carbon Compounds (AREA)
- Composite Materials (AREA)
Abstract
The invention discloses a composite material of nickel hydroxide/graphene or graphite which is structurally Ni(OH)2/graphite or layered Ni(OH)2/graphene composite material alternated with Ni(OH)2 and graphene, wherein the weight content of the nickel hydroxide is 10-90%. The invention further discloses a method for preparing the composite material. The composite material is simple in process, low in cost, environment-friendly and easy for batch production.
Description
Technical field
The present invention relates to the composite material of a kind of nickel hydroxide/Graphene or graphite.
The invention still further relates to the method preparing above-mentioned composite material.
Background technology
Ultracapacitor has that power density is high, the discharge and recharge time is short, advantages of environment protection, is widely used in storing solar energy, wind energy and miniaturized electronics.Day by day deficient along with the whole world more and more higher and fossil energy to environmental requirement, ultracapacitor is considered to the electrical source of power of automobile of future generation.But can not evade, ultracapacitor also faces two at present and challenges greatly: one is that energy density is low, is not enough to the long distance running supporting automobile; Two is that price is relatively expensive.This is mainly because existing electrode material for super capacitor major part adopts active carbon, and its mode storing electric charge is mainly Electrostatic Absorption.
Large but the poorly conductive of active carbon specific area, and pore ratio is high; Graphene has large specific area and excellent electric conductivity, is considered to desirable electrode material for super capacitor, but graphene film exists easily to return and builds up graphite and the shortcoming such as expensive.Conducting polymer composite has the easily problem such as swelling and poor stability.For pseudo-capacitance oxide or hydroxide electrode material, anodizing ruthenium is good pseudo-capacitance electrode material, but ruthenium is expensive; Cobalt hydroxide has high specific area and ion deinsertion speed, but cobalt is poisonous and price is also higher; Manganese oxide has that price is relatively cheap, low toxicity, Environmental security and theoretical ratio capacitance advantages of higher, but exist soluble, specific area is low, conduction is sub and the shortcoming such as the sub-poor performance of diversion; Ferriferous oxide low price, environmental friendliness, but electron conduction difference and self discharge is serious; Vanadic oxide poorly conductive, the ratio capacitance of tin ash is much lower compared with other oxide; Nickel oxide or the theoretical ratio capacitance of nickel hydroxide are up to 3750F g
-1, low price and nontoxic, but resistance is large and cycle performance is poor.In a word, metal oxide or hydroxide have theoretical ratio capacitance advantages of higher, but there is again poorly conductive and particle simultaneously and the problem such as easily to reunite.Therefore, the research and development of current electrode material for super capacitor mainly concentrate on the metal oxide/material with carbon element nano-complex aspect, especially nickel hydroxide/graphene complex of synthesis pattern and structure-controllable.
Be carrier with Graphene, the specific area utilizing it large and excellent electric conductivity, grow particle diameter thereon little and have the nano-sized nickel hydroxide particle of specific morphology, preparation Ni (OH)
2/ graphene nanocomposite material, to ultracapacitor capacitive character can improvement and be of great importance in the application of practical field.Current preparation Ni (OH)
2the main method of/graphene nanocomposite material has: the precipitation method, solid phase method, water (solvent) Re Fa and electrochemical method etc.The precipitation method are relatively simple, easy to operate, but Ni (OH)
2particle size differs, particle size distribution range large, needs ageing certain hour to obtain the good nano particle of degree of crystallinity.In order to control Ni (OH)
2nanoparticle Size, often needs to add urea, hydrazine or surfactant, control OH
-the rate of release of ion or suppression Ni (OH)
2the nuclei growth speed of particle, this causes the reaction time elongated undoubtedly and operation easier becomes large.Solid phase method uses less, Sun
[1]after nickel salt and graphite oxide or Graphene fully being ground, in filter process, make Ni
2+hydrolysis is Ni (OH)
2, Ni
2+the hydrolysis rate rate of dissolution that must be far longer than nickel salt could obtain Ni (OH)
2, it is wayward to there is reaction in the method, equally also there is the shortcoming the same with the precipitation method, i.e. Ni (OH)
2particle size is uneven.
Hydro thermal method or solvent-thermal method are that one can control Ni (OH) preferably
2the preparation method of pattern.Once report was had:
1) on the graphene oxide sheet of reduction, hexagon monocrystalline Ni (OH) is grown by hydro-thermal reaction
2nanometer sheet is 2.8A g in current density
-1, obtaining ratio capacitance is 1335F g
-1.
2) adopt solvent thermal reaction method, in phenmethylol medium, graphite oxide and Ni salt are obtained Ni (OH) at 200 DEG C of reaction 24h
2, the stratiform α-Ni (OH) that replaces of Graphene
2/ graphene composite material, when this composite material is used in super flexible full solid thin film ultracapacitor, its ratio capacitance is 660.8Fcm
-3, and without obviously decline after discharge and recharge 2000 times.
The above-mentioned second way greatly can improve the bulk density of composite material, and that reduces graphene film returns folded trend, the final energy density improving ultracapacitor.But this method weak point is to be difficult to batch preparation and the problem such as consuming time.
Electrochemical deposition method cost is low, and preparation process is simple, the thickness (quality) of electrode active material and the structure-controllable of material and be widely used.Electrochemical deposition method can be divided into anodic deposition method and cathodic deposition by polarity of electrode.Anodic deposition method utilizes salt of weak acid to generate OH at ate electrode generation hydrolysis
-, Ni simultaneously
2+oxidation generates Ni
3+, last OH
-with Ni
3+reaction generates NiOOH, but this depositional mode of general less use.The most frequently used mode or cathodic deposition, can be divided into the mode such as constant potential or galvanostatic deposition, dynamically potential deposition (cyclic voltammetric), pulse current deposition, electrophoretic deposition by applied electronic signal.Dynamic current potential sedimentation is usually used to the current potential determining potentiostatic electrodeposition method, has report to use cyclic voltammetry to prepare Co (OH)
2-Ni (OH)
2binary metal hydroxide, when cobalt/nickle atom is than 66:34, when sweep speed is 50mV/s, its ratio capacitance is 1102F g
-1.The electrolyte that electrophoretic deposition uses is dispersion system of colloid, usually higher unlike its externally-applied potential with constant potential electro-deposition.Report electrophoretic deposition is had to obtain Ni/EMCMBs (expanded mesoporous carbon micron ball) compound, 5A g
-1time this compound ratio capacitance be 491F g
-1.So mode the most frequently used is at present potentiostatic electrodeposition, galvanostatic deposition and pulse current deposition.
There is report potentiostatic electrodeposition method with Ni (NO
3)
2for nickel precursor, directly at nickel foam substrates the Ni of 0.5mg (OH)
2, 4A g
-1time ratio capacitance be 3152F g
-1but, its ratio capacitance loss 48% after 300 circulations.There is report enhancing plasma chemical vapor deposition to prepare the Graphene of vertical arrangement in nickel foam, then adopt galvanostatic deposition mode to obtain Ni (OH) at graphene film substrates
2nano particle, thus obtain Ni (OH)
2be evenly distributed on the compound of graphenic surface, this Ni (OH)
2/ graphene complex active material utilization is high, 2.3A g
-1time ratio capacitance be 2215Fg
-1, 23.1A g
-1time ratio capacitance be 1305F g
-1, and the constant current charge-discharge ratio capacitance after 2000 times that circulates still can keep 77% under this condition, but preparation process is more complicated and unit are active material quality is only 0.43mg.Report pulse current sedimentation is had to prepare CNT/NiO
x(OH)
y, after heat treatment, most high specific capacitance reaches 1451F g
-1, they also with the CNT/NiO prepared by galvanostatic deposition method
x(OH)
yperformance compare, find NiO prepared by pulse current sedimentation
x(OH)
yparticle size is less, and chemical property is also higher, but can find out that the reversible charge-discharge performance of this material is poor from its cyclic voltammetry curve.
The significant challenge that current ultracapacitor faces is that energy density is low and price is partially expensive.Therefore synthesize the composite material that energy density is high, reduce its cost is one of present research emphasis simultaneously.
Summary of the invention
The object of this invention is to provide the composite material of a kind of stratiform high-performance nickel hydroxide/Graphene or graphite.
Another object of the present invention is to provide the method preparing above-mentioned composite material.
For achieving the above object, the composite material of nickel hydroxide/Graphene provided by the invention, its structure is Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene, wherein weight of nickel hydroxide content is 10 ~ 90%; Obtained by following method:
1) by mass ratio 8 ~ 9:2 ~ 1 of expanded graphite and binding agent, expanded graphite and binding agent are joined sonic oscillation preparation expanded graphite suspension in ethanol;
2) expanded graphite suspension step 1 prepared is on electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene.
The composite material of nickel hydroxide/graphite provided by the invention, its structure is Ni (OH)
2/ graphite, wherein weight of nickel hydroxide content is 10 ~ 90%; Obtained by following method:
1) by mass ratio 8 ~ 9:2 ~ 1 of graphite and binding agent, graphite and binding agent are joined sonic oscillation preparation graphite suspension in ethanol;
2) graphite suspension prepared by step 1 is coated in electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain nickel hydroxide/graphite.
In described composite material, add and have carbon black or carbon nano-tube.
In described composite material, binding agent is polytetrafluoroethylene or Nafion solution; Electrode basement is nickel foam or Copper Foil; Soluble nickel salt be nickel chloride, nickelous sulfate, nickel acetate, nickel nitrate one or more; Alkali lye is one or both of KOH, NaOH.
The method of the composite material of the above-mentioned nickel hydroxide/Graphene of preparation provided by the invention:
1) by mass ratio 8 ~ 9:2 ~ 1 of expanded graphite and binding agent, expanded graphite and binding agent are joined sonic oscillation preparation expanded graphite suspension in ethanol;
2) expanded graphite suspension step 1 prepared is on electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene.
The method of the composite material of the above-mentioned nickel hydroxide/graphite of preparation provided by the invention:
1) by mass ratio 8 ~ 9:2 ~ 1 of graphite and binding agent, graphite and binding agent are joined sonic oscillation preparation graphite suspension in ethanol;
2) graphite suspension prepared by step 1 is coated in electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain nickel hydroxide/graphite.
In described method, in step 1, binding agent is polytetrafluoroethylene or polyvinylidene fluoride emulsion or Nafion solution.
In described method, add in step 1 and have carbon black or carbon nano-tube.
In described method, the electrode basement in step 2 is nickel foam or Copper Foil.
In described method, the soluble nickel salt in step 3 be nickel chloride, nickelous sulfate, nickel acetate, nickel nitrate one or more.
In described method, the alkali lye in step 5 is one or both of KOH, NaOH.
Ni of the present invention (OH)
2the composite material of/Graphene or graphite, its layer structure can make the volume energy density of ultracapacitor be significantly improved, select low-cost expanded graphite or graphite simultaneously, avoid using expensive Graphene, its cost can be made to decline to a great extent, thus effectively overcome the significant challenge of ultracapacitor.The method has the features such as extremely simple, consuming time short, nontoxic, the environmental friendliness of operation, amplification production with low cost and easy, is a high-performance Ni (OH) having Commercial Prospect
2the compound of/Graphene or graphite prepares approach.
Accompanying drawing explanation
Fig. 1 is the compound micromodel figure that stratiform of the present invention replaces nickel hydroxide/Graphene.
Fig. 2 is the scanning electron microscope (SEM) photograph that stratiform of the present invention replaces nickel hydroxide/Graphene.
Fig. 3 is the cyclic voltammetry curve figure of made electrode in embodiment 1, is presented at 68wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene; Wherein active material quality is 2.8mg, and electrolyte is 6M KOH solution.
Fig. 4 is the cyclic voltammetry curve figure of made electrode in embodiment 2, is presented at 76wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene, wherein active material quality is 2.1mg, and electrolyte is 6M KOH solution.
Fig. 5 is the cyclic voltammetry curve figure of made electrode in embodiment 3, is presented at 82wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene, wherein active material quality is 2.7mg, and electrolyte is 6M KOH solution.
Fig. 6 is the cyclic voltammetry curve figure of made electrode in embodiment 4, is presented at 80wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene, wherein active material quality is 2.6mg, and electrolyte is 6M KOH solution.
Fig. 7 is the constant-current discharge curve chart of made electrode in embodiment 4, and be presented at the discharge curve of 80wt%Ni (OH) 2/ Graphene under different electric current, wherein active material quality is 2.6mg, and electrolyte is 6M KOH solution.
Fig. 8 is the cyclic voltammetry curve figure of made electrode in embodiment 5, is presented at 67wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene, wherein active material quality is 1.8mg, and electrolyte is 6M KOH solution.
Fig. 9 is the cyclic voltammetry curve figure of made electrode in embodiment 6, is presented at 55wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/Graphene, wherein active material quality is 4.2mg, and electrolyte is 6M KOH solution.
Figure 10 is the cyclic voltammetry curve figure of made electrode in embodiment 7, is presented at 73wt%Ni (OH) under different scanning rates
2the cyclic voltammetry curve of/graphite, wherein active material quality is 3.0mg, and electrolyte is 6M KOH solution.
Embodiment
Nickel hydroxide/graphene composite material of the present invention is made up of nickel hydroxide, Graphene, and weight of nickel hydroxide content is 10 ~ 90%.From expanded graphite or graphite, size tunable W metal nano particle is deposited in graphite layers or graphite surface by controlling electrochemical deposition parameter, the Ni/ graphene complex dry, namely compressing tablet obtains metal nano Ni particle, Graphene stratiform replaces, or the compound of Ni/ graphite.Namely Ni (OH) is obtained by cyclic voltammetry in-situ activation in KOH solution
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene, or Ni (OH)
2the composite material of/graphite.Conductive agent can also be added when preparing the slurries of expanded graphite or graphite if carbon black or carbon nano-tube are to strengthen the conductivity of this compound further simultaneously, and then improve its cycle life and high rate performance.
Specifically, stratiform of the present invention replaces the microstructure models figure of nickel hydroxide/graphene composite material as shown in Figure 1, and scanning electron microscope (SEM) photograph is as Fig. 2; Can be prepared by following method:
The first step: take absolute ethyl alcohol as solvent, control in 8 ~ 9:2 ~ 1 by the mass ratio of expanded graphite and binding agent, expanded graphite and binding agent are joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step: adopt dropwise method, is coated in electrode basement (nickel foam or the Copper Foil) surface after process, and carries out drying by the expanded graphite uniform suspension prepared in the first step.After drying, expanded graphite quality is 0.5 ~ 4mg;
3rd step: compound concentration is 5 ~ 20mg mL
-1soluble nickel salting liquid;
4th step: with the electrode prepared in second step for work electrode, compressing electrode basement is to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls between-0.7 ~-3V; The quality of the metallic nickel of deposition is realized by the electricity of control flow check through work electrode, makes nano metal nickel particles/Graphene that stratiform replaces;
5th step: the electrode in the 4th step is carried out drying in a vacuum or in atmosphere, and at 0.1 ~ 10MPa, hot-forming at 80 ~ 130 DEG C;
6th step: prepare the aqueous solution of certain density water soluble alkali as electrochemical activation electrolyte, concentration is at 0.5mol L
-1~ 6mol L
-1between;
7th step: the electrode the 5th step obtained immerses in alkali lye, adopts cyclic voltammetry to carry out electrochemical activation and obtains nickel hydroxide/Graphene.
The composite material of nickel hydroxide/graphite of the present invention can be prepared by following method:
The first step: take absolute ethyl alcohol as solvent, control in 8 ~ 9:2 ~ 1 by the mass ratio of graphite and binding agent, graphite and binding agent are joined in ethanol sonic oscillation a period of time, obtain homodisperse graphite suspension;
Second step: adopt dropwise method, is evenly coated in electrode basement (nickel foam or the Copper Foil) surface after process, and carries out drying by the graphite suspension prepared in the first step.After drying, graphite quality is 0.5 ~ 4mg;
3rd step: compound concentration is 5 ~ 20mg mL
-1soluble nickel salting liquid;
4th step: with the electrode prepared in second step for work electrode, compressing electrode basement is to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls between-0.7 ~-3V; The quality of the metallic nickel of deposition is realized by the electricity of control flow check through work electrode, makes nano metal nickel particles/graphite;
5th step: the electrode in the 4th step is carried out drying in a vacuum or in atmosphere, and at 0.1 ~ 10MPa, hot-forming at 80 ~ 130 DEG C;
6th step: prepare the aqueous solution of certain density water soluble alkali as electrochemical activation electrolyte, concentration is at 0.5mol L
-1~ 6mol L
-1between;
7th step: the electrode the 5th step obtained immerses in alkali lye, adopts cyclic voltammetry to carry out electrochemical activation and obtains nickel hydroxide/graphite.
In said method:
In step one, binding agent can be polytetrafluoroethylene, Kynoar, Nafion solution;
In step 2, soluble nickel salt can be nickel chloride, nickelous sulfate, nickel acetate etc.;
In step 3, solubility alkali lye can be KOH, NaOH.
The present invention is further illustrated below in conjunction with specific embodiment.Those skilled in the art should understand, described embodiment is only help and understands the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and Nafion, expanded graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/foam nickel electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared is coated in 10 × 10 nickel foam surfaces after process, and carries out drying in the first step.After drying, expanded graphite quality is about 1mg;
3rd step, compound concentration are 10mg mL
-1nickel chloride solution;
Nano metal nickel particles/Graphene/foam nickel electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls at-3V; The electricity flowing through work electrode is 2.08C;
5th step, by the pole drying in the 4th step, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
Nano-sized nickel hydroxide/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 1284F g
-1, 10mV s
-1time still can reach 1068F g
-1, ratio capacitance conservation rate is 83%, and its cyclic voltammetry curve is see Fig. 3.
Embodiment 2: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and polytetrafluoroethylene, expanded graphite and polytetrafluoroethylene joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/copper foil electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared is coated in 10 × 10 copper foil surfaces after process, and carries out drying in the first step.After drying, expanded graphite quality is about 1mg;
3rd step, compound concentration are 20mg mL
-1nickel sulfate solution;
Nano metal nickel/Graphene/copper foil electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing copper foils are to electrode and reference electrode, and in nickel sulfate solution, start electro-deposition under constant current potential, sedimentation potential controls at-3V; The electricity flowing through work electrode is 1.04C;
5th step, the electrode in the 4th step is placed in vacuum condition under dry, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the NaOH aqueous solution;
Nano-sized nickel hydroxide/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 1086F g
-1, 10mV s
-1time still can reach 909F g
-1, ratio capacitance conservation rate is 84%, and its cyclic voltammetry curve is see Fig. 4.
Embodiment 3: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and Nafion, expanded graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/foam nickel electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared is coated in 10 × 10 nickel foam surfaces after process, and carries out drying in the first step.After drying, expanded graphite quality is about 1mg;
3rd step, compound concentration are 20mg mL
-1nickel nitrate solution;
Nano metal nickel particles/Graphene/foam nickel electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel nitrate solution, start electro-deposition under constant current potential, sedimentation potential controls at-2V; The electricity flowing through work electrode is 1.04C;
5th step, the electrode in the 4th step is placed in vacuum condition under dry, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
Nano-sized nickel hydroxide/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 1216F g
-1, 10mV s
-1time still can reach 959F g
-1, ratio capacitance conservation rate is 79%, and its cyclic voltammetry curve is see Fig. 5.
Embodiment 4: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and Nafion, expanded graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/foam nickel electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared is coated in 10 × 10 nickel foam surfaces after process, and carries out drying in the first step.After drying, expanded graphite quality is about 1mg;
3rd step, compound concentration are 20mg mL
-1nickel acetate solution;
Nano metal nickel particles/Graphene/foam nickel electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel acetate solution, start electro-deposition under constant current potential, sedimentation potential controls at-1V; The electricity flowing through work electrode is 1.04C;
5th step, the electrode in the 4th step is placed in vacuum condition under dry, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
Nano-sized nickel hydroxide particle/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 1488F g
-1, 10mV s
-1time still can reach 1206F g
-1, ratio capacitance conservation rate is 81%, and its cyclic voltammetry curve is see Fig. 6; At 1A g
-1time ratio capacitance be 1943Fg-1,10A g
-1time ratio capacitance be 1355F g
-1, ratio capacitance conservation rate is 70%, and its constant-current discharge curve participates in Fig. 7.
Embodiment 5: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and Nafion, expanded graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/foam nickel electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared is coated in 10 × 10 nickel foam surfaces after process, and carries out drying in the first step.After drying, expanded graphite quality is about 1mg;
3rd step, compound concentration are 10mg mL
-1nickel chloride solution;
Nano metal nickel particles/Graphene/foam nickel electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls at-3V; The electricity flowing through work electrode is 1.04C;
5th step, the electrode in the 4th step is placed in vacuum condition under dry, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
Nano-sized nickel hydroxide/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 946F g
-1, 10mV s
-1time still can reach 847F g
-1, ratio capacitance conservation rate is 90%, and its cyclic voltammetry curve is see Fig. 8.
Embodiment 6: prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of expanded graphite and Nafion, expanded graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse expanded graphite suspension;
Second step, making expanded graphite/foam nickel electrode
Adopt dropwise method, the expanded graphite uniform suspension prepared in the first step is coated in 10 × 10 nickel foam surfaces after process, and drying is carried out in air dry oven, temperature-controllable, between room temperature and 250 DEG C, makes the direct oxidation of nano nickel particle be nickel oxide.After drying, expanded graphite quality is about 2mg;
3rd step, compound concentration are 20mg mL
-1nickel chloride solution;
Nano metal nickel particles/Graphene/foam nickel electrode that 4th step, making stratiform replace
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls at-1V; The electricity flowing through work electrode is 4.16C;
5th step, the electrode in the 4th step is placed in air drying, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
Nano-sized nickel hydroxide/Graphene/foam nickel electrode that 7th step, preparation stratiform replace
The electrode 5th step obtained immerses 6mol L
-1in KOH, employing cyclic voltammetry carries out nano-sized nickel hydroxide/Graphene/foam nickel electrode that electrochemical activation acquisition stratiform replaces.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 853F g
-1, 10mV s
-1time still can reach 594F g
-1, ratio capacitance conservation rate is 70%, and its cyclic voltammetry curve is see Fig. 9.
Embodiment 7: prepare nickel hydroxide/graphite composite material
The first step, preparation graphite suspension
Take absolute ethyl alcohol as solvent, be 9:1 by the mass ratio of graphite and Nafion, graphite and Nafion joined in ethanol sonic oscillation a period of time, obtain homodisperse graphite suspension;
Second step, making graphite/foam nickel electrode
Adopt dropwise method, the graphite suspension prepared evenly is coated in 10 × 10 nickel foam surfaces after process, and carries out drying in the first step.After drying, graphite quality is about 1mg;
3rd step, compound concentration are 10mg mL
-1nickel chloride solution;
4th step, making nano metal nickel particles/graphite/foam nickel electrode
With the electrode prepared in second step for work electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference electrode, and in nickel chloride solution, start electro-deposition under constant current potential, sedimentation potential controls at-3V; The electricity flowing through work electrode is 2.08C;
5th step, the electrode in the 4th step is placed in vacuum condition under dry, and at 10MPa, hot-forming at 130 DEG C;
6th step, preparation electrochemical activation electrolyte
Preparation 6mol L
-1the KOH aqueous solution;
7th step, prepare nano-sized nickel hydroxide/graphite/foam nickel electrode
The electrode 5th step obtained immerses 6mol L
-1in KOH, adopt cyclic voltammetry to carry out electrochemical activation and obtain nano-sized nickel hydroxide/graphite/foam nickel electrode.
In the test of this electrode cycle volt-ampere, 2mV s
-1time ratio capacitance be 1103F g
-1, 10mV s
-1time still can reach 818F g
-1, ratio capacitance conservation rate is 74%, and its cyclic voltammetry curve is see Figure 10.
Claims (10)
1. a composite material for nickel hydroxide/Graphene, its structure is Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene, wherein weight of nickel hydroxide content is 10 ~ 90%; Obtained by following method:
1) by mass ratio 8 ~ 9:2 ~ 1 of expanded graphite and binding agent, expanded graphite and binding agent are joined sonic oscillation preparation expanded graphite suspension in ethanol;
2) expanded graphite suspension step 1 prepared, on electrode basement surface, controls mass area ratio at 0.5 ~ 4mg cm
-2;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene.
2. a composite material for nickel hydroxide/graphite, its structure is Ni (OH)
2/ graphite, wherein weight of nickel hydroxide content is 10 ~ 90%; Obtained by following method:
1) by mass ratio 8 ~ 9:2 ~ 1 of graphite and binding agent, graphite and binding agent are joined sonic oscillation preparation graphite suspension in ethanol;
2) graphite suspension prepared by step 1 is coated in electrode basement surface, controls mass area ratio at 0.5 ~ 4mg cm
-2;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out the composite material of electrochemical activation acquisition nickel hydroxide/graphite.
3. composite material according to claim 1 and 2, wherein, adds and has carbon black or carbon nano-tube.
4. composite material according to claim 1 and 2, wherein, binding agent is polytetrafluoroethylene or polyvinylidene fluoride emulsion or Nafion solution; Electrode basement is nickel foam or Copper Foil; Soluble nickel salt be nickel chloride, nickelous sulfate, nickel acetate, nickel nitrate one or more; Alkali lye is one or both of KOH, NaOH.
5. prepare the method for nickel hydroxide/Graphene described in claim 1:
1) by mass ratio 8 ~ 9:2 ~ 1 of expanded graphite and binding agent, expanded graphite and binding agent are joined sonic oscillation preparation expanded graphite suspension in ethanol;
2) expanded graphite suspension step 1 prepared is on electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain Ni (OH)
2, the stratiform Ni (OH) that replaces of Graphene
2/ Graphene.
6. prepare the composite process of nickel hydroxide/graphite described in claim 2:
1) by mass ratio 8 ~ 9:2 ~ 1 of graphite and binding agent, graphite and binding agent are joined sonic oscillation preparation graphite suspension in ethanol;
2) graphite suspension prepared by step 1 is coated in electrode basement surface;
3) solution product prepared by step 2 being placed in soluble nickel salt starts electro-deposition;
4) product drying step 3 prepared is also hot-forming;
5) product of step 4 is immersed in alkali lye, adopt cyclic voltammetry to carry out electrochemical activation and obtain nickel hydroxide/graphite.
7. the method according to claim 5 or 6, wherein, adds in step 1 and has carbon black or carbon nano-tube.
8. the method according to claim 5 or 6, wherein, the electrode basement in step 2 is nickel foam or Copper Foil.
9. the method according to claim 5 or 6, wherein, the soluble nickel salt in step 3 be nickel chloride, nickelous sulfate, nickel acetate, nickel nitrate one or more.
10. method according to claim 4, wherein, the alkali lye in step 5 is one or both of KOH, NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510045280.2A CN104616908B (en) | 2015-01-29 | 2015-01-29 | Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510045280.2A CN104616908B (en) | 2015-01-29 | 2015-01-29 | Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104616908A true CN104616908A (en) | 2015-05-13 |
| CN104616908B CN104616908B (en) | 2017-05-17 |
Family
ID=53151316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510045280.2A Expired - Fee Related CN104616908B (en) | 2015-01-29 | 2015-01-29 | Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104616908B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106024424A (en) * | 2016-07-01 | 2016-10-12 | 东华大学 | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof |
| CN106784644A (en) * | 2016-11-09 | 2017-05-31 | 陕西科技大学 | A kind of piece assembles cube Ni (OH)2The preparation method of/GO composites |
| CN106975489A (en) * | 2017-04-26 | 2017-07-25 | 浙江大学 | A kind of preparation method of nickel oxide in-stiu coating graphene nanocomposite material |
| CN108609599A (en) * | 2018-05-30 | 2018-10-02 | 北京化工大学常州先进材料研究院 | The preparation method of nickel hydroxide nano piece self assembly nickel phosphates cobalt club shaped structure composite material |
| WO2018194769A1 (en) * | 2017-04-17 | 2018-10-25 | Baker Hughes, A Ge Company, Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| CN108987123A (en) * | 2018-06-07 | 2018-12-11 | 武汉科技大学 | A kind of manganese dioxide-expanded graphite-cotton fiber tri compound electrochemical capacitance electrode material and preparation method thereof |
| CN109830381A (en) * | 2019-04-04 | 2019-05-31 | 兰州理工大学 | MXene/MoS for electrode of super capacitor2Composite material and preparation method thereof |
| CN110970225A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Preparation method of nickel hydroxide/graphite composite material |
| CN110970224A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Nickel hydroxide/graphite composite material |
| CN111101149A (en) * | 2020-02-18 | 2020-05-05 | 南昌航空大学 | Electro-catalytic hydrogen evolution porous Ni2Mg alloy electrode and preparation method thereof |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN113120978A (en) * | 2021-04-19 | 2021-07-16 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62208550A (en) * | 1986-03-07 | 1987-09-12 | Matsushita Electric Ind Co Ltd | Manufacture of nonsintered nickel electrode |
| US20060166101A1 (en) * | 2001-11-27 | 2006-07-27 | Srinivasan Venkatesan | Active electrode composition with graphite additive |
| CN102350357A (en) * | 2011-07-27 | 2012-02-15 | 天津大学 | Nano-nickel catalyst loaded on grapheme and preparation method thereof |
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN102583348A (en) * | 2012-02-20 | 2012-07-18 | 北京航空航天大学 | Surface nano-nickel particle modified graphene nano material and preparation method thereof |
| CN103774176A (en) * | 2014-02-07 | 2014-05-07 | 上海理工大学 | Method for performing surface modification on material by forming nickel-based ultrathin film through nickel ion self-adsorption |
-
2015
- 2015-01-29 CN CN201510045280.2A patent/CN104616908B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62208550A (en) * | 1986-03-07 | 1987-09-12 | Matsushita Electric Ind Co Ltd | Manufacture of nonsintered nickel electrode |
| US20060166101A1 (en) * | 2001-11-27 | 2006-07-27 | Srinivasan Venkatesan | Active electrode composition with graphite additive |
| CN102350357A (en) * | 2011-07-27 | 2012-02-15 | 天津大学 | Nano-nickel catalyst loaded on grapheme and preparation method thereof |
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN102583348A (en) * | 2012-02-20 | 2012-07-18 | 北京航空航天大学 | Surface nano-nickel particle modified graphene nano material and preparation method thereof |
| CN103774176A (en) * | 2014-02-07 | 2014-05-07 | 上海理工大学 | Method for performing surface modification on material by forming nickel-based ultrathin film through nickel ion self-adsorption |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106024424A (en) * | 2016-07-01 | 2016-10-12 | 东华大学 | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof |
| CN106784644A (en) * | 2016-11-09 | 2017-05-31 | 陕西科技大学 | A kind of piece assembles cube Ni (OH)2The preparation method of/GO composites |
| CN106784644B (en) * | 2016-11-09 | 2019-04-26 | 陕西科技大学 | A kind of assembling cube Ni (OH)2The preparation method of/GO composite material |
| GB2576651B (en) * | 2017-04-17 | 2022-12-28 | Baker Hughes A Ge Co Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| US10982069B2 (en) | 2017-04-17 | 2021-04-20 | Baker Hughes, A Ge Company, Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| WO2018194769A1 (en) * | 2017-04-17 | 2018-10-25 | Baker Hughes, A Ge Company, Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| GB2576651A (en) * | 2017-04-17 | 2020-02-26 | Baker Hughes A Ge Co Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| CN106975489B (en) * | 2017-04-26 | 2019-12-31 | 浙江大学 | Preparation method of nickel oxide in-situ coated graphene nanocomposite |
| CN106975489A (en) * | 2017-04-26 | 2017-07-25 | 浙江大学 | A kind of preparation method of nickel oxide in-stiu coating graphene nanocomposite material |
| CN108609599A (en) * | 2018-05-30 | 2018-10-02 | 北京化工大学常州先进材料研究院 | The preparation method of nickel hydroxide nano piece self assembly nickel phosphates cobalt club shaped structure composite material |
| CN108987123A (en) * | 2018-06-07 | 2018-12-11 | 武汉科技大学 | A kind of manganese dioxide-expanded graphite-cotton fiber tri compound electrochemical capacitance electrode material and preparation method thereof |
| CN110970225A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Preparation method of nickel hydroxide/graphite composite material |
| CN110970224A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Nickel hydroxide/graphite composite material |
| CN109830381A (en) * | 2019-04-04 | 2019-05-31 | 兰州理工大学 | MXene/MoS for electrode of super capacitor2Composite material and preparation method thereof |
| CN111101149A (en) * | 2020-02-18 | 2020-05-05 | 南昌航空大学 | Electro-catalytic hydrogen evolution porous Ni2Mg alloy electrode and preparation method thereof |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN112647092B (en) * | 2020-12-18 | 2022-02-15 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN113120978A (en) * | 2021-04-19 | 2021-07-16 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
| CN113120978B (en) * | 2021-04-19 | 2022-07-01 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104616908B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104616908A (en) | Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material | |
| Yu et al. | Mesoporous NiCo2O4 nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation | |
| Su et al. | NiCo-LDH nanowires@ nanosheets core-shell structure grown on carbon fiber cloth for high performance flexible supercapacitor electrode | |
| Huang et al. | High performance asymmetric supercapacitor based on hierarchical flower-like NiCo2S4@ polyaniline | |
| Swain et al. | Construction of three-dimensional MnO2/Ni network as an efficient electrode material for high performance supercapacitors | |
| Zhu et al. | Co-precipitation synthesis of nickel cobalt hexacyanoferrate for binder-free high-performance supercapacitor electrodes | |
| Li et al. | Controllable preparation of nanoporous Ni3S2 films by sulfuration of nickel foam as promising asymmetric supercapacitor electrodes | |
| Zhou et al. | Electrodeposition and characterization of ordered mesoporous cobalt hydroxide films on different substrates for supercapacitors | |
| Huang et al. | Facilely synthesized porous ZnCo 2 O 4 rodlike nanostructure for high-rate supercapacitors | |
| Ma et al. | A controllable morphology GO/PANI/metal hydroxide composite for supercapacitor | |
| Lv et al. | Controllable synthesis of Ni-Co nanosheets covered hollow box via altering the concentration of nitrate for high performance supercapacitor | |
| Li et al. | Hydrous RuO2 nanoparticles coated on Co (OH) 2 nanoflakes as advanced electrode material of supercapacitors | |
| Liu et al. | Co (OH) F@ CoP/CC core-shell nanoarrays for high-performance supercapacitors | |
| Xue et al. | Heterostructure of metal–organic framework-derived straw-bundle-like CeO2 decorated with (Ni, Co) 3S4 nanosheets for high-performance supercapacitor | |
| Han et al. | Co3O4 nanowire@ ultrathin Ni-Co layered double hydroxide core-shell arrays with vertical transfer channel for high-performance supercapacitor | |
| Zhou et al. | Enhanced supercapacitive behaviors of poly (3, 4-ethylenedioxythiophene)/graphene oxide hybrids prepared under optimized electropolymerization conditions | |
| CN105957728B (en) | A kind of nickel cobalt double-hydroxide/NiCo2S4Composite nano materials, its preparation method and the application as electrode material for super capacitor | |
| CN103854878A (en) | Supercapacitor based on polypyrrole / manganese dioxide / carbon cloth and manufacturing method thereof | |
| CN102723209A (en) | Preparation method for graphene nanosheet/conducting polymer nanowire composite material | |
| Hu et al. | Urchin-like NiCo2S4 structures synthesized through a one-step solvothermal process for high-performance supercapacitors | |
| Vijayakumar et al. | Electrochemical supercapacitor behaviour of α-Ni (OH) 2 nanoparticles synthesized via green chemistry route | |
| Ma et al. | Core-shell Ni1. 5Sn@ Ni (OH) 2 nanoflowers as battery-type supercapacitor electrodes with high rate and capacitance | |
| Shi et al. | 3D mesoporous hemp-activated carbon/Ni3S2 in preparation of a binder-free Ni foam for a high performance all-solid-state asymmetric supercapacitor | |
| Jiang et al. | Nickel hexacyanoferrate flower-like nanosheets coated three dimensional porous nickel films as binder-free electrodes for neutral electrolyte supercapacitors | |
| Haghshenas et al. | CoFe2O4@ methyl cellulose core-shell nanostructure and their hybrids with functionalized graphene aerogel for high performance asymmetric supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170517 Termination date: 20190129 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |