CN109003824A - Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof - Google Patents
Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof Download PDFInfo
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- CN109003824A CN109003824A CN201810696898.9A CN201810696898A CN109003824A CN 109003824 A CN109003824 A CN 109003824A CN 201810696898 A CN201810696898 A CN 201810696898A CN 109003824 A CN109003824 A CN 109003824A
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- 238000003491 array Methods 0.000 title claims abstract description 78
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical class [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- -1 nickelous selenide Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 14
- 238000013019 agitation Methods 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 230000035484 reaction time Effects 0.000 description 17
- 238000012545 processing Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 239000011669 selenium Substances 0.000 description 11
- 150000003346 selenoethers Chemical class 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 9
- 229910017709 Ni Co Inorganic materials 0.000 description 8
- 229910003267 Ni-Co Inorganic materials 0.000 description 8
- 229910003262 Ni‐Co Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
-
- 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
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- 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
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a kind of ternary cobalt nickel selenides nano-chip arrays electrode materials and preparation method thereof, belong to electrode material preparation technical field.It is made by the following method: by Co (CH3COO)2•4H2O is added to the in the mixed solvent of methyl phenyl ethers anisole and methanol, magnetic agitation to whole dissolutions；By gained Co (CH3COO)2Solution is added in autoclave, then prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template is put into, and is controlled reaction temperature and time, is obtained ternary cobalt nickel selenides nano-chip arrays.The electrode obtained material has excellent chemical property, is 1.0 A g in current density‑1When specific capacitance can reach 3917 F g‑1Even if reaching 10 A g in current density‑1When, specific capacitance still can reach 2150 F g‑1.It is reacted using base exchange method, easy to operate, no coupling product, experiment are controllable, high-efficient, purity is high.Suitable for supercapacitor.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation technical fields, and in particular to a kind of ternary cobalt nickel selenides is received
Rice chip arrays electrode material and preparation method thereof.
Background technique
In current technical field of energy storage, lithium ion battery, fuel cell and supercapacitor are most effective and have real
With the electrochemical energy conversion of value and storage device.In comparison with other two kinds of energy storage systems, super capacitor utensil
There is high power density, quick charge and discharge process, the long-life, low cost, environmental-friendly and safe, however, if
Meet ever-increasing energy requirement, it is necessary to ensure that supercapacitor improves its energy in the case where not wasted power density
Metric density.Hybrid super capacitor is capable of providing higher energy density, because it is by battery-type electrode chose material (energy source)
It is formed with capacitive electrode material (power source), has broader operating voltage and higher capacitor, to be expected to obtain more
High energy density.However, to obtain high performance hybrid super capacitor, the ion of battery-type electrode chose material transmits speed
Rate should match with the ion transportation of two-layer electrode material, to make two different energy-storage systems be complementary to one another, most
Bigization plays the performance of hybrid super capacitor, and presently, this is still the technical problem of a breakthrough.Therefore, how to obtain
Novel battery type electrode material with ideal intrinsic characteristic and external structure is to realize High-performance hybrid supercapacitor
It is crucial.
Compared with monometallic compound-material, bimetallic Ni-Co compound due to the synergistic effect between cobalt and nickel to
Show more preferably chemical property.In bimetallic Ni-Co compound, Ni-Co chalcogenide is due to its high theory electricity
Hold and low cost and receive significant attention.For example, the Ni-Co nano-pillar of core-shell structure, NiCo2O4Nanometer sheet@galapectite nanometer
Pipe, CoNiO2Nanoparticle, NiCo2S4Nano-tube array, CoNi2S4Nanoparticle and CoNi2S4/ graphene nanocomposite material
It has been used as the electrode material of supercapacitor.It is well known that element O, S and Se belong to same main group in the periodic table of elements, tool
There are similar electrochemical properties.But Se (1 × 10-3S m-1) conductivity be much higher than S (1 × 10-28Sm-1), it means that three
First Ni-Co selenides will have higher conductivity and electro-chemical activity than ternary Ni-Co oxide or sulfide, be capable of providing
Faster ion/electron transfer rate.Therefore, the electrode material that ternary Ni-Co selenides is used as hybrid super capacitor is had
Help effectively solve its positive and negative anodes matching problem.Some researchs are using monometallic selenides as the electricity of supercapacitor recently
Pole, such as: three-dimensional Co0.85Se, NiSe nano wire, honeycomb Ni0.85Se nano-chip arrays, SnSe2With SnSe nanometer sheet etc..But
It is less about the synthesis of ternary Ni-Co selenides and the research of chemical property.It can be seen that developing a kind of simple, low cost
Method be suitable for supercapacitor ternary cobalt nickel selenides nanostructure preparation have very important realistic meaning.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of ternary cobalt nickel selenizings of electrochemical performance
The electrode material of object nano-chip arrays；Another object is to provide simple, inexpensive preparation method.
In previous work, using one step hydro thermal method be prepared for cellular nickelous selenide nano-chip arrays (number of patent application:
CN201710932864.0).As the follow-up study to this work, while also purpose to realize the present invention, of the invention
In technical solution, using the nickelous selenide nano-chip arrays obtained in above-mentioned patent as template, it is prepared for having using base exchange method
There are the ternary cobalt nickel selenides nano-chip arrays of metallic character.
Preparation method are as follows: methyl phenyl ethers anisole and methanol are mixed according to certain volume ratio first, form mixed solvent.Then will
Co(CH3COO)2·4H2O is dissolved in wherein.Prefabricated nickelous selenide nano-chip arrays template is put into wherein again, is carried out at solvent heat
Reason.Accurate control reaction temperature and time, the ternary cobalt nickel selenides nano-chip arrays suitable for supercapacitor can be obtained
Electrode material.
It is realized especially by following steps:
1) preparation of mixed solvent: methyl phenyl ethers anisole and methanol are mixed, mixed solvent is configured to；It is preferred that methyl phenyl ethers anisole and methanol
The ratio between volume is 5:1~1:1.
2)Co(CH3COO)2The preparation of solution: by Co (CH3COO)2·4H2O is dissolved in the mixed of step (1) methyl phenyl ethers anisole and methanol
In bonding solvent, it is configured to Co (CH3COO)2Solution；It is preferred that Co (CH3COO)2The molar concentration of solution is 0.1-0.01mol dm-3。
3) synthesis of ternary cobalt nickel nickelous selenide nano-chip arrays: by Co (CH made from step (2)3COO)2Solution is added to
In autoclave, then nickelous selenide nano-chip arrays template is put into reaction kettle, control is reacted under the conditions of 120 DEG C, reaction knot
Shu Hou, reaction kettle natural cooling are taken out product, are cleaned with deionized water and ethyl alcohol, are dried in vacuo, can be obtained ternary cobalt nickel selenium
Compound nano-chip arrays.
What step (3) the nickelous selenide nano-chip arrays template was prepared using CN201710932864.0 the method
Honeycomb nickelous selenide nano-chip arrays.
Preferably 120 DEG C of step (3) the reaction treatment condition are heat-treated 4 hours.
Electrochemical property test: the ternary cobalt nickel nickelous selenide nano-chip arrays of acquisition are directly used as super capacitor electrode
Its chemical property is tested in pole in three-electrode system.Platinum electrode and saturated calomel electrode (SCE) are used separately as to electrode and ginseng
Than electrode, electrolyte is 3.0mol dm-3KOH solution.Cyclic voltammetric is surveyed in electrochemical workstation (CHI660E, Shanghai Chen Hua)
Examination.Constant current charge-discharge is completed on Arbin electrochemical apparatus.
Advantage of the present invention and innovative point are as follows:
1. since the present invention is synthesized using organic solvent hydrothermal method, easy to operate, no coupling product, experiment are controllable, high-efficient, and
It can obtain metallicity ternary cobalt nickel selenides nano-chip arrays well, about 20 nanometers of the thickness of nanometer sheet, free from admixture.
2. being template due to directlying adopt nickelous selenide nano-chip arrays, so that ternary cobalt nickel selenides can be raw with direct in-situ
It grows in conductive substrates, forms array structure, traditional technology for preparing electrode is not only omitted, while also shortening ion expansion
Dissipate path.
3. ternary cobalt nickel selenides nano-chip arrays due to the metallicity of its own, redox reaction abundant and
Unique array structure, so that the electrode material has excellent chemical property, it is 1.0A g in current density-1When ratio electricity
Appearance can reach 3917F g-1Even if reaching 10A g in current density-1When, specific capacitance still can reach 2150F g-1, show institute
Obtaining ternary cobalt nickel selenides nano-chip arrays has excellent chemical property, is highly suitable to be applied for supercapacitor field.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of 1 gained ternary cobalt nickel selenides nano-chip arrays of the embodiment of the present invention.
Fig. 2 is the Energy Dispersive X diffraction pattern of the product stripped down in 1 nickel foam of the embodiment of the present invention.
Fig. 3 is the scanning electricity of the different amplification of 1 gained ternary cobalt nickel selenides nano-chip arrays of the embodiment of the present invention
Mirror photo.
Fig. 4 is the transmission electricity of the different amplification of 1 gained ternary cobalt nickel selenides nano-chip arrays of the embodiment of the present invention
Mirror photo.
Fig. 5 is to be swept under speed based on 2 gained ternary cobalt nickel selenides nano-chip arrays electrode of the embodiment of the present invention in difference
Cyclic voltammogram.
Fig. 6 is based under 2 gained ternary cobalt nickel selenides nano-chip arrays electrode difference current density of the embodiment of the present invention
Constant current charge-discharge figure.
Fig. 7 is the X-ray diffraction comparison map in the different reaction time products therefrom of 120 DEG C of processing.
Fig. 8 is Co/ (Ni+Co) percentage in the different reaction time products therefrom of 120 DEG C of processing.
Fig. 9 is the stereoscan photograph in the different reaction time products therefrom of 120 DEG C of processing: (a) template；(b) 4 is small
When；(c) 6 hours；(d) 8 hours.
Figure 10 is in the different reaction time products therefrom of 120 DEG C of processing in 10mV s-1When cyclic voltammetric correlation curve.
Figure 11 is in the different reaction time products therefrom of 120 DEG C of processing in 1A g-1When comparison discharge curve.
Figure 12 is in the different reaction time products therefrom of 120 DEG C of processing in different current density specific capacitances.
Specific embodiment
It is as follows for embodiment for the present invention is better described, following examples be to it is of the invention furtherly
It is bright, and do not limit the scope of the invention.
Embodiment 1
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 0.4mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20mL methyl phenyl ethers anisole and methanol
10mL, methanol 10mL) in, to whole dissolutions, acquisition concentration is 0.02mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2
Solution.
3. 2. 0.02mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 4 hours, reaction kettle naturally cools to room temperature, is washed for several times with dehydrated alcohol, deionized water, vacuum
It is dry, it can be obtained ternary cobalt nickel selenides nano-chip arrays.
The X ray diffracting spectrum of gained ternary cobalt nickel selenides nano-chip arrays is as shown in Fig. 1.As seen from the figure, allusion quotation
Type diffraction maximum is similar to Ni0.85The diffraction maximum of Se (JCPDS 18-888).However, by examining discovery, the ternary cobalt nickel
The diffraction maximum of selenides is relative to Ni0.85Se is mobile to high angle direction.Slight movement of this diffraction maximum to high angle direction,
It reflects cobalt ions and successfully displaces part nickel ion, while showing that base exchange process will not change the crystal knot of presoma
Structure, the lattice parameter for only resulting in presoma reduce.This is because Co2+To Se2-Polarization force be greater than Ni2+To Se2-Polarization force
(r(Co2+)=65pm < r (Ni2+)=69pm), cause ionic bond to convert to covalent bond, so that ionic bond bond distance be made to reduce.XRD
The result shows that Co ion is successfully doped to Ni0.85In Se nano-array and Ni2+And Co2+Exist jointly in typical sample.It is attached
Fig. 2 is the Energy Dispersive X diffraction pattern of the product stripped down in nickel foam, according to test data it is found that the original of Ni and Co
Son compares close to 1:1.Attached drawing 3 is that the scanning electron microscope of the different amplification of gained ternary cobalt nickel selenides nano-chip arrays is shone
Piece.Fig. 3 a shows that the surface of nickel foam is all covered by cellular nano-chip arrays, shows that this method can synthesize on a large scale
The array structure.By Fig. 3 b as it can be seen that products therefrom is with cellular nano-chip arrays structure, thickness is about 20 nanometers,
The diameter of single hole is about 300-450 nanometers between nanometer sheet.This unique honeycomb structure is with big specific surface area and largely
Electroactive site can accommodate a large amount of electrolyte ions in electrode material surface and participate in electrochemical reaction process.In array
Macropore can store a large amount of electrolyte ion, may advantageously facilitate the quick diffusion of electrolyte ion.Fig. 4 is ternary cobalt nickel selenium
The transmission electron microscope photo figure of compound nano-chip arrays different amplification.Lamellar morphology shown in Fig. 4 a further demonstrates gained
The nanometer chip architecture of sample.The spacing of lattice of 0.267nm is than hexagonal phase Ni0.85(101) interplanar distance of Se (JCPDS) from
(0.270nm) is smaller, and the offset phenomena of this and diffraction maximum in XRD corroborates each other.
Embodiment 2
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 0.8mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20m methyl phenyl ethers anisole and methanol
15mL, methanol 5mL) in, to whole dissolutions, acquisition concentration is 0.04mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2It is molten
Liquid.
3. 2. 0.04mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 4 hours, reaction kettle naturally cools to room temperature for control, is washed for several times with dehydrated alcohol, deionized water,
Vacuum drying, can be obtained ternary cobalt nickel selenides nano-chip arrays.
Gained ternary cobalt nickel selenides nano-chip arrays are directly used as supercapacitor working electrode, and test its electrification
Learn property.Fig. 5 is that the electrode of super capacitor based on ternary cobalt nickel selenides nano-chip arrays of the present invention is swept under speed in difference
Cyclic voltammetric (CV) figure, as seen from the figure, in 3.0mol dm-3In KOH electrolyte, all CV curves have a pair of of shape good
Redox peaks, it was demonstrated that have occurred faraday's redox reaction in electrochemical process.This can be attributed to Ni and Co it
Between electron interaction.In addition, to reflect faraday anti-for the symmetrical feature of ternary cobalt nickel selenides nano-chip arrays CV curve
The excellent reversibility answered.Importantly, with fast increase is swept, the shape of CV curve keeps good.This means that ternary cobalt nickel
Selenides nano-chip arrays have quick mass transfer rate and excellent electric conductivity.However, aoxidizing peak position with fast increase is swept
Mobile to high potential, reduction peak position is mobile to low potential, this is because water phase electrolyte polarization increases and charge spreads internal resistance
Increase.Fig. 6 is constant current charge-discharge figure of the electrode under different current densities, it is found that " bell " the permanent electricity of the electrode
Stream charging and discharging curve again demonstrates the leading position of redox reaction in charge/discharge process, the observation of this and CV curve
As a result consistent.Plateau potential on charging and discharging curve shows that ternary cobalt nickel selenides nano-chip arrays belong to battery-type electrode chose material
Material.According to the calculation formula of specific capacitance: C=I × Δ t/ (m × Δ V), wherein C (F g-1) it is specific capacitance, I (A) is electric discharge electricity
Stream, Δ t (s) is discharge time, and Δ V (V) is voltage window, and m (g) is the active material quality on electrode, it can be deduced that the ternary
Cobalt nickel selenides nanometer plate electrode current density be 1,2,3,4,5 and 10A/g when, specific capacitance difference 3917,3755,
3278,3110,2638 and 2150F g-1, show excellent electrochemical capacitance characteristic.All Electrochemical results show Co/Ni ratio
There is excellent chemical property for the ternary cobalt nickel selenides nano-chip arrays of 1:1, be better than the known cobalt-nickel oxide reported,
Sulfide, the electrode materials such as selenides.The excellent chemical property of ternary cobalt nickel selenides nano-chip arrays is attributable to following
Several reasons: (1) unique honeycomb structure provides big specific surface area, ensure that effectively connecing between electrode and electrolyte
Touching, to improve the utilization rate of electrode.Macropore between nanometer sheet interconnected can serve as " ion caching library " to hold
Receive a large amount of OH-For continuous redox reaction；(2) the ternary cobalt nickel selenides nanometer sheet battle array for being 1:1 with Co/Ni ratio
Column, realize the optimum synergistic effect between Ni and Co ion.(3) the directly contact of nano-chip arrays and collector can be to avoid
Using the binder for increasing resistance, the electric conductivity of electrode material is improved.(5) ternary cobalt nickel selenides nano-chip arrays have gold
Belong to characteristic, helps to realize good electric conductivity.The high conductivity of electrode ensure that the quick conduction of electronics, to accelerate biography
Matter speed.
Embodiment 3
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 2.0mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20m methyl phenyl ethers anisole and methanol
10mL, methanol 10mL) in, to whole dissolutions, acquisition concentration is 0.10mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2
Solution.
3. 2. 0.10mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 4 hours, reaction kettle naturally cools to room temperature for control, is washed for several times with dehydrated alcohol, deionized water,
Vacuum drying, can be obtained ternary cobalt nickel selenides nano-chip arrays.
Object phase, composition, chemical property and the Examples 1 and 2 basic one of gained ternary cobalt nickel selenides nano-chip arrays
It causes.
Embodiment 4
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 0.8mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20m methyl phenyl ethers anisole and methanol
15mL, methanol 5mL) in, to whole dissolutions, acquisition concentration is 0.04mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2It is molten
Liquid.
3. 2. 0.04mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 2 hours, reaction kettle naturally cools to room temperature for control, is washed for several times with dehydrated alcohol, deionized water,
Vacuum drying, can be obtained ternary cobalt nickel selenides nano-array.
Embodiment 5
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 0.8mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20m methyl phenyl ethers anisole and methanol
15mL, methanol 5mL) in, to whole dissolutions, acquisition concentration is 0.04mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2It is molten
Liquid.
3. 2. 0.04mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 6 hours, reaction kettle naturally cools to room temperature for control, is washed for several times with dehydrated alcohol, deionized water,
Vacuum drying, can be obtained ternary cobalt nickel selenides nano-array.
Embodiment 6
1. honeycomb nickelous selenide nano-chip arrays are synthesized according to synthetic method described in CN201710932864.0, by it
Predecessor as synthesis of ternary cobalt nickel selenides.
2. by the Co (CH of 0.8mmol3COO)2·4H2O is added to the mixed solvent (methyl phenyl ethers anisole of 20m methyl phenyl ethers anisole and methanol
15mL, methanol 5mL) in, to whole dissolutions, acquisition concentration is 0.04mol dm within magnetic agitation 30 minutes-3Co (CH3COO)2It is molten
Liquid.
3. 2. 0.04mol dm that 20mL step is prepared-3Co(CH3COO)2Solution is added to poly- four that volume is 30mL
In vinyl fluoride liner autoclave, then by step 1. in prefabricated honeycomb nickelous selenide nano-chip arrays predecessor template be put into
Wherein, after 120 DEG C are handled 8 hours, reaction kettle naturally cools to room temperature for control, is washed for several times with dehydrated alcohol, deionized water,
Vacuum drying, can be obtained ternary cobalt nickel selenides nano-array.
Fig. 7 is the X-ray diffraction comparison map in the different reaction time products therefrom of 120 DEG C of processing.As seen from the figure, institute
There is product to all have similar XRD spectra.However, peak value is gradually mobile to high angle direction with the increase of Co ion concentration.
Fig. 8 is Co/ (Ni+Co) percentage in the different reaction time products therefrom of 120 DEG C of processing.It can be found that selenides nanometer
Co in array2+Doping gradually increased with the increase in reaction time, when reacted between be 4 hours when reach maximum value.
Then, when extending to 6h and 8h with the reaction time, Co2+Doping be gradually reduced.This shows Co2+And Ni2+Exchange in benzene
It is reversible in methyl ether/methanol system.Fig. 9 is that the scanning electron microscope in the different reaction time products therefrom of 120 DEG C of processing is shone
Piece.Typical honeycomb structure is presented in nickelous selenide nano-chip arrays predecessor template known to Fig. 9 a.When ion-exchange time is 2
When hour, the honeycomb structure of script becomes sparse, is extra large banded structure (see Fig. 9 b), at this time the Co/Ni ratio of ternary selenides
For 1:3.This is attributable to the introducing of cobalt ions and original Ni0.85Se presoma is partly dissolved.With ion-exchange time
Increase, ternary selenides forms more extra large banded structures and is connected with each other, and when the reaction time is 4 hours, re-forms honeycomb
Shape structure, Co/Ni ratio are 1:1.(see Fig. 3).When continuing to extend to 6 hours between when reacted, three-dimensional honeycomb shape structure is kept not
Become, but Co/Ni ratio becomes 1:2.57 (see Fig. 9 c).This shows that nickel ion starts to replace cobalt ions.Cation exchange 8 hours
When, honeycomb structure disappears again, presents gully shape structure (see Fig. 9 d), and Co/Ni ratio is 1:9, this may be due to cobalt
Ion exchange between nickel ion repeatedly destroys the honeycomb structure of script.
The chemical property that the differential responses time obtains product is tested in traditional three-electrode system, electrolyte
For 3mol dm-3KOH solution.Figure 10 is in the different reaction time products therefrom of 120 DEG C of processing in 10mV s-1When circulation volt
Pacify correlation curve.Prepared selenides is in 10mV s-1When CV curve become with the variation of sample different-shape and composition
Change, show pattern and organizes the chemical property of Chengdu influence electrode material.In addition, the CV curve institute envelope surface of 4 hours products of reaction
Product is maximum, implies that ternary cobalt nickel selenides nano-chip arrays have optimal chemical property when Co/Ni ratio is 1:1.Figure 11 is
In the different reaction time products therefrom of 120 DEG C of processing in 1A g-1When comparison discharge curve.Wherein, 4 hours products are reacted
Discharge time longest, further demonstrating Co/Ni ratio is 1:1, and there is ternary cobalt nickel selenides nano-chip arrays most forceful electric power lotus to deposit
Energy storage power.Figure 12 is in the different reaction time products therefrom of 120 DEG C of processing in different current density specific capacitances.It can be with from figure
Find out, the product of reaction 4 hours is in 1,2,3,4,5 and 10A g-1When, quality specific capacitance is respectively 3917,3755,3278,
3110,2638 and 2150F g-1, much higher than the sample in other reaction time.The capacity retention for reacting 4 hours products is 55%
(1 arrives 10A g-1), also above predecessor template (47%), 2 hours products (32%), 6 hours products (49%) and 8 hours products
(38%).In short, at a certain temperature, there is larger impact in the reaction time to reaction product.It is obtained within 4 hours in 120 DEG C of processing
Ternary cobalt nickel selenides nano-chip arrays have optimal chemical property, so reaction treatment condition of the invention is preferably
120 DEG C are heat-treated 4 hours.
Claims (6)
1. ternary cobalt nickel selenides nano-chip arrays electrode material, which is characterized in that be prepared via a method which:
1) preparation of mixed solvent: methyl phenyl ethers anisole and methanol are mixed, mixed solvent is configured to；
2) Co (CH3COO)2The preparation of solution: by Co (CH3COO)2•4H2O is dissolved in step (1) methyl phenyl ethers anisole and the mixing of methanol is molten
In agent, it is configured to Co (CH3COO)2Solution；
3) synthesis of ternary cobalt nickel nickelous selenide nano-chip arrays: by Co (CH made from step (2)3COO)2Solution is added to high pressure
In reaction kettle, then nickelous selenide nano-chip arrays template being put into reaction kettle, control is reacted under the conditions of 120 DEG C, after reaction,
Reaction kettle natural cooling is taken out product, is cleaned with deionized water and ethyl alcohol, is dried in vacuo, can be obtained ternary cobalt nickel selenides
Nano-chip arrays；
The honeycomb that step (3) the nickelous selenide nano-chip arrays template uses CN201710932864.0 the method to be prepared
Shape nickelous selenide nano-chip arrays.
2. ternary cobalt nickel selenides nano-chip arrays electrode material as described in claim 1, which is characterized in that methyl phenyl ethers anisole and first
The ratio between volume of alcohol is 5:1~1:1；Co(CH3COO)2The molar concentration of solution is 0.1-0.01 mol dm-3。
3. ternary cobalt nickel selenides nano-chip arrays electrode material as claimed in claim 1 or 2, which is characterized in that step (3)
The reaction condition is 120 DEG C and is heat-treated 4 hours.
4. the method for preparing ternary cobalt nickel selenides nano-chip arrays electrode material as described in claim 1, which is characterized in that
It is achieved by the steps of:
1) preparation of mixed solvent: methyl phenyl ethers anisole and methanol are mixed, mixed solvent is configured to；
2) Co (CH3COO)2The preparation of solution: by Co (CH3COO)2•4H2O is dissolved in step (1) methyl phenyl ethers anisole and the mixing of methanol is molten
In agent, it is configured to Co (CH3COO)2Solution；
3) synthesis of ternary cobalt nickel nickelous selenide nano-chip arrays: by Co (CH made from step (2)3COO)2Solution is added to high pressure
In reaction kettle, then nickelous selenide nano-chip arrays template being put into reaction kettle, control is reacted under the conditions of 120 DEG C, after reaction,
Reaction kettle natural cooling is taken out product, is cleaned with deionized water and ethyl alcohol, is dried in vacuo, can be obtained ternary cobalt nickel selenides
Nano-chip arrays；
The honeycomb that step (3) the nickelous selenide nano-chip arrays template uses CN201710932864.0 the method to be prepared
Shape nickelous selenide nano-chip arrays.
5. the preparation method of ternary cobalt nickel selenides nano-chip arrays electrode material as claimed in claim 4, which is characterized in that
The ratio between volume of methyl phenyl ethers anisole and methanol is 5:1~1:1；Co(CH3COO)2The molar concentration of solution is 0.1-0.01 mol
dm-3。
6. the preparation method of ternary cobalt nickel selenides nano-chip arrays electrode material as described in claim 4 or 5, feature exist
In step (3) reaction condition is 120 DEG C and is heat-treated 4 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274749A (en) * | 2008-03-25 | 2008-10-01 | 大连理工大学 | Universal synthesis method for porous hollow metallic oxide |
| CN103920506A (en) * | 2014-05-08 | 2014-07-16 | 湘潭大学 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
| CN106057480A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof |
| CN106098402A (en) * | 2016-08-11 | 2016-11-09 | 浙江大学 | A kind of CoNiSe for ultracapacitor2nano-array material and preparation method thereof |
| CN106952731A (en) * | 2017-03-01 | 2017-07-14 | 三峡大学 | A kind of DSSC NiS2/CoS2To the preparation method of electrode |
| CN107818873A (en) * | 2017-10-10 | 2018-03-20 | 安阳师范学院 | Cellular nickelous selenide nano-chip arrays electrode material and preparation method thereof |
-
2018
- 2018-06-29 CN CN201810696898.9A patent/CN109003824A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274749A (en) * | 2008-03-25 | 2008-10-01 | 大连理工大学 | Universal synthesis method for porous hollow metallic oxide |
| CN103920506A (en) * | 2014-05-08 | 2014-07-16 | 湘潭大学 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
| CN106057480A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof |
| CN106098402A (en) * | 2016-08-11 | 2016-11-09 | 浙江大学 | A kind of CoNiSe for ultracapacitor2nano-array material and preparation method thereof |
| CN106952731A (en) * | 2017-03-01 | 2017-07-14 | 三峡大学 | A kind of DSSC NiS2/CoS2To the preparation method of electrode |
| CN107818873A (en) * | 2017-10-10 | 2018-03-20 | 安阳师范学院 | Cellular nickelous selenide nano-chip arrays electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KAILU GUO等: ""Hierarchical ternary Ni–Co–Se nanowires for high-performance supercapacitor device design"", 《DALTON TRANSACTIONS》 * |
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