CN109961963A - NiCoP-CoP porous nano line is interweaved the regular hexagon micron chip capacitance material and preparation method of composition - Google Patents
NiCoP-CoP porous nano line is interweaved the regular hexagon micron chip capacitance material and preparation method of composition Download PDFInfo
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- CN109961963A CN109961963A CN201711452578.0A CN201711452578A CN109961963A CN 109961963 A CN109961963 A CN 109961963A CN 201711452578 A CN201711452578 A CN 201711452578A CN 109961963 A CN109961963 A CN 109961963A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims abstract description 9
- 239000002070 nanowire Substances 0.000 claims abstract description 16
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 12
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 12
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 229910003266 NiCo Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of preparation methods of novel electrode material for super capacitor: using nickel nitrate, cobalt nitrate, ammonium fluoride and urea as raw material, it is that 80~100nm nano wire is interweaved the Ni-Co presoma of composition that diameter is first made using hydro-thermal reaction, then carries out phosphatization；Material obtained is the regular hexagon micron chip (about 10 microns of side length, about 100 nanometers of thickness) constituted that is interweaved by porous (3~5nm of the aperture) nano wire of NiCoP-CoP；The advantages of materials combine high-specific surface area and high mechanical stability, it is ensured that higher chemical property；After charge and discharge cycles 10000 times, specific capacitance conservation rate is up to nearly 92%；The preparation method is easy to operate, at low cost, is easy to scale, receives micro- combination electrode material to designing and preparing and is of great significance.
Description
Technical field
The present invention relates to a kind of preparation methods of electrode material for super capacitor, pass through hydro-thermal reaction and inert atmosphere down tube
It is micro- to synthesize the regular hexagon that there is the NiCoP-CoP porous nano line of excellent electrochemical performance to be interweaved composition for phosphatization in formula furnace
Rice chip capacitor material.This method is without any template, easy to operate, at low cost, reproducible and easily controllable.
Background technique
With the fast development of electronic energy device and hybrid vehicle, battery and traditional capacitor are no longer satisfied
Its demand.The advantages that supercapacitor is due to its high power density, fast charging and discharging and long circulation life, by scientific research circle and production
The close attention of industry.Divided by electrode material, supercapacitor include using carbon material as the double layer capacitor of electrode and with
Metal oxide or conducting polymer are the fake capacitance capacitor of electrode material.The latter is not only formed in electrolyte and electrode interface
Electric double layer, and redox reaction occurs in electrode material surface.Therefore, the latter has bigger specific capacitance than the former.
Transition metal hydroxide possesses preferable electro-chemical activity and has been widely studied for fake capacitance capacitor, theoretical
Upper M (OH)2The theoretical specific capacitance of supercapacitor based on fake capacitance reaction can achieve 1500Fg-1More than, but due to hydrogen-oxygen
Compound conductivity is low, and transmission of the electronics between active material is suppressed, therefore is unable to reach higher specific capacitance and excellent always
Different high rate performance.Exploring and having both the fake capacitance electrode material of high conductivity and high specific capacitance is that the current field is pursued always
Target.
The fake capacitance reaction mechanism of transition metal phosphide (TMP) is similar to hydroxide, this is because in alkaline electrolysis
In liquid, the transition metal element of electrode surface forms hydroxide with the hydroxyl in electrolyte first.Due to TMP usually its gold
Belonging to the chemical valence of phosphorus is 0 valence, possesses the property similar to metallic conductor, therefore its electronic conductivity will be significantly higher than hydrogen
Oxide.Furthermore the mass percent of metallic atom is high in the TMP of metal rich phase, and theoretical specific capacitance is higher than hydroxide.
The present invention grows regular hexagon made of obtaining the braiding of NiCo presoma nano wire by controlling the hydro-thermal reaction time
Micron chip, then single nano-wire is converted to NiCoP-CoP porous nano line by phosphatization in tube furnace.Micron chip thickness is about
100nm, about 10 microns of side length, the aperture on single nano wire is 3~5nm.This micropore built-up by nano unit is micro-
Rice electrode material shows higher specific capacitance and good cyclical stability.
Summary of the invention
The purpose of the present invention: the patent proposes a kind of preparation method of novel electrode material for super capacitor, the material
It is to be interweaved the regular hexagon micron chip constituted by NiCoP-CoP porous nano line.It has had both high-specific surface area and high-tensile strength
The advantages of learning stability, it is ensured that higher chemical property；After charge and discharge cycles 10000 times, specific capacitance conservation rate is up to close
92%；The preparation method is easy to operate, at low cost, is easy to scale；Micro- combination electrode material is received with weight to designing and preparing
Want meaning.
The technical scheme is that the nickel nitrate of certain mass, cobalt nitrate, ammonium fluoride and urea are dissolved in deionization
In water, 15~30min of magnetic agitation；Take 40mL mixed solution to be transferred in 50mL reaction kettle, 120~160 DEG C of reaction 8h with
On, by reaction product eccentric cleaning, dry 12h, obtains Ni-Co presoma at 60 DEG C；Then, configure 100~1000mg's
Sodium hypophosphite and 100~200mg presoma are respectively placed in porcelain boat both ends, and porcelain boat is placed in tube furnace, and temperature program 2 is arranged
~5 DEG C/min to 300 DEG C, in 300 DEG C and N22h or more is reacted under atmosphere, then reaction product, is finally centrifuged by Temperature fall
Cleaning, 60 DEG C of dry 12h obtain final product phosphatization cobalt nickel (NiCoP-CoP)
As optimum response parameter, nickel nitrate in mixed reaction solution, cobalt nitrate, ammonium fluoride and urea concentration be respectively
0.7~2.3mM, 1.4~4.6mM, 4.2~13.8mM and 10.5~34.5mM.
As optimal conditions, when hydro-thermal method prepares Ni-Co presoma, reaction temperature is between 120~160 DEG C, when reaction
Between 8h or more；By reaction product eccentric cleaning, dry 12h under 60 DEG C of air environments.
As optimal conditions, when carrying out phosphatization to Ni-Co presoma, the quality of sodium hypophosphite is 100~1000mg, is taken
The quality of presoma is 100~200mg；Under an inert atmosphere, set 2~5 DEG C/min of heating rate, at 300 DEG C reaction 2h with
On；
The phosphide material of this unique morphology structure is made in the present invention for the first time, and structural unit is about 100 nanometers of diameter, hole
The NiCoP-CoP nano wire of 3~5nm of diameter, nano wire is interlaced to constitute the hole of dozens to a few hundred nanometers, to greatly improve
Specific surface area, obtains high capacitance performance；This nano wire be interweaved composition regular hexagon flake side length about 10 it is micro-
Rice, has high structural stability by about 100 nanometers of thickness, this is to ensuring that high circulation stability is of great significance.
Beneficial effects of the present invention:
(1) the invention proposes a kind of new approaches for preparing high conductivity and high capacitance performance electrode material.
(2) material of specific morphology is achieved in preparation process by chemical reaction and heat treatment, it is simple and convenient,
And repeatability is good.
(3) electrode material prepared not only capacitive property with higher but also high rate performance and cyclical stability are all non-
Chang Youyi.
(4) compared with other methods, which has following particular advantages:
1. experimental provision, experiment condition and preparation process are very simple, easy to operate；
2. low in cost, easily controllable and scale has good industrial applications prospect；
3. strong applicability extends to the controllable preparation and large-scale production of other double-metal phosphide materials.
Detailed description of the invention
Fig. 1 is that (b) low power of 1 gained NiCo presoma (a) of embodiment and NiCoP-CoP product and (c) high power SEM scheme；
It (d-f) is the TEM and High-Resolution Map of product
Fig. 2 is the full spectrogram (a) of XPS that embodiment 1 prepares NiCoP-CoP, Ni2p (b) Co2p (c) and P2 (d)
Fig. 3 is the XRD diagram that embodiment 1 prepares product
Fig. 4 is the XRD diagram that embodiment 2-5 prepares product
Fig. 5 is (a) cyclic voltammetry curve that embodiment 1 prepares electrode material；(b) constant current charge-discharge curve；(c) different
Specific capacitance value under current density；(d) the specific capacitance value conservation rate after charge and discharge cycles is repeated
Specific embodiment
Present invention preparation NiCoP-CoP porous nano line, which is interweaved, constitutes regular hexagon micron chip, specific embodiment
It is as follows:
Embodiment 1
NiCoP-CoP porous nano line be interweaved composition regular hexagon micron chip preparation: by 320mg six be hydrated nitre
Sour nickel, 640mg cabaltous nitrate hexahydrate, 245mg ammonium fluoride and 991mg urea are successively dissolved in 40mL deionized water, and magnetic force stirs
Mix 20min；Mixed solution is transferred in 50mL reaction kettle, 120 DEG C of reaction 8h, by reaction product eccentric cleaning, at 60 DEG C
Dry 12h, obtains Ni-Co presoma.Then, 100mg presoma and 1000mg sodium hypophosphite is taken to be respectively placed in the both ends of porcelain boat
It is placed in tube furnace, 2 DEG C/min of temperature program is set under the protection of inert gas N2 and is warming up to 300 DEG C, pyroreaction 2h,
Then Temperature fall, finally by reaction product eccentric cleaning, 60 DEG C of dry 12h obtain final product (phosphatization cobalt nickel and phosphatization cobalt
Composite material) NiCoP-CoP.
Fig. 1 a is the low power SEM figure that embodiment 1 prepares NiCo precursor product, shows that product is that uniform regular hexagon is micro-
Rice piece.Fig. 1 b is the low power SEM figure of NiCoP-CoP product, it can be seen that nano wire is interlaced to be woven into regular hexagon, line
The interlaced distribution between line, angle is 60 ° and forms unique array, to constitute microcellular structure.Fig. 1 c is
The high power SEM of NiCoP-CoP product schemes, can clearly be observed that single nano-wire distribution trend and they be interweaved
Nano-pore is uniform-distribution on micro-structure and single nano-wire.Fig. 1 d and 1e are product NiCoP-CoP product different amplifications
TEM figure, further demonstrating construction unit is that surface is dispersed with the nanowire structure of nano-pore, the interlaced knot of nanotube
Structure is consistent with SEM result.In conjunction with selective electron diffraction (SEAD) map in the HRTEM and illustration in 1f figure, can be confirmed single
Nano wire is polycrystalline NiCoP-CoP.
Fig. 2 is that embodiment 1 prepares product X PS map.The high-resolution XPS spectrum figure (Fig. 2 b) of Ni2p shows the position point at peak
It Wei Yu not be at 856.2eV, 861.2eV and 873.9eV, it follows that the valence state of Ni element is Ni2+And Ni3+；The high-resolution of Co2p
In XPS map (Fig. 2 c), Co can be obtained by the peak of 778.2eV, 781.4eV, 792.6eV and 797.6eV2+And Co3+In the product
It coexists.And in P2p (Fig. 2 d) map, two main peak values respectively appear in 129.4 and 133.9eV, with metal
In conjunction with reduction phosphorus (pδ-) and phosphoric acid (P5+) phosphorus it is corresponding.By full spectrogram (Fig. 2 a) it may be seen that without other elements
Characteristic peak exist, show product be pure NiCoP-CoP.
Fig. 3 is the XRD spectrum for the NiCoP-CoP that embodiment 1 prepares product.It may be seen that experiment from XRD spectrum
Obtained product is the mixing of two kinds of compounds of NiCoP and CoP, this also with we in an experiment used by nickel-to-cobalt ratio kissing
It closes, and exists as we can see from the figure without the peak of other substances, show that we have prepared pure NiCoP-CoP.
Embodiment 2
The molar ratio for preparing Ni-Co presoma agents useful for same Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate is adjusted to 2: 3,
Other conditions and embodiment 1 are identical.
Embodiment 3
The molar ratio for preparing Ni-Co presoma agents useful for same Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate is adjusted to 1: 1,
Other conditions and embodiment 1 are identical.
Embodiment 4
The molar ratio for preparing Ni-Co presoma agents useful for same Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate is adjusted to 3: 2,
Other conditions and embodiment 1 are identical.
Embodiment 5
The molar ratio for preparing Ni-Co presoma agents useful for same Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate is adjusted to 2: 1,
Other conditions and embodiment 1 are identical.
Fig. 4 is the XRD diagram of product obtained by Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate different mol ratio (embodiment 2-5)
Spectrum.From in figure it may be seen that with Ni: Co ratio in reaction mixture variation, product component ratio also changes therewith, table
It is bright to prepare the composite material of different products by regulating and controlling different nickel-to-cobalt ratios.
Fig. 5 is NiCoP-CoP regular hexagon micropore micron chip capacitance material prepared by embodiment 1 in different scanning rates
Under CV figure.With the increase of sweep speed, the area that CV curve is constituted also is gradually increased, and redox peaks show
NiCoP-CoP is in fake capacitance characteristic；Fig. 5 b is constant current charge-discharge curve, and the symmetry of curve shows that material has superior electrification
Learn performance.In 1Ag-1Current density under, specific capacitance is reached for 1968.48Fg-1；Fig. 5 c is the ratio electricity under different current densities
Capacitance, when current density reaches 10Ag-1When, specific capacitance conservation rate is 83.1%；In 10Ag-1Cycle charge discharge under current density
After electricity 10000 times, for the specific capacitance of electrode material almost without reduction, capacity retention reached for nearly 95% (as fig 5d).
Claims (7)
1.NiCoP-CoP porous nano line be interweaved composition regular hexagon micron chip capacitance material preparation method, it is special
Sign is, a certain amount of nickel nitrate, cobalt nitrate, ammonium fluoride and urea are dissolved in deionized water, magnetic agitation 15~
30min；40mL mixed solution is taken to be transferred in 50mL reaction kettle, in 120~160 DEG C of reaction 8h or more, repeatedly by reaction product
Eccentric cleaning is dried to obtain Ni-Co presoma at 60 DEG C；Then, by the sodium hypophosphite of 100~1000mg and 100~200mg
Presoma is placed in tube furnace after being respectively placed in the both ends of porcelain boat together with porcelain boat, is persistently leading to N2Atmosphere under, with 2~
It is heated to 300~400 DEG C of a certain temperature under the heating rate of 5 DEG C/min, 2h or more is then reacted under this constant temperature；
Finally, by the reaction product eccentric cleaning after Temperature fall, 60 DEG C of dry 12h obtain final product NiCoP-CoP.
2. preparation method according to claim 1, which is characterized in that be made of nickel nitrate, cobalt nitrate, ammonium fluoride and urea
Mixed reaction solution in, their respective optium concentration is respectively 0.7~2.3mM, 1.4~4.6mM, 4.2~13.8mM and
10.5~34.5mM.
3. preparation method according to claim 1, which is characterized in that 40mL mixed solution is taken to be transferred to 50mL reaction kettle
In, the hydro-thermal reaction under 120~160 DEG C of a certain steady temperature, by product eccentric cleaning, 60 DEG C of air dryings obtain Ni-
Co presoma.
4. Ni-Co precursor preparation method according to claim 3, which is characterized in that the hydro-thermal reaction time requires certain
In 8h or more；Ni-Co presoma is that smooth nano wire is interweaved the regular hexagon micron chip of composition, and the diameter of nano wire is 80
~100 nanometers.
5. preparation method according to claim 1, which is characterized in that by 100~1000mg sodium hypophosphite and 100~
200mg presoma is respectively placed in the both ends of porcelain boat；Then porcelain boat is placed in tube furnace, is persistently leading to N2Atmosphere under, with 2
300~400 DEG C of a certain temperature is heated under the heating rate of~5 DEG C/min, then under this constant temperature react 2h with
On；Eccentric cleaning is carried out to sample after phosphatization, 60 DEG C of dry 12h obtain final NiCoP-CoP product.
6. preparation method according to claim 1, which is characterized in that the product of generation is by the porous (aperture NiCoP-CoP
3~5nm) nano wire is interweaved the regular hexagon micron chip (about 10 microns of side length, about 100 nanometers of thickness) of composition.
7. the NiCoP-CoP porous nano line of preparation interweaves, the regular hexagon micron chip constituted can be applied to electrode of super capacitor
Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711452578.0A CN109961963B (en) | 2017-12-25 | 2017-12-25 | NiCoP-CoP micropore regular hexagon micron sheet capacitor material and preparation method thereof |
Applications Claiming Priority (1)
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| CN111192762A (en) * | 2020-01-23 | 2020-05-22 | 上海应用技术大学 | Cu-Co-P composite material and preparation method and application thereof |
| CN111604078A (en) * | 2020-05-20 | 2020-09-01 | 中南大学 | NiCoP/CoP/CoSe @ NC catalyst and preparation method thereof |
| CN112687475A (en) * | 2020-12-28 | 2021-04-20 | 暨南大学 | NiCoP/NiCoP/C multi-shell hollow structure electrode material and preparation and application thereof |
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| CN111604078B (en) * | 2020-05-20 | 2022-07-12 | 中南大学 | NiCoP/CoP/CoSe @ NC catalyst and preparation method thereof |
| CN112687475A (en) * | 2020-12-28 | 2021-04-20 | 暨南大学 | NiCoP/NiCoP/C multi-shell hollow structure electrode material and preparation and application thereof |
| CN114643069A (en) * | 2022-03-25 | 2022-06-21 | 桂林电子科技大学 | CoP-NiCoP/NC composite material and preparation method and application thereof |
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