CN106158403A - Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application - Google Patents
Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application Download PDFInfo
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- CN106158403A CN106158403A CN201610567773.7A CN201610567773A CN106158403A CN 106158403 A CN106158403 A CN 106158403A CN 201610567773 A CN201610567773 A CN 201610567773A CN 106158403 A CN106158403 A CN 106158403A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
Abstract
The present invention proposes metal-complexing supermolecule grid and Two-dimensional Carbon composite, formed with Two-dimensional Carbon Material cladding by the metal-complexing supermolecule grid with supermolecule framework, described metal-complexing supermolecule grid and Two-dimensional Carbon composite have huge application potential on chemical electrode, the invention also discloses described metal-complexing supermolecule grid and the preparation method of Two-dimensional Carbon composite and the application on capacitance electrode thereof.
Description
Technical field
The present invention relates to field of compound material, particularly relate to the system of metal-complexing supermolecule grid and Two-dimensional Carbon composite
Standby and application, the present invention also designs metal-complexing supermolecule grid and Two-dimensional Carbon composite and in electrochemical electrode material
Application.
Background technology
Metal-organic framework thing, also known as coordination polymer, the multifunctional material of new generation being well recognized as.Table is compared owing to having
The advantages such as area is big, structure can design, have potential using value at aspects such as gas absorption, molecular sieve and electrochemical energy storages,
Attracted the attention of many researchers.Similar with coordination polymer, coordination supramolecule grid material also has similar porous
Character, and owing to being connected with van der Waals interaction with weak effect such as hydrogen bond between supramolecular structure unit so that it is compare and join
The bonded coordination polymer in position has more preferable configuration flexibility, thus has broader potential research and using value.
Ultracapacitor, as the energy storage material of a new generation, has that power density is big, has extended cycle life, can fast charging and discharging
Etc. plurality of advantages, it is electric automobile, hybrid vehicle and the ideal source of high-power instrument.According to energy storage mechnism, super electricity
Container can be divided into two classes: electrochemical double-layer electric capacity (electric double-layer capacitor, EDLC) and faraday
Fake capacitance (faradaic pseudocapacitor).Wherein electric double layer capacitance is reversibly inhaled by electrode/electrolyte interface
Subsidiary electron ion stores energy, therefore has bigger power density and excellent cycle life, but usual energy density is relatively
Low.The electrode material of electric double layer capacitance is usually material with carbon element, such as activated carbon, CNT and Graphene etc., wherein Graphene material
Material light weight, specific surface area are big and material self-conductive rate is high, are preferable electrode material for super capacitor, but when individualism
Graphene film interlayer easily occurs that agglomeration causes specific surface area to decline.Fake capacitance is then fast by electrode material surface
The reversible faraday's redox reaction of speed stores and releases energy, and therefore significantly improves energy density, but cost is to follow
Ring life-span and the reduction of high rate performance.Nonetheless, its life-span and power density are also much better than conventional batteries.Wherein, common
Fake capacitance electrode material is mainly the inorganic material such as the transition metal oxide of variable valency, hydroxide, sulfide.Wherein, nickel
Compound is owing to having higher theoretical electric capacity and chemical stability and asepsis environment-protecting, cheap, is more satisfactory super
Capacitor electrode material.Although this kind of material has the highest theoretical electric capacity (such as nickel hydroxide reason under 0.5V potential window
Opinion electric capacity still may be up to 2082F g-1), but generally self electric conductivity is poor, and electrolyte ion is difficult to diffuse to block materials
Interior zone, causes actual capacitance performance far from each other with theoretical value.
In order to realize the storage of more preferable electric charge and transmission effect, can be had the electrode material of porous framework structure by structure
Material is with the interior zone making full use of electrode material.And metal coordinating polymer and metal-complexing supermolecule grid are as preferably
Porous material, has an advantage that specific surface area is big, and internal gutter scalable and design, is very suitable in theory as super electricity
The electrode material of container, but actually owing to being connected by singly-bounds such as carboxyls between most coordination polymer construction unit,
Making self-conductance performance the most poor, metal-complexing supermolecule grid is due to the weak effect between its construction unit, and shows
Higher electric conductivity is more beneficial for preparing electrode material.
Summary of the invention
The present invention proposes metal-complexing supermolecule grid and Two-dimensional Carbon composite, both can connect different list of coordination units
Forming the frame structure of similar coordination polymer and transmit electric charge, organic coordination unit can also be mutual with modified graphene simultaneously
Effect, formation conductive grid, to improve material overall conductance performance, has more preferable configuration flexibility, therefore as super capacitor
The electrode material of device has bigger application potential.
The technical scheme is that and be achieved in that: metal-complexing supermolecule grid and Two-dimensional Carbon composite, by gold
Belong to coordination supramolecule grid to form with Two-dimensional Carbon Material cladding.
Further, described metal-complexing supermolecule grid includes each metal complexes and metal coordinating polymer etc., as
Main group metal complexes, transient metal complex, rare earth metal complex.As nickel-2,6-dipicolinic acid (Ni-pydc) coordinates
Thing etc..
Further, described Two-dimensional Carbon material includes monolayer and multilamellar ink alkene, CNT etc..
Nickel-2,6-dipicolinic acid (Ni-pydc) coordination compound is stacked with the π-π of pyridine ring, lp-π by stronger hydrogen bond
Effect, both can connect different list of coordination units and formed the frame structure of similar coordination polymer and transmit electric charge, be coordinated simultaneously
Unit can also interact with modified graphene, forms conductive grid to improve material overall conductance performance.Compare common
Connect the carboxylic acids coordination polymer of unit with coordinate bond, this kind of coordination supramolecule framework has more preferable configuration flexibility
And electric conductivity, therefore the electrode material as ultracapacitor has bigger application potential.
Further, described metal-complexing supermolecule grid and described Two-dimensional Carbon material by multiple weak effect (such as hydrogen bond, halogen
Key, lp-π, pi-pi accumulation, Van der Waals force etc.) connect, form composite structure.
Described metallized metal coordination supramolecule grid and the preparation method of Two-dimensional Carbon composite, surpassed by described metal-complexing
Molecule grid and described Two-dimensional Carbon by chemical reaction (as solution synthesize, prepared by hydro-thermal, electrochemical synthesis etc.) or physics compound
(as ground, heating, pressurization etc.) prepares.
One of preparation method of described metal-complexing supermolecule grid and Two-dimensional Carbon composite, is peeled off by electrochemical process
While Graphene, the Graphene of Hydrothermal Synthesis Ni-pydc coordination supramolecule framework Yu electrochemical stripping is carried out combined in-situ,
Disposably prepare the graphene composite material of the Ni-pydc coordination supramolecule framework cladding of Nidus Vespae form.
Each unit prepared by hydro-thermal contains two hydrionic Ni (pydcH)2Powder, through deprotonation near negative pole
Process produces part [Ni (pydc)2]2-After, positively charged (produced by graphene film in partial oxidation process with what positive pole came off
Carbocationic intermediate and positively charged group provide) electrochemical stripping graphene film attracted each other by electrostatic interaction.So
After combined closely by noncovalent interaction power such as hydrogen bond and π-π stackings again so that it is rebuild honeycomb structure at graphenic surface
Nanoscale twins frame structure, form Ni nanoparticle-pydc@EEG composite, one layer of Nidus Vespae of successful growth on graphene film
The nanometer coordination supramolecule framework of shape, and product structure is firm, quality is controlled.
Preparation side as one of preferred mode, described metal-complexing supermolecule grid and Two-dimensional Carbon combination electrode material
Method, comprises the following steps:
(1) Hydrothermal Synthesis Ni-pydc powder；
(2) Ni-pydc powder is joined Na2SO4In solution, prepare electrolyte；
(3) in described electrolyte, electrochemistry glass peels off Graphene, and separates the Ni-pydc coordination supramolecule that synthesis obtains
The graphene composite material of framework cladding.
Preferably, in step (1), Hydrothermal Synthesis includes procedure below:
By 0.08g Ni (NO3)2·6H2O Yu 0.12g 2, dipicolimic acid 2 (pydc) is dissolved in 15mL deionized water, water
Thermal response still reacts at 160 DEG C 6h；Then naturally cool to room temperature, filter out crystal deionized water and wash respectively with DMF
Wash three times, and dry in 60 DEG C of baking ovens, after grinding, obtain Ni-pydc coordination compound powder.
Preferably, in step (2), the Ni-pydc coordination compound powder prepared by 20mg said method adds 10mL 0.1M
Na2SO4In solution, a little stirring after ultrasonic 10 minutes, formed aaerosol solution as electrolyte.
Preferably, in step (3), including procedure below:
Electrochemical stripping and compound experiment are carried out on electrophresis apparatus, add described electrolyte, by graphite in 20mL beaker
Anode made in by rod, and stainless (steel) wire (as negative electrode, two electrode gap 1cm；5V voltage current limliting 40mA is applied, simultaneously at two interpolars
Solution is kept stirring for state, closes power supply after energising 5-20min, and solution continues stirring 10 minutes.It is then centrifuged for and uses water and second
Alcohol washs, and removes Na in triplicate2SO4, isolated precipitate is Ni-pydc coordination after being placed in 60 DEG C of baking ovens drying super
The graphene composite material of molecular framework cladding.
By the electrochemical method of easy " electrochemical stripping is two-in-one with electrostatic self-assembled ", peel off stone in electrochemical process
While ink alkene, by Hydrothermal Synthesis nickel-2, dipicolimic acid 2 (Ni-pydc) coordination supramolecule framework and electrochemical stripping go out
Graphene is combined, and is successfully prepared the graphene composite material of the Ni-pydc coordination supramolecule grid cladding of Nidus Vespae form
(Ni-pydc@EEG is called for short NiEG).This material, as the electrode material of ultracapacitor, has the highest ratio electric capacity
(1282.8F g-1@1A g-1Maintain excellent cycle performance while) (to remain to after 3000 charge and discharge cycles remain initial
The electric capacity of more than 93%), and have than general fake capacitance material higher high rate charge-discharge ability.This composite with
The asymmetric solid capacitor device that electrochemical stripping Graphene combines can be at 7500W kg-1High power density under realize
14.6Whkg-1Energy density, (energy density is generally below 10Whkg to compare general material with carbon element double electric layers supercapacitor-1) with metal oxide materials fake capacitance (under high power, hydraulic performance decline is obvious), there is more preferable practical value, this only comprises
The microdevice of 60mg electrode material can directly drive the motor of 2.5W.
Described metal-complexing supermolecule grid is huge with Two-dimensional Carbon composite application potential in super capacitor electrode.
A kind of super capacitor electrode, including each component of mass ratio, account for the described metal-complexing supermolecule grid of 85% with
Two-dimensional Carbon composite, the Kynoar binding agent of 10%, with 5% acetylene black.
The preparation method of described super capacitor electrode, by multiple with Two-dimensional Carbon for the described metal-complexing supermolecule grid accounting for 85%
Condensation material, the Kynoar binding agent of 10%, with the acetylene black of 5%, after instilling ethanol, ultrasonic agitation prepares.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, also may be used
To obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 be Hydrothermal Synthesis powder XRD spectra (on) with document Ni (pydcH)2The analogue spectrums of crystal (under)；
Fig. 2 is Ni (pydcH)2The structural formula (omission hydrogen atom) of list of coordination units；
Fig. 3 is the electron-microscope scanning figure of metal-complexing supermolecule grid and Two-dimensional Carbon composite, and (b) is enlarged drawing；
Fig. 4 is the cyclic voltammetry curve figure of NiEG-5/10/20 electrode；
Fig. 5 is the constant current charge-discharge curve of NiEG-5/10/20 electrode and the specific discharge capacity calculated according to this；
Fig. 6 is NiEG-10 electrode cyclic voltammetry curve under different scanning rates.
Fig. 7 is described metal-complexing supermolecule grid and Two-dimensional Carbon composite schematic diagram when electrode.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
Embodiment 1
Metal-complexing supermolecule grid and the preparation method of Two-dimensional Carbon composite, comprise the following steps:
(1) by 0.08g Ni (NO3)2·6H2O Yu 0.12g 2, dipicolimic acid 2 (pydc) is dissolved in 15mL deionized water,
Insert 20mL polytetrafluoroethylliner liner and load in hydrothermal reaction kettle at 160 DEG C, to react 6h.Then room temperature, mistake are naturally cooled to
The green crystals deionized water leached and DMF wash three times respectively, and dry in 60 DEG C of baking ovens, can obtain after grinding
Nickel-2, dipicolimic acid 2 (Ni-pydc) coordination compound powder, characterize and further compound experiment for physical property.
(2) Ni-pydc coordination compound powder addition 10mL 0.1M Na prepared by 20mg said method is taken2SO4In solution, slightly
After adding stirring ultrasonic 10 minutes, form aaerosol solution as electrolyte.
Electrosynthesis experiment is carried out on electrophresis apparatus, adds above-mentioned coordination compound suspension, by native graphite in 20mL beaker
Anode made in by rod, stainless (steel) wire (375 mesh, size 20mm × 15mm) as negative electrode, two electrode gap about 1cm.Instrument is at the two poles of the earth
Between apply 5V voltage current limliting 40mA, solution keeps strong stirring state simultaneously, closes power supply, solution continuation after be energized 5 minutes
Stir 10 minutes.Then 6000rpm is centrifuged and uses water and washing with alcohol, in triplicate to remove Na2SO4, isolated celadon
Precipitate is Ni-pydc cladding EEG combination electrode material after being placed in 60 DEG C of baking ovens drying (Ni-pydc@EEG is called for short
NiEG)。
Embodiment 2
Operating procedure is same as in Example 1, and distinctive points is that in step 2, conduction time is 10 minutes.
Embodiment 3
Operating procedure is same as in Example 1, and distinctive points is that in step 2, conduction time is 20 minutes.
The green coordination compound powder (NiEG) of Hydrothermal Synthesis is characterized by X-ray powder diffraction, as shown in Figure 1.
Its molecular structure as in figure 2 it is shown, one of them nickle atom is by two 2, four carboxyls of 6-cinchomeronic acid (wherein two
Individual also retains hydrogen atom) intersect chelating one Ni (pydcH) of composition2Construction unit, and nickel is with the nitrogen-atoms on pyridine ring also
There is coordination power.By hydrogen bond and C=O between construction unit ... the noncovalent interaction power such as π stacking interconnect, according to having relatively
Strong adhesion.Wherein C=O is obtained ... the combination of π stacking effect can be-24.3kcal mol according to Theoretical Calculation-1, about 102kJ
mol-1, combination is already close to the level of chemical bond.Coordinate the effect of hydrogen bond again, can be the most unlimited between list of coordination units
Extend the stable two-dimentional supramolecular structure formed as shown in Fig. 3-4 (a).Therefore its stability is far above general coordination compound,
Powder after crystalline product or grinding has higher stability in alkaline aqueous solution, is being soaked in 0.5M LiOH aqueous solution
In after 15 days still without significant change.Additionally, the passage at free water place between coordination compound lamella is by relatively in two dimension extended configuration
Weak hydrogen bond action connects, and therefore duct itself has preferable motility, beneficially ion and spreads in the channel.
The product scanning electron microscope (SEM) photograph prepared is as shown in Figure 3.
Embodiment 4
The preparation of electrode of super capacitor and assembling
Before experiment first by the nickel foam of multi-disc a size of 15mm × 10mm and 25mm × 20mm at acetone, ethanol, deionization
Ultrasonic 20 minutes of difference in water, clean and weigh quality respectively after drying, standby.Electrode material serosity is accounted for the work of 85% by mass ratio
Property electrode material, Kynoar (PVDF) binding agent of 10% and 5% acetylene black mixed ethanol after abundant ultrasonic agitation 10
Preparing after minute, for three electrode test systems, solid gross mass used is dripped slightly larger than 2mg, ethanol consumption 2-3, and serosity is uniform
It is applied in 15mm × 10mm foam nickel base, after being placed in 60 DEG C of baking ovens overnight, again weighs the blank bubble before quality deducts
Foam nickel substrate quality, obtains carrying active electrode material quality for afterwards than the calculating of electric capacity.
For two electrode test systems, Ni-pydc@EEG composite is assembled into asymmetric solid with single EEG material
State ultracapacitor microdevice.Wherein electrochemical stripping Graphene (EEG) uses above-mentioned identical instrument and same procedure system
Standby, it is only not at Na2SO4Solution adds Ni-pydc coordination compound.Take 10mg Ni-pydc@EEG and add auxiliary according to the above ratio
After auxiliary agent serosity, be uniformly applied in the foam nickel base of a size of 25mm × 20mm, equally to electrode use 50mg EEG by than
It is applied in the foam nickel base of same size after example configuration serosity.Solid-state electrolytic solution (PVA-NaOH) point is used between two electrodes
Every, wherein PVA film is added by 1g PVA and 0.5g NaOH and is heated to 90 DEG C of stirrings in 10mL water and forms transparent glue in 30 minutes
After, uniformly pour into condensation between two electrodes and formed, then press lightly on to two panels nickel foam spacing about 2mm.Last at device outer layer
Use polytetrafluoroethylraw raw material band to seal, i.e. can be used for testing after standing 1 day.
Ultracapacitor performance test
The test of ultracapacitor chemical property is all carried out at AutoLab PGSTAT-302N electrochemical workstation, supporting
Software is NOVA 1.7, and electrode configuration is respectively three electrodes/bipolar electrode.Wherein the experiment of three-electrode system is at electrochemical cell
In carry out, by scribbling the nickel foam of sample as working electrode, platinized platinum (15mm × 10mm) is as to electrode, and reference electrode is for filling out
Fill the Ag/AgCl electrode of saturated KCl solution.Three electrodes press equilateral triangle distribution, wherein working electrode with to electrode at a distance of 1cm
It is placed in parallel.Electrode is immersed in 0.5M LiOH solution standing and after 5 minutes, starts experiment.Two electrode systems the most directly will
The two poles of the earth of above-mentioned asymmetric solid capacitor device connect work and test with to electrode holder, wherein scribble Ni-pydc EEG material
One pole of material, as working electrode, scribbles a pole of EEG as to electrode.Electrochemical property test include cyclic voltammetric analysis,
Constant current charge-discharge, AC impedance are tested with cycle life.
Wherein under three-electrode system, the cyclic voltammetric analysis of electrode material and constant current charge-discharge choose different scanning respectively
(1 arrives 50mV s to speed-1) and electric current density (1 to 20A g-1), the potential window of common Ni-based pseudocapacitors, 0.2 to 0.6V
(vs.Ag/AgCl) potential range is analyzed.Each electrode is carrying out 50 50mV s-1Rapid Circulation voltammetric scan after
Carrying out official testing again after material activates, than electric capacity, the same discharge time recorded by galvanostatic charge/discharge calculates.And circulate
Life test uses galvanostatic charge/discharge (to be 5A g than electric current-1) carry out repeated charge, by the minimum and maximum potential set
Carry out thousands of time circulations, finally take the discharge curve of circulation every time and calculate ratio electric capacity respectively, then with initially carry out than electric capacity
Relatively calculate the percentage ratio of capacitance values loss to assess life situations.
And under two electrode systems, when the asymmetric capacitor part of assembling is tested, instrument mode of operation is switched to two electricity
Pole, then tests as negative pole using NiEG electrode as positive pole, EEG electrode, and cyclic voltammetric analysis and constant current charge-discharge are same
Sample chooses different voltage ranges (1.1-1.5V) and electric current density (1 to 10A g-1).Than electric capacity by putting in constant current charge-discharge
Electricity curve calculates, and quality is calculated by the gross mass of the two poles of the earth active substance.Cycle life test uses galvanostatic charge/discharge (to compare electric current
For 5A g-1) carry out charge and discharge cycles in 0-1.5V scope.Ac impedance measurement is all carried out in the range of 0.1-100000Hz, just
String wave-amplitude is 5mV.
The electrochemical property test of Ni-pydc@EEG combination electrode
The electro-chemical test of combination electrode is carried out under three electrode modes of electrochemical workstation, and electrolyte uses 0.5M
LiOH solution.In order to probe into the impact on electrode electro Chemical performance of the Ni-pydc@EEG composite proportioning, first to composite
The ratio of middle Ni-pydc with EEG conducts in-depth research.Owing to before electrochemical synthesis, the addition of Ni-pydc powder is solid
Definite value, and the yield of EEG increases along with conduction time and increases.[29]Therefore it is energized by control in electrochemical synthesis step
Time is respectively 5, and 10,20 minutes to obtain the NiEG combination electrode material of different ratio, the electricity then prepared by same method
Pole is respectively labeled as NiEG-5/10/20.First, by NiEG-5/10/20 electrodes different for proportioning respectively 0.2 to 0.6V
(vs.Ag/AgCl) contrast of volt-ampere (sweeping speed 5mv/s) and constant current charge-discharge (than electric current 5A/g) it is circulated in potential range
Test.The result of test is as shown in Figure 4 and Figure 5.Result shows in the material that these three Ni-pydc:EEG ratio is different, electricity
In chemosynthesis step, conduction time is that the NiEG-10 material prepared for 10 minutes has best chemical property.First at 5A/
The NiEG-10 electrode specific capacity that calculates of discharge curve of g constant current charge-discharge test is 835.8F/g, far above other two
Person.Additionally, the charge and discharge platform at the oxidoreduction peak with constant current charge-discharge curve by observing cyclic voltammetry curve, it appeared that
Substantially, the difference of charge and discharge platform is the biggest, illustrative material in the oxidoreduction peak skew of Graphene poor NiEG-5 electrode
Internal driving is relatively big, is difficult to effectively carry out electric charge transfer.Therefore the Ni-pydc material in NiEG-5 electrode interior cannot be complete
Playing its chemical property, electrochemistry capacitance is relatively low.By contrast, the NiEG-20 electrode that Graphene content is bigger then has preferably
Chemical property, but comprise that Ni-pydc material is less and Graphene is more due to it, therefore show from the point of view of test curve
Obvious electric double layer capacitance characteristic, oxidoreduction peak is the most inconspicuous with charge and discharge platform, and as composite electricity
The ratio of the significant contributor's Ni-pydc material held is relatively low, and therefore integral capacitor performance is less than NiEG-10 electrode.
In order to probe into the chemical property of the NiEG-10 electrode behaved oneself best further, it is carried out under different multiplying
Cyclic voltammetry and constant current charge-discharge test.Wherein cyclic voltammetry chooses different scanning speeds (1 arrives 50mV/s),
Scanning potential range is 0.2 to 0.6V (vs.Ag/AgCl).Test gained cyclic voltammetry curve as shown in Figure 6, NiEG electrode
Cyclic voltammetry curve demonstrates typical oxidoreduction peak, has a pair obvious oxidoreduction peak near 0.35V/0.45V, right
Answer Ni2+/Ni3+Reversible redox reaction.And this is fine to oxidoreduction peak symmetry, the good reversibility of reaction is described.
Additionally along with the increase of sweep speed, electric current density increases the most therewith, indicates electrode cycle volt-ampere fast response time, the most forthright
Can be good.To the skew of positive potential direction, the point position, peak of reduction peak is inclined to nagative potential direction in the point position, peak at simultaneous oxidation peak
Moving, this phenomenon is increased by electrode interior diffusion impedance and produces.In addition the curve shape of cyclic voltammetric is the most gradually to flat
Row tetragon transition, illustrates that under the speed conditions that relatively the exposes thoroughly electric double layer capacitance of material accounts for the proportion of total capacitance and increased.
In order to more vivid displaying described metal-complexing supermolecule grid and Two-dimensional Carbon composite are when for electrode
Configuration shows, structure is its schematic diagram as shown in Figure 7.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. metal-complexing supermolecule grid and Two-dimensional Carbon composite, it is characterised in that: by metal-complexing supermolecule grid and two
Dimension material with carbon element is composited.
Metal-complexing supermolecule grid and Two-dimensional Carbon composite the most as described in the appended claim 1, it is characterised in that: described metal
Coordination supramolecule grid includes metal complex and metal coordinating polymer.
Metal-complexing supermolecule grid and Two-dimensional Carbon composite the most as stated in claim 2, it is characterised in that: described metal
Coordination supramolecule grid is Main group metal complexes, or transient metal complex, or rare earth metal complex.
Metal-complexing supermolecule grid and Two-dimensional Carbon composite the most as described in the appended claim 1, it is characterised in that: described two dimension
Material with carbon element includes monolayer and multilamellar ink alkene, CNT.
Metal-complexing Supramolecular Network and Two-dimensional Carbon composite the most as described in the appended claim 1, it is characterised in that: described metal
Coordination supramolecule grid is connected by weak effect with described Two-dimensional Carbon, and overall structure is complex.
6. metal-complexing supermolecule grid and the preparation method of Two-dimensional Carbon composite as described in arbitrary in claim 1-5, its
It is characterised by: prepared by chemical reaction or physics are compound with described Two-dimensional Carbon by described metal-complexing supermolecule grid.
Metal-complexing supermolecule grid and the preparation method of Two-dimensional Carbon composite the most as recited in claim 6, its feature exists
In: while peeling off Graphene in electrochemical process, the Ni-pydc coordination supramolecule framework of Hydrothermal Synthesis is shelled with electrochemistry
The Graphene separated out carries out combined in-situ, prepares the Graphene of the Ni-pydc coordination supramolecule framework cladding of Nidus Vespae form
Composite.
Metal-complexing supermolecule grid and the preparation method of Two-dimensional Carbon composite the most as recited in claim 7, its feature exists
In: comprise the following steps:
(1) Hydrothermal Synthesis Ni-pydc powder；
(2) Ni-pydc powder is joined Na2SO4In solution, prepare electrolyte；
(3) in described electrolyte, electrochemistry glass peels off Graphene, and separates the Ni-pydc coordination supramolecule framework that synthesis obtains
The graphene composite material of cladding.
9. as described in arbitrary in claim 1-5 metal-complexing supermolecule grid and Two-dimensional Carbon composite at super capacitor electrode
In application.
10. a super capacitor electrode, it is characterised in that: include each component of mass ratio, account for 85% described metal-complexing surpass
Molecule grid and Two-dimensional Carbon composite, the Kynoar binding agent of 10%, with 5% acetylene black.
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| WO2023245967A1 (en) * | 2022-06-23 | 2023-12-28 | 郑州大学 | Interface-modified hard-carbon negative electrode material/negative electrode of sodium-ion battery, and preparation method for interface-modified hard-carbon negative electrode material/negative electrode and application thereof |
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