CN108806993A - A kind of combination electrode material and its preparation method and application - Google Patents
A kind of combination electrode material and its preparation method and application Download PDFInfo
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- CN108806993A CN108806993A CN201810514437.5A CN201810514437A CN108806993A CN 108806993 A CN108806993 A CN 108806993A CN 201810514437 A CN201810514437 A CN 201810514437A CN 108806993 A CN108806993 A CN 108806993A
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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
- H01G11/24—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
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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
- 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 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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- 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 relates to a kind of preparation methods of combination electrode material, source metal, organic ligand are dissolved in the mixed solution of organic solvent and water, mixed liquor A is made；By sulphur source obtained mixed liquid B soluble in water；After the mixed liquor A and the mixed liquid B are mixed, kept at 160~180 DEG C 20~24 hours, then through cooling, washing, dry obtained combination electrode material.The present invention prepares combination electrode material using hydro-thermal method, simple for process, at low cost, environmentally friendly, is suitble to produce in enormous quantities.Combination electrode material produced by the present invention is prepared by one step hydro thermal method inlays the fine nanostructure of sulfide on metal organic framework, largely promote the specific surface area of material, the active site that redox reaction occurs for active material is increased, the chemical property of material is inherently promoted.
Description
Technical field
Present invention relates particularly to a kind of combination electrode materials and its preparation method and application.
Background technology
In recent years, the fast development of Nanometer scale science and technology provides contract to develop the electrode material of Novel super capacitor
Machine.Metal-organic framework materials (MOFs) are that a kind of organic ligand by macromolecular and inorganic metal ion pass through self assembly
And the crystalline material of the reticular structure with regularity arrangement formed, therefore had both organic polymer and inorganic compound
Advantage.Utilize low-density in recent years, high-specific surface area, the designing of structure and function, the features such as pore size is adjustable, by MOFs
As a kind of new electrode material, apply in lithium battery, fuel cell, ultracapacitor.The structure and pattern of nano material
Have a great impact to capacitance behavior, if specific surface area and microscopic appearance are the most important influence factors of two of which.MOFs energy
Highest specific surface area is provided, nano level duct and open pore passage structure are conducive to the diffusion of ion.Therefore, MOFs is one
The material of the unique nanostructure of the ideal synthesis of kind.However since individual MOFs material conductivities are poor, MOFs is at present mainly with more
The form of the model or presoma of hole carbon and porous metal oxide material is by the electrode material as ultracapacitor.In view of
The pore passage structure of its high-sequential and abundant organic ligand, MOFs can as template or presoma come be pyrolyzed prepare it is porous
Carbon material, during high temperature pyrolysis MOFs prepares porous carbon, the metal ion in MOFs can be used as catalyst, in ion
The transmission path of electrolyte is advanced optimized under conduction condition.
Therefore, someone utilizes the structure diversity of MOFs materials, itself and metal sulfide are carried out hydridization, learnt from other's strong points to offset one's weaknesses,
The advantage for giving full play to the two, creates better electrode material.Using MOFs as presoma, synthesis porous metals sulfide has only
Special advantage, in the case where not adding any auxiliary material, converts MOFs to metal sulfide first, scheme is simple
It is simple for process, high conversion rate.Second, structural controllability is strong, pattern and grain size based on MOFs particles are controllable, can be indirect
Control the pattern of metal sulfide.Third, metal sulfide/C nano composite material can be prepared by two-step method, between MOFs
Material is both that carbon source and source metal have been effectively maintained the characteristic of two kinds of components, it is multiple to obtain nanometer by controlling synthesis condition
Condensation material.However, the metal sulfide with MOFs hydridization is a kind of two-dimensional material of typical class graphene-structured, in recent years
Just cause the extensive concern of people.When metal sulfide becomes two-dimensional structure from bulk, electronic band structure is by indirect band
Gap becomes direct band gap to which very big change occurs for the performances such as light, the electricity for making metal sulfide.From the point of view of present achievement in research,
The excellent physicochemical properties of two-dimensional metal sulfide, the especially application in terms of electron stored energy device, in addition it is in lithium
The application prospect of battery, sensor, transistor and ultracapacitor etc. is also all particularly wide, will apply valence with great
Value.
Application publication number is that CN104992848 patents of invention disclose a kind of binary metal applied to ultracapacitor and have
Machine framework material and preparation method thereof, the preparation method are hydro-thermal methods, and innovative point is to have machine bone using two kinds of made of metal
Frame material makes to generate synergistic effect between its metal ion, is applied to electrode material for super capacitor, improves stable circulation
Property and specific discharge capacity.The invention distinguishes are compound not with sulfide progress in the place of this patent, and passing through improves electrolysis material
Structure, further promote its chemical property.
Invention content
Technical problem to be solved by the invention is to provide a kind of metal-organic framework materials and sulfide are compound, to logical
Crossing improves the structure of material, further promotes the combination electrode material of chemical property and its preparation method and application of material.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
It is an object of the present invention to provide a kind of preparation methods of combination electrode material, include the following steps：
Source metal, organic ligand are dissolved in the mixed solution of organic solvent and water obtained mixed liquor A by step (1)；
Step (2), by sulphur source obtained mixed liquid B soluble in water；
Step (3) after mixing the mixed liquor A and the mixed liquid B, keeps 20~24 at 160~180 DEG C
Hour, then through cooling, washing, dry obtained combination electrode material.
Preferably, the source metal is Nickelous nitrate hexahydrate, Nickel dichloride hexahydrate, cabaltous nitrate hexahydrate, six hydration chlorine
Change cobalt, Fe(NO3)39H2O or Iron(III) chloride hexahydrate.
Preferably, a concentration of 0.1~0.5mol/L of the source metal in the mixed liquor A, further preferably
For 0.20~0.40mol/L, more preferably 0.30~0.35mol/L.
Preferably, the organic ligand be trimesic acid, terephthalic acid (TPA), 2,5- dihydroxy-terephthalic acid (TPA) or
5- amino isophthalic acids.
Preferably, a concentration of 0.1~0.3mol/L of the organic ligand in the mixed liquor A, it is further excellent
It is selected as 0.10~0.20mol/L, more preferably 0.10~0.15mol/L.
Preferably, the organic solvent is n,N-Dimethylformamide, acetone or ether.
Preferably, the volume ratio that feeds intake of the organic solvent described in the mixed solution and the water is 1:0.9~
1.1。
Preferably, the volume ratio that feeds intake of the mixed liquor A and the mixed liquid B is 1:1~3, further preferably
1:1。
Preferably, the sulphur source be urea, thioacetamide, thiocarbamide, vulcanized sodium, one kind in thioacetyl aniline or
It is a variety of.
Preferably, a concentration of 0.8~1.5mol/L of the sulphur source in the mixed liquid B, further preferably
0.90~1.20mol/L, more preferably 1.1~1.2mol/L.
It is a further object to provide combination electrode materials made from a kind of preparation method.
Third object of the present invention is to provide a kind of application of combination electrode material in ultracapacitor.
The composite material of the present invention not only remains the big skeleton structure of MOFs, but also the fine nanometer with NiSx
Structure.This unique three-dimensional structure promotes the transfer of charge and the diffusion of electrolyte ion, to improve making for material
With rate, the fake capacitance characteristic of composite material is improved.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
The present invention prepares combination electrode material using hydro-thermal method, simple for process, at low cost, environmentally friendly, is suitble to produce in enormous quantities.
Combination electrode material produced by the present invention is prepared by one step hydro thermal method inlays vulcanization on metal organic framework
The fine nanostructure of object largely promotes the specific surface area of material, increases active material and redox reaction occurs
Active site inherently promotes the chemical property of material.
Description of the drawings
Fig. 1 is the XRD diagram of Ni-MOFs@NiSx samples prepared by one-step method:(a) sample prepared by different time；(b) empty
White sample and the lower sample prepared for 24 hours.
Fig. 2 is the SEM figures for the Ni-MOFs@NiSx samples that one-step method is prepared under the different reaction time:(a)12h,(b)
For 24 hours, (c, d) blank sample.
The cyclic voltammetry curve for the Ni-MOFs@NiSx samples that Fig. 3 (a) one-step method is prepared under the different reaction time；
(b) under different scanning rates the specific capacitance value of electrode change curve；(c) curve of constant current charge-discharge；(d) different current densities
The variation relation figure of the voltage drop of lower electrode.
Fig. 4 is the AC impedance spectroscopy of Ni-MOFs@NiSx samples prepared by one-step method.
Specific implementation mode
This patent is with NiCl2·6H2O is having N, N- dimethyl formyls as nickel source, trimesic acid as organic ligand
Nickel based metal organic framework material is synthesized in the presence of amine, sulphur source (thioacetamide) is then added, in the condition of hydro-thermal
It is lower that Ni-based MOFs materials are converted to vulcanization nickel material so that element sulphur replaces the organic ligand position in Ni-based skeleton, is formed
Composite material with porous structure.The phase structure and microscopic appearance of material are characterized using XRD and SEM, by right
Than finding that the composite material not only lumpy structure with MOFs materials, but also the lamellar structure with sulfide, the two combine well,
Form a unique three-dimensional structure.The discovery of its chemical property is tested, the specific capacitance of simple Ni-MOFs materials is sweeping speed
To have reached 124.5F/g when 5mV/s, it is 5mV/s to introduce the porous Ni-MOFs@NiSx composite materials prepared after sulphur source sweeping speed
When reached 1250F/g, after 1000 charge and discharge cycles, capacitance fade is less, it is shown that good cyclical stability illustrates
Ni-MOFs base sulfide has larger application value in ultracapacitor.
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
Embodiment 1：
Ni-MOFs@NiSxThe preparation of material：
A liquid：Nickel dichloride hexahydrate (1.43g, 6mmol), trimesic acid (H3BTC) (0.42g, 2mmol), is dissolved in
20mL, volume ratio 1:In 1 n,N-Dimethylformamide (DMF) and the mixed liquor of deionized water, after being sufficiently stirred label for
A。
B liquid：It weighs thioacetamide (1.8g, 24mmol) to be dissolved in the deionized water of 20mL, label is after stirring evenly
Liquid.
It takes A liquid and each 15mL of B liquid to pour into a beaker respectively, after stirring evenly, is transferred to 50mL polytetrafluoroethyllining linings
Stainless steel autoclave in, kept at 180 DEG C for 24 hours, cooled to room temperature, then use distilled water filtering and washing,
It is dried in vacuo 12h at 60 DEG C and obtains Ni-MOFs@NiSxPowder.
The preparation of working electrode：By sample active made from the above method (Ni-MOFs@NiSx materials), conductive charcoal
Black (super-Li), bonding agent (PVDF) are with 8:1:1 mass ratio mixing, is placed in mortar, and ethanol in proper amount is added, and grinding makes
It is uniformly mixed, and then slurry is coated in nickel foam, and coated weight is 2mg or so, and 60 DEG C of dry 12h obtain ultracapacitor
Electrode slice.Use be coated with the sample foams nickel of active material for working electrode, reference electrode select saturated calomel electrode (SCE),
Platinum electrode is to electrode, and the KOH solution of 6mol/L is as electrolyte.Cyclic voltammetry potential window is -0.1~0.4V,
It is 5~100mV/s to sweep speed；Constant current charge-discharge test potential window is -0.15~0.45V (vs SCE)；The amplitude of AC signal
The frequency of 5mV, ac impedance measurement are 0.01~100kHz.Test result shows that material specific capacity in 0.5mV/s reaches
1250F/g, in the case where current density is 10A/g, specific discharge capacity conservation rate is 92.8% after 1000 cycles.
Comparative example 1
The preparation of Ni-MOFs@NiSx materials：
A liquid：Nickel dichloride hexahydrate (1.43g, 6mmol), trimesic acid (H3BTC) (0.42g, 2mmol), is dissolved in
20mL, volume ratio 1:In 1 n,N-Dimethylformamide (DMF) and the mixed liquor of deionized water, after being sufficiently stirred label for
A。
B liquid：It weighs thioacetamide (1.8g, 24mmol) to be dissolved in the deionized water of 20mL, label is after stirring evenly
Liquid.
It takes A liquid and each 15mL of B liquid to pour into a beaker respectively, after stirring evenly, is transferred to 50mL polytetrafluoroethyllining linings
Stainless steel autoclave in, keep 12h at 180 DEG C, then cooled to room temperature uses distilled water filtering and washing,
It is dried in vacuo 12h at 60 DEG C and obtains the powder of Ni-MOFs@NiSx.
The preparation of working electrode：By sample active made from the above method (Ni-MOFs@NiSx materials), conductive charcoal
Black (super-Li), bonding agent (PVDF) are with 8:1:1 mass ratio mixing, is placed in mortar, and ethanol in proper amount is added, and grinding makes
It is uniformly mixed, and then slurry is coated in nickel foam, and coated weight is 2mg or so, and 60 DEG C of dry 12h obtain ultracapacitor
Electrode slice.Use be coated with the sample foams nickel of active material for working electrode, reference electrode select saturated calomel electrode (SCE),
Platinum electrode is to electrode, and the KOH solution of 6mol/L is as electrolyte.Cyclic voltammetry potential window be -0.15~
0.45V, it is 5~100mV/s to sweep speed；Constant current charge-discharge test potential window is -0.1~0.4V (vs SCE)；AC signal
The frequency of amplitude 5mV, ac impedance measurement are 0.01~100kHz.Test result shows, material specific capacity in 0.5mV/s
Reach 960F/g, in the case where current density is 10A/g, specific discharge capacity conservation rate is 76.3% after 1000 cycles.
Comparative example 2
The preparation of Ni-MOFs：Nickel dichloride hexahydrate (1.43g, 6mmol), trimesic acid (H3BTC) (0.42g,
2mmol), it is dissolved in 20mL, volume ratio 1:In 1 N,N-dimethylformamide (DMF) and the mixed liquor of deionized water.Stirring is equal
After even, it is transferred in 50mL autoclaves.Then the constant temperature 12h at 105 DEG C, cooled to room temperature use DMF and water to filter
Washing, vacuum drying 12h obtains the powder of Ni-MOFs at 60 DEG C.
The preparation of working electrode：By sample active Ni-MOFs made from the above method, conductive black (super-
Li), bonding agent (PVDF) is with 8:1:1 mass ratio mixing, is placed in mortar, and ethanol in proper amount is added, and grinding keeps its mixing equal
It is even, then slurry is coated in nickel foam, coated weight is 2mg or so, and 60 DEG C of dry 12h obtain super capacitor electrode slice.
It uses and is coated with the sample foams nickel of active material as working electrode, reference electrode selection saturated calomel electrode (SCE), platinum electrode
For to electrode, the KOH solution of 6mol/L is as electrolyte.Cyclic voltammetry potential window is -0.1~0.4V, sweep speed for 5~
100mV/s；Constant current charge-discharge test potential window is -0.1~0.4V (vs SCE)；The amplitude 5mV of AC signal, AC impedance
The frequency of test is 0.01~100kHz.Test result shows that material specific capacity in 0.5mV/s reaches 124.5F/g,
Current density is that specific discharge capacity conservation rate is 23.1% after 1000 cycles under 10A/g.
Comparative example 3
Two-step method prepares Ni-MOFs@NiSx materials：
The powder of Ni-MOFs is made first, in accordance with the preparation method of comparative example 2.
Then, Ni-MOFs (0.25g) is weighed, thioacetamide (1.8g, 24mmol) is dissolved in the deionized water of 15mL,
It stirs evenly.
Finally, it is transferred in the autoclave of 25mL, hydro-thermal 12h, naturally cools to room temperature at 180 DEG C.Then it uses
Distilled water filtering and washing is clean, and 12h is dried in vacuo at 60 DEG C and obtains the powder of Ni-MOFs@NiSx.
The preparation of working electrode：By sample active Ni-MOFs@NiSx materials, conductive black made from the above method
(super-Li), bonding agent (PVDF) is with 8:1:1 mass ratio mixing, is placed in mortar, and ethanol in proper amount is added, and grinding makes it
It is uniformly mixed, then slurry is coated in nickel foam, coated weight is 2mg or so, and 60 DEG C of dry 12h obtain super capacitor electrode
Pole piece.It uses and is coated with the sample foams nickel of active material as working electrode, reference electrode selection saturated calomel electrode (SCE), platinum
Silk electrode is to electrode, and the KOH solution of 6mol/L is as electrolyte.Cyclic voltammetry potential window is -0.1~0.4V, is swept
Speed is 5~100mV/s；Constant current charge-discharge test potential window is -0.1~0.4V (vs SCE)；The amplitude 5mV of AC signal,
The frequency of ac impedance measurement is 0.01~100kHz.Test result shows that material specific capacity in 0.5mV/s reaches
552F/g, in the case where current density is 10A/g, specific discharge capacity conservation rate is 61% after 1000 cycles.
Comparative example 4
Two-step method prepares Ni-MOFs@NiSx materials：
The powder of Ni-MOFs is made first, in accordance with the preparation method of comparative example 2.
Then, Ni-MOFs (0.25g) is weighed, thioacetamide (1.8g, 24mmol) is dissolved in the deionized water of 15mL,
It stirs evenly.
Finally, it is transferred in the autoclave of 25mL, hydro-thermal for 24 hours, naturally cools to room temperature at 180 DEG C.Then it uses
Distilled water filtering and washing is clean, and 12h is dried in vacuo at 60 DEG C and obtains the powder of Ni-MOFs@NiSx.
The preparation of working electrode：By sample active Ni-MOFs@NiSx materials, conductive black made from the above method
(super-Li), bonding agent (PVDF) is with 8:1:1 mass ratio mixing, is placed in mortar, and ethanol in proper amount is added, and grinding makes it
It is uniformly mixed, then slurry is coated in nickel foam, coated weight is 2mg or so, and 60 DEG C of dry 12h obtain super capacitor electrode
Pole piece.It uses and is coated with the sample foams nickel of active material as working electrode, reference electrode selection saturated calomel electrode (SCE), platinum
Silk electrode is to electrode, and the KOH solution of 6mol/L is as electrolyte.Cyclic voltammetry potential window is -0.1~0.4V, is swept
Speed is 5~100mV/s；Constant current charge-discharge test potential window is -0.1~0.4V (vs SCE)；The amplitude 5mV of AC signal,
The frequency of ac impedance measurement is 0.01~100kHz.Test result shows that material specific capacity in 0.5mV/s reaches
724F/g, in the case where current density is 10A/g, specific discharge capacity conservation rate is 84.5% after 1000 cycles.
In conjunction with attached drawing, the invention will be further described：
As shown in Fig. 1 (a), one-step method hydrothermal synthesis Ni-MOFs@NiSx samples under conditions of the differential responses time
XRD spectra, wherein corresponding curve is the Ni-MOFs@NiSx samples obtained by embodiment 1 for 24 hours, the corresponding curves of 12h are pair
Ni-MOFs@NiSx samples obtained by ratio 1.Main component is all β-NiS, XRD diagram in sample prepared by the differential responses time
It is corresponded respectively at 2 angles θ is 18.1 °, 30.0 °, 32.1 °, 35.5 °, 40.4 °, 48.6 °, 50.1 °, 52.5 °, 52.2 ° in spectrum
(110) of β-NiS, (101), (300), (021), (211), (131), (410), (401), (330) feature crystal face, with standard card
Piece (JCPDS:It is 12-0041) corresponding.As can be seen that the diffraction maximum of sample is sharp from XRD spectra, crystallinity is preferable, explanation
Synthesized product purity is high, belongs to β-NiS hexagonal phases.The XRD spectra under two reaction time is compared, is synthesized under discovery 12h
Sample diffraction peak intensity is relatively weak, and crystallinity is relatively bad, and there are two miscellaneous peaks to occur, and is respectively 35 ° and 46 ° at 2 angles θ
Place, is respectively belonging to NiS1.03Crystal.Illustrate that in the reaction time be the β-NiS that can synthesize pure phase for 24 hours.
In order to study ligand to synthesizing the effects of Ni-MOFs NiSx samples, do being not added with ligand (blank sample is i.e. pair respectively
Ni-MOFs obtained by ratio 2) and add ligand (the Ni-MOFs@NiSx samples i.e. obtained by embodiment 1) two samples XRD
Spectrogram, as shown in Fig. 1 (b).Comparison is found, blank sample and has added the sample XRD spectra of ligand almost the same, without Ni-MOFs
Characteristic diffraction peak occur, illustrate be in same system in metal salt, ligand and sulphur source, sulphur source preferentially and metal salt formation sulphur
Compound, the crystal form of ligand being added without influencing Ni-MOFs@NiSx samples.
In order to further study after composite sulfur the microscopic appearance of Ni-MOFs@NiSx materials and its with the comparison feelings of blank sample
Condition, We conducted scanning electron microscope characterizations.Fig. 2 (a) is Ni-MOFs@NiSx samples made from comparative example 1, Fig. 2 (b)
For Ni-MOFs@NiSx samples made from embodiment 1, Fig. 2 (c, d) is blank sample, i.e. 2 sample of comparative example.
It can be seen that Ni-MOFs NiSx are made of the nano-particle of many 100nm or so from Fig. 2 (a), Zhong Duo little
Nano-particle is unordered to be stacked, and stick to each other does not form small meso-hole structure.However, after extending the reaction time, hair
Existing synthesized material surface has a countless pore passage structures, and mutually without adhesion, only unordered to be stacked, such as Fig. 2
(b) shown in, the specific surface area of sample is greatly improved in this way, contributes to the diffusion of electrolyte ion, improves the electrification of material
Learn performance.From Fig. 2 (c, d) of blank sample it can be found that be added ligand trimesic acid have to the pattern of sample it is prodigious
Influence, in the absence of ligand, synthesized sample has an alternate random block of size, block size 1 μm~2 μm it
Between.
The SEM for the sample that comparison blank sample and one-step method are prepared under different time schemes the addition pair it can be found that ligand
The pattern of sample has large effect.Not plus when ligand, synthesized sample has the block structure that size differs, and ligand is added
Afterwards, the size of sample is more uniform, and with the extension of time, sample size uniformity, and block surface with countless ducts tie
Structure absolutely proves that prepared Ni-MOFs@NiSx materials have preferable pattern in the presence of ligand for 24 hours.
The chemical property of Ni-MOFs@NiSx electrode materials is under the system of three electrodes, in the potassium hydroxide of 6mol/L
Obtained from being tested in electrolyte.Fig. 3 (a) is under different sweep speed under the differential responses time obtained by a footwork
The cyclic voltammetry curve figure (CV curves) of Ni-MOFs@NiSx electrode materials, wherein corresponding curve is that embodiment 1 is made for 24 hours
The Ni-MOFs@NiSx samples obtained, the corresponding curves of 12h are the Ni-MOFs@NiSx samples obtained by comparative example 1.It can be seen that CV is bent
There is not rectangular shape specific to electric double layer capacitance in line, and in the potential window of -0.15V~0.45V, have a pair of reversible
Redox peaks, illustrate that following electrochemical reaction has occurred during electric potential scanning：
NiS+OH-→NiSOH+e-(1)
NiS and NiSOH is mutually converted during the reaction, produces Faraday pseudo-capacitance.When comparing differential responses
Between lower three samples CV curves, find under same sweep speed, the sample (i.e. the sample of embodiment 1) synthesized lower for 24 hours
The area of CV curves is larger, and response current is also larger, this absolutely proves the oxygen that the sample synthesized under the reaction time for 24 hours occurs
It is more rapidly reversible to change reduction reaction.Meanwhile comparing the cyclic voltammetry curve of blank sample, it is found that the presence of ligand effectively promotes
Sulfide material generates the response current of bigger.
Fig. 3 (b) is the capacitance of Ni-MOFs@NiSx with the variation relation figure of sweep speed, wherein corresponding curve for 24 hours
For the Ni-MOFs@NiSx samples obtained by embodiment 1, the corresponding curves of 12h are the Ni-MOFs@NiSx obtained by comparative example 1
Sample, as shown, being continuously increased with sweep speed, the Ni- that one-step method is prepared under conditions of the differential responses time
Capacitance all decreases to some degree of MOFs@NiSx.The main reason for analysis causes this phenomenon may be in height scanning speed
Under rate, electrolyte is not in time for also fully infiltrating the internal active sites of electrode material.Under relatively high sweep speed, need
Want a large amount of OH-Quickly it is embedded into the interface of electrode and electrolyte, however is limited to relatively low OH-Ion concentration with
And interionic phase repulsive interaction so that this demand can not be met.As it can be seen that the Ni- that the reaction time prepares when being for 24 hours
The capacitance of MOFs@NiSx is more than prepared by 12h and blank sample capacitance.When sweep speed is 100mV/s, Ni-MOFs@NiSx
Capacitance still maintain 760F/g, illustrate the material have good multiplying power property.
It is 10A/g that Fig. 3 (c), which is in current density, Ni-MOFs bases sulfide electricity made from differential responses time next step method
Constant current charge-discharge curve graph of the pole material in -0.15V~0.45V potential windows, wherein corresponding curve is embodiment 1 for 24 hours
Obtained Ni-MOFs@NiSx samples, the corresponding curves of 12h are the Ni-MOFs@NiSx samples obtained by comparative example 1.Ni-
The constant current charge-discharge diagram of MOFs@NiSx electrode materials has apparent charge and discharge platform area, is different from the triangle of electric double layer capacitance
Shape shape shows the characteristic of good fake capacitance, consistent with the test result of CV curves.
Fig. 3 (d) is the relational graph of voltage drop and current density, wherein corresponding curve is obtained by embodiment 1 for 24 hours
Ni-MOFs@NiSx samples, the corresponding curves of 12h are the Ni-MOFs@NiSx samples obtained by comparative example 1.By calculating Fig. 3
(d) slope of a curve in can obtain the internal resistance of ESR, including electrode material of electrode material itself, the diffusion electricity of electrode material
Resistance and contact resistance.As seen from the figure, under same current density, the voltage drop of the sample prepared for 24 hours be respectively less than blank sample and
Sample prepared by 12h illustrates that the material has higher electron conduction, reduces turn of liquid connecting resistance and electrode surface charge
Move resistance.
In order to characterize resistance problems of Ni-MOFs@NiSx electrode materials itself, we are in 0.01~100kHz frequency ranges
Inside test the AC impedance curve of Ni-MOFs@NiSx electrode materials.Fig. 4 is made from differential responses time next step method
The AC impedance figure of sample, wherein corresponding curve is the Ni-MOFs@NiSx samples obtained by embodiment 1 for 24 hours, and 12h is corresponded to
Curve be comparative example 1 obtained by Ni-MOFs@NiSx samples.Three curves in comparison diagram are it can be found that in the reaction time
For for 24 hours when, prepared Ni-MOFs@NiSx samples low frequency range all have larger straight slope, show extend the reaction time
Prepared sample has smaller Charge-transfer resistance, and electrolyte is smaller in the diffusion resistance of electrode material surface, electronics
Migration rate is very fast.All there is obvious radian in three samples of high frequency region, this illustrates prepared Ni-MOFs base sulphur
Compound all has certain resistance characteristic.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of combination electrode material, it is characterised in that：Include the following steps：
Source metal, organic ligand are dissolved in the mixed solution of organic solvent and water obtained mixed liquor A by step (1)；
Step (2), by sulphur source obtained mixed liquid B soluble in water；
Step (3) will keep 20~24 small after the mixed liquor A and the mixed liquid B mix at 160~180 DEG C
When, then through cooling, washing, dry obtained combination electrode material.
2. the preparation method of combination electrode material according to claim 1, it is characterised in that：The source metal is six water
Close nickel nitrate, Nickel dichloride hexahydrate, cabaltous nitrate hexahydrate, cobalt chloride hexahydrate, Fe(NO3)39H2O or Iron(III) chloride hexahydrate.
3. the preparation method of combination electrode material according to claim 1 or 2, it is characterised in that：The source metal exists
A concentration of 0.1~0.5mol/L in the mixed liquor A.
4. the preparation method of combination electrode material according to claim 1, it is characterised in that：The organic ligand is equal
Benzenetricarboxylic acid, terephthalic acid (TPA), 2,5- dihydroxy-terephthalic acid (TPA) or 5- amino isophthalic acids.
5. the preparation method of combination electrode material according to claim 1 or 4, it is characterised in that：The organic ligand
A concentration of 0.1~0.3mol/L in the mixed liquor A.
6. the preparation method of combination electrode material according to claim 1, it is characterised in that：The organic solvent is N,
Dinethylformamide, acetone or ether, the volume that feeds intake of organic solvent and the water described in the mixed solution
Than being 1:0.9~1.1, the volume ratio that feeds intake of the mixed liquor A and the mixed liquid B is 1:1~3.
7. the preparation method of combination electrode material according to claim 1, it is characterised in that：The sulphur source be urea,
It is one or more in thioacetamide, thiocarbamide, vulcanized sodium, thioacetyl aniline.
8. the preparation method of combination electrode material according to claim 1 or claim 7, it is characterised in that：The sulphur source is in institute
A concentration of 0.8~1.5mol/L in the mixed liquid B stated.
9. a kind of combination electrode material as made from preparation method described in any item of the claim 1 to 8.
10. a kind of application of combination electrode material as claimed in claim 9 in ultracapacitor.
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| CN109908963A (en) * | 2019-03-22 | 2019-06-21 | 北京工业大学 | The preparation of MOF base elctro-catalyst and its application of NiS doping |
| CN110075925A (en) * | 2019-05-08 | 2019-08-02 | 南京理工大学 | A kind of preparation method based on metal-organic framework materials oxygen-separating catalyst |
| CN110075925B (en) * | 2019-05-08 | 2022-06-21 | 南京理工大学 | Preparation method of oxygen evolution catalyst based on metal organic framework material |
| CN110415993B (en) * | 2019-07-16 | 2021-09-28 | 上海应用技术大学 | Preparation method and application of Mn-Co-S/Co-MOF nano material |
| CN110415993A (en) * | 2019-07-16 | 2019-11-05 | 上海应用技术大学 | A kind of preparation method and applications of Mn-Co-S/Co-MOF nano material |
| CN110444407A (en) * | 2019-08-12 | 2019-11-12 | 哈尔滨理工大学 | A kind of preparation method and applications based on the porous vulcanization nickel electrode material of metal organic frame nucleocapsid |
| CN110444407B (en) * | 2019-08-12 | 2022-01-11 | 哈尔滨理工大学 | Preparation method and application of core-shell porous nickel sulfide electrode material based on metal organic framework |
| CN110586116B (en) * | 2019-09-25 | 2021-08-17 | 广西师范大学 | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof |
| CN110586116A (en) * | 2019-09-25 | 2019-12-20 | 广西师范大学 | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof |
| CN110838414B (en) * | 2019-12-02 | 2021-04-20 | 大连理工大学 | Nickel-cobalt metal framework compound/graphene compound for supercapacitor and preparation method thereof |
| CN110838414A (en) * | 2019-12-02 | 2020-02-25 | 大连理工大学 | Nickel-cobalt metal framework compound/graphene compound for supercapacitor and preparation method thereof |
| CN113173605A (en) * | 2021-04-27 | 2021-07-27 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
| CN113173605B (en) * | 2021-04-27 | 2022-11-22 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
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