CN109741958A - A kind of method of dopamine cladding MOF production super capacitor material - Google Patents
A kind of method of dopamine cladding MOF production super capacitor material Download PDFInfo
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- CN109741958A CN109741958A CN201811583987.9A CN201811583987A CN109741958A CN 109741958 A CN109741958 A CN 109741958A CN 201811583987 A CN201811583987 A CN 201811583987A CN 109741958 A CN109741958 A CN 109741958A
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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
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- Y02E60/13—Energy storage using capacitors
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Abstract
The present invention relates to a kind of methods of dopamine cladding MOF production super capacitor material, comprising: using bimetallic MOF as template, is coated using dopamine, then annealed, vulcanization is to get ZnxCo1‑ xThe super capacitor material of S@C (x=0.01~1.0) hollow structure；Contain two kinds of metal nodes of Zn, Co in the bimetallic MOF.The present invention, as template and raw material, becomes a kind of stable hollow structure Zn after carrying out dopamine cladding vulcanization by bimetallic MOFxCo1‑ xS@C (x=0.01~1.0) shows good performance as a kind of high performance super capacitor anode material, and energy density is up to 55.47Wh kg‑1, and attainable maximum power density is 16.55kW kg‑1。
Description
Technical field
The invention belongs to supercapacitor manufacturing fields, and in particular to a kind of dopamine cladding MOF production supercapacitor
The method of material.
Background technique
Supercapacitor is a kind of novel energy storage device, has the advantages that charge and discharge are fast, high-efficient, stability is good.It is
A kind of clean green energy resource is the new green energy of 21 century, has biggish market potential and application prospect.It is different
It is a kind of power supply between traditional capacitor and battery, with property in traditional electrochmical power source, relies primarily on double
Electric layer and redox fake capacitance charge store electric energy.
And metal-organic framework materials (MOFs) are due to its composition and various structures, specific surface area is high, pore structure is abundant etc.
Advantage is increasingly becoming a kind of important construction material for constructing supercapacitor.
Such as: patent CN108735523A discloses a kind of system of the Zn-MOF with window girder construction carbon material derived from it
Preparation Method and its application in supercapacitor.With 4,4 '-two (imidazoles -1- base) biphenyl (bibp) and 1,3,5- benzenetricarboxylic acid
(Hbtc) and metal salt Zn (NO) 6HO, by solvent process for thermosynthesizing, successfully synthesis { [Zn (btc) (bibp)
(HO)] (HO) }, it is then calcined in nitrogen environment using the Zn-MOF of acquisition as presoma, to prepare high porosity, ratio
Surface area is big, mesoporous is high, total pore volume is big, and the orderly porous carbon materials of high degree of dispersion (PC), the PC can make suitable electrode material
Material is applied in supercapacitor.
Patent CN108538618A discloses a kind of preparation method of porous ZnO-C composite electrode material for super capacitor,
Zn complex MOF material is closed using solvent structure vanillic aldehyde first, then as persursor material in high temperature anoxybiotic
Calcining obtains porous ZnO-C composite under environment.Using the specific surface of porous ZnO-C made from preparation method of the present invention
Product is 450~500m2/ g is 5A g in current density as electrode material-1When maximum specific capacitance up to 550F g-1,
After carrying out 3000 cycle charge-discharges under high current density, the 92~97% of initial specific capacities can be kept, can express excellent out
Chemical property and good stable circulation performance, be suitable for the electrode material etc. of supercapacitor.
But above-mentioned super capacitor material still has the problems such as electro-chemical activity is insufficient, alkaline environment stability inferior is poor.
Therefore, it is badly in need of developing a kind of Novel super capacitor material.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of sides of dopamine cladding MOF production super capacitor material
Method is prepared for a kind of stable hollow structure ZnxCo1-xS@C (x=0.01~1.0).The cladding of dopamine makes MOF in alkaline ring
Substantially pattern is kept in border, the cladding of carbon effectively increases the stability of capacitor material.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of method of dopamine cladding MOF production super capacitor material, comprising:
It using bimetallic MOF as template, is coated using dopamine, then annealed, vulcanization is to get ZnxCo1-xS@C (x=
0.01~1.0) super capacitor material of hollow structure；
Contain two kinds of metal nodes of Zn, Co in the bimetallic MOF.
In some embodiments, the bimetallic MOF is ZnCo-MOF presoma.
In some embodiments, the ZnCo-MOF presoma the preparation method comprises the following steps: cobalt salt, zinc salt are dissolved in organic molten
In agent, thereto be added dropwise methylimidazole solution, after mixing, stand aging, collect precipitated product, centrifugation, washing to get
ZnCo-MOF presoma.
In some embodiments, the specific steps of the dopamine cladding are as follows: ZnCo-MOF presoma is dispersed in DOPA
In amine aqueous solution, stirring a period of time, centrifuge separation, washing, it is dry to get.
In some embodiments, the preparation method of the dopamine solution are as follows: adjust the pH value of Tris-HCL buffer
To 8 or so, dopamine is added, be uniformly mixed to get.
In some embodiments, the condition of the annealing are as follows: 500~600 DEG C, keep the temperature 2~3h.
In some embodiments, the step of vulcanizing treatment are as follows: the product after annealing is dispersed in sodium sulfide solution
In, be uniformly mixed, hydro-thermal reaction, centrifuge separation, it is dry to get.
In some embodiments, the hydrothermal reaction condition is that 12~14h is reacted under 120~130 DEG C of air-proof conditions.
The present invention also provides the super capacitor materials of any above-mentioned method preparation.
The present invention also provides above-mentioned super capacitor materials in manufacture electric car, electronic storage device, household electric
Application in device, space flight and aviation equipment.
The beneficial effects of the present invention are:
(1) present invention becomes a kind of stable after carrying out dopamine cladding vulcanization by bimetallic MOF as template and raw material
Hollow structure ZnxCo1-xS@C (x=0.01~1.0) is shown good as a kind of high performance super capacitor anode material
Good performance, energy density are up to 55.47Wh kg-1, and attainable maximum power density is 16.55kW kg-1。
(2) preparation method of the present invention is simple, electrochemical performance, practical, easy to spread.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1, Fig. 2 are the hollow Zn prepared in the embodiment of the present invention 1xCo1-xS@C (x=0.01~1.0) scanning electron microscope
Figure.
Fig. 3, Fig. 4 are the hollow Zn prepared in the embodiment of the present invention 1xCo1-xS@C (x=0.01~1.0) transmission electron microscope
Figure.
Fig. 5 is the Zn prepared in embodiment 1xCo1-xSolid Zn in S@C (x=0.01~1.0) and comparative examplexCo1-xS@C
(x=0.01~1.0) and hollow Co3ZnC@C multiplying power figure comparison diagram.
Fig. 6 is the Zn prepared in embodiment 1xCo1-xS@C (x=0.01~1.0) cyclical stability figure.
Fig. 7 is the Zn prepared in embodiment 1xCo1-xScanning electron microscope (SEM) photograph after S@C (x=0.01~1.0) circulation.
Fig. 8 is the Zn prepared in embodiment 1xCo1-xS C (x=0.01~1.0) is the supercapacitor of anode assembling
It can figure.
Fig. 9 is the solid Zn in comparative example 1xCo1-xS (x=0.01~1.0) chemical property figure.
Figure 10 is the hollow Co in comparative example 23ZnC@C chemical property figure.
Figure 11 is the hollow ZnS@C chemical property figure in comparative example 3.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, still have that electro-chemical activity is insufficient, alkali for current super capacitor material
The problem of property environment stability inferior difference.Therefore, the present invention proposes a kind of side of dopamine cladding MOF production super capacitor material
Method.By bimetallic MOF as template and raw material, become a kind of stable hollow structure after carrying out dopamine cladding vulcanization
ZnxCo1-xS@C (x=0.01~1.0), as a kind of high performance super capacitor anode material, specific preparation method includes
Following steps:
A. ZnCo-MOF presoma is prepared at room temperature；
B. prepared ZnCo-MOF dispersion is subjected to dopamine cladding in the solution；
C. the product after collecting cladding is made annealing treatment；
D. vulcanizing treatment is carried out to the product after annealing and obtains ZnxCo1-xS@C (x=0.01~1.0) hollow structure.
The specific steps of ZnCo-MOF presoma are prepared described in step a at room temperature are as follows:
A1, cabaltous nitrate hexahydrate and zinc nitrate hexahydrate are added in methanol and stir 3 minutes formation homogeneous solutions；
A2, methylimidazole is added in methanol and stirs 3 minutes formation homogeneous solutions；
Solution in a3, a2 is added dropwise in a1 liquid, is stirred continuously the homogeneous solution to form mixing；
A4, the mixed solution of formation is obtained into precipitated product in aging 24 hours at room temperature；
A5, it is collected and is precipitated by centrifugal treating, washed 3 times with methanol and obtain ZnCo-MOF presoma.
Dopamine described in step b coats concrete operation method are as follows: the Tris-HCL that configuration 100mL concentration is 10mM
Buffer, with NaOH by PH be adjusted to 8 or so addition 100mg dopamines stir it is uniform to solution, by 130mg presoma ZnCo-
MOF is added in solution, and ultrasonic treatment makes presoma be uniformly dispersed, and stirs 24 hours progress dopamine claddings；Later by from
The method of the heart is dried in vacuo 5 hours at 60 DEG C with water and each wash products of ethyl alcohol 3 times.
Product is made annealing treatment in step c specifically: product is placed in magnetic boat, in a nitrogen atmosphere with 5 DEG C
Every point is warming up to 600 DEG C, and heat preservation obtains after 2 hours.
Zn is obtained to the product progress vulcanizing treatment after annealing in step d0.76Co0.24The method of S@C hollow structure are as follows:
Product after annealing is put into 40mL 0.1M sodium sulfide solution, is transferred to polytetrafluoroethyllining lining after obtaining uniform liquid
In autoclave, seals and be heated to 120 DEG C of heat preservations 12 hours in an oven；Product centrifugation after reaction is washed with water and ethyl alcohol
Wash 3 times, after be dried in vacuo 5 hours at 60 DEG C again.
In order to enable those skilled in the art can clearly understand technical solution of the present invention, below with reference to tool
The embodiment of body and the technical solution that the present invention will be described in detail.
Embodiment 1
0.291g cabaltous nitrate hexahydrate and 0.595g zinc nitrate hexahydrate are added in 25mL methanol, stirring forms uniform
Solution.0.985g methylimidazole is added to stirring in 15mL methanol and forms homogeneous solution.The methanol of methylimidazole is molten
Liquid is added dropwise in nitrate solution, is stirred continuously, and is stood 24 hours after formation homogeneous solution and is precipitated；At centrifugation
Reason collects precipitating, washs 3 times with methanol and obtains ZIF-8 presoma.
130mg ZnCo-MOF presoma is added in the 100mL Tris-HCL buffer containing 100mg dopamine
(PH=8.5), ultrasound is after 2 minutes, and stirring is for 24 hours.Collect sediment by the method for centrifugation, successively with deionized water and ethyl alcohol into
Row washing, it is 5 hours dry at 60 DEG C.By the ZnCo-MOF@PDA polyhedron after drying, under nitrogen protection, with 5 DEG C every point
Heating rate, be warming up to 600 DEG C and keep the temperature one hour, Co is obtained after annealing3ZnC@C。
The Co that will be obtained3ZnC@C is put into 40mL 0.1M sodium sulfide solution, is transferred to polytetrafluoro after obtaining uniform liquid
In the autoclave of ethylene liner, seals and be heated to 120 DEG C of heat preservations 12 hours in an oven；With water and ethyl alcohol to reaction after
Product centrifuge washing 3 times, after be dried in vacuo 5 hours at 60 DEG C again, obtain ZnxCo1-xS@C (x=0.01~1.0) hollow structure
Super capacitor material.
Above-mentioned super capacitor material (80wt%), active carbon (10wt%) and ptfe micropowder (10wt%) are set
Enter in ethyl alcohol and stir 3 hours, slurry is uniformly applied in nickel foam, is dried in vacuo 5 hours at 60 DEG C, obtains positive work
Make electrode.Later, the nickel foam for being coated with active material is rolled under roll squeezer, uses 6M KOH as electrolyte, platinum filament conduct
To electrode, saturated calomel electrode carries out the electro-chemical test of three electrodes as reference electrode.It is filled by cyclic voltammetric and constant current
Discharge test is it is known that the electrode material has very high specific capacity, in 1A g-1Current density under up to 2082F g-1。
The multiplying power test chart of Fig. 5 electrode material is it is known that current density is up to 20A g again-1Shi Rongliang is still able to maintain
56%.
Fig. 6 demonstrates the stability that electrode material recycles under alkaline condition, and after 40000 circle circulations, capacity remains to protect
Hold 112%.It can see (Fig. 7) from the shape appearance figure after circulation, hollow polyhedral structure can still be maintained after circulation.
Equally, electrode material is used as performance of the anode in Asymmetric Supercapacitor and is also tested.The oxidation stone of reduction
Black alkene is prepared as cathode with same method, after carrying out quality matches according to charge balance concept, uses 6M KOH as electrolysis
Liquid carries out the assembling in Asymmetric Supercapacitor.Asymmetric Supercapacitor after assembling shows good performance, energy
Density is up to 55.47Wh kg-1, and attainable maximum power density is 16.55kW kg-1.(Fig. 8)
Comparative example 1:
Concrete operation method and parameter are identical with embodiment 1, the difference is that not carrying out the cladding of dopamine, obtain
To be solid ZnxCo1-xS (x=0.01~1.0).
Using same test method in same embodiment 1, three-electrode electro Chemical test is carried out to comparative example 1, from the knot of Fig. 9
Fruit is it is found that capacitor performance is poor.
Comparative example 2:
Concrete operation method and parameter are with embodiment 1, the difference is that not carrying out vulcanizing treatment, what is obtained is empty
The Co of the heart3ZnC@C。
Using same test method in same embodiment 1, three-electrode electro Chemical test is carried out to comparative example 2, from Figure 10's
As a result it is found that capacitor performance is poor.
Comparative example 3:
Concrete operation method and parameter are with embodiment 1, the difference is that cabaltous nitrate hexahydrate is not added, what is obtained is
Hollow structure ZnS@C.
Using same test method in same embodiment 1, three-electrode electro Chemical test is carried out to comparative example 3, from Figure 11's
As a result it is found that capacitor performance is poor.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (10)
1. a kind of method of dopamine cladding MOF production super capacitor material characterized by comprising
It using bimetallic MOF as template, is coated using dopamine, then annealed, vulcanization is to get ZnxCo1-xS@C (x=0.01~
1.0) super capacitor material of hollow structure；
Contain two kinds of metal nodes of Zn, Co in the bimetallic MOF.
2. the method as described in claim 1, which is characterized in that the bimetallic MOF is ZnCo-MOF presoma.
3. the method as described in claim 1, which is characterized in that the ZnCo-MOF presoma the preparation method comprises the following steps: by cobalt salt,
Zinc salt dissolves in organic solvent, and methylimidazole solution is added dropwise thereto, after mixing, stands aging, collects precipitating and produces
Object, centrifugation, washing are to get ZnCo-MOF presoma.
4. method according to claim 2, which is characterized in that the specific steps of the dopamine cladding are as follows: by ZnCo-MOF
Presoma is dispersed in dopamine solution, stirring a period of time, centrifuge separation, washing, it is dry to get.
5. the method as described in claim 1, which is characterized in that the preparation method of the dopamine solution are as follows: by Tris-HCL
The pH value of buffer is adjusted to 8 or so, and dopamine is added, be uniformly mixed to get.
6. the method as described in claim 1, which is characterized in that the condition of the annealing are as follows: 500~600 DEG C, heat preservation 2
~3h.
7. the method as described in claim 1, which is characterized in that the step of the vulcanizing treatment are as follows: by the product after annealing point
Be dispersed in sodium sulfide solution, be uniformly mixed, hydro-thermal reaction, centrifuge separation, it is dry to get.
8. the method as described in claim 1, which is characterized in that the hydrothermal reaction condition is in 120~130 DEG C of air-proof conditions
12~14h of lower reaction.
9. the super capacitor material of the described in any item method preparations of claim 1-8.
10. super capacitor material as claimed in claim 9 is in manufacture electric car, electronic storage device, household electrical appliance, space flight
Application in air equipment.
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Cited By (6)
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| CN111293300A (en) * | 2020-02-28 | 2020-06-16 | 中南大学 | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof |
| CN111292965A (en) * | 2020-02-25 | 2020-06-16 | 东南大学 | Lithium ion hybrid capacitor cathode material with core-shell structure, preparation and application |
| CN111524719A (en) * | 2020-04-16 | 2020-08-11 | 华东师范大学 | ED-Mn @ ZIF-67 composite material, and preparation method and application thereof |
| CN112103092A (en) * | 2020-07-27 | 2020-12-18 | 浙江工业大学 | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof |
| CN112939707A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Aluminum-based energetic MOFs and preparation method thereof |
| CN115007176A (en) * | 2022-05-13 | 2022-09-06 | 江苏亚泰化工有限公司 | Double-shell ZnS @ ZnxCo1-xS catalyst and synthetic method and application thereof |
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Cited By (9)
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| CN111292965A (en) * | 2020-02-25 | 2020-06-16 | 东南大学 | Lithium ion hybrid capacitor cathode material with core-shell structure, preparation and application |
| CN111293300A (en) * | 2020-02-28 | 2020-06-16 | 中南大学 | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof |
| CN111524719A (en) * | 2020-04-16 | 2020-08-11 | 华东师范大学 | ED-Mn @ ZIF-67 composite material, and preparation method and application thereof |
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| CN112103092B (en) * | 2020-07-27 | 2022-02-11 | 浙江工业大学 | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof |
| CN112939707A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Aluminum-based energetic MOFs and preparation method thereof |
| CN112939707B (en) * | 2021-02-05 | 2022-03-29 | 西安近代化学研究所 | Aluminum-based energetic MOFs and preparation method thereof |
| CN115007176A (en) * | 2022-05-13 | 2022-09-06 | 江苏亚泰化工有限公司 | Double-shell ZnS @ ZnxCo1-xS catalyst and synthetic method and application thereof |
| CN115007176B (en) * | 2022-05-13 | 2024-03-08 | 江苏亚泰化工有限公司 | Double-shell ZnS@Zn x Co 1-x S catalyst and synthesis method and application thereof |
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