CN109559902A - Derivative cobalt nickel boron sulphide material of a kind of metal organic frame and the preparation method and application thereof - Google Patents
Derivative cobalt nickel boron sulphide material of a kind of metal organic frame and the preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- JRTBYPZGEKBYPO-UHFFFAOYSA-N [B]=S.[Ni].[Co] Chemical compound [B]=S.[Ni].[Co] JRTBYPZGEKBYPO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 229910020630 Co Ni Inorganic materials 0.000 claims description 50
- 229910002440 Co–Ni Inorganic materials 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical group NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000006260 foam Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- -1 FeCo2S4 Chemical compound 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- CYEPGGGMSRDRBI-UHFFFAOYSA-N cobalt gold nickel Chemical compound [Ni][Co][Au] CYEPGGGMSRDRBI-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJFNJZGXHWYGMQ-UHFFFAOYSA-N [Ni].B#[Co] Chemical compound [Ni].B#[Co] JJFNJZGXHWYGMQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CPTTWDDSVZIXIO-UHFFFAOYSA-N sulfanylideneboron Chemical compound S=[B] CPTTWDDSVZIXIO-UHFFFAOYSA-N 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses derivative cobalt nickel boron sulphide materials of a kind of metal organic frame and the preparation method and application thereof, specific aim supercapacitor applications redesign the preparation of the derivative cobalt nickel boron sulphide material of the metal organic frame, and it is selected and is optimized especially by the overall flow technological design to preparation method, Parameter Conditions used by each step, control is optimized by concrete composition to cobalt nickel boron sulphide material and microscopic appearance, should be able to mutually obtain the cobalt nickel boron sulphide electrode material that chemical property greatly improves.
Description
Technical field
The invention belongs to new energy materials and electrochemical energy switching device field, have more particularly, to a kind of metal
Derivative cobalt nickel boron sulphide material of machine frame and the preparation method and application thereof, the derivative cobalt nickel boron sulphide material of the metal organic frame
Material is electrode material, can be used as supercapacitor applications.
Background technique
Currently, supercapacitor due to advantages such as high power density, fast recharge capability and excellent cycle lives and
It is concerned.Exploring has high capacitance, and avirulent novel low-cost electrode material for super capacitor has become current research
Hot topic.As common one of electrode material, transient metal sulfide is because of its oxygen enrichment reduction reaction and good conduction
Property and be widely studied.In particular, some bimetallic sulfide, such as FeCo2S4, Zn-Co-S and Co2NiS4, since its is multiple
Sulfided state and low electronegativity have reversible faraday's reaction and excellent electric conductivity as electrode material.And they are logical
Often there is richer redox active site than one pack system sulfide, to further increase chemical property.Wherein,
Co-Ni bimetallic sulfide is due to its excellent electronic conductivity, the features such as cheapness and thermal stability, it is considered to be most has uncommon
The oxidation-reduction electrode material of prestige.
Metal organic frame (Metal-Organic Framework, MOFs) be it is a kind of by metal ion or metal cluster and
The inorganic-organic hybridization crystalline material of organic ligand composition, has various crystal structures and pattern, while having high table
The advantages that area and high porosity.MOFs can be converted into carbon, gold by being simply heat-treated as presoma or template
Belong to oxide/hydroxide, metal sulfide and its composite material, can not only obtain big specific surface area, can also keep it
Primary morphology and hole attributes.Han et al. is prepared for the nickel-cobalt sulfide nano-chip arrays of classification in nickel foam, not only protects
The pattern of MOFs itself is stayed, and in 0.5A g-1There is down 1406.9F g-1High specific capacitance [Han Q et al.,
Dalton Trans,2018,47,3496-3502].MOFs with specific nanometer sheet form has biggish surface area and table
Highdensity active site on face.Major part electrode material can reach increase material specific surface area by various templates at present
Enhance the storage of its capacitor to increase the contact with electrolyte, is bound to cause the waste of preparation.
Unique 3D layered structure, big surface area are conducive to the electrochemical reaction on surface, can also effectively facilitate fast
Fast ion transmission, to improve specific capacity.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of metal organic frames
Derivative cobalt nickel boron sulphide material and the preparation method and application thereof, specific aim supercapacitor applications of the present invention are organic to the metal
The preparation of the derivative cobalt nickel boron sulphide material of frame is redesigned, and is set especially by the overall flow technique to preparation method
Meter, Parameter Conditions (material ratio of such as reactant) used by each step improve and further preferably, can be to cobalt nickel
The concrete composition and microscopic appearance of boron sulphide material advanced optimize control, mutually should be able to obtain chemical property substantially
The cobalt nickel boron sulphide electrode material of raising, can effectively solve the problem that current business electrode material in price compared with prior art
Disadvantage and the undesirable technical problem of electrochemical properties such as specific capacity, stability.
To achieve the above object, according to one aspect of the present invention, a kind of derivative cobalt nickel boron of metal organic frame is provided
Sulfide material, the material are made using metal organic framework compound as presoma, then after passing sequentially through boronation and vulcanizing treatment
Standby obtained cobalt nickel boron sulphide material, i.e. Co-Ni MOF-B-S.
Preferably, which has even piece pattern.
Another aspect of the present invention provides a kind of preparation side of derivative cobalt nickel boron sulphide material of metal organic frame
Method, which comprises the following steps:
(1) solvable cobalt salt and solvable nickel salt are pressed into certain mol proportion, is dissolved in organic solvent under violent magnetic agitation
In, obtain solution I；Meanwhile in organic solvent by organic ligand dissolution, solution II is obtained；Then the two is mixed, stirring is equal
After even, mixed solution is transferred in stainless steel cauldron, solvent thermal reaction is carried out, dries after reaction, obtains cobalt nickel gold
Belong to organic frame, i.e. Co-Ni MOF；
(2) certain density sodium borohydride solution is added drop-wise in the aqueous solution of Co-Ni MOF under magnetic stirring, is continued
Stirring.Subsequent filtration washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B；
(3) under magnetic stirring, certain density sodium sulfide solution is added drop-wise in the aqueous solution of Co-Ni MOF-B, is held
Continuous stirring.Subsequent filtration washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B-S.
Preferably, in step (1), the solvable cobalt salt is cobalt acetate, and the solvable nickel salt is nickel acetate, described organic to match
Body is 1,2,3,4- butane tetracarboxylic acid, and the organic solvent is n,N-dimethylacetamide, the solvable cobalt salt and solvable nickel salt
The molar ratio of the two is 1:(0.25-10), the concentration of the solution I is 0.01-0.1mol/L, and the concentration of the solution II is
0.01-0.1mol/L。
Preferably, in step (1), the reaction temperature is 100-180 DEG C, reaction time 12-36h, and drying temperature is
50-100℃。
Preferably, in step (2), the concentration of the Co-Ni MOF aqueous solution is 0.1-0.5mol/L, the sodium borohydride
The concentration of solution is 0.01-0.3mol/L, and solvent is deionized water, and the mixing time is 1-3h.
Preferably, in step (3), the concentration of the Co-Ni MOF-B aqueous solution is 0.1-0.5mol/L, the vulcanized sodium
The concentration of solution is 0.01-0.3mol/L, and solvent is deionized water, and the mixing time is 1-3h.
Another aspect of the present invention provides the cobalt nickel boron sulphide material being prepared using the above method as super
The application of capacitor electrode material.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention prepares cobalt nickel boron sulphide material, and it is organic that the first step uses solvent thermal reaction to prepare cobalt nickel metal
Frame precursor, further by presoma boronation and vulcanization, preparation method is simple, safe and efficient and controllable.
For the short slab of existing business electrode material, the purpose of the present invention is to provide a kind of derivative cobalts of metal organic frame
Nickel boron sulphide and preparation method thereof, it is intended to solve disadvantage and specific capacitance, stability of the existing business electrode material in price
The undesirable problem of equal chemical properties.The present invention is exposed more from base metal raw material by preparation nanometer sheet
Redox active site, its specific capacitance is improved, according to measured chemical property, it was demonstrated that this new think of of the invention
Road, new method are very useful.
(2) the cobalt nickel boron sulphide material that preparation method obtains through the invention can be used as electrode material for super electricity
Container.Cobalt nickel boron sulphide material produced by the present invention especially has nanometer sheet pattern, therefore can expose more oxidations
Reduction activation site has high electro-chemical activity, and Co-Ni MOF-B-S/NF electrode has ultra-high capacity characteristic, has superelevation
Specific capacitance (1A g-1When be 1281.2F g-1), have excellent high rate performance (in 20A g-1When be 802.9F g-1), and have
Cyclical stability outstanding (capacity retention is 92.1% after 10000 circulations).Meanwhile being surpassed with the asymmetric of the electrode structure
Grade capacitor, power density are 857.7W Kg-1When, it is capable of providing 44.96Wh Kg-1Energy density, and followed at 5000 times
There is 87.7% capacity retention ratio after ring, show good circulation stability.
Detailed description of the invention
Fig. 1 is the preparation method implementation flow chart for the cobalt nickel boron sulphide that the embodiment of the present invention 1 provides；
Fig. 2 is the SEM figure for the cobalt nickel boron sulphide that the embodiment of the present invention 1 provides；
Fig. 3 is the XRD diagram for the cobalt nickel boron sulphide that the embodiment of the present invention 1 provides；
Fig. 4 is that the cyclic voltammetry curve of cobalt nickel boron sulphide in alkaline electrolyte that the embodiment of the present invention 1 provides shows
It is intended to；
Fig. 5 is the constant current charge-discharge curve of cobalt nickel boron sulphide in alkaline electrolyte that the embodiment of the present invention 1 provides
Schematic diagram；
Fig. 6 is the ac impedance spectroscopy of cobalt nickel boron sulphide in alkaline electrolyte that the embodiment of the present invention 1 provides；
Fig. 7 is the curve of the stability for the cobalt nickel boron sulphide full battery that the embodiment of the present invention 1 provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
The present invention provides a kind of preparation methods of the derivative cobalt nickel boron sulphide of metal organic frame, include the following steps:
(1) solvable cobalt salt and solvable nickel salt are pressed into certain mol proportion, is dissolved in organic solvent under violent magnetic agitation
In, obtain solution I；Meanwhile in organic solvent by organic ligand dissolution, solution II is obtained；Then the two is mixed, stirring is equal
After even, mixed solution is transferred in stainless steel cauldron, solvent thermal reaction is carried out, dries after reaction, obtains cobalt nickel gold
Belong to organic frame, i.e. Co-Ni MOF；
Solvable cobalt salt is preferably cobalt acetate, and solvable nickel salt is preferably nickel acetate, and organic ligand is preferably 1,2,3,4- butane
Tetrabasic carboxylic acid, organic solvent are preferably n,N-dimethylacetamide, and the molar ratio of both solvable cobalt salt and solvable nickel salt can be 1:
The concentration of (0.25-10), solution I can be 0.01-0.1mol/L, and the concentration of the solution II can be 0.01-0.1mol/L；
Reaction temperature can be 100-180 DEG C, and the reaction time can be 12-36h, and drying temperature can be 50-100 DEG C.
(2) certain density sodium borohydride solution is added drop-wise in the aqueous solution of Co-Ni MOF under magnetic stirring, is continued
Stirring.Subsequent filtration washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B；
The concentration of Co-Ni MOF aqueous solution can be 0.1-0.5mol/L, and the concentration of sodium borohydride solution can be 0.01-
0.3mol/L, solvent are deionized water, and mixing time can be 1-3h.
(3) under magnetic stirring, certain density sodium sulfide solution is added drop-wise in the aqueous solution of Co-Ni MOF-B, is held
Continuous stirring.Subsequent filtration washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B-S；
The concentration of Co-Ni MOF-B aqueous solution can be 0.1-0.5mol/L, and the concentration of sodium sulfide solution can be
0.01-0.3mol/L, solvent are deionized water, and mixing time can be 1-3h.
The present invention provides a kind of derivative cobalt nickel boron sulphide materials of metal organic frame, prepare according to above-mentioned preparation method
It obtains, with even piece pattern, more redox active sites can be exposed, improve its electro-chemical activity.Co-
Ni MOF-B-S/NF electrode has ultra-high capacity characteristic, has superelevation specific capacitance (1A g-1When be 1281.2F g-1), have excellent
Different high rate performance is (in 20A g-1When be 802.9F g-1), and have cyclical stability outstanding (10000 times circulation after capacitor
92.1%) conservation rate is.Meanwhile with the Asymmetric Supercapacitor of the electrode structure, power density is 857.7W Kg-1When, energy
44.96Wh Kg is enough provided-1Energy density, and there is 87.7% capacity retention ratio after 1000 circulations, show good
Cyclical stability.
The following are embodiments:
Embodiment 1:
Fig. 1 shows the preparation flow of the derivative cobalt nickel boron sulphide electrode material of metal organic frame of this example offer, packet
Include following steps:
(1) cobalt nickel metal organic frame precursor preparation: 8mmol cobalt acetate, 2mmol nickel acetate raw material are dissolved in 50mL
In n,N-dimethylacetamide, 160 DEG C of hydro-thermal reactions are for 24 hours.Filtering, and washed three times with ethyl alcohol and deionized water, vacuum drying,
Obtain cobalt nickel metal organic frame presoma, i.e. Co-Ni MOF.
(2) borax treatment: under magnetic stirring, 10mg Co-Ni MOF is dispersed in 50mL deionized water.Meanwhile it will
0.25mol sodium borohydride is dissolved completely in 10mL deionized water.Then, sodium borohydride solution is added drop-wise in above-mentioned solution simultaneously
It is kept stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B。
(3) vulcanizing treatment: under magnetic stirring, 10mg Co-Ni MOF-B is dispersed in 50mL deionized water.Meanwhile
0.25mol vulcanized sodium is dissolved completely in 10mL deionized water.Then, sodium sulfide solution is added drop-wise in above-mentioned solution and is protected
Hold stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B-S。
Fig. 2 shows the scanning electron microscope for the derivative cobalt nickel boron sulphide of metal organic frame that present example provides
Image, image displaying material after boronation vulcanization reaction, reunite there is no apparent by material, illustrates reaction only in single ball
It is generated between body or in small spacing range.Fig. 3 is the XRD diagram of the product, can be obtained from image, and boronation or vulcanization can all lead to material
The generation of undefined structure.
(4) preparation of electrode: firstly, being ultrasonically treated nickel foam (2cm × 2cm) in 3M HCl solution, 10 minutes to remove
The oxide on surface is removed, and is cleaned with ethyl alcohol and deionized water.Then, by Co-Ni MOF-B-S and Super P, PVDF with
Mass ratio is 80:10:10 mixing, is uniformly mixed in N-Methyl pyrrolidone (NMP), slurry is finally coated on nickel foam
On, area activated quality is 5.2-6.3mg cm-2.The chemical property of electrode material carries out in three electrode test ponds, Hg/
HgO is as reference electrode, and platinized platinum is to electrode, and electrolyte is 6M KOH, and cyclic voltammetry curve is as shown in Figure 4.In 5mV s-1-
40mV s-1It sweeps under speed, material shows good stability, and as can be seen from the figure material has typical mixed type capacitor
Device characteristic, in the case where sweeping speed increase, the redox peaks that material is shown are not substantially change, represent it with good
Good high rate performance.Fig. 5 is the constant current charge-discharge curve graph of material, can show the good high rate performance of material.Fig. 6 is
It is minimum in the transmitting resistance of material internal to obtain electronics by fitting, is 0.094 for the ac impedance spectroscopy of Co-Ni MOF-B-S
Ohm.Fig. 7 is Co-Ni MOF-B-S in 15A g-1Current density under single electrode cycle life test, can from figure
Out, the specific capacity that material also maintains 92.1% by 10000 circulations is remaining, has good cycle performance.
Embodiment 2
(1) cobalt nickel metal organic frame precursor preparation: 2mmol cobalt acetate, 2mmol nickel acetate raw material are dissolved in 50mL
In n,N-dimethylacetamide, 160 DEG C of hydro-thermal reactions are for 24 hours.Filtering, and washed three times with ethyl alcohol and deionized water, vacuum drying,
Obtain cobalt nickel metal organic frame presoma, i.e. Co-Ni MOF.
(2) borax treatment: under magnetic stirring, 10mg Co-Ni MOF is dispersed in 50mL deionized water.Meanwhile it will
0.25mol sodium borohydride is dissolved completely in 10mL deionized water.Then, sodium borohydride solution is added drop-wise in above-mentioned solution simultaneously
It is kept stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B。
(3) vulcanizing treatment: under magnetic stirring, 10mg Co-Ni MOF-B is dispersed in 50mL deionized water.Meanwhile
0.25mol vulcanized sodium is dissolved completely in 10mL deionized water.Then, sodium sulfide solution is added drop-wise in above-mentioned solution and is protected
Hold stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B-S。
(4) preparation of electrode: firstly, being ultrasonically treated nickel foam (2cm × 2cm) in 3M HCl solution, 10 minutes to remove
The oxide on surface is removed, and is cleaned with ethyl alcohol and deionized water.Then, by Co-Ni MOF-B-S and Super P, PVDF with
Mass ratio is 80:10:10 mixing, is uniformly mixed in N-Methyl pyrrolidone (NMP), slurry is finally coated on nickel foam
On, area activated quality is 5.2-6.3mg cm-2.The chemical property of electrode material carries out in three electrode test ponds, Hg/
HgO is as reference electrode, and platinized platinum is to electrode, and electrolyte is 6M KOH, and the chemical property shown is omited compared to embodiment 1
Difference, caused by the active site that mainly can be provided as different cobalt nickel ratios is different from capacitor, but its performance gap with
Embodiment one is within error range.
Embodiment 3
(1) cobalt nickel metal organic frame precursor preparation: 4mmol cobalt acetate, 2mmol nickel acetate raw material are dissolved in 50mL
In n,N-dimethylacetamide, 160 DEG C of hydro-thermal reactions are for 24 hours.Filtering, and washed three times with ethyl alcohol and deionized water, vacuum drying,
Obtain cobalt nickel metal organic frame presoma, i.e. Co-Ni MOF.
(2) borax treatment: under magnetic stirring, 10mg Co-Ni MOF is dispersed in 50mL deionized water.Meanwhile it will
0.25mol sodium borohydride is dissolved completely in 10mL deionized water.Then, sodium borohydride solution is added drop-wise in above-mentioned solution simultaneously
It is kept stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B。
(3) vulcanizing treatment: under magnetic stirring, 10mg Co-Ni MOF-B is dispersed in 50mL deionized water.Meanwhile
0.25mol vulcanized sodium is dissolved completely in 10mL deionized water.Then, sodium sulfide solution is added drop-wise in above-mentioned solution and is protected
Hold stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B-S。
(4) preparation of electrode: firstly, being ultrasonically treated nickel foam (2cm × 2cm) in 3M HCl solution, 10 minutes to remove
The oxide on surface is removed, and is cleaned with ethyl alcohol and deionized water.Then, by Co-Ni MOF-B-S and Super P, PVDF with
Mass ratio is 80:10:10 mixing, is uniformly mixed in N-Methyl pyrrolidone (NMP), slurry is finally coated on nickel foam
On, area activated quality is 5.2-6.3mg cm-2.The chemical property of electrode material carries out in three electrode test ponds, Hg/
HgO is as reference electrode, and platinized platinum is to electrode, and electrolyte is 6M KOH, and the chemical property shown is omited compared to embodiment 1
Difference, caused by the active site that mainly can be provided as different cobalt nickel ratios is different from capacitor, but its performance gap with
Embodiment one is within error range.
Embodiment 4
(1) cobalt nickel metal organic frame precursor preparation: 8mmol cobalt acetate, 2mmol nickel acetate raw material are dissolved in 50mL
In n,N-dimethylacetamide, 160 DEG C of hydro-thermal reactions are for 24 hours.Filtering, and washed three times with ethyl alcohol and deionized water, vacuum drying,
Obtain cobalt nickel metal organic frame presoma, i.e. Co-Ni MOF.
(2) borax treatment: under magnetic stirring, 10mg Co-Ni MOF is dispersed in 50mL deionized water.Meanwhile it will
0.25mol sodium borohydride is dissolved completely in 10mL deionized water.Then, sodium borohydride solution is added drop-wise in above-mentioned solution simultaneously
It is kept stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B。
(3) vulcanizing treatment: under magnetic stirring, 10mg Co-Ni MOF-B is dispersed in 50mL deionized water.Meanwhile
0.25mol vulcanized sodium is dissolved completely in 10mL deionized water.Then, sodium sulfide solution is added drop-wise in above-mentioned solution and is protected
Hold stirring 1 hour.The sample prepared by collected by suction, and be washed with deionized three times, vacuum drying obtains Co-Ni
MOF-B-S。
(4) preparation of electrode: firstly, being ultrasonically treated nickel foam (2cm × 2cm) in 3M HCl solution, 10 minutes to remove
The oxide on surface is removed, and is cleaned with ethyl alcohol and deionized water.Then, by Co-Ni MOF-B-S and Super P, PVDF with
Mass ratio is 80:10:10 mixing, is uniformly mixed in N-Methyl pyrrolidone (NMP), slurry is finally coated on nickel foam
On, area activated quality is 5.2-6.3mg cm-2.The chemical property of electrode material carries out in three electrode test ponds, Hg/
HgO is as reference electrode, and platinized platinum is to electrode, and electrolyte is 6M KOH, and the chemical property shown is omited compared to embodiment 1
Difference, caused by the active site that mainly can be provided as different cobalt nickel ratios is different from capacitor, but its performance gap with
Embodiment one is within error range.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of derivative cobalt nickel boron sulphide material of metal organic frame, which is characterized in that the material is with metal organic frame
Compound is presoma, then passes sequentially through the cobalt nickel boron sulphide material being prepared after boronation and vulcanizing treatment, i.e. Co-Ni
MOF-B-S。
2. the derivative cobalt nickel boron sulphide material of a kind of metal organic frame according to claim 1, which is characterized in that the cobalt
Nickel boron sulphide material has nanometer sheet pattern.
3. a kind of preparation side for deriving cobalt nickel boron sulphide material such as metal organic frame of any of claims 1-2
Method, which comprises the following steps:
(1) solvable cobalt salt and solvable nickel salt are dissolved in organic solvent under violent magnetic agitation, obtains solution I；Meanwhile
In organic solvent by organic ligand dissolution, solution II is obtained；Then two solution are mixed, after mixing evenly, by mixed solution
It is transferred in stainless steel cauldron, carries out solvent thermal reaction, dry after reaction, obtain cobalt nickel metal organic frame, i.e. Co-
Ni MOF；
(2) sodium borohydride solution is added drop-wise in the aqueous solution of Co-Ni MOF under magnetic stirring, it is lasting to stir；Then filtering
Washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B；
(3) under magnetic stirring, sodium sulfide solution is added drop-wise in the aqueous solution of Co-Ni MOF-B, it is lasting to stir；Then filtering
Washing, vacuum drying, collects the sample of preparation, i.e. Co-Ni MOF-B-S.
4. the preparation method of the derivative cobalt nickel boron sulphide material of the metal organic frame according to claim 3,
It is characterized in that, in the step (1), the solvable cobalt salt is cobalt acetate, and the solvable nickel salt is nickel acetate, the organic ligand
It is 1,2,3,4- butane tetracarboxylic acid, the organic solvent is n,N-dimethylacetamide；The solvable cobalt salt and solvable nickel salt two
The molar ratio of person is 1:(0.25-10), the concentration of the solution I is 0.01-0.1mol/L, and the concentration of the solution II is
0.01-0.1mol/L。
5. the preparation method of the derivative cobalt nickel boron sulphide material of the metal organic frame according to claim 3,
It is characterized in that, in the step (1), the reaction temperature is 100-180 DEG C, reaction time 12-36h, drying temperature 50-
100℃。
6. the preparation method of the derivative cobalt nickel boron sulphide material of the metal organic frame according to claim 3,
It is characterized in that, in the step (2), the concentration of the Co-Ni MOF aqueous solution is 0.1-0.5mol/L, and the sodium borohydride is molten
The concentration of liquid is 0.01-0.3mol/L, and solvent is deionized water, and the mixing time is 1-3h.
7. the preparation method of the derivative cobalt nickel boron sulphide material of the metal organic frame according to claim 3,
It is characterized in that, in the step (3), the concentration of the Co-Ni MOF-B aqueous solution is 0.1-0.5mol/L, and the vulcanized sodium is molten
The concentration of liquid is 0.01-0.3mol/L, and solvent is deionized water, and the mixing time is 1-3h.
8. a kind of metal organic frame described in any one of -2 derivative cobalt nickel boron sulphide material is answered according to claim 1
With, which is characterized in that using derivative cobalt nickel boron sulphide material the answering as electrode material for super capacitor of the metal organic frame
With.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921721A (en) * | 2019-12-03 | 2020-03-27 | 西北师范大学 | Preparation and application of metal organic framework-derived bimetallic hydroxide |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN113539703A (en) * | 2021-07-19 | 2021-10-22 | 桂林电子科技大学 | MOFs derivative Co-Ni-B-P composite material and preparation method and application thereof |
| CN114664569A (en) * | 2022-04-20 | 2022-06-24 | 陕西科技大学 | Boron-doped cobalt-nickel flexible electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
| CN104795245A (en) * | 2015-05-14 | 2015-07-22 | 安徽师范大学 | Wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite, and preparation method and purpose thereof |
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| KR20170043138A (en) * | 2015-10-12 | 2017-04-21 | 한양대학교 에리카산학협력단 | Method for manufacturing a cobalt sulfide based on MOF(Metal Organic Framework), and method for manufacturing a dye sensitized solar cell using same |
| CN106966443A (en) * | 2017-03-24 | 2017-07-21 | 福州大学 | A kind of preparation method of transition metal oxide/sulfide nano composite material |
| CN108987759A (en) * | 2018-07-03 | 2018-12-11 | 河南师范大学 | The application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst |
-
2018
- 2018-11-15 CN CN201811356150.0A patent/CN109559902B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
| CN104795245A (en) * | 2015-05-14 | 2015-07-22 | 安徽师范大学 | Wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite, and preparation method and purpose thereof |
| CN104992848A (en) * | 2015-06-30 | 2015-10-21 | 中国地质大学（武汉） | Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material |
| KR20170043138A (en) * | 2015-10-12 | 2017-04-21 | 한양대학교 에리카산학협력단 | Method for manufacturing a cobalt sulfide based on MOF(Metal Organic Framework), and method for manufacturing a dye sensitized solar cell using same |
| CN106966443A (en) * | 2017-03-24 | 2017-07-21 | 福州大学 | A kind of preparation method of transition metal oxide/sulfide nano composite material |
| CN108987759A (en) * | 2018-07-03 | 2018-12-11 | 河南师范大学 | The application of nickel, cobalt, sulphur, boron codope carbon material in zinc-air battery catalyst |
Non-Patent Citations (1)
| Title |
|---|
| KAI TAO等: "A metal-organic framework derived hierarchical nickel-cobalt sulfide nanosheet array on Ni foam with enhanced electrochemical performance for supercapacitors", 《DALTON TRANSACTIONS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921721A (en) * | 2019-12-03 | 2020-03-27 | 西北师范大学 | Preparation and application of metal organic framework-derived bimetallic hydroxide |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN112886024B (en) * | 2021-03-05 | 2022-04-08 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN113539703A (en) * | 2021-07-19 | 2021-10-22 | 桂林电子科技大学 | MOFs derivative Co-Ni-B-P composite material and preparation method and application thereof |
| CN114664569A (en) * | 2022-04-20 | 2022-06-24 | 陕西科技大学 | Boron-doped cobalt-nickel flexible electrode material and preparation method thereof |
| CN114664569B (en) * | 2022-04-20 | 2023-09-19 | 陕西科技大学 | Boron doped cobalt-nickel flexible electrode material and preparation method thereof |
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