CN108281299A - A kind of preparation method of bimetallic MOFs derivative electrode materials - Google Patents
A kind of preparation method of bimetallic MOFs derivative electrode materials Download PDFInfo
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- CN108281299A CN108281299A CN201810178186.8A CN201810178186A CN108281299A CN 108281299 A CN108281299 A CN 108281299A CN 201810178186 A CN201810178186 A CN 201810178186A CN 108281299 A CN108281299 A CN 108281299A
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Abstract
The invention discloses a kind of preparation methods of bimetallic MOFs derivative electrode materials, including：One, hydro-thermal method prepares powdered nickel cobalt bimetallic MOFs materials；Two, N is added in Kynoar, conductive black and powdered nickel cobalt bimetallic MOFs materials, in N dimethylformamides, is stirred after ultrasonic disperse, obtain paste mixture；Three, paste mixture is dropped in the nickel foam cleaned up, is dried in vacuo after natural drying, obtain nickel cobalt bimetallic MOFs electrode materials；Four, nickel cobalt bimetallic MOFs electrode materials are placed in potassium hydroxide aqueous solution, first use cyclic voltammetry, then with galvanostatic charge/discharge cycle charge-discharge, obtains bimetallic MOFs derivative electrode materials.Bimetallic MOFs derivatives electrode material specific capacitance maximum prepared by method using the present invention is up to 990.8F/g, and specific capacitance is maintained as 523.1F/g after charge and discharge 5000 times.
Description
Technical field
The invention belongs to the interleaving techniques fields of energy storage material and synthesis chemistry, and in particular to a kind of bimetallic MOFs derivatives
The preparation method of object electrode material.
Background technology
Nearly more than 10 years, synthesis and the performance study of MOFs were grown rapidly.It is a kind of with periodic network knot
The crystalline state porous material of structure, has the rigidity of inorganic material and the flexible characteristic of organic material concurrently.Most of MOFs have high
The chemical stability that porosity is become reconciled.Since its pore structure is adjustable, large specific surface area has more metallic sites, the spies such as extremely-low density
Point, MOFs have wider application prospect than other porous materials, such as catalyst, sorbing material, magnetic material, optical material
And the fields such as energy storage material.In recent years, it is used as the research of electrode material in lithium ion battery and ultracapacitor in relation to MOFs
It reports more, but is mostly monometallic MOFs, and simple MOFs electrode materials store charge generally in the form of electric double layer, therefore
Specific capacitance is relatively low, also unstable；Though it is reported currently, there is the forward position for the conductive MOFs for storing charge in a manner of fake capacitance to study,
Its ligand is expensive, and technique is sufficiently complex；In order to improve the capacitance of MOFs, most researcher can be converted into porous charcoal, gold
Belong to oxide (hydroxide) or porous charcoal/metal oxide (hydroxide), this process is more, and technique is also more complex.In addition,
MOFs mostly uses greatly solvent structure, and environmental pollution and operation hidden danger are big.
Invention content
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of bimetallic MOFs
The preparation method of derivative electrode material.This method is activated using electrochemistry, and electrolyte ion is rapidly introduced into nickel cobalt bimetallic
In the surface or hole of MOFs, it is made to be transformed into derivative, and surface or hole by constantly circulating in nickel cobalt bimetallic MOFs
It is middle to replace fresh electrolyte ion, so that it is quickly converted to the derivative of rock-steady structure；The nickel cobalt obtained after electrochemistry activation
Bimetallic MOFs derivatives, XRD diffraction maximums are different from initial nickel cobalt bimetallic MOFs, also different from NixCoyOzOr
NixCo1-x(OH)2, it is really a kind of nickel cobalt bimetallic MOFs derivatives of special construction, with the nickel cobalt for not carrying out electrochemistry activation
Bimetallic MOFs electrode materials are compared, and specific capacitance greatly improves, and specific capacitance maximum is up to 990.8F/g, after charge and discharge 5000 times
Specific capacitance is maintained as 523.1F/g.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of bimetallic MOFs derivatives electrode material
The preparation method of material, which is characterized in that include the following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, are prepared using hydro-thermal method
Powdered nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials that will be prepared in Kynoar, conductive black and step 1
It is added in n,N-Dimethylformamide, 4h~12h is stirred after ultrasonic disperse 20min~30min, obtains paste mixture；It is described
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in Kynoar, conductive black and step 1 be (10~
15)：(10~15)：(75~80)；The volume of the N,N-dimethylformamide is powdered nickel cobalt bimetallic MOFs material matter
1.5~2.5 times of amount, the wherein unit of volume are mL, and the unit of quality is g；
Step 3: by paste mixture described in step 2 according to 0.4mg/cm2~0.6mg/cm2Load capacity drop to clearly
In the nickel foam of wash clean, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 are placed in potassium hydroxide aqueous solution, first use
Cyclic voltammetry is recycled 20~200 times with the sweep speed of 10mV/s~100mV/s, then with galvanostatic charge/discharge, 5A/g~
Cycle charge-discharge 50~400 times under the current density of 10A/g obtain bimetallic MOFs derivative electrode materials.
A kind of preparation method of above-mentioned bimetallic MOFs derivative electrode materials, which is characterized in that metal in step 1
The molar ratio of salt and ligand 4,4 '-biphenyl dicarboxylic acid is (1~2.03)：1, the molar ratio of nickel nitrate and cobalt nitrate is in metal salt
(0.5~2)：1.
A kind of preparation method of above-mentioned bimetallic MOFs derivative electrode materials, which is characterized in that powder in step 1
The preparation method of shape nickel cobalt bimetallic MOFs materials includes the following steps：
A concentration of 1mol/L is added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 8g/L~24g/L in step 101
The sodium hydroxide solution of~3mol/L stirs when being added dropwise, obtains mixed solution；The 4,4 '-biphenyl dicarboxylic acid aqueous solution with
The volume ratio of sodium hydroxide solution is 30：(2~5)；
Nickel nitrate is added in mixed solution described in step 101 step 102, stirs evenly, obtains emulsion；
Cobalt nitrate is added into emulsion described in step 102 for step 103, in 130 DEG C~190 DEG C items after stirring evenly
Hydro-thermal reaction 12h~48h under part；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, clear with deionized water after centrifugation
The solid matter for washing separation, is finally freeze-dried, and obtains white powder nickel cobalt bimetallic MOFs materials.
A kind of preparation method of above-mentioned bimetallic MOFs derivative electrode materials, which is characterized in that hydrogen-oxygen in step 101
The rate of addition for changing sodium solution is 1 drop/sec.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that stirred in step 102
Time be 15min~25min.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that stirred in step 103
Time be 25min~35min.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that described in step 3
Nickel foam is cleaned by ultrasonic successively using acetone, ethyl alcohol, dilute hydrochloric acid and deionized water.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that the dilute hydrochloric acid
A concentration of 0.1mol/L~0.5mol/L.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that described in step 3
Vacuum drying temperature is 50 DEG C~70 DEG C.
The preparation method of above-mentioned a kind of bimetallic MOFs derivative electrode materials, which is characterized in that described in step 4
A concentration of 1mol/L~3mol/L of potassium hydroxide aqueous solution.
Compared with the prior art, the present invention has the following advantages：
1, the present invention prepares nickel cobalt bimetallic MOFs using the hydro-thermal method of environmental protection, and the reaction time is shorter than solvent-thermal method, production
Rate is higher than solvent-thermal method, and process safety is also some higher.
2, for the ligand that uses of the present invention for 4,4 '-biphenyl dicarboxylic acids can construct many macropores by the carboxyl in ligand
The MOFs materials of diameter, and strong coordinate bond is formed with central ion as with physical efficiency using organic carboxyl acid, and have preferable cluster
The MOFs stability of Forming ability, formation is strong.Compared with common phthalic acid ligand, 4,4 '-biphenyl dicarboxylic acid ligands can be with
More large aperture MOFs materials more preferably flexible, nickel cobalt bimetallic MOFs prepared by the present invention are constructed, average pore size is
22.82nm, what what the two-dimentional synusia by being mingled with one-dimensional flexible fiber formed be made of the cuboid of corner angle.The present invention adopts
Central ion is two kinds of adjoining dimensions, property is close, nickel ion and cobalt ions similar in crystal type, two kinds of hybrid ionics
The distortion of lattice very little of the MOFs crystal of formation, and oxide or double-hydroxide derived from both hybrid ionics all have compared with
High specific capacitance.
3, electrolyte ion is rapidly introduced into the surface of nickel cobalt bimetallic MOFs by the present invention using the method for electrochemistry activation
Or in hole, it is made to be transformed into derivative, and is replaced in the surface or hole by constantly circulating in nickel cobalt bimetallic MOFs fresh
Electrolyte ion, so that it is quickly converted to the derivative of rock-steady structure；The nickel cobalt bimetallic MOFs obtained after electrochemistry activation
Derivative, XRD diffraction maximums are different from initial nickel cobalt bimetallic MOFs, also different from NixCoyOzOr NixCo1-x(OH)2, really
The actually nickel cobalt bimetallic MOFs derivatives of a kind of special construction, with the nickel cobalt bimetallic MOFs electrodes for not carrying out electrochemistry activation
Material is compared, and specific capacitance greatly improves, and specific capacitance maximum is up to 990.8F/g, and specific capacitance is maintained as after charge and discharge 5000 times
523.1F/g。
With reference to the accompanying drawings and examples, technical scheme of the present invention will be described in further detail.
Description of the drawings
Fig. 1 is the SEM figures of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1, and amplification factor is 1000 times.
Fig. 2 is the SEM figures of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1, and amplification factor is 5000 times.
Fig. 3 is the SEM figures of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1, and amplification factor is 10000 times.
Fig. 4 be the embodiment of the present invention 1 prepare nickel cobalt bimetallic MOFs materials, comparative example 1 prepare Ni-BPDC powders and
The XRD diagram of Co-BPDC powders prepared by comparative example 2.
Fig. 5 is the nickel cobalt bimetallic MOFs materials that are prepared using the embodiment of the present invention 1 as active material, is supported on graphite paper
The electrode of making, the XRD diagram of the nickel cobalt bimetallic MOFs derivative electrode materials obtained after electrochemistry activates.
Fig. 6 be the embodiment of the present invention 1 prepare nickel cobalt bimetallic MOFs materials, comparative example 1 prepare Ni-BPDC powders and
The infrared spectrogram of Co-BPDC powders prepared by comparative example 2.
Fig. 7 is the Raman spectrogram of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1.
Fig. 8 is the low temperature nitrogen isothermal adsorption desorption line of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1.
Fig. 9 is the pore size distribution curve of nickel cobalt bimetallic MOFs materials prepared by the embodiment of the present invention 1.
Figure 10 is that the cycle that bimetallic MOFs derivatives electrode material prepared by the embodiment of the present invention 1 is swept in difference under speed lies prostrate
Pacify curve.
Figure 11 is perseverance of the bimetallic MOFs derivatives electrode material of the preparation of the embodiment of the present invention 1 under different current densities
Flow charging and discharging curve.
Figure 12 is the multiplying power property curve of bimetallic MOFs derivative electrode materials prepared by the embodiment of the present invention 1.
Figure 13 be the embodiment of the present invention 1 prepare bimetallic MOFs derivatives electrode material under the current density of 1A/g,
The change curve of specific capacitance in 5000 charge and discharge process.
Specific implementation mode
Embodiment 1
The preparation method of the bimetallic MOFs derivative electrode materials of the present embodiment specifically includes following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, are prepared using hydro-thermal method
Powdered nickel cobalt bimetallic MOFs materials, the specific steps are：
A concentration of 2mol/L of 2mL are added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 8g/L of 30mL for step 101
Sodium hydroxide solution, rate of addition be 1 drop/sec, while be added dropwise while stir, obtain mixed solution；
Step 102, by 0.29g Ni (NO3)2·6H2O is added in mixed solution described in step 101, stirs 15min, obtains
To emulsion；
0.29g Co (NO are added into emulsion described in step 102 for step 1033)2·6H2O turns after stirring 25min
Enter in closed reactor, hydro-thermal reaction 12h under the conditions of 170 DEG C；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, clear with deionized water after centrifugation
The solid matter for washing separation, is finally freeze-dried, and obtains white powder nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials that will be prepared in Kynoar, conductive black and step 1
It is added in n,N-Dimethylformamide, stirs 4h after ultrasonic disperse 30min, obtain paste mixture；The Kynoar is led
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in electric carbon black and step 1 is 10：10：80；The N, N- diformazan
The volume of base formamide is 2 times of powdered nickel cobalt bimetallic MOFs quality of materials, and wherein the unit of volume is mL, the list of quality
Position is g；
Step 3: by paste mixture described in step 2 according to 0.5mg/cm2Load capacity drop to the 1cm cleaned up
In × 4cm nickel foams, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；The nickel foam
It is cleaned by ultrasonic successively using acetone, ethyl alcohol, 0.3mol/L dilute hydrochloric acid and deionized water；The vacuum drying temperature is 60 DEG C；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 to be placed in the potassium hydroxide of a concentration of 2mol/L
In aqueous solution, cyclic voltammetry is first used, is recycled 200 times with the sweep speed of 100mV/s, then with galvanostatic charge/discharge, in 5A/g
Current density under cycle charge-discharge 50 times, obtain bimetallic MOFs derivative electrode materials.
Fig. 1, Fig. 2 and Fig. 3 are that the SEM of nickel cobalt bimetallic MOFs materials manufactured in the present embodiment schemes, this from microcosmic
Nickel cobalt bimetallic MOFs materials, incomplete degree that the two-dimentional synusia by being mingled with one-dimensional flexible fiber forms it is different have rib
The cuboid composition at angle.Fig. 5 is that nickel cobalt bimetallic MOFs derivative electrode materials manufactured in the present embodiment are supported on graphite paper
On XRD diagram, it can be seen from the figure that its diffraction maximum be different from nickel cobalt bimetallic MOFs materials, also different from NixCoyOzOr
NixCo1-x(OH)2, but it is transformed to the nickel cobalt bimetallic MOFs derivative electrode materials of special construction.Fig. 7 is the present embodiment
The Raman spectrogram of the nickel cobalt bimetallic MOFs materials of synthesis, the peak position occurred in figure are coincide with the peak position of infrared spectrum substantially,
Demonstrate again that the substance of synthesis is a kind of complex of nickel cobalt ion and the formation of 4,4 '-biphenyl dicarboxylic acid ligands.By Fig. 8 and Fig. 9
Absorption test can be seen that with pore analysis result, the present embodiment synthesis nickel cobalt bimetallic MOFs materials with 5nm~30nm's
Based on mesoporous.It is calculated through different theories, it is 40.024m to obtain its BET specific surface area2/ g, BJH average pore size is
22.82nm is suitble to electrolyte ion to spread wherein, adsorbs and storage.
Comparative example 1
The preparation of Ni-BPDC derivative electrode materials, specific method are：
Step 1: being added dropwise a concentration of 2mol/L's of 2mL into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 8g/L of 30mL
Sodium hydroxide solution, rate of addition are 1 drop/sec, are stirred when being added dropwise, obtain mixed solution；
Step 2: by 0.29g Ni (NO3)2·6H2O is added in mixed solution described in step 1, stirs 15min, obtains
Emulsion；
Step 3: emulsion described in step 2 is added in a closed reactor, hydro-thermal at a temperature of 170 DEG C
12h is reacted, is centrifuged after being cooled to room temperature, the solid matter of separation is cleaned with deionized water, is finally freeze-dried, obtains pale green
The powdered Ni-BPDC powders of color；
Step 4: Ni-BPDC powders described in Kynoar, conductive black and step 3 are pressed 10:10:80 quality
It is added in n,N-Dimethylformamide than mixing, is stirred for 4h after ultrasonic 30min, obtains paste mixture；By paste mixture
Drip to pre- first pass through in 1cm × 4cm nickel foams after acetone, ethyl alcohol, 0.3mol/L dilute hydrochloric acid and deionized water are cleaned by ultrasonic；From
After so drying, it is dried under vacuum to constant weight at 60 DEG C, obtains Ni-BPDC electrode materials；The body of the N,N-dimethylformamide
Product is 2 times of Ni-BPDC powder qualities, and wherein the unit of volume is mL, and the unit of quality is g；
Step 5: Ni-BPDC electrode materials described in step 4 is placed in the potassium hydroxide aqueous solution of 2mol/L, first use
Cyclic voltammetry is recycled 200 times with the sweep speed of 100mV/s, then with galvanostatic charge/discharge, is followed under the current density of 5A/g
Ring charge and discharge 50 times obtain Ni-BPDC derivative electrode materials.
Comparative example 2
The preparation of Co-BPDC derivative electrode materials, specific method are：
Step 1: being added dropwise a concentration of 2mol/L's of 2mL into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 8g/L of 30mL
Sodium hydroxide solution, rate of addition are 1 drop/sec, are stirred when being added dropwise, obtain mixed solution；
Step 2: by 0.29g Co (NO3)2·6H2O is added in mixed solution described in step 1, stirs 15min, obtains
Emulsion；
Step 3: emulsion described in step 2 is added in a closed reactor, hydro-thermal at a temperature of 170 DEG C
12h is reacted, is centrifuged after being cooled to room temperature, the solid matter of separation is cleaned with deionized water, is finally freeze-dried, obtains pale purple
The powdered Co-BPDC powders of color；
Step 4: Co-BPDC powders described in Kynoar, conductive black and step 3 are pressed 10:10:80 quality
It is added in n,N-Dimethylformamide than mixing, is stirred for 4h after ultrasonic 30min, obtains paste mixture；By paste mixture
Drip to pre- first pass through in 1cm × 4cm nickel foams after acetone, ethyl alcohol, 0.3mol/L dilute hydrochloric acid and deionized water are cleaned by ultrasonic；From
After so drying, it is dried under vacuum to constant weight at 60 DEG C, obtains Co-BPDC electrode materials；The body of the N,N-dimethylformamide
Product is 2 times of Ni-BPDC powder qualities, and wherein the unit of volume is mL, and the unit of quality is g；
Step 5: Co-BPDC electrode materials described in step 4 is placed in the potassium hydroxide aqueous solution of 2mol/L, first use
Cyclic voltammetry is recycled 200 times with the sweep speed of 100mV/s, then with galvanostatic charge/discharge, is followed under the current density of 5A/g
Ring charge and discharge 50 times obtain Co-BPDC derivative electrode materials.
Fig. 4 is the nickel cobalt bimetallic MOFs materials (NiCo-BPDC in figure) of the synthesis of the embodiment of the present invention 1, the preparation of comparative example 1
Ni-BPDC powders (Ni-BPDC in figure) and comparative example 2 prepare Co-BPDC powders (Co-BPDC in figure) XRD diagram, from figure
In as can be seen that the peak shape of the diffraction maximum of three and position are almost the same, and all have the characteristics that more diffraction maximums of MOFs crystal.Table
The crystal structure of these three bright MOFs is similar, crystal form having the same, and the introducing of cobalt ions does not cause Ni-BPDC crystal to generate
Big distortion of lattice.Fig. 6 is the nickel cobalt bimetallic MOFs materials (NiCo-BPDC in figure) of the synthesis of the embodiment of the present invention 1, comparative example
1 prepare Ni-BPDC powders (Ni-BPDC in figure) and comparative example 2 preparation Co-BPDC powders (Co-BPDC in figure) it is infrared
Spectrogram has some functional groups on 4,4 '-biphenyl dicarboxylic acids it can be seen from the figure that the peak shape of three is substantially similar
Characteristic absorption peak, such as 1684cm-1The carbonylic stretching vibration peak at place, 1593cm-1And 1390cm-1The carboxyl antisymmetry at place is flexible to shake
Dynamic and symmetrical stretching vibration peak, 1538cm-1The stretching vibration peak of C-H, 3606cm on the phenyl ring at place-1The free OH at place–It is flexible to shake
Dynamic peak.But also there is nuance, such as 481cm-1And 525cm-1Place is respectively the stretching vibration peak of Ni-O and Co-O.This proves gold
Belong to ion to be coordinated really with ligand, is successfully formed MOFs structures.
Embodiment 2
The preparation method of the bimetallic MOFs derivative electrode materials of the present embodiment specifically includes following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, are prepared using hydro-thermal method
Powdered nickel cobalt bimetallic MOFs materials, the specific steps are：
A concentration of 1mol/L of 5mL are added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 12g/L of 30mL for step 101
Sodium hydroxide solution, rate of addition be 1 drop/sec, while be added dropwise while stir, obtain mixed solution；
Step 102, by 0.29g Ni (NO3)2·6H2O is added in mixed solution described in step 101, stirs 20min, obtains
To emulsion；
0.58g Co (NO are added into emulsion described in step 102 for step 1033)2·6H2O turns after stirring 30min
Enter in closed reactor, hydro-thermal reaction is for 24 hours under the conditions of 150 DEG C；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, clear with deionized water after centrifugation
The solid matter for washing separation, is finally freeze-dried, and obtains white powder nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials that will be prepared in Kynoar, conductive black and step 1
It is added in n,N-Dimethylformamide, stirs 12h after ultrasonic disperse 25min, obtain paste mixture；The Kynoar,
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in conductive black and step 1 is 10：15：75；The N, N- bis-
The volume of methylformamide is 1.5 times of powdered nickel cobalt bimetallic MOFs quality of materials, and wherein the unit of volume is mL, quality
Unit be g；
Step 3: by paste mixture described in step 2 according to 0.4mg/cm2Load capacity drop to the 1cm cleaned up
In × 4cm nickel foams, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；The nickel foam
It is cleaned by ultrasonic successively using acetone, ethyl alcohol, 0.1mol/L dilute hydrochloric acid and deionized water；The vacuum drying temperature is 70 DEG C；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 to be placed in the potassium hydroxide of a concentration of 3mol/L
In aqueous solution, cyclic voltammetry is first used, is recycled 20 times with the sweep speed of 10mV/s, then with galvanostatic charge/discharge, 5A/g's
Cycle charge-discharge 400 times under current density obtain bimetallic MOFs derivative electrode materials.
SEM, XRD of nickel cobalt bimetallic MOFs materials manufactured in the present embodiment, the test knot of FT-IR ＆ FT-RAMAN spectra
Fruit is similar to Example 1, there is similar form, identical crystal form, similar infrared absorption peak position and Raman scattering peak position.
Embodiment 3
The preparation method of the bimetallic MOFs derivative electrode materials of the present embodiment specifically includes following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, are prepared using hydro-thermal method
Powdered nickel cobalt bimetallic MOFs materials, the specific steps are：
A concentration of 2mol/L of 5mL are added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 24g/L of 30mL for step 101
Sodium hydroxide solution, rate of addition be 1 drop/sec, while be added dropwise while stir, obtain mixed solution；
Step 102, by 0.44g Ni (NO3)2·6H2O is added in mixed solution described in step 101, stirs 25min, obtains
To emulsion；
0.44g Co (NO are added into emulsion described in step 102 for step 1033)2·6H2O turns after stirring 35min
Enter in closed reactor, hydro-thermal reaction 48h under the conditions of 130 DEG C；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, clear with deionized water after centrifugation
The solid matter for washing separation, is finally freeze-dried, and obtains white powder nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials that will be prepared in Kynoar, conductive black and step 1
It is added in n,N-Dimethylformamide, stirs 12h after ultrasonic disperse 20min, obtain paste mixture；The Kynoar,
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in conductive black and step 1 is 15：10：75；The N, N- bis-
The volume of methylformamide is 2.5 times of powdered nickel cobalt bimetallic MOFs quality of materials, and wherein the unit of volume is mL, quality
Unit be g；
Step 3: by paste mixture described in step 2 according to 0.6mg/cm2Load capacity drop to the 1cm cleaned up
In × 4cm nickel foams, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；The nickel foam
It is cleaned by ultrasonic successively using acetone, ethyl alcohol, 0.5mol/L dilute hydrochloric acid and deionized water；The vacuum drying temperature is 50 DEG C；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 to be placed in the potassium hydroxide of a concentration of 1mol/L
In aqueous solution, cyclic voltammetry is first used, is recycled 50 times with the sweep speed of 50mV/s, then with galvanostatic charge/discharge, 6A/g's
Cycle charge-discharge 300 times under current density obtain bimetallic MOFs derivative electrode materials.
SEM, XRD of nickel cobalt bimetallic MOFs materials manufactured in the present embodiment, the test knot of FT-IR ＆ FT-RAMAN spectra
Fruit is similar to Example 1, there is similar form, identical crystal form, similar infrared absorption peak position and Raman scattering peak position.
Embodiment 4
The preparation method of the bimetallic MOFs derivative electrode materials of the present embodiment specifically includes following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, are prepared using hydro-thermal method
Powdered nickel cobalt bimetallic MOFs materials, the specific steps are：
A concentration of 2mol/L of 4mL are added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 16g/L of 30mL for step 101
Sodium hydroxide solution, rate of addition be 1 drop/sec, while be added dropwise while stir, obtain mixed solution；
Step 102, by 0.58g Ni (NO3)2·6H2O is added in mixed solution described in step 101, stirs 15min, obtains
To emulsion；
0.29g Co (NO are added into emulsion described in step 102 for step 1033)2·6H2O turns after stirring 25min
Enter in closed reactor, hydro-thermal reaction 12h under the conditions of 190 DEG C；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, clear with deionized water after centrifugation
The solid matter for washing separation, is finally freeze-dried, and obtains white powder nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials that will be prepared in Kynoar, conductive black and step 1
It is added in n,N-Dimethylformamide, stirs 8h after ultrasonic disperse 20min, obtain paste mixture；The Kynoar is led
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in electric carbon black and step 1 is 11：12：77；The N, N- diformazan
The volume of base formamide is 2 times of powdered nickel cobalt bimetallic MOFs quality of materials, and wherein the unit of volume is mL, the list of quality
Position is g；
Step 3: by paste mixture described in step 2 according to 0.5mg/cm2Load capacity drop to the 1cm cleaned up
In × 4cm nickel foams, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；The nickel foam
It is cleaned by ultrasonic successively using acetone, ethyl alcohol, 0.5mol/L dilute hydrochloric acid and deionized water；The vacuum drying temperature is 60 DEG C；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 to be placed in the potassium hydroxide of a concentration of 2mol/L
In aqueous solution, cyclic voltammetry is first used, is recycled 100 times with the sweep speed of 100mV/s, then with galvanostatic charge/discharge, in 10A/g
Current density under cycle charge-discharge 200 times, obtain bimetallic MOFs derivative electrode materials.
SEM, XRD of nickel cobalt bimetallic MOFs materials manufactured in the present embodiment, the test knot of FT-IR ＆ FT-RAMAN spectra
Fruit is similar to Example 1, there is similar form, identical crystal form, similar infrared absorption peak position and Raman scattering peak position.
To the electrochemistry of derivative electrode material prepared by the embodiment of the present invention 1 to 4 and comparative example 1 and comparative example 2
It can be tested, test method is：Using three-electrode system, respectively using various derivative electrode materials as working electrode, Ag/
AgCl (saturation KCl solution) is reference electrode, and Pt pieces are auxiliary electrode, and 2mol/L KOH aqueous solutions are electrolyte, in Shanghai occasion
Cyclic voltammetric and constant current charge-discharge test are carried out on magnificent CE660d electrochemical workstations.Figure 10 and Figure 11 is respectively that embodiment 1 is made
Standby bimetallic MOFs derivatives electrode material is swept in difference under cyclic voltammetric (CV) curve and different current densities under speed
Constant current charge-discharge curve.It can be seen from the figure that cyclic voltammetry curve has apparent redox peaks, charging and discharging curve to have obviously
Redox inflection point or platform, this illustrate prepare bimetallic MOFs derivatives electrode material can significantly play fake capacitance spy
Property, rather than the electric double layer capacitance characteristic that common MOFs materials are shown.The CV curves of Figure 10 are with the increase redox for sweeping speed
Spike potential has apparent offset, but the shape of ring does not occur significantly to change, and shows that the cycle characteristics of the electrode material is preferable.Figure
12 multiplying power property curve shows the increase with current density, the specific capacitances of bimetallic MOFs derivative electrode materials can under
Drop, but under the high current density of 20A/g, remain to the high power capacity for keeping 405.1F/g.The curve of Figure 13 shows with cycle time
The specific capacitance of several increases, bimetallic MOFs derivative electrode materials can decrease, but tend towards stability at 2500 times or so,
Specific capacitance is 523.1F/g at 5000 times.
It can be quantified by constant current charge-discharge curve and calculate specific capacitance, calculation formula is：
Cs=I Δ t/m Δs E (1)
Wherein, CsFor specific capacitance, unit F/g；I is discharge current, unit A；M is the matter of the active material on electrode
Amount, unit g；Δ E is the difference of charge cutoff voltage and discharge cut-off voltage, unit V；Δ t is discharge time, unit s.
The result of calculation of the specific capacity of various derivative electrode materials see the table below 1.
The result of calculation and yield of 1 constant current charge-discharge test of table (constant current density is 1A/g)
As can be seen from the table, electrochemistry activation method is a kind of effective ways for the capacitance improving MOFs materials, using this
Bimetallic MOFs derivatives electrode material prepared by the method for invention has higher capacitance, in the constant current density of 1A/g
Under, for specific capacitance after 518F/g or more, 5000 cycles, specific capacitance remains at 357F/g or more.
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, every according to invention skill
Art essence changes any simple modification, change and equivalent structure made by above example, still falls within the technology of the present invention
In the protection domain of scheme.
Claims (10)
1. a kind of preparation method of bimetallic MOFs derivative electrode materials, which is characterized in that include the following steps：
Step 1: with 4,4 '-biphenyl dicarboxylic acids are ligand, and nickel nitrate and cobalt nitrate are metal salt, and powder is prepared using hydro-thermal method
Shape nickel cobalt bimetallic MOFs materials；
Step 2: the powdered nickel cobalt bimetallic MOFs materials prepared in Kynoar, conductive black and step 1 are added
In n,N-Dimethylformamide, 4h~12h is stirred after ultrasonic disperse 20min~30min, obtains paste mixture；It is described poly- inclined
The mass ratio of the powdered nickel cobalt bimetallic MOFs materials prepared in vinyl fluoride, conductive black and step 1 is (10~15)：(10
~15)：(75~80)；The volume of the N,N-dimethylformamide is the 1.5 of powdered nickel cobalt bimetallic MOFs quality of materials
~2.5 times, the wherein unit of volume is mL, and the unit of quality is g；
Step 3: by paste mixture described in step 2 according to 0.4mg/cm2~0.6mg/cm2Load capacity to drop to cleaning dry
In net nickel foam, it is dried under vacuum to constant weight after natural drying, obtains nickel cobalt bimetallic MOFs electrode materials；
Step 4: the MOFs electrode materials of nickel cobalt bimetallic described in step 3 are placed in potassium hydroxide aqueous solution, first with cycle
Voltammetry is recycled 20~200 times with the sweep speed of 10mV/s~100mV/s, then with galvanostatic charge/discharge, in 5A/g~10A/
Cycle charge-discharge 50~400 times under the current density of g obtain bimetallic MOFs derivative electrode materials.
2. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 1, which is characterized in that step
The molar ratio of metal salt and ligand 4,4 '-biphenyl dicarboxylic acid is (1~2.03) in rapid one：1, nickel nitrate and cobalt nitrate in metal salt
Molar ratio be (0.5~2)：1.
3. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 2, which is characterized in that step
The preparation method of powdered nickel cobalt bimetallic MOFs materials includes the following steps in rapid one：
Step 101, be added dropwise into the 4,4 '-biphenyl dicarboxylic acid aqueous solutions of a concentration of 8g/L~24g/L a concentration of 1mol/L~
The sodium hydroxide solution of 3mol/L stirs when being added dropwise, obtains mixed solution；The 4,4 '-biphenyl dicarboxylic acid aqueous solution and hydrogen
The volume ratio of sodium hydroxide solution is 30：(2~5)；
Nickel nitrate is added in mixed solution described in step 101 step 102, stirs evenly, obtains emulsion；
Cobalt nitrate is added into emulsion described in step 102 for step 103, after stirring evenly under the conditions of 130 DEG C~190 DEG C
Hydro-thermal reaction 12h~48h；
Product after hydro-thermal reaction in step 103 is cooled to room temperature by step 104, is cleaned point with deionized water after centrifugation
From solid matter, be finally freeze-dried, obtain white powder nickel cobalt bimetallic MOFs materials.
4. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 3, which is characterized in that step
The rate of addition of sodium hydroxide solution is 1 drop/sec in rapid 101.
5. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 3, which is characterized in that step
The time stirred in rapid 102 is 15min~25min.
6. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 3, which is characterized in that step
The time stirred in rapid 103 is 25min~35min.
7. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 1, which is characterized in that step
Nickel foam described in rapid three is cleaned by ultrasonic successively using acetone, ethyl alcohol, dilute hydrochloric acid and deionized water.
8. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 7, which is characterized in that institute
State a concentration of 0.1mol/L~0.5mol/L of dilute hydrochloric acid.
9. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 1, which is characterized in that step
Vacuum drying temperature described in rapid three is 50 DEG C~70 DEG C.
10. a kind of preparation method of bimetallic MOFs derivative electrode materials according to claim 1, which is characterized in that
A concentration of 1mol/L~3mol/L of potassium hydroxide aqueous solution described in step 4.
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