CN105977050B - A kind of preparation method of carbon nanotubes/metal zirconium organic framework material for ultracapacitor - Google Patents
A kind of preparation method of carbon nanotubes/metal zirconium organic framework material for ultracapacitor Download PDFInfo
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Abstract
A kind of preparation method for ultracapacitor carbon nanotubes/metal zirconium organic framework material, this method comprise the following steps：Carbon nanotubes, zirconium chloride and the organic ligand of 5 ~ 50% carbon atom carboxylated of surface are weighed, is placed into and fills in DMF solution, 12h is stirred to react in 80 DEG C of water, filters to isolate solid matter；Solid matter is re-dispersed into DMF again, then is separately added into the zirconium chloride and organic ligand of certain mass number, reacts 12 ~ 48h in the case where temperature is 100 ~ 200 DEG C；It refilters and is cleaned three times with DMF and ethyl alcohol respectively after isolating solids, be subsequently placed in 90 DEG C of drying boxes dry 12h, obtain carbon nanotubes/metal zirconium organic framework material；Its advantage is that preparation process is simple, reaction condition is mild, easily realizes large-scale production；Obtained electrode material has higher specific discharge capacity, excellent high rate performance and cyclical stability.
Description
Technical field
The present invention relates to electrochemical technology field, particularly with regard to the electrode material applied to ultracapacitor, tool
Body say be a kind of carbon nanotubes/metal zirconium organic framework material preparation method.
Background technology
Ultracapacitor is a kind of a kind of novel energy storage apparatus between electric double layer capacitance and battery, has charge and discharge
The advantages such as rate is fast, power density is big, have extended cycle life, chemical stability is good.Metal-organic framework materials（MOFs）Be by
Transition metal ions and organoligand coordination are formed a kind of with the poly- of the characteristics such as porous, large specific surface area, structure diversity
Close object.Therefore, MOFs is widely used in the every field such as optics, magnetics, electricity, and wherein MOFs is applied energy storage field
Highest attention is arrived.Wherein, centered on transition metal zirconium, the multiple tooth organic ligand with oxygen-containing, nitrogen etc.（It is aromatics mostly
Object and polybase）The effect for the MOFs that self assembly forms is especially prominent.However, metal zirconium organic framework material generally existing electric conductivity
It is weak, greatly limit application of the metal zirconium organic framework material in energy storage field.Carbon nanotubes has good electricity and machine
The advantages that tool performance, high chemistry and high stability, be one of preferable electrode material of ultracapacitor.Use carbon nanotubes and gold
Category zirconium organic framework material is compound, can be effectively combined the outstanding advantage of the two, can not only overcome carbon material itself specific surface area
The small, problems such as power density is low, moreover it is possible to solve the problems such as metal Zr base organic framework material electric conductivity is weak.
In existing document report, most of carbon pipes are only attached to the surface of MOFs, can not be fully solved inside MOFs
The problem of poorly conductive.Patent（CN 104437378 A）A kind of carbon nanotubes and the preparation method of MOFs are disclosed, by not
Same method activates carbon nanotubes, with aluminium base MOFs solvent thermal reactions, obtains the aluminium base MOFs of doped carbon nanometer pipe, however should
The structure of material is not directed in invention, and does not study its electrochemical energy storage property.In addition, document report carbon nanotubes can run through
MOF-5 [Chemistry of Materials, 2009,21 (9) of pore passage structure:1893-1897] and ZIF-8 [RSC
Advances, 2014, 4(91): 49614-49619.].Compared to the MOF-5 and ZIF-8 of pore passage structure, metal zirconium MOFs
（UIO-66 series）, since its unique cage structure causes carbon nanotubes to be difficult to run through inside it.
The content of the invention
The technical problem to be solved by the present invention is to overcome existing technical bottleneck, success synthesizing carbon nanotubes run through caged
Structure MOFs（UIO-66 series）Composite material so that original UIO-66 series MOFs electric conductivity significantly improves, this is compound
Material is used for electrode material for super capacitor, shows excellent electrochemical energy storage property.
The present invention technical solution be：One kind is used for ultracapacitor carbon nanotubes/metal zirconium organic framework material
Preparation method, specifically include following steps：
1st, 1 ︰ in mass ratio, 0.25 ~ 2.5 ︰ 0.1 ~ 1, weigh respectively 5 ~ 50% carbon atom carboxylated of surface carbon nanotubes, four
Above-mentioned raw material are placed into and fill 100 ~ 500 mL n,N dimethylformamide by zirconium chloride and organic ligand（DMF）Solution
In beaker, and ultrasonic 10 ~ 30 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 100 ~ 500 mL, adds a certain amount of tetrachloro
Change zirconium and organic ligand, react 12 ~ 48h in the case where temperature is 100 ~ 200 DEG C after stirring and dissolving；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
Above-mentioned preferred terephthalic acid (TPA) of organic ligand or derivatives thereof.
3 a certain amount of zirconium chloride of above-mentioned steps and organic ligand, quality are the solid matter in step 2 respectively
0.35 ~ 6.7 times and 0.65 ~ 12.3 Bei ︰ zirconium chlorides.
During electrochemical gaging, by Nano carbon tube-metal zirconium organic framework material and the conductive charcoal that excessively prepared by the present invention
Black and polytetrafluoroethylene (PTFE)（PVDF）With mass ratio 7:2:After 1 mixing, it is tuned into slurry with two pyrrolidones of N- methyl and is uniformly coated onto
Foam nickel surface, as working electrode after 80 DEG C of dry 12h, platinized platinum is used as to electrode, and mercury/mercury oxide is reference electrode,
Electrolyte is 6M potassium hydroxide solutions, and using three-electrode system, test voltage 0.1 ~ 0.6V of window, test equipment is Shanghai Chen Hua
CHI 660C electrochemical workstations.
The invention has the advantages that：
1. carbon nanotubes is through entire metal zirconium in carbon nanotubes prepared by the present invention/metal zirconium organic framework material
Organic framework material；
2. preparation method process of the present invention is simple, reaction condition is mild, easily realizes large-scale production.
3. carbon nanotubes/metal zirconium organic framework material prepared by the present invention has as electrode material for super capacitor
There are higher specific discharge capacity, excellent high rate performance and cyclical stability.
Specific embodiment
Embodiment one：
1st, 1 ︰ in mass ratio, 0.25 ︰ 0.1, weigh respectively the carbon nanotubes of 5% carboxylated of surface carbon atom, zirconium chloride and
Above-mentioned raw material are placed into and fill 100 mL n,N dimethylformamide by terephthalic acid (TPA) or derivatives thereof（DMF）Solution
In beaker, and ultrasound 10min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 100 mL, then is separately added into mass fraction and is
0.35 zirconium chloride and 0.65 phthalic acid or derivatives thereof react 12h after stirring and dissolving in the case where temperature is 100 DEG C；
4th, by the method for filtering, DMF and ethyl alcohol are used after the solid matter in step 3 after reaction is filtered out respectively
Cleaning three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 681F/g.
Embodiment two:
1st, 1 ︰ in mass ratio, 0.5 ︰ 0.2, weigh respectively the carbon nanotubes of 10% carbon atom carboxylated of surface, zirconium chloride and
Above-mentioned raw material are placed into and fill 150 mL n,N dimethylformamide by terephthalic acid (TPA) or derivatives thereof（DMF）Solution
In beaker, and ultrasonic 15 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 150 mL, then is separately added into mass fraction as 0.7
Zirconium chloride and 0.14 phthalic acid or derivatives thereof, react 24 h in the case where temperature is 150 DEG C after stirring and dissolving；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 700F/g.
Embodiment three：
1st, 1 ︰ in mass ratio, 1 ︰ 0.4 weigh the carbon nanotubes of 15% carbon atom carboxylated of surface, zirconium chloride and right respectively
Above-mentioned raw material are placed into and fill 200 mL n,N dimethylformamide by phthalic acid or derivatives thereof（DMF）The burning of solution
In cup, and ultrasonic 20 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 200 mL, then is separately added into mass fraction as 1.4
Zirconium chloride and 2.6 phthalic acid or derivatives thereof, react 24 h in the case where temperature is 200 DEG C after stirring and dissolving；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 736F/g.
Example IV：
1st, 1 ︰ in mass ratio, 1.5 ︰ 0.6, weigh respectively the carbon nanotubes of 30% carbon atom carboxylated of surface, zirconium chloride and
Above-mentioned raw material are placed into and fill 300 mL n,N dimethylformamide by terephthalic acid (TPA) or derivatives thereof（DMF）Solution
In beaker, and ultrasonic 30 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 300 mL, then is separately added into mass fraction as 2.1
Zirconium chloride and 3.9 phthalic acid or derivatives thereof, react 36 h in the case where temperature is 200 DEG C after stirring and dissolving；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 980F/g.
Embodiment five：
1st, 1 ︰ in mass ratio, 2 ︰ 0.8 weigh the carbon nanotubes of 40% carbon atom carboxylated of surface, zirconium chloride and right respectively
Above-mentioned raw material are placed into and fill 400 mL n,N dimethylformamide by phthalic acid or derivatives thereof（DMF）The burning of solution
In cup, and ultrasonic 30 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 400 mL, then is separately added into mass fraction and is
5.6 zirconium chloride and 10.4 phthalic acid or derivatives thereof react 12 ~ 48h after stirring and dissolving in the case where temperature is 200 DEG C；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 1125F/g.
Embodiment six
1st, 1 ︰ in mass ratio, 2 ︰ 0.8 weigh the carbon nanotubes of 50% carbon atom carboxylated of surface, zirconium chloride and right respectively
Above-mentioned raw material are placed into and fill 500 mL n,N dimethylformamide by phthalic acid or derivatives thereof（DMF）The burning of solution
In cup, and ultrasonic 30 min dispersing and dissolvings；
2nd, the beaker that solution is filled in step 1 is placed into 80 DEG C of water and is stirred to react 12h, then using the side of filtering
Formula separates the solid matter in solution；
3rd, the solid matter in step 2 is re-dispersed into the DMF of 500 mL, then is separately added into mass fraction and is
6.7 zirconium chloride and 12.3 phthalic acid or derivatives thereof react 12 ~ 48h after stirring and dissolving in the case where temperature is 200 DEG C；
4th, it is clear with DMF and ethyl alcohol respectively after the solid matter in step 3 after reaction is filtered out by the method for filtering
It washes three times, is subsequently placed in 90 DEG C of drying boxes dry 12h, obtains carbon nanotubes/metal zirconium organic framework material.
In the case where current density is 0.1A/g, electric discharge specific capacitance is 648F/g.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Several equivalent substitute or obvious modifications are made on the premise of not departing from present inventive concept, and performance or purposes are identical, then should
It is considered as belonging to the protection domain that claims that the present invention is submitted determine.
Claims (2)
1. a kind of preparation method of carbon nanotubes/metal zirconium organic framework material for ultracapacitor, specifically includes following
Step：
(1) 1 ︰ in mass ratio, 0.25~2.5 ︰ 0.1~1, weigh respectively 5~50% carbon atom carboxylated of surface carbon nanotubes,
Above-mentioned raw material are placed into the beaker for filling 100~500mL n,N dimethylformamide solution by zirconium chloride and organic ligand
In, and through ultrasonication 10~30min dispersing and dissolvings；
(2) beaker that solution is filled in step (1) is placed into 80 DEG C of water and is stirred to react 12h, then filtering will be in solution
Solid matter separate；
(3) solid matter in step (2) is re-dispersed into the n,N dimethylformamide DMF of 100~500mL, then distinguished
Add in the zirconium chloride and organic ligand of certain mass number, after stirring and dissolving in the case where temperature is 100~200 DEG C reaction 12~
48h；
(4) respectively with N, N-dimethylformamide and ethyl alcohol cleaning three after the solid matter in step (3) after reaction is filtered out
It is secondary, dry 12h is subsequently placed in 90 DEG C of drying boxes, obtains carbon nanotubes/metal zirconium organic framework material.
2. preparation method according to claim 1, it is characterised in that：The organic ligand is terephthalic acid (TPA) and its spreads out
Biology.
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| CN104745149A (en) * | 2015-03-05 | 2015-07-01 | 北京科技大学 | Preparation method for carbon-containing material metal organic framework-based composite phase change material |
| CN105294749A (en) * | 2015-11-06 | 2016-02-03 | 河北工业大学 | Modified organic metal framework used for efficiently adsorbing elemental mercury in flue gas |
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| CN104437378A (en) * | 2013-09-17 | 2015-03-25 | 中国科学院大连化学物理研究所 | Metal organic framework material doped with carbon nanotube and application thereof |
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