CN112201485A - Metal organic framework compound/graphene electrode material, and preparation method and application thereof - Google Patents
Metal organic framework compound/graphene electrode material, and preparation method and application thereof Download PDFInfo
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- CN112201485A CN112201485A CN202010906263.4A CN202010906263A CN112201485A CN 112201485 A CN112201485 A CN 112201485A CN 202010906263 A CN202010906263 A CN 202010906263A CN 112201485 A CN112201485 A CN 112201485A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 12
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 146
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 104
- 229910052757 nitrogen Inorganic materials 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 35
- 238000000967 suction filtration Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 18
- 150000002918 oxazolines Chemical class 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- 150000000376 2-oxazolines Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 2
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 abstract 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 20
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 14
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical group C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229910007932 ZrCl4 Inorganic materials 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
- H01G11/02—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 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
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- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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Abstract
The invention discloses a metal organic framework compound/graphene electrode material, a preparation method and application thereof, and belongs to the technical field of synthesis of electrode materials of supercapacitors. The method mainly comprises the following steps: the preparation method comprises the following steps of carrying out graft reaction on graphene oxide and oxazoline derivatives, then initiating radical polymerization on the oxazoline derivatives to obtain graphene oxide-polyoxazoline, then reacting with pyridine carboxylic acid substances, and reacting with aliphatic dibasic acid to enable polyoxazoline to beAnd (3) crosslinking the subchains, and then coordinating with transition metal ions to obtain the metal organic framework compound/graphene supercapacitor electrode material. The electrode material obtained by the invention has excellent performance, stable structure, strong variability, no toxicity, and specific capacitance of 720.7F g‑1The charge-discharge cycle stability is excellent, and the specific capacitance retention rate after 1000 cycles reaches more than 95%.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of supercapacitors, and particularly relates to a metal organic framework compound/graphene electrode material, and a preparation method and application thereof.
Background
In the modern times, the problems of climate change, environmental pollution and energy crisis caused by the rapid consumption of fossil fuels are becoming more and more serious. The source of solving the problem lies in finding a green renewable energy source substitute and developing an energy storage technology corresponding to the green renewable energy source substitute. The super capacitor is widely concerned by people as a new generation energy storage device, has the advantages of high power density, high charging and discharging speed, high cycle stability and the like, and has been applied and developed to a certain extent in the industries of new energy automobiles, portable electronic equipment and the like. Therefore, further research and development of supercapacitor devices with better performance are the direction of continuous efforts of researchers, the electrode material is used as a core component of the supercapacitor, and the quality of the performance of the electrode material directly determines the quality of the overall performance of the supercapacitor device, so that the development of the electrode material with excellent electrochemical performance is the basis and the importance of obtaining the supercapacitor devices with excellent performance.
Currently, electrode materials commonly used in supercapacitors can be mainly classified into carbon materials, transition metal oxides/hydroxides, and conductive polymers. Among the materials, the carbon material has good cycle stability because the energy storage mechanism is an electric double layer energy storage mechanism mainly based on the formation of an interface electric double layer, and the whole process does not involve chemical changes, but the specific capacitance of the carbon material is 100F g compared with that of a graphene material with a single atomic layer thickness prepared by Stoller et al, which has a smaller capacitance-1On the left and right, the specific capacitance of a single graphene material is not large (DOI:10.1021/nl802558 y); the transition metal oxide/hydroxide and the conducting polymer are both a pseudo-capacitance energy storage mechanism mainly generating Faraday current by oxidation-reduction reaction, and obvious chemical changes occur in the electrochemical reaction process, so that the capacitance of the transition metal oxide/hydroxide and the conducting polymer is generally larger and can basically reach 10-100 times of the double electric layer capacitance (DOI:10.1039/C1CS 15)060J) In that respect However, their cyclic stability is relatively poor due to the structural changes caused by chemical changes, and some materials with good thermal and mechanical stability are usually required as the matrix (DOI:10.1016/j. rser.2015.12.249). Therefore, a supercapacitor device having excellent electrochemical properties in all aspects cannot be obtained by using a single kind of material as an electrode material of a supercapacitor. The development of composite materials combining different materials is a main research direction for preparing high-performance supercapacitor electrode materials, and has great theoretical significance and practical application value.
Disclosure of Invention
In order to obtain an electrode material with excellent electrochemical performance, the invention aims to provide a metal organic framework compound/graphene supercapacitor electrode material and a preparation method and application thereof. The metal ion ligand modified graphene with a cross-linked structure is obtained through a series of chemical reactions, and then the metal ion ligand and transition metal ions are coordinated to obtain a metal organic framework compound/graphene supercapacitor electrode material. Therefore, the provided composite material has different energy storage mechanisms and a good microstructure, the overall specific capacitance of the material is enhanced, and the material has higher cycling stability. The material obtained by the invention has excellent performance and strong combination variability.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a metal organic framework compound/graphene supercapacitor electrode material comprises the following steps:
(1) preparing graphene oxide-oxazoline: dispersing graphene oxide in anhydrous N, N-dimethylformamide, performing ultrasonic dispersion, adding an oxazoline derivative, reacting under the protection of inert gas, performing suction filtration, washing and drying after the reaction is finished to obtain graphene oxide-oxazoline;
(2) preparing graphene oxide-polyoxazoline: ultrasonically dispersing the graphene oxide-oxazoline in the step (1) in anhydrous N, N-dimethylformamide, then adding a monomer oxazoline derivative, adding an initiator to initiate polymerization, reacting under the protection of inert gas, and performing suction filtration, washing and drying after the reaction is finished to obtain the graphene oxide-polyoxazoline;
(3) preparing graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing the graphene oxide-polyoxazoline in the step (2) in anhydrous N, N-dimethylformamide, then adding pyridine carboxylic acid substances, reacting under the protection of inert gas, and performing suction filtration, washing and drying after the reaction is finished to obtain graphene oxide-polyoxazoline-pyridine;
(4) preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing the graphene oxide-polyoxazoline-pyridine in the step (3) in anhydrous N, N-dimethylformamide, then adding aliphatic dibasic acid, reacting under the protection of inert gas, and performing suction filtration, washing and drying after the reaction is finished to obtain cross-linked graphene oxide-polyoxazoline-pyridine;
(5) preparing a metal organic framework compound/graphene supercapacitor electrode material: and (3) ultrasonically dispersing the cross-linked graphene oxide-polyoxazoline-pyridine in the step (4) in anhydrous N, N-dimethylformamide, then adding inorganic salt of transition metal ions, reacting under the protection of inert gas, and after the reaction is finished, performing suction filtration, washing and drying to obtain the metal organic framework compound/graphene supercapacitor electrode material.
Further, the ultrasonic dispersion time in the step (1-5) is 0.5-2 hours;
preferably, the ultrasonic dispersion time in the steps (1-5) is 1 hour.
Further, the inert gas atmosphere in the step (1-5) is a gas atmosphere such as nitrogen, helium or argon;
preferably, the inert gas atmosphere in the step (1-5) is nitrogen atmosphere.
Further, the washing in the step (1-5) is N, N-dimethylformamide, absolute ethyl alcohol and deionized water.
Further, the drying environment in the step (1-5) is vacuum, the temperature is 40-60 ℃, and the drying time is 12-24 hours;
preferably, the drying environment in the step (1-5) is vacuum, the temperature is 60 ℃, and the drying time is 12 hours.
Further, the mass ratio of the graphene oxide to the oxazoline derivative in the step (1) is 5:1-1: 5;
preferably, the mass ratio of the graphene oxide to the oxazoline derivative in the step (1) is 1: 1.
Further, the oxazoline derivative in the step (1) is a 2-oxazoline derivative with a double-bond substituent group; preferably, the oxazoline derivative is 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline; more preferably, the oxazoline derivative of step (1) is 2-vinyl-2-oxazoline.
Further, the reaction time in the step (1) is 12-24 hours; the reaction temperature is 100-150 ℃;
preferably, the reaction time in the step (1) is 16 hours, and the reaction temperature is 120 DEG C
Further, the mass ratio of the graphene oxide-oxazoline to the monomer oxazoline derivative in the step (2) is 1:1-1: 5;
preferably, the mass ratio of the graphene oxide-oxazoline to the monomeric oxazoline derivative in the step (2) is 1: 2.
Further, the initiator in the step (2) is an oil-soluble oxidation-reduction initiation system; preferably, the initiator is one of azobisisobutyronitrile, dibenzoyl peroxide and dibenzoyl peroxide/N, N-dimethylaniline; more preferably, the initiator in step (2) is azobisisobutyronitrile.
Further, the mass ratio of the monomer oxazoline derivative and the initiator in the step (2) is 10:1-1: 1;
preferably, the mass ratio of the monomeric oxazoline derivative and the initiator in the step (2) is 5: 1.
Further, the reaction time in the step (2) is 8-16 hours, and the reaction temperature is 40-100 ℃;
preferably, the reaction time in step (2) is 10 hours, and the reaction temperature is 60 ℃.
Further, the mass ratio of the graphene oxide-polyoxazoline to the pyridine carboxylic acid substances in the step (3) is 5:1-1: 1;
preferably, the mass ratio of the graphene oxide-polyoxazoline to the pyridine carboxylic acid in the step (3) is 2: 1.
Further, the pyridine carboxylic acid substance in the step (3) comprises one of pyridine substances with carboxylic acid groups, such as 2-pyridine carboxylic acid, 2, 4-pyridine dicarboxylic acid, 2, 5-pyridine dicarboxylic acid, 2' -bipyridine-4-carboxylic acid, 2':6', 2' -terpyridine-4 ' -carboxylic acid and the like;
preferably, the pyridine carboxylic acid substance in the step (3) is 2,2':6',2 '-terpyridine-4' -carboxylic acid.
Further, the reaction time in the step (3) is 2-10 hours, and the reaction temperature is 100-150 ℃;
preferably, the reaction time in step (3) is 5 hours, and the reaction temperature is 140 ℃.
Further, the mass ratio of the graphene oxide-polyoxazoline-pyridine to the aliphatic dibasic acid in the step (4) is 3:1-1: 1;
preferably, the mass ratio of the graphene oxide-polyoxazoline-pyridine to the aliphatic dibasic acid in the step (4) is 2: 1.
Further, the aliphatic dibasic acid in the step (4) is aliphatic dibasic acid with carboxyl at two ends; preferably, the aliphatic dibasic acid is malonic acid, succinic acid, glutaric acid, azelaic acid and the like; more preferably, the aliphatic dibasic acid in the step (4) is azelaic acid.
Further, the reaction time in the step (4) is 12-24 hours, and the reaction temperature is 100-150 ℃;
preferably, the reaction time in step (4) is 15 hours, and the reaction temperature is 110 ℃.
Further, the mass ratio of the cross-linked graphene oxide-polyoxazoline-pyridine to the inorganic salt of the transition metal ion in the step (5) is 1:1-1: 5;
preferably, the mass ratio of the cross-linked graphene oxide-polyoxazoline-pyridine to the inorganic salt of the transition metal ion in the step (5) is 1: 3.
Further, the inorganic salt of transition metal ion in the step (5) includes Fe3+、Mn2+、Zn2+、Zr4+、V5+、Co2 +、Ni2+、Ti2+、Mo2+At least one of chloride, nitrate, sulfate, etc. of transition metal ions;
preferably, the inorganic salt of transition metal ion in step (5) is ZrCl4。
Further, the reaction time in the step (5) is 8-12 hours, and the reaction temperature is 80-120 ℃;
preferably, the reaction time in step (5) is 10 hours, and the reaction temperature is 100 ℃.
The metal organic framework compound/graphene supercapacitor electrode material prepared by one of the preparation methods.
The application of the metal organic framework compound/graphene supercapacitor electrode material in the supercapacitor is disclosed.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the optimal performance of the mass specific capacitance of the metal organic framework compound/graphene supercapacitor electrode material synthesized by the method is more than 700F g by integrating the pseudocapacitance of transition metal ions and the electric double layer capacitance of graphene-1The material is a super capacitor electrode material with excellent electrochemical performance.
2. The metal organic framework compound/graphene composite material with the micro cross-linked structure obtained through the series of reactions has good circulation stability, and the specific capacitance retention rate of the material after 1000 cycles is over 95%.
3. The metal framework has strong variability, and can be used for preparing various metal organic framework compounds/graphene composite materials with different ion coordination.
Drawings
FIG. 1 is a cycle test chart of an electrode material prepared in example 2 of the present invention;
FIG. 2 is a constant current charging/discharging curve diagram of the electrode material prepared in example 3 of the present invention.
Detailed Description
The following is a more detailed description of the embodiments of the present invention with reference to the examples and the drawings, but the scope of the present invention is not limited thereto.
Example 1
(1) Preparing graphene oxide-oxazoline: dispersing 50mg of graphene oxide in 25mL of anhydrous N, N-dimethylformamide, ultrasonically dispersing for 0.5 hour, adding 10mg of 2-vinyl-2-oxazoline, introducing nitrogen, reacting for 12 hours at 100 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(2) Preparing graphene oxide-polyoxazoline: ultrasonically dispersing 50mg of graphene oxide-oxazoline in 25mL of anhydrous N, N-dimethylformamide for 0.5 hour, then adding 50mg of monomer 2-vinyl-2-oxazoline, adding 5mg of azobisisobutyronitrile to initiate polymerization, introducing nitrogen, reacting at 40 ℃ for 8 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(3) Preparing graphene oxide-polyoxazoline-pyridine: 50mg of graphene oxide-polyoxazoline is ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 0.5 hour, 10mg of 2,2', 6',2 '-terpyridine-4' -carboxylic acid is added, nitrogen is introduced, the mixture reacts at 100 ℃ for 2 hours under the protection of nitrogen, after the reaction is finished, the suspension is filtered, the suspension is washed by N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and the washed sample is dried in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline-pyridine.
(4) Preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline-pyridine in 25mL of anhydrous N, N-dimethylformamide for 0.5 hour, then adding 16.7mg of azelaic acid, introducing nitrogen, reacting for 12 hours at 100 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the cross-linked graphene oxide-polyoxazoline-pyridine.
(5) Preparing a metal organic framework compound/graphene supercapacitor electrode material: 50mg of crosslinked graphene oxide-polyoxazoline-pyridine was ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 0.5 hour, followed by addition of 50mg of ZrCl4And introducing nitrogen, reacting for 8 hours at 80 ℃ under the protection of nitrogen, filtering the suspension after the reaction is finished, washing with N, N-dimethylformamide, absolute ethyl alcohol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the metal organic framework compound/graphene supercapacitor electrode material.
The constant current charge and discharge test is carried out on the prepared product, and the constant current charge and discharge test can be calculated to obtain the following results: the electrode material is 0.5Ag-1The specific capacitance can reach 580.7F g under the current density-1After 1000 times of circulation, the specific capacitance retention rate is 91.4%.
Example 2
(1) Preparing graphene oxide-oxazoline: dispersing 50mg of graphene oxide in 25mL of anhydrous N, N-dimethylformamide, ultrasonically dispersing for 1 hour, adding 16.7mg of 2-vinyl-2-oxazoline, introducing nitrogen, reacting for 18 hours at 125 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(2) Preparing graphene oxide-polyoxazoline: ultrasonically dispersing 50mg of graphene oxide-oxazoline in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then adding 150mg of monomer 2-vinyl-2-oxazoline, adding 30mg of azobisisobutyronitrile to initiate polymerization, introducing nitrogen, reacting at 60 ℃ for 8 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline.
(3) Preparing graphene oxide-polyoxazoline-pyridine: 50mg of graphene oxide-polyoxazoline is ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then 16.7mg of 2,2', 6',2 '-terpyridine-4' -carboxylic acid is added, nitrogen is introduced, the mixture reacts at 125 ℃ for 6 hours under the protection of nitrogen, after the reaction is finished, the suspension is filtered, the suspension is washed by N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and the washed sample is dried in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline-pyridine.
(4) Preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline-pyridine in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then adding 25mg of azelaic acid, introducing nitrogen, reacting at 125 ℃ for 18 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the cross-linked graphene oxide-polyoxazoline-pyridine.
(5) Preparing a metal organic framework compound/graphene supercapacitor electrode material: 50mg of crosslinked graphene oxide-polyoxazoline-pyridine was ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 1 hour, followed by addition of 150mg of ZrCl4And introducing nitrogen, reacting for 10 hours at 100 ℃ under the protection of the nitrogen, filtering the suspension after the reaction is finished, washing with N, N-dimethylformamide, absolute ethyl alcohol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the metal organic framework compound/graphene supercapacitor electrode material.
The constant current charge and discharge test is carried out on the prepared product, and the constant current charge and discharge test can be calculated to obtain the following results: the electrode material is 0.5Ag-1Current ofThe specific capacitance under the density can reach 670.4F g-1. FIG. 1 shows that the concentration of Ag is 0.5Ag-1The cyclic test chart of 1000 times of constant current charging and discharging under the current density shows that the specific capacitance still remains 95.2 percent of the original specific capacitance after 1000 times of cyclic operation.
Example 3
(1) Preparing graphene oxide-oxazoline: dispersing 50mg of graphene oxide in 25mL of anhydrous N, N-dimethylformamide, ultrasonically dispersing for 1 hour, adding 50mg of 2-vinyl-2-oxazoline, introducing nitrogen, reacting for 16 hours at 120 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(2) Preparing graphene oxide-polyoxazoline: ultrasonically dispersing 50mg of graphene oxide-oxazoline in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then adding 100mg of monomer 2-vinyl-2-oxazoline, adding 20mg of azobisisobutyronitrile to initiate polymerization, introducing nitrogen, reacting at 60 ℃ for 10 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline.
(3) Preparing graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then adding 25mg of 2,2', 6',2 '-terpyridine-4' -carboxylic acid, introducing nitrogen, reacting for 5 hours at 140 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline-pyridine.
(4) Preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline-pyridine in 25mL of anhydrous N, N-dimethylformamide for 1 hour, then adding 25mg of azelaic acid, introducing nitrogen, reacting for 15 hours at 110 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the cross-linked graphene oxide-polyoxazoline-pyridine.
(5) Preparing a metal organic framework compound/graphene supercapacitor electrode material: 50mg of crosslinked graphene oxide-polyoxazoline-pyridine was ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 1 hour, followed by addition of 150mg of ZrCl4And introducing nitrogen, reacting for 10 hours at 100 ℃ under the protection of the nitrogen, filtering the suspension after the reaction is finished, washing with N, N-dimethylformamide, absolute ethyl alcohol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the metal organic framework compound/graphene supercapacitor electrode material.
The resulting product was tested for constant current charge and discharge, which is shown in FIG. 2 to be at 0.5A g-1The constant current charge-discharge diagram under the current density is obtained by calculation: the electrode material is 0.5A g-1The specific capacitance can reach 720.7F g under the current density-1After 1000 times of circulation, the specific capacitance retention rate is 94.5%.
Example 4
(1) Preparing graphene oxide-oxazoline: dispersing 50mg of graphene oxide in 25mL of anhydrous N, N-dimethylformamide, ultrasonically dispersing for 1.25 hours, adding 150mg of 2-vinyl-2-oxazoline, introducing nitrogen, reacting for 20 hours at 140 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(2) Preparing graphene oxide-polyoxazoline: ultrasonically dispersing 50mg of graphene oxide-oxazoline in 25mL of anhydrous N, N-dimethylformamide for 1.25 hours, then adding 200mg of monomer 2-vinyl-2-oxazoline, adding 100mg of azobisisobutyronitrile to initiate polymerization, introducing nitrogen, reacting at 80 ℃ for 12 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(3) Preparing graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline in 25mL of anhydrous N, N-dimethylformamide for 1.25 hours, then adding 50mg of 2,2', 6',2 '-terpyridine-4' -carboxylic acid, introducing nitrogen, reacting for 8 hours at 130 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline-pyridine.
(4) Preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline-pyridine in 25mL of anhydrous N, N-dimethylformamide for 1.25 hours, then adding 50mg of azelaic acid, introducing nitrogen, reacting for 18 hours at 130 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the cross-linked graphene oxide-polyoxazoline-pyridine.
(5) Preparing a metal organic framework compound/graphene supercapacitor electrode material: 50mg of crosslinked graphene oxide-polyoxazoline-pyridine was ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 1.25 hours, followed by addition of 200mg of ZrCl4And introducing nitrogen, reacting for 11 hours at 110 ℃ under the protection of the nitrogen, filtering the suspension after the reaction is finished, washing with N, N-dimethylformamide, absolute ethyl alcohol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the metal organic framework compound/graphene supercapacitor electrode material.
The constant current charge and discharge test is carried out on the prepared product, and the constant current charge and discharge test can be calculated to obtain the following results: the electrode material is 0.5A g-1The specific capacitance can reach 690.3F g under the current density-1After 1000 times of circulation, the specific capacitance retention rate is 93.4%.
Example 5
(1) Preparing graphene oxide-oxazoline: dispersing 50mg of graphene oxide in 25mL of anhydrous N, N-dimethylformamide, performing ultrasonic dispersion for 2 hours, adding 250mg of 2-vinyl-2-oxazoline, introducing nitrogen, reacting for 24 hours at 150 ℃ under the protection of nitrogen, performing suction filtration on the suspension after the reaction is finished, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-oxazoline.
(2) Preparing graphene oxide-polyoxazoline: ultrasonically dispersing 50mg of graphene oxide-oxazoline in 25mL of anhydrous N, N-dimethylformamide for 2 hours, then adding 250mg of monomer 2-vinyl-2-oxazoline, adding 250mg of azobisisobutyronitrile to initiate polymerization, introducing nitrogen, reacting at 100 ℃ for 16 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, washing with N, N-dimethylformamide, anhydrous ethanol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline.
(3) Preparing graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline in 25mL of anhydrous N, N-dimethylformamide for 2 hours, then adding 50mg of 2,2', 6',2 '-terpyridine-4' -carboxylic acid, introducing nitrogen, reacting for 10 hours at 150 ℃ under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the graphene oxide-polyoxazoline-pyridine.
(4) Preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing 50mg of graphene oxide-polyoxazoline-pyridine in 25mL of anhydrous N, N-dimethylformamide for 2 hours, then adding 50mg of azelaic acid, introducing nitrogen, reacting at 150 ℃ for 24 hours under the protection of nitrogen, after the reaction is finished, carrying out suction filtration on the suspension, respectively washing with N, N-dimethylformamide, anhydrous ethanol and deionized water, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the cross-linked graphene oxide-polyoxazoline-pyridine.
(5) Preparation of metal organic framework compound/graphene supercapacitor electrode materialPreparing: 50mg of crosslinked graphene oxide-polyoxazoline-pyridine was ultrasonically dispersed in 25mL of anhydrous N, N-dimethylformamide for 2 hours, followed by addition of 250mg of ZrCl4And introducing nitrogen, reacting for 12 hours at 120 ℃ under the protection of nitrogen, filtering the suspension after the reaction is finished, washing with N, N-dimethylformamide, absolute ethyl alcohol and deionized water respectively, and drying the washed sample in a vacuum oven at 60 ℃ for 12 hours to obtain the metal organic framework compound/graphene supercapacitor electrode material.
The constant current charge and discharge test is carried out on the prepared product, and the constant current charge and discharge test can be calculated to obtain the following results: the electrode material is 0.5A g-1The specific capacitance can reach 706.2F g under the current density-1After 1000 times of circulation, the specific capacitance retention rate is 92.9%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a metal organic framework compound/graphene electrode material is characterized by comprising the following steps:
(1) preparing graphene oxide-oxazoline: dispersing graphene oxide in anhydrous N, N-dimethylformamide, performing ultrasonic dispersion, adding an oxazoline derivative, introducing inert gas, reacting under the protection of the inert gas, performing suction filtration after the reaction is finished, washing, and drying to obtain graphene oxide-oxazoline;
(2) preparing graphene oxide-polyoxazoline: ultrasonically dispersing the graphene oxide-oxazoline in the step (1) in anhydrous N, N-dimethylformamide, then adding the oxazoline derivative in the step (1), adding an initiator to initiate polymerization, introducing inert gas, reacting under the protection of the inert gas, and after the reaction is finished, performing suction filtration, washing and drying to obtain the graphene oxide-polyoxazoline;
(3) preparing graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing the graphene oxide-polyoxazoline in the step (2) in anhydrous N, N-dimethylformamide, then adding pyridine carboxylic acid substances, introducing inert gas, reacting under the protection of the inert gas, and performing suction filtration, washing and drying after the reaction is finished to obtain graphene oxide-polyoxazoline-pyridine;
(4) preparing cross-linked graphene oxide-polyoxazoline-pyridine: ultrasonically dispersing the graphene oxide-polyoxazoline-pyridine in the step (3) in anhydrous N, N-dimethylformamide, then adding aliphatic dibasic acid, introducing inert gas, reacting under the protection of the inert gas, and after the reaction is finished, performing suction filtration, washing and drying to obtain cross-linked graphene oxide-polyoxazoline-pyridine;
(5) preparing a metal organic framework compound/graphene supercapacitor electrode material: and (3) ultrasonically dispersing the cross-linked graphene oxide-polyoxazoline-pyridine in the step (4) in anhydrous N, N-dimethylformamide, then adding inorganic salt of transition metal ions, introducing inert gas, reacting under the protection of the inert gas, and after the reaction is finished, performing suction filtration, washing and drying to obtain the metal organic framework compound/graphene supercapacitor electrode material.
2. The method according to claim 1, wherein the ultrasonic dispersion time in steps (1-5) is 0.5-2 hours, the inert gas is nitrogen, helium or argon, the washing is N, N-dimethylformamide, absolute ethanol and deionized water, respectively, the drying environment is vacuum, the drying temperature is 40-60 ℃, and the drying time is 12-24 hours.
3. The method according to claim 1, wherein the oxazoline derivative in the step (1) is a 2-oxazoline derivative with a double bond substituent group, the mass ratio of the graphene oxide to the oxazoline derivative is 5:1-1:5, the reaction time is 12-24 hours, and the reaction temperature is 100-150 ℃.
4. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide-oxazoline to the monomer oxazoline derivative in the step (2) is 1:1-1:5, the initiator is an oil-soluble oxidation-reduction initiation system, the mass ratio of the monomer oxazoline derivative to the initiator is 10:1-1:1, the reaction time is 8-16 hours, and the reaction temperature is 40-100 ℃.
5. The method of claim 4, wherein the oil-soluble redox initiator system is one of azobisisobutyronitrile, dibenzoyl peroxide and dibenzoyl peroxide/N, N-dimethylaniline.
6. The method according to claim 1, wherein the pyridine carboxylic acid in the step (3) is one of 2-pyridine carboxylic acid, 2, 4-pyridine dicarboxylic acid, 2, 5-pyridine dicarboxylic acid, 2' -bipyridine-4-carboxylic acid and 2,2':6', 2' -terpyridine-4 ' -carboxylic acid, the mass ratio of the graphene oxide-polyoxazoline to the pyridine carboxylic acid is 5:1-1:1, the reaction time is 2-10 hours, and the reaction temperature is 100-150 ℃.
7. The preparation method according to claim 1, wherein the aliphatic dibasic acid in the step (4) is an aliphatic dibasic acid with carboxyl groups at two ends, the mass ratio of the graphene oxide-polyoxazoline-pyridine to the aliphatic dibasic acid is 3:1-1:1, the reaction time is 12-24 hours, and the reaction temperature is 100-150 ℃.
8. The method according to claim 1, wherein the inorganic salt of transition metal ion in the step (5) is Fe3+、Mn2+、Zn2+、Zr4+、V5+、Co2+、Ni2+、Ti2+And Mo2+At least one of chloride, nitrate and sulfate, the mass ratio of the cross-linked graphene oxide-polyoxazoline-pyridine to the inorganic salt of the transition metal ion is 1:1-1:5, the reaction time is 8-12 hours, and the reaction is carried outThe temperature is 80-120 ℃.
9. A metal organic framework compound/graphene supercapacitor electrode material prepared by the preparation method of any one of claims 1 to 8.
10. The use of a metal organic framework compound/graphene supercapacitor electrode material according to claim 9 in a capacitor.
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