CN114315704B - Bipyridine compound and synthetic method and application thereof - Google Patents
Bipyridine compound and synthetic method and application thereof Download PDFInfo
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- CN114315704B CN114315704B CN202111452671.8A CN202111452671A CN114315704B CN 114315704 B CN114315704 B CN 114315704B CN 202111452671 A CN202111452671 A CN 202111452671A CN 114315704 B CN114315704 B CN 114315704B
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- -1 Bipyridine compound Chemical class 0.000 title claims abstract description 41
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 15
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000010439 graphite Substances 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 20
- 239000010453 quartz Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000000276 potassium ferrocyanide Substances 0.000 description 9
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical class [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 9
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000012528 membrane 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Pyridine Compounds (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a bipyridine compound, a synthesis method and application thereof, wherein main constituent elements of the bipyridine compound are carbon, hydrogen, oxygen and nitrogen, the bipyridine compound is wide in source and easy to obtain, and the cost of the bipyridine compound is far lower than that of an all-vanadium redox flow battery which is in the process of production and utilization of a large-scale redox flow battery. Compared with the traditional bipyridine compounds, the bipyridine compound introduces functional groups at four positions of 2,6 and 6, enlarges the molecular conjugation area, improves the molecular stability and further prolongs the service life of the battery.
Description
Technical Field
The invention belongs to the technical field of large-scale energy storage, and particularly relates to a bipyridine compound, a synthesis method and application thereof.
Background
With the rapid development of human society, the problems of environmental pollution and energy shortage caused by fossil energy are increasingly aggravated, and the demand of human beings for renewable energy sources such as wind energy, solar energy and the like is increasingly urgent. However, these regeneratable features are discontinuous and unstable, which makes it difficult to connect to network and has low utilization rate. Therefore, development of energy storage technology matched with the energy storage device is necessary.
In many chemical energy storage technologies, the flow battery has the advantages of independent energy and power control, high safety performance, long service life, low cost and the like, and is particularly suitable for large-scale energy storage. In the existing flow battery technology, the main flow batteries which reach the commercial application level are all-vanadium flow batteries and zinc-bromine flow batteries, and the flow batteries have the defects that the price of vanadium metal raw materials is continuously increased, the manufacturing cost of the batteries is increased, the severe toxicity and the strong corrosiveness of bromine are improved, and the large-scale application of the flow batteries is limited. The aqueous organic flow battery adopts water as a solvent, and organic molecules which are soluble in water are used as active substances. The organic molecules are composed of C, H, O, N and other elements, have the advantages of low cost, abundant resources, green, safety and the like, and are widely focused at home and abroad. In recent years, anthraquinone, TEMPO, oxazine, ferrocene active substances have been reported to be used in familiarity with aqueous organic flow batteries and to exhibit good electrochemical performance.
However, the current aqueous organic flow battery still faces some challenges, such as low solubility of active materials (organic matters), cross contamination of electrolyte through a separator, low oxidation-reduction potential of positive electrode materials, high oxidation-reduction potential of negative electrode materials, and the like. Therefore, the development overcomes the defects, and the development of new organic molecules as active materials has great significance for the development and application of aqueous organic flow batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a bipyridine compound, a synthesis method and application thereof, so as to solve the problem of low stability of active substances of the existing flow battery in the prior art.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a bipyridine compound having the structural formula:
wherein the substituents R 1 ，R 2 ，R 3 ，R 4 Are Me, OMe, OEt, COOH and COONH 4 Any one of them; r is R 5 And R is 6 Are OH, me, OMe, N (Me) 3 、SO 3 - COOH and PO 3 2- Any one of them; the value range of n is 1-16.
The invention further improves that:
preferably, the molecule of the bipyridine compound has a symmetrical or asymmetrical structure.
A synthetic method of bipyridine compound comprises bipyridine and X 1 -(CH 2 ) n -R is according to 1: putting the equivalent ratio of (1-15) into a reactor, mixing a solvent in the reactor, and heating and refluxing to react to obtain a product, thereby synthesizing bipyridine compounds;
X 1 -(CH 2 ) n -in R, X 1 Is one of Cl, br and I, R is OH, me, OMe, N (Me) 3 、SO 3 - COOH and PO 3 2- Any one of n is 1-16.
Preferably, the X 1 -(CH 2 ) n -R is one of 3 bromo 1 propanol or 2 bromo ethanol.
Preferably, the solvent is one of acetonitrile, toluene, tetrahydrofuran or N, N dimethylformamide.
Preferably, the microwave heating power is 50-100W and the heating time is 3-10 min.
Preferably, after the heating reflux reaction, the reaction product is filtered, washed, recrystallized and dried in sequence to obtain the product.
The application of the bipyridine compound is that the bipyridine compound is used as a negative electrode active material in the aqueous organic redox flow battery.
Compared with the prior art, the invention has the following beneficial effects:
the bipyridine compound provided by the invention has the main constituent elements of carbon, hydrogen, oxygen and nitrogen, is wide in source and easy to obtain, and has the cost far lower than that of the currently-used all-vanadium redox flow battery in the production and utilization of a large-scale redox flow battery. Compared with the traditional bipyridine compounds, the bipyridine compound introduces functional groups at four positions of 2,6 and 6 of bipyridine, enlarges a molecular conjugation area, regulates and controls the distribution of electron clouds on pyridine rings, enriches electrons on the pyridine rings, presents electronegativity, enhances coulomb repulsion between molecules, effectively inhibits dimerization phenomenon between molecules, and improves molecular stability; the introduced functional group has large steric hindrance and forms hydrogen bond acting force with nitrogen atoms in the collar thereof, thereby forming a protective effect on the nitrogen oxidation reduction active site, having repulsive interaction on OH < - > in water, inhibiting the attack of OH < - > in water solution on the nitrogen active site and improving the stability of molecules; the hydrogen bonding acting force of molecules and water molecules is improved, the solubility of the molecules in water is increased, and the battery capacity is further improved.
The invention also provides a synthesis method of the bipyridine compound, which is simple, high in synthesis speed, low in cost and high in product yield. The compound is used as a negative electrode of the aqueous organic redox flow battery, and the characteristics of reversible redox reaction, good electrochemical reversibility, good stability and the like of the bipyridine compound are utilized, so that the aqueous organic redox flow battery with high energy density can be obtained.
The invention also discloses application of the bipyridine compound, which has good electrochemical performance; the bipyridine water-based organic flow battery has the advantages of power energy design flexibility, low cost and large-scale assembly application, and is very suitable for large-scale energy storage application.
Drawings
FIG. 1 is a CV diagram of a solution in example 1 of the present invention.
Fig. 2 is a capacity-voltage curve of the battery mounted in example 1 of the present invention.
Fig. 3 is a graph of the number of turns-coulombic efficiency-energy efficiency-discharge capacity of the battery equipped in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
in the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are based on directions or positional relationships shown in the drawings, are merely for convenience of description and simplification of description, and do not indicate or imply that the apparatus or element to be referred to must have a specific direction, be constructed and operated in the specific direction, and thus should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixed or removable, for example; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The invention discloses a bipyridine compound, which has a chemical reaction formula as follows:
wherein the substituents R, R 1 ，R 2 ，R 3 ，R 4 Are Me, OMe, OEt, COOH and COONH 4 Any one of them; r is R 5 ，R 6 Are OH, me, OMe, N (Me) 3 SO 3 - 、COOH、PO 3 2- The bipyridine compound has a symmetrical or asymmetrical structure. n represents the length of the alkyl chain, and the value range of n is 1-16. X is X 1 Is one of Cl, br and I.
As one of the preferred embodiments, X 1 -(CH 2 ) n R may be one of 3 bromo 1 propanol or 2 bromo ethanol.
The specific process of the above reaction is to combine bipyridine and X 1 -(CH 2 ) n R is added into a reactor according to the equivalent ratio of 1 (1-15), heated for 2-10 min under the power of 50-100W, filtered, washed, recrystallized and dried after the reaction is finished to obtain the product.
The reaction solvent is one of acetonitrile, toluene, tetrahydrofuran, N, N dimethylformamide.
The bipyridine molecule can be obtained by carrying out limited-step addition and oxidation reaction on simple molecules of pyridine.
The bipyridine compound prepared by the method can be applied to a water-based organic redox flow battery, and the specific process is that organic molecules containing the bipyridine compound are used as negative electrode active substances; mixing one or more of potassium ferrocyanide, TEMPO derivatives, ferrocene derivatives, iodine, sodium iodide, potassium iodide, ammonium iodide, bromine, potassium bromide, sodium bromide and ammonium bromide to obtain an anode active material; one or more of alkaline aqueous solution or neutral aqueous solution of salt are mixed as electrolyte; taking a perfluorosulfonic acid-polytetrafluoroethylene copolymer membrane as an ion exchange membrane; two copper plates are used as current collectors of the battery; the graphite plate with flow channels is used as a flow field plate of a positive electrode and a negative electrode, and high-temperature oxidation or dilute acid carbon paper or graphite felt is used as an electrode of a battery. The assembling sequence of the battery is a copper current collector, a graphite plate runner, a carbon paper/graphite felt electrode, a perfluorosulfonic acid-polytetrafluoroethylene copolymer film, a carbon paper/graphite felt electrode, a graphite plate runner and a copper current collector in sequence.
Preferably, the neutral aqueous solution of the salt is one or more of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium phosphate, potassium sulfate and sodium sulfate. More preferably, the neutral aqueous solution is potassium chloride solution with the concentration of 0.1 to 2mol/L
Preferably, the alkaline aqueous solution is prepared by dropping KOH aqueous solution into neutral aqueous solution of salt, controlling pH to 7-9 and concentration to 1-6 mol/L.
Further, when the electrolyte is an alkaline aqueous solution, the positive electrode of the flow battery is an aqueous solution of potassium ferrocyanide; when the electrolyte is a neutral aqueous solution of salt, the positive electrode of the flow battery is one or more of potassium ferrocyanide, TEMPO, ferrocene, iodine, sodium iodide, potassium iodide, ammonium iodide, bromine, potassium bromide, sodium bromide and ammonium bromide aqueous solution. Bipyridine compounds undergo reversible oxidation-reduction reactions in the aqueous environment.
In an embodiment of the invention, a method for assembling a bipyridine compound aqueous organic flow battery comprises: bipyridine organic molecules are used as negative electrode active materials; potassium ferrocyanide is used as an anode active material; KCl aqueous solution is used as electrolyte; the assembling sequence of the battery is sequentially a copper current collector, a graphite plate runner, a carbon paper/graphite felt electrode, a perfluorosulfonic acid-polytetrafluoroethylene copolymer film, a carbon paper/graphite felt electrode, a graphite plate runner and a copper current collector.
The following is a description of specific embodiments.
Example 1
1) Synthesis of bis (3-sulfopropyl) -2,2', 6' -tetramethyl-4, 4' -bipyridine
2,2', 6' -tetramethoxy-4, 4' -bipyridine (1 eq) and 3 bromo 1-propanol (5 eq) were first mixed in tetrahydrofuran solution, added to a round bottom flask, stirred to dissolve all solids completely, and filled into a sealed quartz tube. The quartz tube was placed in a microwave oven and heated at 60W power for 5min, and the reaction mixture was cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuo to give a pink powder, designated bis (3 hydroxy-propyl) -2,2', 6' -tetramethoxy-4, 4' -bipyridine in 75% yield.
2) Dissolving the product in 10mL of 1mol/L potassium chloride aqueous solution, stirring to form a uniform solution with the concentration of 0.002mol/L, and performing cyclic voltammetry test on the prepared mixed solution by using a three-electrode system, wherein silver/silver chloride is used as a reference electrode, a platinum electrode is used as a counter electrode, a glassy carbon electrode is used as a working electrode, and the scanning speed is 100mV/s. The cyclic voltammetry scanning result is shown in figure 1.
As can be seen from the data in FIG. 1, the bipyridine compound has a pair of significantly reversible redox peaks in a neutral aqueous solution, has good electrochemical reversibility, and has an average potential of-0.58V as a negative electrode material with a Standard Hydrogen Electrode (SHE) as a reference electrode.
3) Flow battery testing
The product of example 1 was weighed and dissolved in 1mol/L aqueous potassium chloride solution, stirred to form a uniform solution, prepared into 0.1mol/L aqueous solution, 7mL was taken as the negative electrode, potassium ferrocyanide was weighed and dissolved in 1mol/L aqueous potassium chloride solution, stirred to form a uniform solution, prepared into 0.1mol/L potassium ferrocyanide solution, and 10mL was taken as the positive electrode. And (3) putting the commercial graphite felt into a 1mol/L sulfuric acid solution, stirring and soaking for 10 hours, taking out, and cleaning with deionized water for later use. The cells were assembled in the order and position of copper current collector-graphite plate flow channel-graphite felt-ion exchange membrane-graphite felt-graphite plate flow channel-copper current collector, and the liquid was driven by peristaltic pump.
Performing performance test on the battery, performing constant-current charging on the battery with current of 200mA, keeping constant-voltage charging after 1.2V, and stopping charging after the current is less than 5 mA; and (3) carrying out constant-current discharge on the battery at a current of 200mA, keeping constant-voltage discharge after 0.65V, and stopping charging after the current is less than 5 mA. According to the system, charge-discharge cycle test is performed. From fig. 3, the battery can work normally, the coulomb efficiency of the assembled battery is close to 100%, the energy efficiency is 87% and the discharge capacity of the battery is stable in the charge-discharge cycle test exceeding 1900 circles. The battery is stable in circulation and long in service life
And (3) weighing the synthesized product, dissolving the synthesized product in 1mol/L potassium chloride aqueous solution, stirring to form a uniform 0.5mol/L solution, taking 7mL as a negative electrode, weighing potassium ferrocyanide, dissolving the potassium ferrocyanide in 1mol/L potassium chloride aqueous solution, stirring to form a uniform solution, preparing a 0.25mol/L potassium ferrocyanide solution, and taking 20mL as a positive electrode. And (3) putting the commercial graphite felt into a 1mol/L sulfuric acid solution, stirring and soaking for 10 hours, taking out, and cleaning with deionized water for later use. The cells were assembled in the order and position of copper current collector-graphite plate flow channel-graphite felt-ion exchange membrane-graphite felt-graphite plate flow channel-copper current collector, and the liquid was driven by peristaltic pump.
Example 2
2,2', 6' -tetramethoxy-4, 4' -bipyridine (1 eq), 3 bromopropyl 3 methyl amine bromide (15 eq) was added to a round bottom flask and dissolved completely with an appropriate amount of N, N dimethylformamide. The mixed solution was filled into a sealed quartz tube. The quartz tube was placed in a microwave oven and heated at 100W power for 6min, and the reaction mixture was cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuo and named bis (3-bromophenyl-aminopropyl) -2,2', 6' -tetramethoxy-4, 4' -bipyridine in 45% yield.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 3
2,2', 6' -tetramethoxy-4, 4' -bipyridine (1 eq) was mixed with diethyl-bromopropyl phosphonate (10 eq) in anhydrous acetonitrile until the solid was fully dissolved. Placing the mixed solution into a sealed quartz tube, heating the quartz tube in a microwave oven at 80W for 3min, cooling, filtering, washing the precipitate with acetonitrile, and vacuum drying to obtain white solid 1,1 '-bis (3- (diethoxyphosphoryl) propyl) - [2,2',6 '-tetramethoxy-4, 4' -bipyridine]-1,1' -diammonium bromide (yield: 70%). The product (1 eq) was combined with bromotrimethylsilane (10 eq) in dichloromethane N 2 And (5) mixing. The reaction mixture was stirred at room temperature overnight to give an orange solution. Then quenched with excess anhydrous isopropanol to give an orange solution. The precipitate was filtered and dried in vacuo. Designated as 1,1 '-bis (3-phosphopropyl) -2,2',6 '-tetramethoxy 4,4' -bipyridine in a yield of 90%.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 4
2,2', 6' -tetramethoxy-4, 4' -bipyridine (1 eq), 3 bromo-1-methoxy (12 eq) and an appropriate amount of toluene were mixed first until the solid was fully dissolved. The mixed liquid is filled into a sealed quartz tube, the quartz tube is placed into a microwave oven, heated for 5min under the power of 50W, and after stopping for 30s, heated for 5min again, and the reactant is cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuo to give a pink powder, designated bis (3 methoxy-propyl) -2,2', 6' -tetramethoxy-4, 4' -bipyridine in 76% yield.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 5
2,2', 6' -tetraethoxy-4, 4' -bipyridine (1 eq), 3-bromo-1-methoxy (10 eq) and an appropriate amount of tetrahydrofuran were mixed first until the solid was fully dissolved. The mixed liquid was filled into a sealed quartz tube, the quartz tube was placed in a microwave oven, heated for 10min at 50W power, and the reactants were cooled and filtered. Then washed 3 times with tetrahydrofuran solution and finally dried in vacuo to give a powder designated bis (3 hydroxy-propyl) -2,2', 6' -tetraethoxy-4, 4' -bipyridine in 80% yield.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 6
2,2', 6' -tetra-carboxy-4, 4' -bipyridine (1 eq), 3-bromo-1-propanol (10 eq) and appropriate amount of N, N dimethylformamide were mixed until the solid was fully dissolved. The mixed liquid is filled into a sealed quartz tube, the quartz tube is placed into a microwave oven, heated for 5min under the power of 100W, and after stopping for 30s, heated for 5min again, and the reactant is cooled and filtered. Then washed 3 times with N, N dimethylformamide solution and finally vacuum dried to obtain powder named bis (3 hydroxy-propyl) -2,2', 6' -tetra-carboxy-4, 4' -bipyridine in a yield of 70%.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 7
The product (1 equivalent) of example 6 was dissolved in water, aqueous ammonia was added dropwise, the solution was monitored with pH paper to 7 to 8, then the dropwise addition was stopped, stirring was carried out at room temperature for 1 hour, and the solvent was removed by spin evaporation to give a solid powder designated as bis (3-hydroxy-propyl) -2,2', 6' -tetracarboxylic acid ammonium-4, 4' -bipyridine in a yield of 100%.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 8
2,2' -dicarboxyl, 6' -dimethyl-4, 4' -bipyridine (1 eq), 3-bromo-1-propanol (1 eq) and a suitable amount of acetonitrile were mixed until all estimated to dissolve, the mixed liquid was placed in a sealed quartz tube, the quartz tube was placed in a microwave oven, heated for 5min at a power of 60W, and the reaction was cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuum to obtain powder. The powder was dissolved in anhydrous N, N dimethylformamide solution, propylsultone (2 eq) was added, the mixed solution was put into a sealed quartz tube, the quartz tube was placed in a microwave oven, heated for 3min at 100W power, and the reaction was cooled and filtered. Then washing 3 times with N, N dimethylformamide solution, finally vacuum drying to obtain powder named 3-hydroxy-propyl-3-sulfonic acid-propyl-2, 2' -dicarboxy-, 6' -dimethyl-4, 4' -bipyridine with a yield of 60%.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 9
The product (1 equivalent) obtained in example 8 was dissolved in water, aqueous ammonia was added dropwise, the solution was monitored by pH paper until the pH was 7 to 8, and then the dropwise addition was stopped, and the mixture was stirred at room temperature for 1 hour, and the solvent was removed by spin evaporation to obtain a solid powder designated as 3-hydroxy-propyl-3-sulfonic acid-propyl-2, 2' -dicarboxylic acid ammonium-, 6' -dimethyl-4, 4' -bipyridine in a yield of 100%.
Example 10
2,2', 6' -Tetracarboxy-4, 4' -bipyridine (1 eq), 3-bromo-1-butyric acid (10 eq) and appropriate amounts of N, N dimethylformamide were mixed until the solid was completely dissolved. The mixed liquid was filled into a sealed quartz tube, the quartz tube was placed in a microwave oven, heated for 10min at a power of 60W, and the reaction mass was cooled and filtered. Then washed 3 times with N, N dimethylformamide solution and finally dried in vacuo to give a powder designated bis (3-carboxy-propyl) -2,2', 6' -tetra-carboxy-4, 4' -bipyridine in a yield of 70%.
Assembling a flow battery by using the product; the processes and parameters not indicated in this example are the same as in example 1.
Example 11
The product (1 equivalent) obtained in example 10 was dissolved in water, aqueous ammonia was added dropwise, the solution was monitored with pH paper until the pH was 7 to 8, and then the dropwise addition was stopped, and the mixture was stirred at room temperature for 1 hour, and the solvent was removed by spin evaporation to obtain a solid powder designated as bis (3-ammonium carboxylate-propyl) -2,2', 6' -ammonium tetracarboxylic acid-4, 4' -bipyridine in a yield of 100%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. A method for synthesizing bipyridine compounds is characterized in that 2,2', 6' -tetramethoxy-4, 4' -bipyridine and 3-bromo-1-propanol are put into a reactor, tetrahydrofuran solution is mixed in the reactor as solvent, and microwave irradiation heating is carried out to obtain products, thus synthesizing the bipyridine compounds;
the bipyridine compound product is bis (3 hydroxy-propyl) -2,2', 6' -tetramethoxy-4, 4' -bipyridine, and the structural formula is as follows:
the equivalent ratio of 2,2', 6' -tetramethoxy-4, 4' -bipyridine to 3 bromo 1-propanol is 1:5, a step of;
the power of microwave heating is 60W, and the heating time is 5 min.
2. The method for synthesizing bipyridine compounds according to claim 1, wherein after the reaction of heating and refluxing, the reaction product is filtered, washed, recrystallized and dried to obtain the product.
3. A bipyridine compound prepared by the preparation method of any one of claims 1 to 2, wherein the compound has a structural formula:
。
4. the use of the bipyridine compound according to claim 3, wherein the bipyridine compound is used as a negative electrode active material in an aqueous organic redox flow battery.
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