CN108997562A - A kind of fluorinated copolymer and its preparation method and application, solar battery - Google Patents
A kind of fluorinated copolymer and its preparation method and application, solar battery Download PDFInfo
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- CN108997562A CN108997562A CN201810897921.0A CN201810897921A CN108997562A CN 108997562 A CN108997562 A CN 108997562A CN 201810897921 A CN201810897921 A CN 201810897921A CN 108997562 A CN108997562 A CN 108997562A
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- fluorinated copolymer
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- -1 bromo- 4- n-hexyl Chemical group 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000006619 Stille reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000004088 simulation Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 229910052731 fluorine Inorganic materials 0.000 description 19
- 239000011737 fluorine Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000004770 highest occupied molecular orbital Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- QILZDWMMWFCBPW-UHFFFAOYSA-N 3,4-difluorobenzene-1,2-diamine Chemical compound NC1=CC=C(F)C(F)=C1N QILZDWMMWFCBPW-UHFFFAOYSA-N 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 229910006124 SOCl2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002026 chloroform extract Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PVSCLHDHWOAWGV-UHFFFAOYSA-N oxygen;toluene Chemical compound [O].CC1=CC=CC=C1 PVSCLHDHWOAWGV-UHFFFAOYSA-N 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 229910000080 stannane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N thianaphthalene Natural products C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000013087 polymer photovoltaic Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
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- C—CHEMISTRY; METALLURGY
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/592—Stability against heat
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention provides a kind of fluorinated copolymers, with fluoro- 4,7-, bis- (the bromo- 4- n-hexyl -2- thienyls of 5-) -2 of 5,6- bis-, donor D of 1, the 3- diazosulfide as receptor and different proportion1[(the tin trimethyl) -2,2'- of 5,5'- bis- bithiophene], donor D2[fluoro- bis- (the tin trimethyl) -2,2'- bithiophene of 5,5'- of 3,4'- bis-] constitutes donor D1With donor D2The different fluorinated copolymer of ratio.The Photophysics of fluorinated copolymer provided by the invention have biggish promotion, and short circuit current reaches 12.40mA/cm2；Energy conversion efficiency is up to 5.57%.By a series of characterization method (UV absorption, cyclic voltammetric, thermogravimetric, gel permeation chromatography), and corresponding simulation calculates discovery: fluorinated copolymer provided by the invention can be used as the use of solar battery donor element, and all have good ultravioletvisible absorption energy, thermal stability.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of fluorinated copolymer and its preparation method and application,
Solar battery.
Background technique
The Energies control of organic polymer, the photon including low strap gap material designed for collecting wide solar spectrum,
And then promote the promotion of short circuit current.Regulation donor material HOMO energy level can promote open-circuit voltage.Polymeric donor and fowler
LUMO is effectively deviated between alkene receptor, is the Key Strategy for realizing high-performance polymer solar cell.
In a large amount of D-A polymer, there is the polymer of fluorination structural unit to cause the great interest of people recently,
Because realizing the energy conversion efficiency more than 7% by the fluorination of unit alreadys exceed 10% till now.Polymer
In the research of a certain unit fluorination reaction be concentrated mainly on A unit, the fluorination on D unit on photovoltaic performance influence research compared with
It is few.
Random 1D-2A and 2D-1A terpolymer includes D and two A unit, or mono- including two D and A
Member, above two terpolymer are the effective ways for overcoming alternate D-A copolymer energy conversion efficiency bottleneck.In addition to effective
It covers outside solar spectrum, random ter-polymers also have the advantages that other, such as: can effectively adjust molecular orbit level, synthesis side
Method is simple, and solubility/processability is good.
However, few people's research improves polymer photovoltaic performance by introducing fluorine on terpolymer (2D, 1A).
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of fluorinated copolymers and its preparation method and application, solar energy
Battery.Fluorinated copolymer provided by the invention has excellent Photophysics, is prepared using fluorinated copolymer of the invention
Solar battery is even more to have excellent photovoltaic performance.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of fluorinated copolymer with structure shown in Formulas I,
In Formulas I, R is-C6H13；It is shared poly- in entire fluorinated copolymer that m and n represents different monomers in fluorinated copolymer
Composition and division in a proportion example；M is [0,1], and n is [0,1], m+n=1.
Preferably, as m=0, n=1；As m=0.3, n=0.7；As m=0.5, n=0.5；As m=0.7, n
=0.3；As m=1, n=0.
The present invention also provides the preparation methods of fluorinated copolymer described in above-mentioned technical proposal, comprising the following steps:
By donor D1, donor D2, receptor and toluene mixing, then be added catalyst carry out stille coupling reaction, obtain institute
State fluorinated copolymer；
Wherein, the donor D1With structure shown in Formula II, the donor D2With structure shown in formula III, the receptor tool
There is structure shown in formula IV；
Preferably, the donor D1With donor D2Mole summation and receptor mole ratio be 1:1.
Preferably, the catalyst is Pd2dba3, CuO and P (o-tolyl)3Mixture.
Preferably, Pd in the catalyst2dba3, CuO and P (o-tolyl)3Mass ratio be 1:4~10:1~2.
Preferably, the amount ratio of the receptor, toluene and catalyst is 1g:50~100mL:0.2~0.5g.
Preferably, the temperature of the stille coupling reaction is 80~110 DEG C, and the time is 48~96h.
The present invention also provides the application of fluorinated copolymer described in above-mentioned technical proposal in solar cells.
The present invention also provides a kind of solar batteries, including the glass/ITO/PEDOT:PSS/ being cascading
Polymer:PC71BM/Ca/Al, wherein the Polymer is fluorinated copolymer described in above-mentioned technical proposal；It is described
Polymer and PC71The weight ratio of BM is 1:1.2；The effective area of the solar battery is 4mm2。
The present invention provides a kind of fluorinated copolymers, with fluoro- 4, the 7- bis- (the bromo- 4- n-hexyl -2- thienyl of 5-)-of 5,6- bis-
Donor D of 2,1, the 3- diazosulfides as receptor and different proportion1[(the tin trimethyl) -2,2'- of 5,5'- bis- bithiophene] supplies
Body D2[fluoro- bis- (the tin trimethyl) -2,2'- bithiophene of 5,5'- of 3,4'- bis-] constitutes donor D1With donor D2Ratio is different to be contained
Fluo-copolymer.The Photophysics of fluorinated copolymer provided by the invention have biggish promotion, and short circuit current reaches 12.40mA/
cm2；Energy conversion efficiency is up to 5.57%.By a series of characterization method (UV absorption, cyclic voltammetric, thermogravimetric, gel infiltration
Chromatography), and corresponding simulation calculating discovery: fluorinated copolymer provided by the invention can be used as solar battery donor element
It uses, and all there is good ultravioletvisible absorption energy, thermal stability.
Detailed description of the invention
Fig. 1 is the flow chart that the present invention prepares fluorinated copolymer；
Fig. 2 is the thermogravimetric curve of fluorinated copolymer in Examples 1 to 5；
Fig. 3 is the normalization absorption spectrum in chloroformic solution of fluorinated copolymer in Examples 1 to 5；
Fig. 4 is the cyclic voltammetry curve of fluorinated copolymer in Examples 1 to 5；
Fig. 5 is the current -voltage curve of fluorinated copolymer in Examples 1 to 5.
Specific embodiment
The present invention provides a kind of fluorinated copolymer with structure shown in Formulas I,
In Formulas I, R is-C6H13；It is shared poly- in entire fluorinated copolymer that m and n represents different monomers in fluorinated copolymer
Composition and division in a proportion example；M is [0,1], and n is [0,1], m+n=1.
In an embodiment of the present invention, the structure of the fluorinated copolymer is preferred are as follows:
The present invention also provides the preparation methods of fluorinated copolymer described in above-mentioned technical proposal, comprising the following steps:
By donor D1, donor D2, receptor and toluene mixing, then be added catalyst carry out stille coupling reaction, obtain institute
State fluorinated copolymer.
Wherein, the donor D1With structure shown in Formula II, the donor D2With structure shown in formula III, the receptor tool
There is structure shown in formula IV；
In the present invention, the donor D1With donor D2Mole summation and the ratio of receptor mole be preferably 1:1.
The present invention is to the donor D1With donor D2Molar ratio there is no special restriction, as long as donor D can be made1With donor D2Mole
Summation and receptor mole ratio are 1:1.
In the present invention, the catalyst is preferably Pd2dba3, CuO and P (o-tolyl)3Mixture.In the present invention
In, Pd in the catalyst2dba3, CuO and P (o-tolyl)3Mass ratio be preferably 1:4~10:1~2, more preferably 1:5
~9:1.2~1.8, most preferably 1:6~8:1.4~1.6.In the present invention, the amount ratio of the receptor, toluene and catalyst
Preferably 1g:50~100mL:0.2~0.5g, more preferably 1g:60~90mL:0.25~0.45g, most preferably A Wei 1g:0.7
~0.8mL:0.3~0.4g.
In the present invention, the toluene is preferably through deoxidation gas disposal.The present invention does not have the preparation method of deoxidation gas toluene
There is special restriction, using solvent deoxidation gas method well known to those skilled in the art.
The present invention is to the donor D1And D2Source there is no special restriction, using city well known to those skilled in the art
Sell product.
The present invention does not have special restriction to the source of the receptor, using commercial product known to those skilled in the art or
Person is prepared using customary preparation methods.In an embodiment of the present invention, the preparation method of the receptor preferably includes following
Step:
(a) synthesis of (5,6- bis- fluoro- 2,1,3- diazosulfide): in three neck round bottom flask, by 5,6- bis- fluoro- 1,2-
Phenylenediamine 1 (5.5g, 38.2mmol) is completely dissolved in methylene chloride (200mL) and triethylamine (30mL)；By 50mL methylene chloride
With SOCl2(6.1mL, 83.0mmol) is mixed, and mixing liquid is slowly added dropwise under conditions of 0 DEG C, 80 DEG C of magnetic agitations
Overnight；After completion of the reaction, make mixture cooling and 250mL deionized water be added, reaction mixture is transferred in separatory funnel,
It is washed with deionized water 3 times, collection, which merges organic phase and dried, filtered with anhydrous magnesium sulfate, has been concentrated to get 5.2g quinoxaline sample gas
Taste white solid 2 (the fluoro- 2,1,3- diazosulfide of 5,6- bis-)；
(b) 4,7- the synthesis of the bis- fluoro- 2,1,3- diazosulfide of bromo- 5,6- bis- of 4,7-: is added into three neck round bottom flask
Two bromo- 5,6- bis- fluoro- 2,1,3- diazosulfide (2.48g, 14.4mmol) then add 48% hydrobromic acid (30mL)；With
Bromine (14.9mL, 28.5mmol) is slowly added dropwise in syringe, after injection, is warming up at 128 DEG C and flows back 4 hours, during which needs
It builds an exhaust gas processing device and absorbs hydrogen bromide；End of reaction is cooled to room temperature, and is poured into methylene chloride；It will be double
Phase mixture is transferred in separatory funnel, is washed with deionized 3 to 5 times, is then rinsed with saturated sodium sulfite and is used saturation
Sodium hydrogen carbonate washings react away extra bromine and hydrobromic acid；It collects organic phase solution is filtered and is concentrated under reduced pressure；Use dichloro
Methane carries out silica gel column chromatography purifying as mobile phase, dry with magnesium sulfate after purification, and separation rotary evaporation obtains 3.15g white
The bis- fluoro- 2,1,3- diazosulfide of bromo- 5,6- bis- of solid 4,7-；
(c) synthesis of fluoro- 4,7- bis- (4- n-hexyl -2- the thienyl) -2,1,3- diazosulfide of 5,6- bis-: dry to 25mL
Bromo- 5, the 6- bis- fluoro- 2 of 4,7- bis-, 1,3- diazosulfide (326mg, 0.998mmol), tributyl (4- are added in dry two-mouth bottle
Hexyl -2- thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, body
System uses nitrogen displaced air three times, then by tetrakis triphenylphosphine palladium Pd (PPh3)4(50mg, 0.04mmol) is added in system, then
It is secondary to use nitrogen displaced air three times, it is heated to 80 DEG C and flows back 48 hours；After cooling, substance is loaded on silica gel, using hexane/
Chloroform (4:1) is purified as mobile phase silica gel column chromatography；Obtaining the fluoro- 4,7- bis- of 0.256g red solid 5,6- bis-, (4- is just
Hexyl -2- thienyl) -2,1,3- diazosulfide；
(d) synthesis of fluoro- 4,7- bis- (the bromo- 4- n-hexyl -2- thienyl of the 5-) -2,1,3- diazosulfide of 5,6- bis-: to
Fluoro- 4,7- bis- (4- n-hexyl -2- the thienyl) -2,1,3- benzo thiophene two of 5,6- bis- is added in the 50mL single port bottle that tinfoil wraps
Azoles (250mg, 0.495mmol), N-bromosuccinimide (NBS) (220mg, 1.238mmol) and chloroform (10mL)；Make
Reaction mixture is cooled to 0 DEG C and reacts 12 hours；After being warming up to room temperature, adds 20mL deionized water quenching reaction, use separatory funnel
Organic phase is separated, chloroform extracts remaining water phase three times, and separation merges organic phase, and n-hexane is used to carry out after concentration as eluent
Silica gel column chromatography purifying；It collects purified fraction and is dried with anhydrous sodium sulfite, filtering and concentrating obtains brick-red solid.
In the present invention, the temperature of the stille coupling reaction is preferably 80~110 DEG C, and more preferably 85~105 DEG C,
Most preferably 90~100 DEG C.In the present invention, the time of the stille coupling reaction is preferably 48~96h, and more preferably 60
~84h, most preferably 66~72h.
After the completion of the stille coupling reaction, the present invention obtains the fluorinated copolymer preferably through post-processing.At this
In invention, the post-processing is preferably included after stille coupling reaction product is cooled to room temperature, is added drop-wise in methanol, then according to
It is secondary to be separated by solid-liquid separation, purified and extracted, obtain thick fluorinated copolymer；Thick fluorinated copolymer is added drop-wise in methanol, then
It is successively separated by solid-liquid separation and is dried, obtain the fluorinated copolymer.The present invention is not special to the mode of the separation of solid and liquid
Restriction, using solid-liquid separation method well known to those skilled in the art, specifically, as filter.The present invention is to purification
Mode does not have special restriction, using purification mode well known to those skilled in the art.In an embodiment of the present invention, institute
Stating purification mode is preferably Soxhlet purification.In the present invention, the solvent of the Soxhlet purification preferably includes methanol, hexane or third
Ketone.In the present invention, the solvent of the extraction preferably includes chloroform.In the present invention, the temperature of the drying be preferably 50~
100 DEG C, more preferably 60~90 DEG C, most preferably 70~80 DEG C.In the present invention, the time of the drying be preferably 12~
For 24 hours, more preferably 15~20h, most preferably 18h.
The present invention also provides the application of fluorinated copolymer described in above-mentioned technical proposal in solar cells.The present invention mentions
The fluorinated copolymer of confession can be applied in solar battery because having excellent Photophysics.
The present invention also provides a kind of solar batteries, including the glass/ITO/PEDOT:PSS/ being cascading
Polymer:PC71BM/Ca/Al, wherein the Polymer is fluorinated copolymer described in above-mentioned technical proposal；It is described
The weight ratio of Polymer and PC71BM is 1:1.2；The effective area of the solar battery is 4mm2.The present invention to it is described too
The preparation method of positive energy battery, not special restriction, using the battery preparation method of this field routine.Of the invention
In embodiment, the preparation method of the solar battery is the following steps are included: glass/ITO substrate is cleaned with detergent, third
It is ultrasonically treated in ketone and isopropanol, and is dried overnight in 100 DEG C of baking ovens；In glove box, by 3,4-ethylene dioxythiophene/poly-
Styrene sulfonate (PEDOT:PSS) hole transmission layer is dissolved in chlorobenzene, and is spin-coated on the conduction after treatment with ultraviolet light
On glass tin indium oxide (ITO) anode；By active layer (Polymer:PC71BM=1:1.2wt) blend solution is spin-coated on
The top of PEDOT:PSS；Device is placed in vacuum chamber (< 10-6Pa in), in the vacuum chamber, the calcium film and 70nm of 40nm thickness are thick
Aluminium film is deposited on active layer；Obtaining structure is glass/ITO/PEDOT:PSS/Polymer:PC71BM/Ca/Al, battery
Effective area is 4mm2Solar battery.Wherein, the Polymer is fluorinated copolymer provided by the invention.
Fig. 1 is that the present invention prepares the flow chart of fluorinated copolymer, the present invention with fluoro- 4, the 7- of 5,6- bis- bis- (the bromo- 4- of 5- just oneself
Base -2- thienyl) -2,1,3- diazosulfide is receptor, with [5,5'- bis- (tin trimethyl) -2,2'- bithiophene], [3,4'-
Two fluoro- 5,5'-, bis- (tin trimethyl) -2,2'- bithiophenes] it is donor, stille coupling reaction is carried out, fluorinated copolymer is obtained.
Below with reference to embodiment to fluorinated copolymer provided by the invention and its preparation method and application, solar battery into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
The donor D used in the present embodiment1With structure shown in Formula II, the donor D2With structure shown in formula III, institute
Receptor is stated with structure shown in formula IV；
Embodiment 1
In 50mL three-necked flask, by donor D1(0.1483g, 0.3mmol), receptor (0.2g, 0.3mmol) and 15mL are de-
The mixing of oxygen toluene；Then catalyst Pd is added2dba3(8mg)/CuO(50mg)/P(o-tolyl)3(10mg), is replaced with nitrogen
Three times, under nitrogen protection, in 110 DEG C of progress stille coupling reaction 72h；End of reaction, stille coupling reaction is cooling
To room temperature, be slowly dropped in 300mL methanol allow fluoropolymer, filtering, obtain fluorinated copolymer；By fluorinated copolymer in rope
Purified in family name's purifying plant with acetone, finally extracts fluorinated copolymer with chloroform；Chloroformic solution concentration is slowly added into
Co-polymer is precipitated again in 300mL methanol, by filter solid and is dried in vacuo, obtains 0.15g red solid 4-P1, yield is
74.58%.
Wherein receptor preparation method the following steps are included:
(a) synthesis of (5,6- bis- fluoro- 2,1,3- diazosulfide): in three neck round bottom flask, by 5,6- bis- fluoro- 1,2-
Phenylenediamine 1 (5.5g, 38.2mmol) is completely dissolved in methylene chloride (200mL) and triethylamine (30mL)；By 50mL methylene chloride
With SOCl2(6.1mL, 83.0mmol) is mixed, and mixing liquid is slowly added dropwise under conditions of 0 DEG C, 80 DEG C of magnetic agitations
Overnight；After completion of the reaction, make mixture cooling and 250mL deionized water be added, reaction mixture is transferred in separatory funnel,
It is washed with deionized water 3 times, collection merging organic phase is simultaneously dry with anhydrous magnesium sulfate；Filtering and concentrating has obtained 5.2g quinoxaline sample gas
Taste white solid 2 (5,6- bis- fluoro- 2,1,3- diazosulfide), yield 79.15%；
(b) 4,7- the synthesis of the bis- fluoro- 2,1,3- diazosulfide of bromo- 5,6- bis- of 4,7-: is added into three neck round bottom flask
Two bromo- 5,6- bis- fluoro- 2,1,3- diazosulfide (2.48g, 14.4mmol) then add 48% hydrobromic acid (30mL)；With
Bromine (14.9mL, 28.5mmol) is slowly added dropwise in syringe, after injection, is warming up at 128 DEG C and flows back 4 hours, during which needs
It builds an exhaust gas processing device and absorbs hydrogen bromide；End of reaction is cooled to room temperature, and is poured into methylene chloride；It will be double
Phase mixture is transferred in separatory funnel, is washed with deionized 3 to 5 times, is then rinsed with saturated sodium sulfite and is used saturation
Sodium hydrogen carbonate washings react away extra bromine and hydrobromic acid.It collects organic phase solution is filtered and is concentrated under reduced pressure；Use dichloro
Methane carries out silica gel column chromatography purifying as mobile phase, dry with magnesium sulfate after purification, and separation rotary evaporation obtains 3.15g white
Solid 4, bromo- 5, the 6- bis- fluoro- 2 of 7- bis-, 1,3- diazosulfide, yield 66.27%；
(c) synthesis of fluoro- 4,7- bis- (4- n-hexyl -2- the thienyl) -2,1,3- diazosulfide of 5,6- bis-: dry to 25mL
Bromo- 5, the 6- bis- fluoro- 2 of 4,7- bis-, 1,3- diazosulfide (326mg, 0.998mmol), tributyl (4- are added in dry two-mouth bottle
Hexyl -2- thienyl) stannane (1.130g, 2.5mmol), and dissolved with the tetrahydrofuran (15mL) after dry and deoxygenation, body
System uses nitrogen displaced air three times, then by tetrakis triphenylphosphine palladium Pd (PPh3)4(50mg, 0.04mmol) is added in system, then
It is secondary to use nitrogen displaced air three times, it is heated to 80 DEG C and flows back 48 hours；After cooling, substance is loaded on silica gel, using hexane/
Chloroform (4:1) is purified as mobile phase silica gel column chromatography；Obtaining the fluoro- 4,7- bis- of 0.256g red solid 5,6- bis-, (4- is just
Hexyl -2- thienyl) -2,1,3- diazosulfide, yield 51.35%；1H NMR(CDCl3, 400MHz, δ/ppm): 8.13
(s,2H),7.21(s,2H),2.72(t,4H),1.53-1.65(m,14H),1.29-1.38(m,12H),0.87(t,12H)；
13C NMR(CDCl3, 100MHz, δ/ppm): 144.44,136.87,136.26,125.51,31.75,30.71,30.01,
29.15,29.10,28.99,28.24,27.88,27.56,27.27,27.15,26.98,22.65,16.43,15.62,
14.09,13.69,13.65,12.56,12.48,10.79,9.10,9.02。
(d) synthesis of fluoro- 4,7- bis- (the bromo- 4- n-hexyl -2- thienyl of the 5-) -2,1,3- diazosulfide of 5,6- bis-: to
Fluoro- 4,7- bis- (4- n-hexyl -2- the thienyl) -2,1,3- benzo thiophene two of 5,6- bis- is added in the 50mL single port bottle that tinfoil wraps
Azoles (250mg, 0.495mmol), N-bromosuccinimide (NBS) (220mg, 1.238mmol) and chloroform (10mL)；Make
Reaction mixture is cooled to 0 DEG C and reacts 12 hours；After being warming up to room temperature, adds 20mL deionized water quenching reaction, use separatory funnel
Organic phase is separated, chloroform extracts remaining water phase three times, and separation merges organic phase, and n-hexane is used to carry out after concentration as eluent
Silica gel column chromatography purifying；It collects purified fraction and is dried with anhydrous sodium sulfite, it is brick-red solid that filtering and concentrating obtains 0.28g
Body yield 85.31%；1HNMR(CDCl3, 400MHz, δ/ppm): 7.76 (s, 2H), 2.51 (t, 4H), 1.55 (d, 4H), 1.17
(s,8H),0.77(t,6H)；13C NMR(CDCl3, 100MHz, δ/ppm): 149.82,149.62,147.23,147.16,
147.11,147.07,147.03,141.06,130.57,130.52,130.47,130.15,113.50,113.46,113.42,
109.77,109.73,109.68,109.64,40.34,36.42,36.09,35.06,32.71,31.75,30.93,30.63,
30.58,29.04,28.73,28.70,28.69,28.52,28.36,28.05,27.97,26.66,26.09,25.74,
24.27,23.47,21.79,21.69,21.63,21.59,19.43,18.71,18.41,17.74,13.30,13.09,
10.40。
Embodiment 2
In 50mL three-necked flask, by donor D1(0.1038g, 0.21mmol), donor D2(0.0477g, 0.09mmol),
Receptor (0.2g, 0.3mmol) and the mixing of 15mL deoxidation gas toluene；Then catalyst Pd is added2dba3(8mg)/CuO(50mg)/P
(o-tolyl)3(10mg), three times with nitrogen displacement, under nitrogen protection, in 110 DEG C of progress stille coupling reaction 72h；Instead
Should finish, stille coupling reaction is cooled to room temperature, be slowly dropped in 300mL methanol allow fluoropolymer, filtering, obtain
Fluorinated copolymer；Fluorinated copolymer is purified in Soxhlet purifying plant with methanol, finally extracts fluorine-containing copolymerization with chloroform
Object；Chloroformic solution concentration is slowly added into 300mL methanol, co-polymer is precipitated again, by filter solid and is dried in vacuo,
Obtain 0.16g red solid 4-P2, yield 78.3%.
The preparation method of receptor is same as Example 1.
Embodiment 3
In 50mL three-necked flask, by donor D1(0.0742g, 0.15mmol), donor D2(0.0795g, 0.15mmol),
Receptor (0.2g, 0.3mmol) and the mixing of 15mL deoxidation gas toluene；Then catalyst Pd is added2dba3(8mg)/CuO(50mg)/P
(o-tolyl)3(10mg), three times with nitrogen displacement, under nitrogen protection, in 110 DEG C of progress stille coupling reaction 72h；Instead
Should finish, stille coupling reaction is cooled to room temperature, be slowly dropped in 300mL methanol allow fluoropolymer, filtering, obtain
Fluorinated copolymer；Fluorinated copolymer is purified in Soxhlet purifying plant with methanol, finally extracts fluorine-containing copolymerization with chloroform
Object；Chloroformic solution concentration is slowly added into 300mL methanol, co-polymer is precipitated again, by filter solid and is dried in vacuo,
Obtain 0.12g red solid 4-P3, yield 58.11%.
The preparation method of receptor is same as Example 1.
Embodiment 4
In 50mL three-necked flask, by donor D1(0.0445g, 0.09mmol, donor D2(0.113g, 0.21mmol), by
Body ((0.2g, 0.3mmol) and 15mL deoxidation gas toluene mixing；Then catalyst Pd is added2dba3(8mg)/CuO(50mg)/P
(o-tolyl)3(10mg), three times with nitrogen displacement, under nitrogen protection, in 110 DEG C of progress stille coupling reaction 72h；Instead
Should finish, stille coupling reaction is cooled to room temperature, be slowly dropped in 300mL methanol allow fluoropolymer, filtering, obtain
Fluorinated copolymer；Fluorinated copolymer is purified in Soxhlet purifying plant with methanol, finally extracts fluorine-containing copolymerization with chloroform
Object；Chloroformic solution concentration is slowly added into 300mL methanol, co-polymer is precipitated again, by filter solid and is dried in vacuo,
Obtain 0.10g red solid 4-P4, yield 47.93%.
The preparation method of receptor is same as Example 1.
Embodiment 5
In 50mL three-necked flask, by donor D2(0.1590g, 0.3mmol), receptor (0.2g, 0.3mmol) and 15mL are de-
The mixing of oxygen toluene；Then catalyst Pd is added2dba3(8mg)/CuO(50mg)/P(o-tolyl)3(10mg), is replaced with nitrogen
Three times, under nitrogen protection, in 110 DEG C of progress stille coupling reaction 72h；End of reaction, stille coupling reaction is cooling
To room temperature, be slowly dropped in 300mL methanol allow fluoropolymer, filtering, obtain fluorinated copolymer；By fluorinated copolymer in rope
Purified in family name's purifying plant with methanol, finally extracts fluorinated copolymer with chloroform；Chloroformic solution concentration is slowly added into
Co-polymer is precipitated again in 300mL methanol, by filter solid and is dried in vacuo, obtains 0.18g red solid 4-P5, yield is
84.96%.
The preparation method of receptor is same as Example 1.
Embodiment 6: the preparation of solar battery
Glass/ITO substrate is cleaned with detergent, is ultrasonically treated in acetone and isopropanol, and is done in 100 DEG C of baking ovens
It is dry overnight；In glove box, 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS) hole transmission layer is dissolved
In chlorobenzene, and it is spin-coated on electro-conductive glass tin indium oxide (ITO) anode after treatment with ultraviolet light；By active layer
(Polymer:PC71BM=1:1.2wt) blend solution is spin-coated on the top of PEDOT:PSS；Device is placed in vacuum chamber (< 10-6Pa in), in the vacuum chamber, the calcium film and 70nm thickness aluminium film of 40nm thickness are deposited on active layer；Obtain structure be glass/
ITO/PEDOT:PSS/Polymer:PC71BM/Ca/Al, the effective area of battery are 4mm2。
The thermal stability of fluorinated copolymer in Examples 1 to 5, fluorine-containing copolymerization in Examples 1 to 5 are characterized using thermogravimetric analysis
The thermogravimetric curve of object is as shown in Fig. 2, as can be seen from Figure 2: the 5% of fluorinated copolymer 4-P1,4-P2,4-P3,4-P4,4-P5
Mass loss temperature (Td) is respectively 308 DEG C, 395 DEG C, 311 DEG C, 350 DEG C, 365 DEG C and 335 DEG C；It can be seen that: this hair
The fluorinated copolymer of bright offer has good thermal stability, is feasible applied to solar battery.
Characterize the molecular weight and dispersibility of fluorinated copolymer 4-P1~4-P5 using GPC, in test with THF eluent and
Gel permeation chromatography is carried out as standard in polystyrene；It is tested three times under the same conditions with a batch fluorinated copolymer, and all
With similar number-average molecular weight (Mn), weight average molecular weight (Mw) and monodispersity index PDI, as a result shown in table 1.It can be with from table 1
Find out: with the increase of fluorine content, downward trend after first rising is presented in the molecular weight of fluorinated copolymer.Wherein, 4-P2 molecule
Amount is maximum, while its thermal stability is preferably also.
The molecular weight of fluorinated copolymer and dispersed test result in 1 Examples 1 to 5 of table
| Serial number | Mn(kg.mol-1) | MW(kg.mol-1) | PDI |
| 4-P1 | 9.08 | 11.45 | 1.26 |
| 4-P2 | 12.88 | 16.63 | 1.30 |
| 4-P3 | 10.98 | 13.56 | 1.23 |
| 4-P4 | 9.53 | 12.38 | 1.30 |
| 4-P5 | 9.32 | 11.81 | 1.26 |
Fluorinated copolymer is dissolved in chloroform, using the optics of ultraviolet-ray visible absorbing research fluorinated copolymer chloroformic solution
Performance；Normalization absorption spectrum of the fluorinated copolymer 4-P1~4-P5 in chloroformic solution is as shown in Figure 3.As can be seen from Figure 3:
Absorption region of the fluorinated copolymer in chloroformic solution is roughly the same.In addition to 4-P4, four additional fluorinated copolymer it is ultraviolet can
Light-exposed region has four characteristic peaks.The specific data of the absorption peak of five fluorinated copolymers are as follows: 4-P1:325nm, 382nm,
514nm,710nm；4-P2:315nm, 385nm, 516nm, 708nm；4-P3:318nm, 376nm, 508nm, 695nm；4-P4:
318nm, 379nm, 509nm, 4-P5:313nm, 382nm, 510nm, 690nm.With fluorine-containing donor D2Content increases in solution
Slight blue shift (10-20nm) is shown in absorption, wherein absorption of the 4-P1 and 4-P5 within the scope of 650~800nm all compared with
The absorption of the other three fluorinated copolymer wants high.And 4-P2 to 4-P4 is with fluorine-containing D2Unit content increases, and absorbs and occurs
Blue shift and the absorption within the scope of 650~800nm are begun to decline.From figure 3, it can be seen that fluoropolymer 4-P1~4-P5
It is respectively 785nm, 775nm, 770nm, 765nm, 772nm that boundary, which absorbs,；According to formula: optical band gap=1240/ absorbing boundary,
Available optical band gap is respectively 1.58eV, 1.60eV, 1.61eV, 1.62eV, 1.61eV.Fluorine-containing copolymerization is listed in table 2
Absorption peak (the λ of objectmax), absorbing boundary (λonset) and optical band gap (Eg opt).It can be seen that: with fluorine-containing donor D2Increase
Add, significant change does not occur for optical band gap, and fluorinated copolymer band gap is in 1.60eV or so.
The cyclic voltammetry curve of fluorinated copolymer 4-P1~4-P5 is measured, as a result such as Fig. 4.As can be seen from Figure 4: the present invention
Fluorinated copolymer 4-P1~4-P5 cyclic voltammetry curve in without there is apparent reduction peak, only oxidation peak is brighter
It is aobvious.When forward scan, it is respectively according to the oxidizing potential that fluorinated copolymer oxidation peak position in Fig. 4 can obtain 4-P1~4-P5
0.85V,0.944V,0.945V,0.994V,1.12V.According to HOMO=- (oxidizing potential+4.32) eV can calculate five kinds it is fluorine-containing total
The HOMO energy level of polymers.Its electrochemistry band gap is approximately equal to optical band gap, according to formula LUMO=HOMO+Eg optIt can calculate
Lumo energy.The HOMO and lumo energy numerical value of five kinds of fluorinated copolymers are shown in Table 2.As can be seen from Table 2: with fluorine-containing D2Donor
The increase of content, HOMO energy level constantly decline, therefore the fluorinated copolymer maker being theoretically stepped up with above-mentioned fluorine content
When part, open-circuit voltage can constantly increase.
The HOMO and lumo energy numerical value and optical parameter of 2 fluorinated copolymer of table
| Serial number | HOMOcv/eV | LUMOb/eV | λonest/nm | Eg opt/ev | λmax/nm |
| 4-P1 | -5.17 | -3.59 | 785 | 1.58 | 325,382,514,710 |
| 4-P2 | -5.26 | -3.66 | 775 | 1.60 | 315,385,516,708 |
| 4-P3 | -5.27 | -3.66 | 770 | 1.61 | 318,376,508,695 |
| 4-P4 | -5.31 | -3.69 | 765 | 1.62 | 318,379,509 |
| 4-P5 | -5.44 | -3.83 | 772 | 1.61 | 313,382,510,690 |
The current density voltage curve of fluorinated copolymer 4-P1~4-P5 is measured, as a result as shown in Figure 5.According to fluorine-containing total
The current -voltage curve of polymers obtain in embodiment 6 open-circuit voltage of each solar battery, short circuit current, fill factor with
And energy conversion efficiency；The results are shown in Table 3.As can be seen from Table 3: as fluorine-containing thiophene bithiophene content improves, solar energy
The voltage of battery is all improved, and degree results in HOMO energy level 0 to the introduction between 0.06V, having benefited from fluorine atom
Decline.It is noted herein that 4-P1 and 4-P5 are by single D1Donor and D2Donor synthesis, it is intramolecular mixed
There is no these three fluorinated copolymers of 4-P2~4-P4 are high for random degree.Using 4-P2,4-P3,4-P4 as comparison other, with containing
The D of fluorine2Donor content increases, and downward trend is presented in short circuit current, from 12.40mA/cm2(4-P2) has decreased to 9.41mA/
cm2(4-P4).It may be from increasing in fluorine content, result in the excessive aggregation of phase to which short circuit current presents decline
Trend.And the short circuit current of 4-P5 increases instead, it may be low related with its interior molecules confusion degree.Meet on the whole in donor
D2With on receptor simultaneously introduce fluorine ratio individually in D2Fluorine is introduced on donor can more improve the transfer efficiency of solar battery.
The photovoltaic parameter of five solar batteries in 3 embodiment 6 of table
| Serial number | Short circuit current/mA/cm2 | Open-circuit voltage/V | Fill factor * 100 | Energy conversion efficiency * 100 |
| 4-P1:PC71BM | 7.31±0.22(7.52) | 0.69±0.01(0.70) | 62.2±1.03(63.23) | 3.14±0.18(3.32) |
| 4-P2:PC71BM | 12.1±0.3(12.40) | 0.71±0.01(0.72) | 60.89±1(61.89) | 5.23±0.34(5.57) |
| 4-P3:PC71BM | 10±0.42(10.42) | 0.71±0.01(0.72) | 50.3±0.22(50.52) | 3.57±0.25(3.82) |
| 4-P4:PC71BM | 9.31±0.1(9.41) | 0.72±0.02(0.74) | 51.5±0.7(52.20) | 3.45±0.22(3.67) |
| 4-P5:PC71BM | 11.3±0.13(11.43) | 0.75±0.02(0.77) | 52±0.51(52.51) | 4.41±0.24(4.65) |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of fluorinated copolymer with structure shown in Formulas I,
In Formulas I, R is-C6H13；M and n represents the polymerization ratio that different monomers are shared in entire fluorinated copolymer in fluorinated copolymer
Example；M is [0,1], and n is [0,1], m+n=1.
2. fluorinated copolymer according to claim 1, it is characterised in that: as m=0.3, n=0.7；
As m=0.5, n=0.5；As m=0.7, n=0.3；As m=1, n=0.
3. the preparation method of fluorinated copolymer as claimed in claim 1 or 2, comprising the following steps:
By donor D1, donor D2, receptor and toluene mixing, catalyst is then added and carries out stille coupling reaction, obtains described contain
Fluo-copolymer；
Wherein, the donor D1With structure shown in Formula II, the donor D2With structure shown in formula III, the receptor has formula
Structure shown in IV；
4. preparation method according to claim 3, which is characterized in that the donor D1With donor D2Mole summation with
The ratio of receptor mole is 1:1.
5. preparation method according to claim 3, which is characterized in that the catalyst is Pd2dba3, CuO and P (o-
tolyl)3Mixture.
6. preparation method according to claim 5, which is characterized in that Pd in the catalyst2dba3, CuO and P (o-
tolyl)3Mass ratio be 1:4~10:1~2.
7. the preparation method according to claim 4 or 6, which is characterized in that the amount ratio of the receptor, toluene and catalyst
For 1g:50~100mL:0.2~0.5g.
8. preparation method according to claim 3, which is characterized in that the temperature of the stille coupling reaction be 80~
110 DEG C, the time is 48~96h.
9. the application of fluorinated copolymer as claimed in claim 1 or 2 in solar cells.
10. a kind of solar battery, including the glass/ITO/PEDOT:PSS/Polymer:PC being cascading71BM/Ca/
Al, wherein the Polymer is fluorinated copolymer of any of claims 1 or 2；The Polymer and PC71The weight ratio of BM
For 1:1.2；The effective area of the solar battery is 4mm2。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030790A (en) * | 2012-12-14 | 2013-04-10 | 华南理工大学 | Conjugated polymer containing fluorobenzothiadiazole and preparation method and application thereof |
| WO2015100441A1 (en) * | 2013-12-26 | 2015-07-02 | Raynergy Tek Incorporation | Conjugated polymers and devices incorporating the same |
| CN105885016A (en) * | 2014-12-26 | 2016-08-24 | 宁波大学 | Synthetic method of narrow band gap terpolymer solar cell donor material |
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| CN103030790A (en) * | 2012-12-14 | 2013-04-10 | 华南理工大学 | Conjugated polymer containing fluorobenzothiadiazole and preparation method and application thereof |
| WO2015100441A1 (en) * | 2013-12-26 | 2015-07-02 | Raynergy Tek Incorporation | Conjugated polymers and devices incorporating the same |
| CN105885016A (en) * | 2014-12-26 | 2016-08-24 | 宁波大学 | Synthetic method of narrow band gap terpolymer solar cell donor material |
Non-Patent Citations (2)
| Title |
|---|
| JEA WOONG JO ET AL.: ""Comparison of Two D-A Type Polymers with Each Being Fluorinated on D and A Unit for High Performance Solar Cells"", 《ADV. FUNCT. MATER.》 * |
| ZHE ZHANG ET AL.: ""Enhancing the Efficiency of Polymer Solar Cells by Incorporation of 2,5-Difluorobenzene Units into the Polymer Backbone via Random Copolymerization"", 《ACS APPL. MATER. INTERFACES》 * |
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