CN107964091B - 一种多功能双极性导电聚合物及其制备方法与应用 - Google Patents
一种多功能双极性导电聚合物及其制备方法与应用 Download PDFInfo
- Publication number
- CN107964091B CN107964091B CN201711172634.5A CN201711172634A CN107964091B CN 107964091 B CN107964091 B CN 107964091B CN 201711172634 A CN201711172634 A CN 201711172634A CN 107964091 B CN107964091 B CN 107964091B
- Authority
- CN
- China
- Prior art keywords
- polymer
- conductive polymer
- preparation
- bipolar conductive
- super capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 229920006254 polymer film Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000006254 arylation reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 3
- 239000011449 brick Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 241000282414 Homo sapiens Species 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- GNGACRATGGDKBX-UHFFFAOYSA-N dihydroxyacetone phosphate Chemical compound OCC(=O)COP(O)(O)=O GNGACRATGGDKBX-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 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 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012265 solid product Substances 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 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 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
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- 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
- C08G2261/30—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
- C08G2261/3242—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran
-
- 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
- C08G2261/30—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
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- 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
- C08G2261/30—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
-
- 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
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本申请提供一种多功能双极性导电聚合物及其制备方法与应用。该聚合物可随施加电位不同而实现N型掺杂和P型掺杂，并且可以在中性态、氧化态和还原态产生相应的(绿色‑深灰色‑砖红色)颜色转变。具有稳定性良好、可溶液制备、掺杂‑去掺杂速度快、存储电荷密度高等特点。可以解决现有Ⅲ型聚合物超级电容器材料N型掺杂不稳定，溶解度不佳，较难应用于柔性、大面积超级电容器器件制备及批量生产的问题。同时，该聚合物材料兼具电致变色性能，制得的超级电容器的充放电状态可根据颜色变化判断，是集电致变色与储能性能为一体的新型智能超级电容器，可能将推动新一代能量储存体系的发展，在人类应对能量危机与环境污染之路上发挥巨大作用。
Description
技术领域
本发明涉及有机光电材料器件领域，特别涉及一种多功能双极性导电聚合物及其制备方法与应用。
背景技术
导电聚合物是由具有共扼π-键的高分子经化学或电化学“掺杂”由绝缘体转变为导体的一类高分子材料。自20世纪70年代中期发现导电聚合物以来，在许多科学研究单位内，导电聚合物已成为研究的热门课题。经过不断发展突破，目前最新一代的导电聚合物以D-A聚合物为主。因其性质的多样化，导电聚合物在多重领域都有很好大的应用。良好的导电性和电活性，使导电聚合物成为一类重要的超级电容器电极材料，其电容主要来自于法拉第准电容。电极材料是超级电容器最为关键的部分，也是决定其性能的主要因素，因此开发具有优异性能的电极材料是超级电容器研究中最核心的课题。导电聚合物是一类重要的超级电容器电极材料，在充放电过程中发生氧化和还原反应，在聚合物膜上快速产生N型或P型掺杂，从而使聚合物存储了很高密度的电荷，产生了很大的法拉第赝电容。Ⅲ型聚合物超级电容器(2个电极的电极材料由既可以N型掺杂又可以P型掺杂的双极性导电聚合物构成)在充放电时能充分利用溶液中的阴阳离子，具有类似于蓄电池的放电特征，因此被认为是最有发展前景的超级电容器。对于多数导电聚合物来说，其N型的掺杂往往不稳定。此外，目前大多数D-A聚合物均溶解度不佳，难以应用于柔性、大面积超级电容器器件制备及批量生产。
发明内容
针对上述现存的问题及市场的巨大需求，本发明提供一种多功能双极性导电聚合物，结合双极性与溶解性的D-A聚合物突破Ⅲ型聚合物超级电容器的瓶颈。
本发明解决上述技术问题的方案为，提供一种多功能双极性导电聚合物，其特征在于，其分子结构式通式如下所示：
其中，x＝1，y＝0或者x＝0，y＝1；
D1为
及其衍生物中的一种；
A为
及其衍生物中的一种；
D2为
及其衍生物中的一种，R为-H或-CnH2n+1或-OCnH2n+1，1<n≤50。
在本发明提供的多功能双极性导电聚合物中，所述D2中，-CnH2n+1或-OCnH2n+1为直链或叉链。
本发明还提供该多功能双极性导电聚合物的制备方法，统一表示如图2所示。将D1-A单元与加侧链的D2单元在催化剂的作用下进行直接芳基化聚合，得到所述双极性导电聚合物；
具体地，本制备方法通过对不可溶D-A-D(给体-受体-给体)聚合物一侧的D(给体)进行溶解性改善，由D-A(给体-受体)单元与加侧链的D(给体)单元在催化剂的作用下进行直接芳基化聚合(DHAP)得到双极性导电聚合物。通过给一侧给体单元加不同长度、形状的侧链修饰调节聚合物的溶解性。
本发明还在于保护所述多功能双极性导电聚合物材料在用于制备包括但不限于超级电容器以及电致变色装置的各种装置中的应用；
进一步，本发明还在于保护含有所述多功能双极性导电聚合物材料的器件；
器件优选为聚合物薄膜，所述聚合物薄膜可采用已有技术的任一种成膜方法制备得到，本发明优选成膜方法如下：
将聚合物溶于氯仿/氯苯溶液(氯仿/氯苯体积比＝4:1)，使用喷涂装置(包含但不限于与空气压缩机连接的美工喷笔)喷涂聚合物溶液于镀有ITO或FTO的玻璃表面而形成电致变色薄膜。其中，聚合物的氯仿/氯苯溶液浓度为1mg/mL。
实施本发明，具有如下有益效果：本发明的多功能双极性导电聚合物，使用直接芳基化聚合(DHAP)聚合而得，是通过对不可溶给体-受体-给体(D-A-D)聚合物一侧的给体进行溶解性改善，由给体-受体(D-A)单元与加侧链改善溶解性的给体(D)单元拼接而成的双极性导电聚合物。聚合物薄膜可随施加电位不同而实现N型掺杂和P型掺杂，并且可以在中性态、氧化态和还原态产生相应的(绿色-深灰色-砖红色)颜色转变。具有稳定性良好、可溶液制备、掺杂-去掺杂速度快、存储电荷密度高等特点。可以解决现有Ⅲ型聚合物超级电容器材料N型掺杂不稳定，溶解度不佳，较难应用于柔性、大面积超级电容器器件制备及批量生产的问题。同时，所述材料兼具电致变色性能，制得的超级电容器的充放电状态可根据颜色变化判断，是集电致变色与储能性能为一体的新型智能超级电容器。此类双极性导电聚合物，作为超级电容器电极材料，必将推动新一代能量储存体系的发展，在人类应对能量危机与环境污染之路上发挥巨大作用。
附图说明
图1为本发明所述多功能双极性导电聚合物分子结构式；
图2为本发明所述多功能双极性导电聚合物材料制备方法示意图；
图3为本发明实施例1中所述Pro-BT-ED共聚物分子结构式；
图4为本发明实施例1中所述聚合物薄膜的循环伏安曲线；
图5为本发明实施例1中所述聚合物薄膜的原位吸收光谱；
图6为本发明实施例1中所述聚合物作为超级电容器电极材料在铂单电极上不同扫速下的循环伏安曲线；
图7为本发明实施例1中所述聚合物作为超级电容器电极材料在铂单电极上不同扫速下的面电容。
具体实施方式
下面将结合实施例对本发明内容做具体说明。
实施例1
D1为3,4-乙烯二氧噻吩(ED)，A为苯并噻二唑(BT)，D2为(Pro)，R为-OC6H13；所述聚合物为ED-BT-Pro共聚物，其分子结构式为图3所示，其制备方法如下：
a.将4,7-二溴-2,1,3-苯并噻二唑(1.77g，6.00mmol)与2-(三丁基锡)-3,4-乙烯二氧噻吩(1.73g，6.00mmol)加入甲苯(60.0mL)中，在氮气氛围下搅拌15分钟后，加入四(三苯基膦)钯(0.5mmol，0.35g),在110℃下回流搅拌18小时，待反应完全后，冷却至室温。有机相经旋蒸移除有机溶剂，用柱层析方法取得深黄色固体产物ED-BT-Br(1.07g，产率76％)
b.将步骤a所得产物ED-BT-Br(1.07g，3.00mmol)用N-溴代丁二酰亚胺(NBS)(0.59g，3.3mmol)进行溴化，反应溶剂为二甲基酰胺(DMF)；在室温下反应3小时，反应完全后用水和二氯甲烷萃取，有机相用无水硫酸钠干燥、过滤后，通过在乙醇与氯仿混合溶剂中重结晶得到橙色固体产物Br-ED-BT-Br(1.22g，产率94％)
c.直接芳基化聚合(DHAP)：将步骤b所得产物Br-ED-BT-Br(0.37g,0.85mmol)与Pro(0.40g，0.85mmol)溶于N,N-二甲基乙酰胺(DMAc)(85mL)中，加入醋酸钯(7.85mg，0.035mmol)，特戊酸(25.53mg，0.25mmol)以及碳酸钾(82.9mg，0.6mmol)，通氮气10分钟后，置于140℃下搅拌24小时，反应完全后，将混合物滴入甲醇，过滤得到沉淀物，经索氏提取得到最终产物Pro-BT-ED共聚物。
实施例2：
包含实施例1所述多功能双极性导电聚合物材料Pro-BT-ED共聚物的电致变色器件，优选为喷涂的电致变色薄膜。该电致变色薄膜可在绿色-深灰色-砖红色之间转化。聚合物的起始氧化电位为-0.62V，起始还原电位为-1.45V，最大吸收波长为735nm。
本实施例所述聚合物薄膜在不同扫速下的循环伏安曲线如图4所示，测试的对电极为铂丝，参比电极为银离子电极，此图说明聚合物的起始氧化电位为-0.62V，起始还原电位为-1.45V。
本实施例所述聚合物薄膜的原位吸收光谱如图5所示，图中为从-1.7V至1.1V间不同电压下的吸收光谱，可见薄膜处于中性态时(施加电压-0.1V)最大吸收波长为735nm，随着电压升高，该波长下的吸收减弱，吸收峰逐渐红移，当薄膜处于完全氧化状态时(施加电压1.1V)在1500nm处有最大吸收。随着电压降低，吸收峰逐渐蓝移，当薄膜处于完全还原状态时(施加电压-1.7V)在455nm处有最大吸收。这一系列的变化与薄膜的颜色变化可对应起来。中性态的吸收光谱截止波长为1107.1nm，计算得其带隙为1.12eV。
实施例3
包含实施例1所述多功能双极性导电聚合物材料Pro-BT-ED共聚物的超级电容器，此例中采用的为将所述电极喷涂在铂电极制成的超级的电容器。
本实施例所述聚合物薄膜在铂单电极上，不同扫速下的循环伏安曲线如图6所示，测试的对电极为铂丝，参比电极为银/银离子电极。可见薄膜具有良好的双极性，N-型掺杂和P-型掺杂均可逆。并且有较低的起始氧化电位(-0.62V)，较宽的电位窗口(-2.0V至1.0V)。
本实施例所述聚合物薄膜在铂单电极上的面电容如图7所示。
本发明的导电聚合物，除了作为超级电容器的电极材料之外，也是一类重要的有机电致变色材料，这类材料具有较高的比容量、良好的导电性和柔性，且分子结构多样可调易得到丰富多彩的颜色。一种兼具储能与变色性能的双极性可溶D-A聚合物材料及其制备的新型智能超级电容器，必将极大改善打破阻碍现有超级电容器发展的制约。
以上实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
Claims (7)
1.一种多功能双极性导电聚合物，其特征在于，其分子结构式通式如下所示：
其中，x＝1，y＝0或者x＝0，y＝1；
D1为
A为
D2为
R为-CmH2m+1或-OCmH2m+1，1<m≤50。
2.根据权利要求1中所述的多功能双极性导电聚合物，其特征在于，所述D2中，-CmH2m+1或-OCmH2m+1为直链或叉链。
3.一种多功能双极性导电聚合物的制备方法，其特征在于，将D1-A单元与加侧链的D2单元在催化剂的作用下进行直接芳基化聚合，得到所述双极性导电聚合物，反应式如下：
其中，x＝1，y＝0或者x＝0，y＝1；
D1为
A为
D2为
R为-CmH2m+1或-OCmH2m+1，1<m≤50。
4.权利要求1-2中任意一项所述的多功能双极性导电聚合物，或者权利要求3制备得到的多功能双极性导电聚合物，在用于制备超级电容器中的应用。
5.权利要求1-2中任意一项所述的多功能双极性导电聚合物，或者权利要求3制备得到的多功能双极性导电聚合物，在用于制备电致变色装置中的应用。
6.含有权利要求1-2中任意一项所述的多功能双极性导电聚合物或者权利要求3制备得到的多功能双极性导电聚合物的器件。
7.根据权利要求6所述的器件，其特征在于，所述器件为聚合物薄膜。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711172634.5A CN107964091B (zh) | 2017-11-22 | 2017-11-22 | 一种多功能双极性导电聚合物及其制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711172634.5A CN107964091B (zh) | 2017-11-22 | 2017-11-22 | 一种多功能双极性导电聚合物及其制备方法与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107964091A CN107964091A (zh) | 2018-04-27 |
| CN107964091B true CN107964091B (zh) | 2020-05-19 |
Family
ID=62001419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711172634.5A Active CN107964091B (zh) | 2017-11-22 | 2017-11-22 | 一种多功能双极性导电聚合物及其制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107964091B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115167050B (zh) * | 2022-07-07 | 2024-05-28 | 北京工业大学 | 基于新型变色材料的丛林野战伪装可穿戴显示系统 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450878A (zh) * | 2012-05-29 | 2013-12-18 | 海洋王照明科技股份有限公司 | 双极性共聚物发光材料、其制备方法及应用 |
-
2017
- 2017-11-22 CN CN201711172634.5A patent/CN107964091B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450878A (zh) * | 2012-05-29 | 2013-12-18 | 海洋王照明科技股份有限公司 | 双极性共聚物发光材料、其制备方法及应用 |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and characterization of aromatic polyoxadiazoles containing 3,4-alkylenedioxythiophenes";Uma P.Ojha et al.;《Synthetic Metals》;20131231;第132卷;第279-283页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107964091A (zh) | 2018-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ju et al. | Synthesis and electrochemical capacitive performance of thieno [3, 4-b] pyrazine-based Donor-Acceptor type copolymers used as supercapacitor electrode material | |
| Sun et al. | Solution-processable, hypercrosslinked polymer via post-crosslinking for electrochromic supercapacitor with outstanding electrochemical stability | |
| Yao et al. | Flexible conjugated polyfurans for bifunctional electrochromic energy storage application | |
| Zhu et al. | Electropolymerization of DAD type monomers consisting of thiophene and quionaxline moieties for electrochromic devices and supercapacitors | |
| Chen et al. | Electropolymerization of DA type EDOT-based monomers consisting of camphor substituted quinoxaline unit for electrochromism with enhanced performance | |
| Zhang et al. | A conjugated polymer with Electron-withdrawing cyano group enables for flexible asymmetric electrochromic supercapacitors | |
| Mo et al. | Alkyl functionalized bithiophene end-capped with 3, 4-ethylenedioxythiophene units: synthesis, electropolymerization and the capacitive properties of their polymers | |
| KR20100061838A (ko) | 셀레노펜 및 셀레노펜계 폴리머, 그의 제조 방법 및 용도 | |
| Wang et al. | One-step electropolymerized thieno [3, 2-b] thiophene-based bifunctional electrode with controlled color conversion for electrochromic energy storage application | |
| Chu et al. | Synthesis and electrochromic properties of cross-linked and soluble conjugated polymers based on 5, 8, 14, 17-tetrabromoquinoxaline [2′, 3': 9, 10] phenanthro [4, 5-abc] phenazine as the multifunctionalized acceptor unit | |
| CN114907551B (zh) | 一种红色电致变色聚合物、制备方法、薄膜及器件 | |
| Xue et al. | Effects on optoelectronic performances of EDOT end-capped oligomers and electrochromic polymers by varying thienothiophene cores | |
| Niu et al. | Supercapacitor properties of nanowire poly ((3, 4-dihydro-2H-thieno [3, 4-b][1, 4] dioxepin-3-yl) methanol) free-supporting films | |
| CN107964091B (zh) | 一种多功能双极性导电聚合物及其制备方法与应用 | |
| CN111323980B (zh) | 一种二氧化钛/聚三[2-(4-噻吩)苯]胺复合薄膜的制备方法和应用 | |
| Yiğit et al. | Capacitive properties of novel N-alkyl substituted poly (3, 6-dithienyl-9H-carbazole) s as redox electrode materials and their symmetric micro-supercapacitor applications | |
| Pan et al. | Electropolymerization of DA type monomers consisting of mono-triphenylamine moiety for electrochromic devices and supercapacitors | |
| CN107674183B (zh) | 含萘[1,2-c；5,6-c]二[1,2,5]噻二唑的共轭聚合物及制备方法和应用 | |
| CN108003329B (zh) | 一种多功能双极性导电聚合物及其制备方法与应用 | |
| Lin et al. | Star-shaped trithiophene and hexathiophene functionalized truxenes: synthesis, electropolymerization, and electrochromism | |
| Tao et al. | Molecular engineering of novel DA conjugated polymers for electrochromic energy storage devices toward enhanced performance | |
| CN109053675B (zh) | 一种苯-甲基-二联噻吩衍生物及其制备方法与应用 | |
| CN108840993B (zh) | 一种d-a-d′非对称结构的聚合膜pewt及其制备方法与应用 | |
| CN108538646B (zh) | 一种纳米花状聚吡咯氧化锰复合材料的制备方法及应用 | |
| Shao et al. | Liquid/liquid interfacial cross-linking reaction of conjugated polymer prepared cross-linked films with improved electrochromic and capacitance properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |