Polymer electrolytic capacitor comprising solution processed n-type conductive polymer

Abstract

The present invention relates to a polymer electrolytic capacitor comprising an anode, a dielectric layer and a cathode wherein the cathode comprises a solution processed n-type conductive polymer.

Description

TECHNICAL FIELD

[0001] The present invention relates to a polymer electrolytic capacitor comprising a solution-processed n-type conductive polymer and a method for manufacturing a water-based n-type conductive polymer for use in such devices. BACKGROUND

[0002] Water-based conductive polymer inks have a wide range of industrial applications such as antistatic coatings, polymer electrolytic capacitors, organic solar cells, displays (LCD / OLED) and printed electronics. PEDOT:PSS is a commercially available p-type (hole transport) water-based conductive polymer ink with an intrinsic conductivity of >1 S cm -1 and values of >4000 S cm -1 after secondary doping or post-processing. However, water-based n-type (electron transport type) conductive polymers are of paramount importance when considering complementary components in semiconductor devices and circuits.

[0003] The BBL:PEI ethanol-based inks reported in WO 2022 / 106017 and WO 2022 / 106018 are the first step towards environmentally friendly solvent n-type inks. However, there are several issues that partially limit their application. First, ethanol has strict requirements for fire protection during production, transportation, storage and use. In addition, due to the large particle size, the inks disclosed in the above cited applications are mainly limited to deposition methods (such as spray casting, spin casting, etc.). As can be seen from the above cited references, the highest conductivity of the BBL:PEI inks is below 10 S cm -1 which makes them unsuitable for devices sensitive to sheet resistance.

[0004] Recently, Fei Huang et al. reported a solution-processed n-type conductive polymer poly(benzodifuran dione) (PBFDO) with an electrical conductivity exceeding 2000 S / cm (Nature, 2022, s41586-022-05295-8).

[0005] Developing a water-based n-type CP ink with high conductivity, processability and stability comparable to PEDOT:PSS is still a challenging scientific and industrial effort with a wide impact in low-cost printed organic electronics.

[0006] Polymer electrolytic capacitors are electrolytic capacitors (e-caps) with a solid conductive polymer electrolyte. There are four different types: polymer tantalum electrolytic capacitors (polymer Ta-e-caps), polymer aluminum electrolytic capacitors (polymer Al-e-caps), hybrid polymer capacitors (hybrid polymer Al-e-caps), and polymer niobium electrolytic capacitors.

[0007] Polymer Ta-e-caps are available in rectangular surface mount device (SMD) chip style. Polymer Al-e-caps and hybrid polymer Al-e-caps are available in rectangular SMD chip style, cylindrical SMD (V-chip) style, or as a radial lead type (single-ended) version.

[0008] Polymer electrolytic capacitors are characterized by particularly low internal equivalent series resistance (ESR) and high ripple current ratings. Their electrical parameters have similar temperature dependence, reliability, and useful life compared to solid tantalum capacitors, but have much better temperature dependence and significantly longer useful life compared to aluminum electrolytic capacitors with non-solid electrolytes. Typically, polymer e-caps have higher leakage current ratings than other solid or non-solid electrolytic capacitors.

[0009] Polymer electrolytic capacitors are also available in hybrid construction. Hybrid polymer aluminum electrolytic capacitors combine a solid polymer electrolyte with a liquid electrolyte. These types are characterized by low ESR values, but have low leakage current and are not sensitive to transients, however they have similar temperature-dependent useful life as non-solid e-caps.

[0010] Polymer electrolytic capacitors are used primarily as buffer, bypass, and decoupling capacitors in power supplies for integrated electronic circuits, especially in devices with flat or compact design. Therefore, they compete with MLCC capacitors, but offer higher capacitance values than MLCCs, and they do not exhibit the microphonic effect (such as 2nd and 3rd ceramic capacitors).

[0011] The most important electrical property of the electrolyte in electrolytic capacitors is its electrical conductivity. The electrolyte forms the counter electrode (cathode) of the e-cap. The benefit provided by solid polymer electrolytes is significantly lower ESR of the capacitor and low temperature dependence of the electrical parameters.

[0012] Currently available polymer electrolytes are made from precursors that consist of very small building materials that are able to penetrate even the smallest pores. The size of such precursors is a limiting factor for the size of the pores in etched aluminum anode foils or the size of the tantalum powder. For capacitor manufacturing, the polymerization rate has to be controlled. Too fast polymerization does not lead to complete anode coverage, while too slow polymerization increases production costs. Neither the precursors, the polymers, nor their residues chemically or mechanically attack the anodic oxide. Polymer electrolytes have to be highly stable over a wide temperature range for a long time. Currently available polymer e-caps employ polypyrrole (PPy) or polythiophene (PEDOT). However, capacitors containing these polymers have the disadvantage of poor thermal stability. The daily use temperature of supercapacitors used in fields such as autonomous driving can be higher than 170°C. Even in airless packaging, the electrical conductivity of conventional conductive polymers decreases at such temperatures.

[0013] Therefore, there is a need for a polymer electrolytic capacitor comprising a solution-processed, preferably water-based n-type CP ink with high electrical conductivity, processability, and stability. SUMMARY

[0014] In view of the above, the present invention aims to solve the problems of the prior art. To this end, the present invention relates to a polymer electrolytic capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-processed n-type conductive polymer.

[0015] The anode can be tantalum (Ta) in the form of high purity sintered tantalum powder with tantalum pentoxide (Ta2O5) as dielectric.

[0016] Alternatively, the anode can be aluminum (Al) in the form of high purity and electrochemically etched (roughened) aluminum foil with aluminum oxide (Al2O3) as dielectric.

[0017] The solution-processed n-type conductive polymer can be poly(benzodifuran dione) (PBFDO).

[0018] The polymer electrolytic capacitor can be in the form of a rectangular SMD chip, usually molded with a plastic case, with sintered tantalum anode or stacked aluminum anode foil as an option.

[0019] Alternatively, the polymer electrolytic capacitor can be in the form of a cylinder.

[0020] The polymer electrolytic capacitor can be encapsulated by, for example, a resin. The encapsulation prevents air contact and thereby improves the stability of the capacitor.

[0021] The solution-processed n-type conductive polymer used in the polymer electrolytic capacitor according to the present application can be manufactured from an ink comprising the solution-processed n-type conductive polymer and a solvent system. The solvent system can comprise a polar aprotic solvent and / or a polar protic solvent.

[0022] In particular, the polar aprotic solvent can be selected from DMF, DMSO and combinations thereof. The polar protic solvent can be selected from water, ethanol, propanol, butanol and combinations thereof.

[0023] The ink can be applied to the polymer electrolytic capacitor by dip coating.

[0024] It has to be mentioned that the polymer electrolytic capacitor according to the present application shows a remarkable thermal stability of up to 200 °C.

[0025] In a particular embodiment, the solution-processed n-type conductive polymer for use in a polymer electrolytic capacitor can be manufactured by a method comprising the steps of:

[0026] a) adding a monomer to a solvent system comprising water in the presence of a catalyst, thereby providing a reaction solution;

[0027] b) allowing the monomer to polymerize in the reaction solution, thereby obtaining a n-type conductive polymer solution;

[0028] c) post-treating the n-type conductive polymer solution, thereby obtaining a n-type conductive polymer soluble in water.

[0029] The monomer has a centrosymmetric benzene ring as backbone, a reactive hydrogen and at least one electron withdrawing group at the benzylic position. The electron withdrawing group can be a carbonyl group, a carboxyl group, an amide, an alkoxyacyl group, etc.

[0030]

[0031] Further, the monomer can be in the form of a heterocyclic moiety having a centrosymmetric benzene ring fused to at least one, preferably at least two, rings, preferably five-membered rings. The monomer further comprises a reactive hydrogen and at least one electron withdrawing group at the benzylic position. In particular, the monomer can be 3,7-dihydrobenzo[l,2-b:4,5-b']difuran-2,6-dione (HBFDO), 5,7-dihydropyrrolo[2,3-f]indol-2,6(lH,3H)-dione, or 3,7-dihydrobenzo[l,2-b:4,5-b']dithiophene-2,6-dione.

[0032]

[0033] In particular, the monomer can be 3,7-dihydrobenzo[l,2-b:4,5-b]difuran-2,6-dione (HBFDO). In such embodiments, the n-type conductive polymer is poly(benzodifuranedione) (PBFDO). The general overview of the method of the present invention can be summarized as follows:

[0034]

[0035] where TMQ or AQ is the catalyst, as follows.

[0036]

[0037] According to a first embodiment, the solvent system consists of water. In other words, the solvent system comprises essentially only water, for example at least 99 vol% water. Such embodiments provide the advantage of a cost-effective and environmentally friendly manufacturing method.

[0038] In embodiments wherein the solvent system consists of water, the method further comprises the following step:

[0039] a') adding a base to the reaction solution.

[0040] Step a') can be performed during step a) or immediately after step a). In other words, the base can be added to the reaction solution together with the monomer and the catalyst, or the base is added immediately after the addition of the monomer and the catalyst.

[0041] Further, the method can further comprise the following step:

[0042] a") adding a surfactant to the reaction solution.

[0043] Step a') can be performed during step a) or immediately after step a). In other words, the surfactant can be added to the reaction solution together with the monomer and the catalyst, or the surfactant is added immediately after the addition of the monomer and the catalyst. In addition, step a") can be performed immediately before step a'), immediately after step a') or simultaneously with step a').

[0044] As can be understood from the above, the surfactant is not essential for the method according to the first embodiment. However, if the polymer is intended for rotational casting, the surfactant has to be added.

[0045] According to the first embodiment, the catalyst can be an alkyl and carboxyl substituted benzoquinone (AQ). Such a catalyst can be selected from the group consisting of 3-(2,4,5-trimethyl-3,6-dioxocyclohexa-l,4-dien-l-yl)propanoic acid (AMMMQ, R 0 = R 1 = R3 =Me), 3,3'-(4,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,2-diyl)dipropionic acid (AAMMQ, R) 0 =R 1 =Me,R 3 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me), 3,3'-(2,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,4-diyl)dipropionic acid (AMAMQ, R 1 =R 3 =Me,R 0 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me) and their combinations.

[0046] The catalyst can be easily separated, recovered, and recycled for further polymerization of PBFDO, as shown in the following scheme.

[0047]

[0048] AQ can be synthesized via Michael addition followed by oxidation with N-bromosuccinimide (NBS), as described in more detail below. AQ is a highly crystalline organic acid insoluble in water. However, when neutralized with a strong base, AQ is converted into the highly water-soluble [AQ]. - When the solvent system consists of water, [AQ] - The water-insoluble HBFDO monomer can be polymerized into water-soluble PBFDO in the presence of a surfactant. Notably, after polymerization, the aqueous solution becomes strongly acidic, and [AQ]... - The ink will be converted into water-insoluble AHQ and AQ, which can be separated from PBFDO ink by simple suction filtration. A mixture of AHQ and AQ can be converted back to pure AQ through gentle oxidation. Therefore, AQ is easily recyclable, thus offering the advantages of high cost-effectiveness and low environmental impact.

[0049] According to a first embodiment of the present invention, the base may be MOH, wherein M is selected from Li + Na + K + Me4N + Bu4N + Or a combination thereof.

[0050] The surfactant can be selected from polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium polystyrene sulfonate (PSSNa), poly(styrene sulfonate) acid (PSSH), sodium dodecylbenzene sulfonate (DBSNa), polyquaternium-4 (PQ-4), polyquaternium-10 (PQ-10), polydiallyl dimethyl ammonium chloride (PDADMAC), and polydiallyl diethyl ammonium chloride (PDADEAC). 20. 80, κ-carrageenan, PEG-PPG-PEG, polyoxyethylene (10) tridecyl ether, Triton TM X-100 or a combination thereof.

[0051]

[0052] PBFDO, dissolved in DMSO and obtained using the polymerization method reported by Huang et al., precipitated upon the addition of water to the DMSO solution. In other words, PBFDO polymerized in DMSO was insoluble in water, even in the presence of surfactants such as polyethylene glycol (PEG). The inventors unexpectedly discovered that initial polymerization in water in the presence of AQ and alkali promoted the formation of water-soluble PBFDO micelles, which were further stabilized by the addition of surfactants.

[0053] According to a second embodiment of the present invention, the solvent system may contain a polar aprotic solvent. In such an embodiment, the method further includes the following steps:

[0054] d) Solvent exchange, which removes the polar aprotic solvent.

[0055] The polar aprotic solvent can be dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), or a combination thereof. The ratio between water and the polar aprotic solvent can be from 5:95 to 95:5, preferably from 40:60 to 60:40.

[0056] According to a second embodiment of the present invention (i.e., wherein the solvent system comprises a polar aprotic solvent), the catalyst may be a quinone oxidant selected from tetramethylbenzoquinone (TMQ), alkyl-substituted benzoquinone and carboxyl-substituted benzoquinone (AQ), or combinations thereof.

[0057] The inventors have unexpectedly discovered that polymerization in a solvent system containing water and a polar aprotic solvent promotes the formation of water-soluble PBFDO micelles, which can be further stabilized by adding surfactants, for example as described above. It should be noted that, according to a second embodiment of the invention, a surfactant is not necessary. If used, the surfactant can be added during step d).

[0058] Even after complete removal of the polar aprotic solvent, PBFDO micelles remain soluble in water.

[0059] The polymerization step, i.e., step b), can occur at temperatures ranging from 20°C to 150°C. In particular, [AQ]- exhibits significantly stronger catalytic activity compared to TMQ. According to a second embodiment of the invention (i.e., where the solvent system comprises a polar aprotic solvent), [AQ]- can catalyze the polymerization of HBFDO to PBFDO at room temperature, which is a significant advantage in terms of cost efficiency.

[0060] As described above, the method of the present invention may further include the following steps:

[0061] c') The catalyst is removed by filtration and oxidation and then recycled.

[0062] Finally, the method of the present invention may include additional steps, such as post-treatment and purification steps. Such steps may also be performed in water.

[0063] The present invention further relates to a water-soluble n-type conductive polymer obtained by the above method. This polymer can exist in the form of micelles with a diameter less than 200 nm. The particle size can be easily verified by filtering the polymer solution through a 20 μm filter; therefore, the solution remains colored, indicating that the polymer micelles have passed through the filter.

[0064] Furthermore, the present invention relates to a water-based ink comprising the water-soluble n-type conductive polymer as described above.

[0065] Therefore, the n-type conductive ink of the present invention can be spin-coated or drop-cast in air and at ambient temperature to form a film with a thickness of 1 nm to 1 cm, more preferably 10 nm to 10 μm. Such a film can exhibit a conductivity on the order of 5 S / cm. Attached Figure Description

[0066] Embodiments of the present invention will now be described by way of example with reference to the accompanying drawings, wherein:

[0067] Figure 1 Schematic diagrams of different embodiments of the polymer electrolytic capacitor according to the present invention are shown;

[0068] Figure 2, 3a And 3b shows Figure 1 Perspective view and cross-section of a polymer electrolytic capacitor depicted in the image;

[0069] Figure 4 The conductivity change of the polymer electrode during annealing in nitrogen at 200 °C was depicted;

[0070] Figure 5 The figure illustrates the change in conductivity of a polymer electrode during annealing in air at 200°C, wherein the capacitor includes a resin encapsulation.

[0071] Figure 6 The conductivity change of the polymer electrode during annealing in nitrogen at 300°C is shown.

[0072] Figure 7 The conductivity changes of polymer inks stored in air were depicted;

[0073] Figures 8-9 The steps of a method for manufacturing a water-based n-type conductive polymer for use in a polymer electrolytic capacitor according to the invention are described. Detailed Implementation

[0074] As described above, the present invention provides a polymer electrolytic capacitor comprising an anode, a dielectric layer and a cathode, wherein the cathode comprises a solution-processed n-type conductive polymer.

[0075] exist Figure 1 In the illustrated embodiments, different types of polymer electrolytic capacitors are shown from left to right: polymer aluminum electrolytic capacitors (polymer Al-e-cap), polymer tantalum electrolytic capacitors (polymer Ta-e-cap), and hybrid polymer capacitors (hybrid polymer Al-e-cap). Additionally, Figure 2 a shows a perspective view and a cross-sectional view of the polymer Al-e-cap. Similarly, Figure 3a Perspective and cross-sectional views of the polymer Ta-e-cap are shown. Figure 3b Perspective and cross-sectional views of the hybrid polymer Al-e-cap are shown.

[0076] As in Figure 2 As can be seen in the image, a polymer electrolytic capacitor 10 is depicted. The capacitor 10 includes two terminals 1 and 1', a silver paste layer 2, and an encapsulation layer 3 in the form of molded resin. In a vertical cross-sectional view, an aluminum foil 4 acts as the anode, an aluminum oxide layer 5 acts as the dielectric, and a polymer layer 6 containing a solution-processed n-type conductive polymer acts as the cathode.

[0077] Figure 3aAnother embodiment of a rectangular capacitor 210 is depicted, which has a tantalum anode 204, a tantalum pentoxide dielectric 205, a cathode layer 206 comprising a solution-processed n-type conductive polymer, and a silver paste layer 202. (See also...) Figure 3a As can be seen, capacitor 210 includes an encapsulation layer 203 in the form of molded resin.

[0078] at last, Figure 3b The illustration shows a polymer electrolytic capacitor 310 having a cylindrical shape and including an aluminum anode 304, an alumina dielectric 305, a separator 312, and a hybrid cathode 306 comprising a solution-processed n-type conductive polymer and an electrolyte and impregnating the separator 312.

[0079] Figure 4 The conductivity change of the polymer electrode during annealing in nitrogen at 200°C was depicted. As can be seen, the capacitor of the present invention exhibits excellent thermal stability, with almost unchanged conductivity even after 8 hours.

[0080] Capacitors, including those encapsulated in resin, can be annealed in air with good results. For example, in... Figure 5 As can be seen, the conductivity only decreased slightly after 6 hours of annealing in air at 200°C.

[0081] When the annealing temperature is increased to 300℃, the thermal stability is impaired, and the electrical conductivity decreases significantly after 2 hours in a nitrogen atmosphere.

[0082] The ink containing a solution-processed n-type conductive polymer used in the polymer electrolytic capacitor of the present invention exhibits excellent storage stability, as shown in... Figure 7 As can be seen in the text.

[0083] like Figure 8 and 9 As shown, the water-based n-type conductive polymer used in polymer electrolytic capacitors can be manufactured by a method comprising the following steps:

[0084] a) Adding the monomer to a solvent system containing water in the presence of a catalyst to provide a reaction solution;

[0085] b) Allow the monomer to polymerize in the reaction solution to obtain an n-type conductive polymer solution;

[0086] c) Post-process the n-type conductive polymer solution to obtain a water-soluble n-type conductive polymer.

[0087] The monomer is 3,7-dihydrobenzo[1,2-b:4,5-b]difuran-2,6-dione (HBFDO). In such embodiments, the n-type conductive polymer is poly(benzodifuran-dione) (PBFDO). A general overview of the method of the present invention can be summarized as follows:

[0088]

[0089] TMQ or AQ is a catalyst, as shown below.

[0090]

[0091] According to such Figure 8 In the first embodiment shown, the solvent system consists of water. In other words, the solvent system contains essentially only water, for example, at least 99 vol% water. Such an embodiment offers the advantage of a cost-effective and environmentally friendly manufacturing method.

[0092] In embodiments where the solvent system comprises water, the method further includes the following steps:

[0093] a') Add alkali to the reaction solution.

[0094] Step a') can be performed during step a) or immediately after step a). In other words, the base can be added to the reaction solution along with the monomer and catalyst, or the base can be added immediately after the monomer and catalyst are added.

[0095] also, Figure 8 The method shown further includes the following steps:

[0096] a) Add a surfactant to the reaction solution.

[0097] Step a') can be performed during step a) or immediately after step a). In other words, the surfactant can be added to the reaction solution together with the monomer and catalyst, or the surfactant can be added immediately after the monomer and catalyst. Alternatively, step a”) can be performed exactly before step a'), immediately after step a'), or simultaneously with step a').

[0098] As can be understood from the above, a surfactant is not required for the method according to the first embodiment. However, if the polymer is intended for use in spin casting, a surfactant must be added.

[0099] According to the first embodiment, the catalyst can be an alkyl- and carboxyl-substituted benzoquinone (AQ). Such a catalyst can be selected from the group consisting of: 3-(2,4,5-trimethyl-3,6-dioxocyclohexyl-1,4-dien-1-yl)propionic acid (AMMMQ, R0 =R 1 =R 3 =Me), 3,3'-(4,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,2-diyl)dipropionic acid (AAMMQ, R) 0 =R 1 =Me,R 3 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me), 3,3'-(2,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,4-diyl)dipropionic acid (AMAMQ, R 1 =R 3 =Me,R 0 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me) and their combinations.

[0100] According to a first embodiment of the present invention, the base may be MOH, wherein M is selected from Li + Na + K + Me4N + Bu4N + Or a combination thereof.

[0101] The surfactant can be selected from polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium polystyrene sulfonate (PSSNa), poly(styrene sulfonate) acid (PSSH), sodium dodecylbenzene sulfonate (DBSNa), polyquaternium-4 (PQ-4), polyquaternium-10 (PQ-10), polydiallyl dimethyl ammonium chloride (PDADMAC), and polydiallyl diethyl ammonium chloride (PDADEAC). 20. 80, κ-carrageenan, PEG-PPG-PEG, polyoxyethylene (10) tridecyl ether, Triton TM X-100 or a combination thereof.

[0102]

[0103] PBFDO, dissolved in DMSO and obtained using the polymerization method reported by Huang et al., precipitated upon the addition of water to the DMSO solution. In other words, PBFDO polymerized in DMSO was insoluble in water, even in the presence of surfactants such as polyethylene glycol (PEG). The inventors unexpectedly discovered that initial polymerization in water in the presence of AQ and alkali promoted the formation of water-soluble PBFDO micelles, which were further stabilized by the addition of surfactants.

[0104] According to the present invention Figure 7 In the second embodiment shown, the solvent system may contain a polar aprotic solvent, such as DMSO. In such an embodiment, the method further includes the following steps:

[0105] d) Solvent exchange, which removes the polar aprotic solvent.

[0106] The ratio between water and polar aprotic solvent can be from 5:95 to 95:5, preferably from 40:60 to 60:40.

[0107] According to a second embodiment of the present invention (i.e., wherein the solvent system comprises a polar aprotic solvent), the catalyst may be a quinone oxidant selected from tetramethylbenzoquinone (TMQ), alkyl-substituted benzoquinone and carboxyl-substituted benzoquinone (AQ), or combinations thereof.

[0108] The inventors have unexpectedly discovered that polymerization in a solvent system containing water and a polar aprotic solvent promotes the formation of water-soluble PBFDO micelles, which can be further stabilized by adding surfactants, for example as described above. It should be noted that, according to a second embodiment of the invention, a surfactant is not necessary. If used, the surfactant can be added during step d).

[0109] Even after complete removal of the polar aprotic solvent, PBFDO micelles remain soluble in water.

[0110] The polymerization step, i.e., step b), can occur at temperatures ranging from 20°C to 150°C. In particular, [AQ]- exhibits significantly stronger catalytic activity compared to TMQ. According to a second embodiment of the invention (i.e., where the solvent system comprises a polar aprotic solvent), [AQ]- can catalyze the polymerization of HBFDO to PBFDO at room temperature, which is a significant advantage in terms of cost efficiency.

[0111] As described above, the method of the present invention may further include the following steps:

[0112] c') The catalyst is removed by filtration and oxidation and then recycled.

[0113] Finally, the method of the present invention may include additional steps, such as post-treatment and purification steps. Such steps may also be performed in water.

[0114] According to the first embodiment, the catalyst can be an alkyl- and carboxyl-substituted benzoquinone (AQ). Such a catalyst can be selected from the group consisting of: 3-(2,4,5-trimethyl-3,6-dioxocyclohexyl-1,4-dien-1-yl)propionic acid (AMMMQ, R 0 =R 1 =R 3 =Me), 3,3'-(4,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,2-diyl)dipropionic acid (AAMMQ, R) 0 =R 1 =Me,R 3 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me), 3,3'-(2,5-dimethyl-3,6-dioxocyclohex-1,4-diene-1,4-diyl)dipropionic acid (AMAMQ, R 1 =R 3 =Me,R 0 =-CH2R 4 R 5 COOH, R 4 R 5 =H or Me) and their combinations.

[0115] According to a specific embodiment of the present invention, the catalyst can be synthesized as follows: Methanesulfonic acid (10 mL) was heated to 70 °C in an oil bath, and 2,3,5-trimethylbenzene-1,4-diol (1 g, 6.57 mmol) and tert-butyl acrylate (1.09 mL, 7.42 mmol) were added with stirring. The reaction was continued at 70 °C for 90 min, and then the mixture was diluted to 100 mL of water and extracted three times with ethyl acetate. The extract was washed with water, saturated NaHCO3, and saturated NaCl and dried (Na2SO4). The solvent was removed by rotary evaporator. The residue was purified by silica gel chromatography to provide pure solid lactone 3MCQ (0.81 g, 60% yield). A solution of NBS (1.63 g, 9.16 mmol) in 18 mL of acetonitrile was added dropwise to a solution of lactone 3MCQ (1.8 g, 8.73 mmol) in 90 mL of 10% aqueous acetonitrile. The reaction mixture was stirred at 25 °C for 1 h, and the solvent was removed by rotary evaporator. The residue was diluted with water and extracted with several portions of ether. The combined ether extracts were washed with water and brine and dried (using Na2SO4). The solvent was removed and crystallized (acetone-hexane) to give 1.5 g of product AMMMQ (80% yield).

[0116]

[0117] Water-soluble PBFDO micelles were synthesized as follows. NaOH (0.42 ml, 0.5 M) was added to a suspension of catalyst AMMMQ (46.75 mg, 0.21 mmol) in 1.6 ml of water, and the suspension turned into a bright yellow solution after stirring for 10 min. Then, surfactant PDADMAC (100 mg, 0.63 mmol) and monomer HBFDO (40 mg, 0.21 mmol) were added to the reaction mixture and stirred overnight at 100 °C. The catalyst was separated by filtration, and the filtrate PBFDO-water solution was transferred to a dialysis bag and dialyzed in deionized water for 2 days to remove oligomers, thus obtaining PBFDO-water ink. PBFDO-water ink can be diluted or concentrated to 1-50 mg / mL by centrifugal dialysis for use in spin casting, drop casting, and other thin film processing methods.

[0118] The catalyst was recycled as follows. A solution of FeCl3·6H2O (215 mg, 0.8 mmol) in 1 mL H2O was added to the separated AMMMQ / AMMMHQ (45 mg, 0.2 mmol, 95% recovery) in 5 mL acetonitrile:H2O (1:1). The reaction mixture was stirred at room temperature for 10 min and diluted with water, followed by extraction with several fractions of ether. The combined ether extracts were washed with water and brine and dried (Na2SO4). The solvent was removed and crystallization (acetone-hexane) yielded 41 mg (92% yield) of the catalyst AMMMQ.

[0119] Using the AQ described above, the inventors have provided the world's first example of an n-type conductive polymer polymerized in pure water. According to the method of the invention, a PBFDO water-based ink with a micelle size of 120 nm has been manufactured. The PBFDO water-based ink, exhibiting similarly excellent solution processing properties, can be spin-cast and drop-cast in air to achieve a film conductivity exceeding 50 S / cm.

[0120] Although the invention has been described with reference to various embodiments, those skilled in the art will recognize that changes can be made without departing from the scope of the invention. The detailed description is intended to be illustrative and the appended claims, including all equivalents, are intended to define the scope of the invention.

Claims

1. A polymer electrolytic capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-processed n-type conductive polymer.

2. The polymer electrolytic capacitor according to claim 1, wherein, The anode is tantalum (Ta), and the dielectric layer is tantalum oxide (Ta2O5).

3. The polymer electrolytic capacitor according to claim 1, wherein, The anode is aluminum (Al), and the dielectric layer is tantalum oxide (Al2O3).

4. The polymer electrolytic capacitor according to any one of the preceding claims, wherein, The n-type conductive polymer used in the solution processing is poly(benzodifurandione) (PBFDO).

5. The polymer electrolytic capacitor according to any one of the preceding claims, wherein, The polymer electrolytic capacitor is in the form of a rectangular SMD chip.

6. The polymer electrolytic capacitor according to any one of claims 1-4, wherein, The polymer electrolytic capacitor is in the form of a cylinder.

7. The polymer electrolytic capacitor according to any one of the preceding claims, wherein, The polymer electrolytic capacitor is encapsulated.

8. The polymer electrolytic capacitor according to any one of the preceding claims, wherein, The solution-processed n-type conductive polymer is manufactured from an ink comprising the solution-processed n-type conductive polymer and a solvent system.

9. The polymer electrolytic capacitor according to claim 8, wherein, The solvent system comprises a polar aprotic solvent and / or polar protic water.

10. The polymer electrolytic capacitor according to claim 9, wherein, The polar aprotic solvent is selected from DMF, DMSO, and combinations thereof.

11. The polymer electrolytic capacitor according to claim 9 or 10, wherein, The polar protic solvent is selected from water, ethanol, propanol, butanol, and combinations thereof.

12. The polymer electrolytic capacitor according to any one of claims 8-11, wherein, The ink is applied to the polymer electrolytic capacitor by dip coating.

13. A method for manufacturing an n-type conductive polymer for solution processing, the method comprising the following steps: d) Adding the monomer to a solvent system containing water in the presence of a catalyst to provide a reaction solution; e) Allow the monomer to polymerize in the reaction solution to obtain an n-type conductive polymer solution; f) Post-process the n-type conductive polymer solution to obtain a water-soluble n-type conductive polymer.

14. The method according to claim 13, wherein, The solvent system is composed of water, and the method further includes the following steps: a') Add alkali to the reaction solution. Step a') is performed during step a) or immediately after step a).

15. The method according to claim 13, wherein, The solvent system further comprises a polar aprotic solvent, and the method further comprises the following steps: g) Solvent exchange, which removes the polar aprotic solvent.

Images