Polymer capacitor comprising a solution-treated n-type conductive polymer

Abstract

The present invention relates to a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-processed n-type conducting polymer having a conductivity of at least 100 S / cm, preferably at least 500 S / cm.

Description

[Technical Field]

[0001] The present invention relates to polymer capacitors comprising a solution-treated n-type conductive polymer, and to a method for producing aqueous n-type conductive polymers for use in such devices. [Background technology]

[0002] Water-based conductive polymer inks have a wide range of industrial applications, including antistatic coatings, polymer 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 a pure electrical conductivity of 1 S cm. -1 If exceeding 4000 S cm by secondary doping or post-treatment -1 It reaches values ​​exceeding [a certain threshold]. However, when considering complementary components for semiconductor devices and circuits, aqueous n-type (electron transport) conductive polymers become important.

[0003] The BBL:PEI ethanol-based inks reported in International Publications 2022 / 106017 and 2022 / 106018 represent a first step toward environmentally friendly solvent-type n inks. However, several issues partially limit their application. First, ethanol has stringent requirements regarding fire prevention during manufacture, transport, storage, and use. Furthermore, the inks disclosed in the above applications are limited to deposition methods such as spray casting, spin casting, and similar methods due to their large particle size. As can be seen from the above references, the maximum electrical conductivity of BBL:PEI ink is 10 S cm. -1 It is less than [a certain value] and is not suitable for devices sensitive to sheet resistance.

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

[0005] Developing water-based n-type CP inks with high conductivity, processability, and stability comparable to PEDOT:PSS remains a challenging scientific and industrial endeavor with far-reaching implications for cost-effective printed organic electronics.

[0006] Polymer capacitors are electrolytic capacitors (e-caps) that have a solid conductive polymer electrolyte. There are four 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 oxide electrolytic capacitors.

[0007] Polymeric Ta-e-cap is available in rectangular surface-mount device (SMD) chip style. Polymeric Al-e-cap and hybrid polymeric Al-e-cap are available in rectangular surface-mount device (SMD) chip style, cylindrical SMD (V-chip) style, or radial lead versions (single-ended).

[0008] Polymer capacitors are characterized by particularly low internal equivalent series resistance (ESR) and high ripple current ratings. While these electrical parameters are similar to solid tantalum capacitors in terms of temperature dependence, reliability, and service life, they exhibit significantly better temperature dependence and a considerably longer service life than aluminum electrolytic capacitors with non-solid electrolytes. Polymer e-caps typically have higher leakage current ratings than other solid or non-solid electrolytic capacitors.

[0009] Polymer capacitors are also available in hybrid structures. Hybrid polymer-aluminum electrolytic capacitors combine solid polymer electrolytes and liquid electrolytes. These types are characterized by low ESR values, low leakage current, and resistance to transients. However, like non-solid e-caps, they have a temperature-dependent lifespan.

[0010] Polymer capacitors are primarily used in power supplies for integrated electronic circuits as buffer, bypass, and decoupling capacitors in flat or compact designs. Therefore, they compete with multilayer ceramic capacitors (MLCCs), but offer higher capacitance values ​​and do not exhibit microphonic effects (such as Class 2 and Class 3 ceramic capacitors).

[0011] The most important electrical characteristic of the electrolyte in an electrolytic capacitor is its electrical conductivity. The electrolyte forms the counter electrode, i.e., the cathode, of the electrolytic capacitor (e-cap). The advantages of solid polymer electrolytes are that the capacitor's ESR is significantly lower and the electrical parameters have less temperature dependence.

[0012] Currently available polymer electrolytes are made from precursors consisting of extremely small base materials that can penetrate even the smallest pores. The size of this precursor limits the pore size of the etched aluminum anode foil or the size of the tantalum powder. Capacitor manufacturing requires controlling the polymerization rate. Polymerization that is too fast does not completely cover the anode, while polymerization that is too slow increases production costs. Neither the precursor, the polymer, nor its residues can chemically or mechanically attack the anode oxide. Polymer electrolytes must possess high stability over long periods and across a wide temperature range. Currently available polymer e-capacitors employ either polypyrrole (PPy) or polythiophene (PEDOT). However, capacitors containing these polymers suffer from poor thermal stability. Supercapacitors used in fields such as autonomous driving can operate at temperatures exceeding 170°C. Conventional conductive polymers, even in airless encapsulation, exhibit reduced conductivity at such temperatures.

[0013] Therefore, there is a need for polymer capacitors comprising a solution-treated, preferably aqueous, n-type CP ink, which possesses high conductivity, processability, and stability. [Overview of the project]

[0014] With the above in mind, the present invention aims to solve the problems of the prior art. For this purpose, the present invention relates to a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S / cm, preferably at least 500 S / cm.

[0015] The above solution-treated n-type conductive polymer may further have a work function of at least 4.7 eV, preferably at least 4.9 eV. Furthermore, the above solution-treated n-type conductive polymer may not contain side chains. In the present invention, the term “side-chain-free” means that there is only one carbon atom extending from the conjugated backbone of the polymer. Such embodiments offer the advantage that the interface of the active material to the nanoparticles and / or electron collector surface is improved, as side chains can introduce some distance between the polymer’s π system and the surface of the electron collector, thereby reducing charge transfer. Furthermore, the above solution-treated n-type conductive polymer may comprise repeating units comprising a centrally symmetric benzene ring as a backbone, active hydrogen, and at least one electron-withdrawing group at the benzyl position. In particular, the solution-treated n-type conductive polymer may be poly(benzodifraione) (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-co-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid) (PDADF-P)], or a mixture thereof, as shown below. The structure of PDADF-P is similar to that of PDADF, but lacks a heterocyclic segment. [ka]

[0016] The n-type conductive polymer used in the polymer capacitor of the present invention is 1) A step of obtaining a reaction solution by adding a monomer to a solvent system comprising a polar aprotic solvent and an oxidizing agent in the presence of a catalyst, 2) A step of polymerizing the above monomer in the above reaction solution to obtain an ink containing an n-type conductive polymer. It can be manufactured by a method comprising [the specified element].

[0017] The catalyst described above is a quinone or quinone precursor and comprises at least one branched side chain. The term "quinone precursor" means a species capable of forming a quinone structure. The side chain may comprise 3 to 100 carbon atoms. The side chain may further comprise at least one functional group, such as a hydroxyl group. Furthermore, the side chain may further comprise a branched center. Furthermore, the side chain may comprise at least one chiral center. Catalysts prepared in this manner have been shown not to crystallize during polymerization reactions because at least one branched side chain prevents such crystallization. Since the catalyst does not crystallize, it does not need to be removed from the ink, and dialysis steps such as those described in International Publication No. 2022 / 262159 are eliminated.

[0018] Therefore, one advantage of the above method is that the catalyst produced by this method does not crystallize due to the presence of at least one branched side chain, thus eliminating the need for a dialysis step to remove the catalyst. Sufficiently long branched side chains do not crystallize, while branched side chains with 3-4 carbon atoms do crystallize.

[0019] The above monomer has a centrally symmetric benzene ring as its backbone, an active hydrogen atom, and at least one electron-withdrawing group at the benzyl position. Examples of the electron-withdrawing group include carbonyl, carboxyl, amide, alkoxyacyl, or the same. [ka]

[0020] Furthermore, the monomer may be in the form of a heterocyclic moiety having at least one, preferably at least two rings, preferably a centrosymmetric benzene ring condensed with a 5-membered ring. The monomer further comprises an active hydrogen and at least one electron-withdrawing group at the benzyl position. In particular, the monomer may be 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (HBFDO), 5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione, or 3,7-dihydrobenzo[1,2-b:4,5-b']dithiophene-2,6-dione.

Chemical formula

[0021] In particular, the monomer is 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (HBFDO). In such an embodiment, the n-type conductive polymer is polybenzodifurandione (PBFDO).

[0022] According to a particular embodiment, the catalyst may be vitamin E. As is well known in the art, vitamin E is a group of eight fat-soluble compounds comprising four tocopherols and four tocotrienols, as shown below.

Chemical formula

[0023] It should be noted that, according to the method described above, the term vitamin E means at least one of the species described above. In other words, each of the species described above may be present in pure form in the reaction solution, or at least two of the species described above may be present in any combination. Thus, vitamin E can be selected from the group consisting of α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol, and mixtures thereof.

[0024] Vitamin E (a collective term for tocopherols and tocotrienols) is a natural product with high redox activity. Vitamin E is synthesized in photosynthetic plants and can be extracted in large quantities from plants. All vitamin E molecules have branched, long hydrocarbon side chains and are natural oily substances that do not crystallize at room temperature. According to the above method, using vitamin E as a catalyst, an ink containing an n-type conductive polymer can be synthesized in one step or one pot without requiring post-treatment such as dialysis and solvent removal. Compared to the three-step method reported by Fei Huang, the above method represents a significant simplification.

[0025] Surprisingly, it was found that while vitamin E itself does not have catalytic activity, its oxidized form does. In the presence of an oxidizing agent, vitamin E forms a benzoquinone derivative. According to the above method, the polymerization reaction is initiated by in-situ oxidation. Therefore, the above method offers the advantage of being a simplified and cost-effective method for producing inks containing n-type conductive polymers compared to methods known in the art. The major advantages of using vitamin E as a catalyst are its availability, low cost, and non-toxicity.

[0026] In certain embodiments, the polar aprotic solvent is DMSO, and the oxidizing agent is hydrogen bromide (HBr). HBr is volatile and does not affect film formation when the ink is printed.

[0027] Alternatively, the oxidizing agent is an ionic liquid comprising a cation and an anion. In such an embodiment, the method further comprises: 3) electrolyzing the reaction solution and Step 3) is carried out simultaneously with or after Step 1).

[0028] In particular, Step 3) can be carried out using a nickel cathode and a carbon anode at a voltage within the range of 4 to 6 V for a period within the range of 10 to 60 minutes.

[0029] The cation in the ionic liquid can be selected from the group consisting of 1-ethyl-3-methylimidazolium (EMIM), 1-butyl-3-methylimidazolium (BMIM), 1-allyl-3-methylimidazolium (AMIM), 1-hexyl-3-methylimidazolium (HMIM), butylmethylpyrrolidinium (BMP), propylmethylpyrrolidinium (PMP), triethylsulfonium, and mixtures thereof. The structure of the cation is shown below. [Chemical formula]

[0030] According to the above method, the anion can be chloride (Cl - ), bromide (Br - ), iodide (I - ), acetate (OAc), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6 - ), bistrifluoromethanesulfonimide (TFSI), trifluoromethanesulfonic acid (OTf), dicyanamide (DCA), hydrogen sulfate (HSO4 - ), ethyl sulfate (ESO4 - ), thiocyanate (SCN), tosylate (OTs), mesylate (OMs), tetrachloroaluminate (AlCl4 -The anions can be selected from the group consisting of ), diethyl phosphate (DEP), dimethyl phosphate (DMP), lactic acid (La), L-alanine anion (APP), and mixtures thereof. The structures of the above anions are shown below. [ka]

[0031] As described above, the solvent system obtained by the above method comprises a polar aprotic solvent. The polar aprotic solvent may be dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), or a combination thereof.

[0032] The ratio of the above-mentioned oxidizing agent to the above-mentioned vitamin E is in the range of 0.1 to 100, preferably 0.25 to 5, and more preferably 1 to 3.

[0033] The polymerization reaction, i.e., step b) of the above method, can occur at temperatures between 20°C and 150°C.

[0034] The above method, 4) A process to remove the catalyst by extraction and recycle the catalyst. It may further include the following.

[0035] Extraction can be carried out using alkanes or ethers.

[0036] The overall outline of the above method can be summarized as follows: [ka]

[0037] Therefore, an ink containing an n-type conductive polymer manufactured by the above method can be used in the manufacture of the polymer capacitor of the present invention. Accordingly, the n-type conductive ink 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 may exhibit an electrical conductivity of about 1000 S / cm.

[0038] The above anode may be tantalum (Ta) in the form of high-purity sintered tantalum powder, using tantalum pentoxide (Ta2O5) as the dielectric.

[0039] Alternatively, the anode may be aluminum (Al) in the form of high-purity, electrochemically etched (roughened) aluminum foil having aluminum oxide (Al2O3) as a dielectric.

[0040] Alternatively, the anode may be niobium dioxide (NbO) with niobium pentoxide (Nb2O5) as the dielectric.

[0041] The polymer capacitor described above is in the form of a rectangular SMD chip, typically molded into a plastic case, and may be used with a sintered tantalum anode or laminated aluminum anode foil.

[0042] Alternatively, the polymer capacitor may be in cylindrical form (only in the case of Al).

[0043] The polymer capacitor described above may be sealed with a resin, such as epoxy resin. Sealing prevents contact with air, improving the stability of the capacitor.

[0044] The present invention relates to a method for manufacturing a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S / cm, preferably at least 500 S / cm, and the method is as follows: a) A step of preparing the anode and dielectric layer, b) A step of preparing a polymer capacitor by applying a cathode material onto the dielectric layer, c) A step of drying the polymer capacitor mentioned above. Further details will be given regarding methods that include the following:

[0045] The method according to the present invention is a) The process of sealing the polymer capacitor described above. It may also include

[0046] Step d) may be performed by applying a sealing material, such as epoxy, onto the polymer capacitor and curing the polymer capacitor at a temperature of 100°C to 150°C for 1 to 24 hours. For example, the sealing material may be cured overnight at 120°C. The curing temperature is preferably maintained at a level that avoids premature degradation of the polymer capacitor before the capacitance test.

[0047] The method according to the present invention is a') A process of forming an anode and a dielectric layer by anodizing the anode material. It may also include, Process a') is performed before process a).

[0048] Hereinafter, embodiments of the present invention will be described as examples with reference to the attached drawings. [Brief explanation of the drawing]

[0049] [Figure 1] This figure shows a schematic diagram of the cross-sectional structure of the polymer capacitor according to the present invention. [Figure 2] This figure shows various embodiments of the polymer capacitor according to the present invention. [Figure 3] Figure 2 shows a perspective view and a cross-sectional view of the polymer capacitor. [Figure 4] Figure 2 shows a perspective view and a cross-sectional view of the polymer capacitor. [Figure 5] This figure shows the change in conductivity of a polymer electrode annealed in nitrogen at 200°C. [Figure 6] This figure shows the change in conductivity of a polymer electrode annealed in air at 200°C in a resin-encapsulated capacitor. [Figure 7] This figure shows the change in conductivity of a polymer electrode annealed in nitrogen at 300°C. [Figure 8] This figure shows the change in conductivity of polymer ink stored in air. [Figure 9-1] This figure shows the thermal stability of a solution-treated n-type conductive polymer used in a polymer capacitor according to the present invention. [Figure 9-2] This figure shows the thermal stability of a solution-treated n-type conductive polymer used in a polymer capacitor according to the present invention. [Figure 10] This figure shows the capacitance retention rate of the polymer capacitor of the present invention compared to a reference capacitor. [Figure 11] This figure shows the results of the thermal stability of capacitance of the capacitor according to the present invention compared with a reference capacitor. [Figure 12] This diagram shows models of an ideal capacitor and a real-world capacitor. [Figure 13] This figure shows an impedance spectroscopy comparison between a polymer capacitor according to the present invention and a reference capacitor. [Modes for carrying out the invention]

[0050] As described above, the present invention provides a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S / cm, preferably at least 500 S / cm.

[0051] Figure 1 shows a schematic cross-sectional view of a polymer capacitor according to the present invention. As can be seen from the figure, the polymer capacitor comprises an aluminum electrode (Al / Al2O3) comprising an aluminum (Al) foil and an oxide layer. The n-type conductive polymer is spin-coated onto the aluminum electrode. The upper electrode is in the form of aluminum (Al) applied by vapor deposition. The thickness of the upper electrode is 50 to 500 nm. The polymer capacitor is sealed with epoxy.

[0052] In the embodiment shown in Figure 2, different types of polymer 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). Furthermore, Figure 3 shows a perspective view and a cross-sectional view of polymer Al-e-cap. Similarly, Figure 4a shows a perspective view and a cross-sectional view of polymer Ta-e-cap, and Figure 4b shows a perspective view and a cross-sectional view of hybrid polymer Al-e-cap.

[0053] As can be seen in Figure 3, a polymer capacitor 10 is illustrated. This capacitor 10 comprises two terminals 1 and 1', a silver paste layer 2, and a sealing layer 3 in the form of molded resin. In the vertical cross-sectional view, the aluminum foil 4 functions as the anode, the aluminum oxide layer 5 functions as the dielectric, and the polymer layer 6, which comprises a solution-treated n-type conductive polymer, functions as the cathode.

[0054] Figure 4a shows yet another embodiment of a rectangular capacitor 210 having a tantalum anode 204, a tantalum pentoxide dielectric 205, a cathode layer 206 comprising a solution-treated n-type conductive polymer, and a silver paste layer 202. As can be seen from Figure 4a, the capacitor 210 comprises a sealing layer 203 in the form of a molded resin.

[0055] Figure 4b shows a cylindrical polymer capacitor 310 comprising an aluminum anode 304, an aluminum oxide dielectric 305, a separator sheet 312, and a hybrid cathode 306 impregnated in the separator sheet 312, which comprises a solution-treated n-type conductive polymer and an electrolyte.

[0056] Figure 5 shows the change in conductivity of a polymer electrode annealed in nitrogen at 200°C. As can be seen from the figure, the capacitor of the present invention exhibits excellent thermal stability, with almost no change in conductivity even after 8 hours.

[0057] The resin-sealed capacitors described above can be annealed in air to obtain good results. As can be seen in Figure 6, even after annealing in air at 200°C for 6 hours, the decrease in conductivity was minimal.

[0058] When the annealing temperature rose to 300°C, thermal stability was compromised, and conductivity had already decreased significantly after 2 hours in a nitrogen atmosphere (Figure 7).

[0059] The ink comprising a solution-treated n-type conductive polymer used in the polymer capacitor of the present invention exhibited excellent storage stability, as shown in Figure 8.

[0060] Figures 9a and 9b show the thermal stability of the n-type conductive polymer, i.e., polybenzodiflaione (PBFDO), used in the polymer capacitor of the present invention. As can be seen from the figures, PBFDO exhibits excellent thermal stability, with almost no decrease in conductivity up to 200°C. As can be confirmed in Figure 9c, the solution-treated n-type conductive polymer can have heat resistance up to 225°C. The term "heat resistance" means that the solution-treated n-type conductive polymer maintains its conductivity up to 225°C within the film.

[0061] The polymer capacitor and reference capacitor according to the present invention were manufactured as follows: A commercially available 50 μm thick anodized aluminum foil (ANOFOL, H18) with a 4 μm oxide layer was obtained from Steinert.

[0062] A reference sample was obtained using PEDOT:PSS as the conductive polymer. PEDOT:PSS (Clevios PH 1000 with 5 wt% ethylene glycol added as a secondary dopant) was spin-coated onto anodized aluminum (1500 rpm for 30 seconds) and dried on a hot plate (110°C). PEDOT:PSS did not appear to penetrate the oxide layer, and the resistance measured with a multimeter was in the range of 100 kΩ (compared to over 10 MΩ when measured directly on the oxide, and less than 1 Ω when probed on unanodized foil).

[0063] The resistance and capacitance of the manufactured films were tested using a multimeter and an LCR meter. The resistance of the PEDOT:PSS film was approximately 400 Ω / square. The capacitance of this structure was approximately 20 nF. When only anodized aluminum was probed, a capacitance of approximately 20 pF was obtained.

[0064] The sample of the present invention was obtained using PBFDO as the n-type conductive polymer. Spin coating was performed at 500 / 1000 rpm for 3 minutes, followed by 3000 rpm for 30 seconds.

[0065] Drying was performed on a hot plate at 40°C for the (n-ink) sample of the present invention, and at 110°C for the reference (PEDOT:PSS) sample. The 100 nm thick upper electrode was obtained by aluminum deposition. The samples did not short-circuit during processing (i.e., the conductive polymer did not penetrate the oxide).

[0066] Floating particles resulting from spin coating and evaporation were removed from the edges of the sample by applying and then removing Kapton tape. This prevents short circuits caused by evaporated aluminum at the edges of the sample, where there is no thick oxide layer.

[0067] One end of each strip was etched with 0.5 M sodium hydroxide (NaOH) to remove oxides and ensure electrical contact with the aluminum (Al) electrode below.

[0068] Three inventive samples and three reference samples were placed in a mold and epoxy was cast. Two inventive samples and two reference samples were placed in an oven without sealing.

[0069] The epoxy (COTRONICS Duralco 4460) was cured overnight at 120°C. To prevent premature degradation of the polymer capacitor before capacitance testing, the curing temperature was kept below 125°C.

[0070] Cables and alligator clip connectors were used to connect to the above samples. The cables are rated for operation up to 200°C and include aluminum shielding. All shields are connected to each other and grounded. Nine cables were used in total, eight of which were used for the four caps and one for grounding or shielding.

[0071] The LCR meter was calibrated to match the new setup and high-temperature cables. Before epoxy sealing, all samples were measured at room temperature using both the LCR meter and potentiostat impedance spectroscopy.

[0072] The above capacitors were tested at 125°C, 150°C, and 200°C, and the LCR and impedance values ​​were monitored twice a day at 200°C.

[0073] The capacitance results are summarized in Table 1. The measured capacitance and normalized capacitance of each sample before and after the high-temperature test are shown. [Table 1]

[0074] Figure 10 shows the capacitance retention of the sample of the present invention and the reference sample as a function of time and temperature. As can be seen from the figure, the capacitance of the reference sample containing PEDOT:PSS decreases continuously with increasing temperature. On the other hand, the sample of the present invention containing n-ink appears to stabilize after the initial decrease. Figure 11 shows the capacitance values ​​of the above samples.

[0075] Impedance spectroscopy was performed using an Ivium potentiostat at a frequency range of 100–100,000 Hz and a voltage of 10 mV AC.

[0076] The impedance data was modeled using the equivalent circuit shown in Figure 12. The model proposes three different capacitance layers / processes. The three components are Al / AlO x / CP interface, CP / Al bilayer (with mobile ions), and Al / AlO at the contact point between the alligator clip and the sample. x It is suggested to be a metal.

[0077] The phase angles are shown in Figure 13, indicating which process is dominant at various frequencies. An ideal capacitor is assumed to have a phase angle of -90° across all frequencies.

[0078] In both n-ink capacitors and PEDOT:PSS capacitors, a small phase angle toward -90° is initially observed at high frequencies. This behavior is more pronounced in PEDOT:PSS samples and is thought to be related to the ion resistance (dissipation) process.

[0079] In the case of n-ink samples, the phase angle improves after sealing and heating, but there is no change in the PEDOT:PSS samples. The reason for this difference is likely that PEDOT:PSS has a phase rich in ionic PSS, which makes it a less ideal material for polymer capacitors.

[0080] The above samples were measured using an LCR meter and impedance spectroscopy (potentiostat) at RT (air), 125°C (vacuum), 150°C (vacuum), 200°C (vacuum), RT (vacuum), and RT (air).

[0081] Figure 13a shows the phase angle of the sample of the present invention before sealing, Figure 13b shows the phase angle of the sample of the present invention at 200°C, and Figure 13c shows the phase angle of the reference sample at 200°C. LCR meter data shows that the capacitance degradation of the PEDOT:PSS sample is much faster than that of the n-ink sample, confirming that the n-ink capacitor is more stable at high temperatures. Furthermore, impedance spectroscopy data shows that the capacitance behavior of the n-ink capacitor is more ideal compared to that of the PEDOT:PSS capacitor.

[0082] While the present invention has been described with reference to various embodiments, those skilled in the art will understand that modifications are possible without departing from the scope of the invention. The detailed description is to be considered illustrative, and the appended claims, including all equivalents, are intended to define the scope of the invention.

Claims

1. A polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S / cm, and the n-type conductive polymer is poly(benzodifraglan) (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-co-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid) (PDADF-P), or a mixture thereof.

2. The polymer capacitor according to claim 1, wherein the solution-treated N-type conductive polymer has heat resistance up to 225°C.

3. The polymer capacitor according to claim 1, wherein the work function of the solution-treated n-type conductive polymer is at least 4.7 eV.

4. The polymer capacitor according to claim 1, wherein the solution-treated n-type conductive polymer does not contain side chains.

5. The anode is tantalum (Ta), and the dielectric layer is tantalum oxide (Ta) ２ O ５ The polymer capacitor according to claim 1, wherein the polymer capacitor is as described in claim 1.

6. The anode is niobium(II) oxide (NbO), and the dielectric layer is niobium(V) oxide (NbO). ２ O ５ The polymer capacitor according to claim 1, wherein the polymer capacitor is as described in claim 1.

7. The anode is aluminum (Al), and the dielectric layer is aluminum oxide (Al ２ O ３ The polymer capacitor according to claim 1, wherein the polymer capacitor is as described in claim 1.

8. The polymer capacitor according to claim 1, wherein the polymer capacitor is in the form of a rectangular SMD chip.

9. The polymer capacitor according to claim 1, wherein the polymer capacitor is cylindrical in shape.

10. The polymer capacitor according to any one of claims 1 to 9, wherein the polymer capacitor is sealed.

11. A method for manufacturing a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S / cm, and the n-type conductive polymer is poly(benzodifraglan) (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-co-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid) (PDADF-P), or a mixture thereof, and the method is a) A step of preparing the anode and dielectric layer, b) A step of preparing a polymer capacitor by applying a cathode material onto the dielectric layer, c) A step of drying the polymer capacitor and A method that includes the following:

12. The method described above is a) The process of sealing the polymer capacitor. The method according to claim 11, further comprising the following:

13. The method described above is a') A process of preparing the anode and dielectric layer by anodizing the anode material. It further includes, The method according to claim 11, wherein step a') is performed before step a).

Images