Patent Publication Number: US-2019194441-A1

Title: Method for manufacturing a polymer composite material and method for manufacturing a capacitor package structure using the polymer composite material

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This is a divisional application of U.S. application Ser. No. 15/672,933, filed on Aug. 9, 2017 and entitled “POLYMER COMPOSITE MATERIAL, METHOD FOR MANUFACTURING THE POLYMER COMPOSITE MATERIAL, CAPACITOR PACKAGE STRUCTURE USING THE POLYMER COMPOSITE MATERIAL AND METHOD FOR MANUFACTURING THE CAPACITOR PACKAGE STRUCTURE”, the entire disclosures of both are incorporated herein by reference. 
    
    
     BACKGROUND 
     1. Technical Field 
     The instant disclosure relates to a polymer composite material, and in particular, to a polymer composite material for capacitor package structures. 
     2. Description of Related Art 
     Capacitors are widely used in consumer appliances, computers, power supplies, communication products and vehicles, and hence, are important elements for electronic devices. The main effects of the capacitors are filtering, bypassing, rectification, coupling, decoupling and phase inverting, etc. Based on different materials and uses thereof, capacitors can be categorized into aluminum electrolytic capacitors, tantalum electrolytic capacitors, laminated ceramic capacitors and thin film capacitors. In the existing art, solid electrolytic capacitors have the advantages of small size, large capacitance and excellent frequency property and can be used in the decoupling of the power circuits of central processing units. Solid electrolytic capacitors use solid electrolytes instead of liquid electrolytic solutions as cathodes. Conductive polymers are suitable for the cathode material of the capacitors due to its high conductivity, and the manufacturing process using conductive polymers are simple and low cost. Conductive polymers comprise polyaniline (PAni), polypyrrole (PPy) and polythiophene (PTh) and their derivatives. 
     In the technical field of the instant disclosure, there is a need to improve the electrical performance of the solid electrolytic capacitor package structures. 
     SUMMARY 
     In order to achieve the object mentioned above, an embodiment of the present disclosure provides a polymer composite material for a cathode portion of a capacitor. The polymer composite material comprises a poly(3,4-ethylenedioxythiophene) unit, a polystyrene sulfonate unit and a carbon nanomaterial, the polystyrene sulfonate unit is connected between the poly(3,4-ethylenedioxythiophene) unit and the carbon nanomaterial, and the polystyrene sulfonate unit is bonded to poly(3,4-ethylenedioxythiophene) through a polymerization process. A content of the carbon nanomaterial ranges from 0.01-1.5 wt. % based on a weight of the polymer composite material. 
     Another embodiment of the instant disclosure provides a capacitor package structure comprising at least a capacitor, and a cathode portion of the capacitor comprises the polymer composite material mentioned above. 
     Another embodiment of the instant disclosure provides a method for manufacturing a polymer composite material, comprising: mixing a carbon nanomaterial with polystyrene sulfonate to form a carbon nanomaterial modified by polystyrene sulfonate; adding 3,4-ethylenedioxythiophene into a solution comprising the carbon nanomaterial modified by polystyrene sulfonate; and initiating a polymerization reaction to allow a reaction between 3,4-ethylenedioxythiophene and the carbon nanomaterial modified by polystyrene sulfonate in the solution for forming a product stream comprising the polymer composite material. The polymer composite material comprises a poly(3,4-ethylenedioxythiophene) unit, a polystyrene sulfonate unit and the carbon nanomaterial. The polystyrene sulfonate unit is connected between the poly(3,4-ethylenedioxythiophene) unit and the carbon nanomaterial, and the polystyrene sulfonate unit is bonded to the poly(3,4-ethylenedioxythiophene) unit through a polymerization process. A content of the carbon nanomaterial ranges from 0.01-1.5 wt. % based on a weight of the polymer composite material. 
     Another embodiment of the present disclosure provides a method for manufacturing a capacitor package structure, comprising: providing at least a capacitor having a cathode comprising the polymer composite material manufactured by the method mentioned above; and packaging the capacitor with a package structure, wherein a positive pin and a negative pin both electrically connected to the capacitor are exposed from the package structure. 
     The main technical means of the instant disclosure is that the polymer composite material comprises a carbon nanomaterial of specific content and thus has excellent electric property. Therefore, the solid electrolytic capacitor comprising the polymer composite has improved conductivity, improved thermal stability, improved polymer impregnating rate, improved capacitance, reduced equivalent series resistance, reduced loss factor and reduced leak current. In addition, the method of manufacturing the polymer composite material of the instant disclosure has reduced manufacturing cost and hence, the overall manufacturing cost of the solid electrolytic capacitor is reduced. 
     In order to further understand the techniques, means and effects of the instant disclosure, the following detailed descriptions and appended drawings are hereby referred to, such that, and through which, the purposes, features and aspects of the instant disclosure can be thoroughly and concretely appreciated; however, the appended drawings are merely provided for reference and illustration, without any intention to be used for limiting the instant disclosure. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The accompanying drawings are included to provide a further understanding of the instant disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the instant disclosure and, together with the description, serve to explain the principles of the instant disclosure. 
         FIG. 1  is a sectional view of one of the capacitor packaging using a polymer composite material provided by the embodiments of the instant disclosure; 
         FIG. 2  is a sectional view of one of the capacitor packaging provided by the embodiments of the instant disclosure; 
         FIG. 3  is a three-dimensional schematic view of another capacitor using the polymer composite material provided by the embodiments of the instant disclosure. 
         FIG. 4  is a side schematic view of another capacitor package structure provided by the embodiments of the instant disclosure; 
         FIG. 5  is a structural schematic view of the polymer composite material provided by one of the embodiments of the instant disclosure; 
         FIG. 6  is a flow chart of the method for manufacturing the polymer composite material provided by one of the embodiments of the instant disclosure; 
         FIG. 7  shows the chemical structures of the poly(3,4-ethylenedioxythiophene) unit and the polystyrene sulfonate unit of the polymer composite material provided by the embodiments of the instant disclosure. 
         FIG. 8  is one of the structural schematic view of the carbon nanomaterial of the polymer composite material provided by the embodiments of the instant disclosure; 
         FIG. 9  is another structural schematic view of the carbon nanomaterial of the polymer composite material provided by the embodiments of the instant disclosure; 
         FIG. 10  is the structural schematic view of the polymer composite material provided by another one of the embodiments of the instant disclosure; and 
         FIG. 11  is a flow chart of the method for manufacturing a polymer composite material provided by another one of the embodiments of the instant disclosure. 
     
    
    
     DESCRIPTION OF THE EXEMPLARY EMBODIMENTS 
     Reference will now be made in detail to the exemplary embodiments of the instant disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts. 
     Please refer to  FIG. 1  and  FIG. 2 .  FIG. 1  is a sectional view of one of the capacitor packaging using a polymer composite material provided by the embodiments of the instant disclosure, and  FIG. 2  is a sectional view of one of the capacitor packaging provided by the embodiments of the instant disclosure. Specifically, the polymer composite material  2  provided by the instant disclosure can be used in the conductive polymer layer  102  of the cathode portion N of the capacitor  1 . In  FIG. 2 , the capacitor  1  is the capacitor unit  42  of the stacked type solid electrolytic capacitor  4 . 
     For example, as shown in  FIG. 1 , the capacitor  1  comprises the metal foil  100 , the oxide layer  101  enclosing the metal foil  100 , the conductive polymer layer  102  enclosing a part of the conductive polymer layer  102 , the carbon paste layer  103  enclosing the conductive polymer layer  102 , and the silver paste layer  104  enclosing the carbon paste layer  103 . The structure of the capacitor  1  can be adjusted according to the requirement of the products. The conductive polymer layer  102  is used as the solid electrolytic of the capacitor  1 . 
     As shown in  FIG. 2 , the stacked type solid electrolytic capacitor  4  comprises a plurality of capacitor units  42  stacked one above another. In addition, the stacked type solid electrolytic capacitor  4  comprises a conductive frame  41 . The conductive frame  41  comprises a first conductive terminal  411  and a second conductive terminal  412  separated from the first conductive terminal  411  for a predetermined distance. The plurality of capacitor units  42  has a first positive electrode portion P 1  electrically connected to the first conductive terminal  411  of the corresponding conductive frame  41  and a first negative electrode portion N 1  electrically connected to the second conductive terminal  412  of the corresponding conductive frame  41 . In addition, a plurality of capacitor units  42  electrically connected to each other and stacked one above another are enclosed by a package  43 , thereby forming the stacked type solid electrolytic capacitor  4 . 
     Please refer to  FIG. 3  and  FIG. 4 .  FIG. 3  is a three-dimensional schematic view of another capacitor using the polymer composite material provided by the embodiments of the instant disclosure, and  FIG. 4  is a side schematic view of another capacitor package structure provided by the embodiments of the instant disclosure. In  FIG. 3  and  FIG. 4 , the capacitor  1  is the capacitor unit in the wound type solid electrolytic capacitor  3 . 
     As shown in  FIG. 4 , the wound type solid electrolytic capacitor  3  comprises a wound type component  31 , a packaging component  32  and a conductive component  33 . Please refer to  FIG. 3 . The wound type component  31  comprises a wound type positive electrode conductive foil  311 , a wound type negative electrode conductive foil  312  and two wound type isolating foils  313 . Furthermore, one of the wound type isolating foils  313  is disposed between the wound type positive electrode conductive foil  311  and the wound type negative electrode conductive foil  312 , and one of the wound type positive electrode conductive foil  311  and the wound type negative electrode conductive foil  312  is disposed between the two wound type isolating foils  313 . The wound type isolating foils  313  can be isolating papers or paper foils having the polymer composite material coated thereon by impregnation. 
     Please refer to  FIG. 4 . The wound type component  31  is enclosed in the packaging component  32 . For example, the packaging component  32  comprises a capacitor casing structure  321  (such as an aluminum casing or a casing made of other metals) and a bottom end sealing structure  322 . The capacitor casing structure  321  has an accommodating space  3210  for accommodating the wound type component  31 . The bottom end sealing structure  322  is disposed in the accommodating space  3210  located at the bottom end of the capacitor casing structure  321 . In addition, the packaging component  32  can be a package made of any insulating materials. 
     The conductive component  33  comprises a first conductive pin  331  electrically contacting the wound type positive electrode conductive foil  311  and a second conductive pin  332  electrically contacting the wound type negative electrode conductive foil  312 . For example, the first conductive pin  331  has a first buried portion  3311  enclosed in the packaging component  32  and a first exposed portion  3312  exposed from the packaging component  32 . The second conductive pin  332  has a second buried portion  3321  enclosed in the packaging component  32  and a second exposed portion  3322  exposed from the packaging component  32 . 
     Please refer to  FIG. 5 , and  FIG. 7  to  FIG. 9 .  FIG. 5  is a structural schematic view of the polymer composite material provided by one of the embodiments of the instant disclosure,  FIG. 7  shows the chemical structures of the poly(3,4-ethylenedioxythiophene) unit and the polystyrene sulfonate unit of the polymer composite material provided by the embodiments of the instant disclosure,  FIG. 8  is one of the structural schematic view of the carbon nanomaterial of the polymer composite material provided by the embodiments of the instant disclosure, and  FIG. 9  is another structural schematic view of the carbon nanomaterial of the polymer composite material provided by the embodiments of the instant disclosure. The polymer composite material  2  provided by the embodiments of the instant disclosure comprises the poly(3,4-ethylenedioxythiophene) unit (formed by  3 , 4 -ethylenedioxythiophene  211 ′), a polystyrene sulfonate unit  212  and a carbon nanomaterial  22 . 3,4-ethylenedioxythiophene  211 ′ and the polystyrene sulfonate unit  212  can be used to form a PEDOT:PSS composite  21 . 
     Please refer to  FIG. 7 , the PEDOT:PSS composite  21  is a mixture of two ionic polymers. The two ionic polymers are sodium polystyrene sulfonate and poly(3,4-ethylenedioxophene), in which sodium polystyrene sulfonate is a polystyrene sulfonate and poly(3,4-ethylenedioxophene) is a polythiophene-based conjugated polymer. The above ionic polymers together form a macromolecule salt, referred to as the PEDOT:PSS composite  21 . 
     The PEDOT:PSS composite  21  has excellent conductivity. Compared to other polymer compounds such as Pani and PPy, the PEDOT:PSS composite  21  has lower polymerization velocity and is able to perform polymerization reaction under room temperature and hence, the preparation of the PEDOT:PSS composite  21  is easier than that of other polymer compounds. Besides, the PEDOT:PSS composite  21  has the advantages of good dispersing property, low manufacturing cost, high transparency and excellent processability. Therefore, using the PEDOT:PSS composite  21  as the material for forming the conductive polymer layer  102  on the cathode portion N of the capacitor  1  allows the capacitor  1  to exhibit enhanced electric performance. 
     In the embodiments of the instant disclosure, the carbon nanomaterial  22  is carbon nanotubes, carbon nanospheres, carbon freak graphenes or any combination thereof.  FIG. 8  shows the structure of graphenes, and  FIG. 9  shows the structure of carbon nanotubes.  FIG. 5  is the structural schematic view of the polymer composite material  2  using graphenes as the carbon nanomaterial  22 . Graphenes are planer films formed by carbon atom in sp 2  hybrid orbital and have a thickness equal to a diameter of single carbon atom. Graphenes have high thermal conductivity, low resistance rate and high stability and hence, are excellent electrical and thermal conductance. Carbon nanotubes are formed by a single layer or multi-layered graphite of sp 2  hybrid orbitals through winding respect to a same axial. Carbon nanotubes have good thermal resistance, good electric conductivity, high mechanical strength, flexibility and high surface area. 
     One of the technical features of the instant disclosure is to combine the three materials each having excellent property, i.e., the poly(3,4-ethylenedioxythiophene) unit  211 , the polystyrene sulfonate unit  212  and the carbon nanomaterial  22 , and to apply the polymer composite material  2  formed by chemical reactions between the three materials in the cathode portion of a capacitor, thereby effectively improving the electric performance of the capacitor, i.e., the capacitor can have improved conductivity, improved thermal stability, improved polymer impregnating rate, improved capacitance, reduced equivalent series resistance, reduced loss factor and reduced leak current. 
     As shown in  FIG. 5 , in an embodiment, the poly(3,4-ethylenedioxythiophene) unit  211 , the polystyrene sulfonate unit  212  and the carbon nanomaterial  22  co-react to form the polymer composite material  2  of the instant disclosure. For example, the PEDOT:PSS composite  21  constituted by the poly(3,4-ethylenedioxythiophene) unit  211  and the polystyrene sulfonate unit  212  bonds to the carbon nanomaterial  22  after the reactions. The carbon nanomaterial  22  surrounds the PEDOT:PSS composite  21 , or encloses the PEDOT:PSS composite  21 . For example, in the embodiments of the instant disclosure, the PEDOT:PSS composite  21  and the carbon nanomaterial  22  can be bonded to each other through surface modification and stabilizing techniques. 
     In the embodiments of the instant disclosure, based on the weight of the polymer composite material  2 , the content of the carbon nanomaterial  22  ranges from 0.01-1.5 wt. %. Preferably, in the embodiments of the instant disclosure, the carbon nanomaterial  22  having the above content can improve the electric properties of the capacitor. In other words, the polymer composite material  2  provided by the instant disclosure can improve the electric properties of the capacitor by using a small amount (less than 0.1 wt %) of the carbon nanomaterial  22 . 
     In addition, before forming the polymer composite material  2  provided by the instant disclosure, the surface of the carbon nanomaterial  22  can be modified. The surface modification techniques of the carbon nanomaterial  22  can be categorized into (1) acidizing the defects on the surface of the carbon nanomaterial  22 , then functionalizing the carbon nanomaterial  22 , and (2) directly attaching or bonding specific functional groups onto the surface of the carbon nanomaterial  22 . For example, the carbon nanomaterial  22  can be modified through carboxylic group or hydroxyl group for improving the reactivity of the carbon nanomaterial  22  to enable the carbon nanomaterial  22  to be dispersed in solvents such as de-ionized water or organic solvents, or to allow the carbon nanomaterial  22  to be well-mixed with polymer materials (such as the PEDOT:PSS composite  21 ). However, the modification process and the modifier for the carbon nanomaterial  22  are not limited in the instant disclosure. 
     Please refer to  FIG. 6 .  FIG. 6  is a flow chart of the method for manufacturing the polymer composite material provided by one of the embodiments of the instant disclosure. The embodiment shown in  FIG. 6  comprises mixing 3,4-ethylenedioxythiophene (EDOT), polystyrene sulfonate (PSS) and a carbon nanomaterial for forming a mixture (S 100 ); and initiating a polymerization reaction to allow a reaction between 3,4-ethylenedioxythiophene, polystyrene sulfonate (PSS) and the carbon nanomaterial for forming a product stream (S 102 ). 
     Specifically, the polymer composite material  2  provided by the instant disclosure can be formed by different methods. In the method for manufacturing the polymer composite material  2  shown in  FIG. 6 , the carbon nanomaterial  22  can be graphenes or carbon nanotubes, and the graphenes or carbon nanotubes can be pre-treated, for example, by surface-modification. For example, graphene oxide (GO) or reduced graphene oxide (RGO) can be used as the material for manufacturing the polymer composite material  2 . 
     In one embodiment of the instant disclosure, 3,4-ethylenedioxythiophene  211 ′, the polystyrene sulfonate unit  212  and the carbon nanomaterial  22  form the polymer composite material  2  through an in-situ polymerization reaction. In the present embodiment, the carbon nanomaterial  22  is reduced graphene oxides (RGO). The RGO and the polystyrene sulfonate unit  212  are first dissolved in a solvent for forming a solution. The polystyrene sulfonate unit  212  in the solution can be served as the reactant for forming the PEDOT:PSS composite  21  and the dispersant for dispersing RGO. The solvent can be an organic solvent or water. 
     Next, 3,4-ethylenedioxythiophene  211 ′ is added into the solution. The polymerization reaction can be initiated by adding an oxidant. Meanwhile, the mixture solution of 3,4-ethylenedioxythiophene  211 ′, the polystyrene sulfonate unit  212  and the carbon nanomaterial  22  can be heated and stirred. For example, by flowing air or oxygen through the mixture solution or adding iron (III) sulfate or sodium persulfate, the polymerization reaction is initiated. The use of a stir bar or a stirrer which provide mechanical stirring can facilitate the reaction. During the polymerization process, the reaction temperature can be controlled. For example, the mixture solution is heated to a temperature between 30 to 60° C. The time of stirring such as ultrasonic stirring can be 1 to 24 hours. 
     In addition, during the polymerization process, nitrogen gas can be input into the reaction environment to avoid the poly(3,4-ethylenedioxythiophene) unit  211  being over-oxided and reduce the electric conductivity of the polymer composite material  2  formed therefrom. After the reaction is completed, remained ions in the product stream can be removed by purifying processes such as a process using an ion exchange resin. 
     A dispersing agent can be further added into the mixture solution during the polymerization process to facilitate the dispersion and stability of the mixture solution. For example, the dispersing agent can be sodium dodecyl-sulfonate. For example, when the carbon nanomaterial  22  is graphenes, the structure of the graphenes can be folded and forms a folded structure in the solvent, thereby reducing the possibility of combing (bonding) with the PEDOT:PSS composite  21 . Therefore, a dispersing agent can solve the above problem to ensure the graphenes to be surface-modified with the PEDOT:PSS composite  21  for forming the polymer composite material  2  provided by the instant disclosure. 
     Alternatively, in another embodiment of the instant disclosure, graphenes dissolved in a solvent can be directly mixed with the PEDOT:PSS composite  21  for bonding the graphenes with the PEDOT:PSS composite  21 . In this embodiment, the graphenes can be graphene oxide (GO) or reduced graphene oxide (RGO). However, since GO has relatively low electric conductivity, when the GO is used as a material for forming the polymer composite material  2 , a further reduction reaction may be needed after mixing the GO with the PEDOT:PSS composite  21  for improving the electric conductivitiy of the graphenes. The reducing agent for performing the reduction reaction is, for example, hydrazine (N 2 H 4 ). However, the instant disclosure is not limited thereto. 
     The polymer composite material  2  manufactured by the method provided by the instant disclosure can be directly used as the material for forming the cathode of a capacitor. For example, the polymer composite material  2  can be coated on the cathode of the capacitor through a film-forming process. Specifically, a capacitor unit can be impregnated into a solution comprising the polymer composite material  2  for forming a conductive polymer layer on the surface thereof. 
     Alternatively, after step S 102 , the product stream can be further purified for separating the polymer material. Therefore, the purity of the polymer composite material  2  can be ensured. For example, the product stream comprising the polymer composite material  2  can be purified by at least one of centrifugation, dialysis, column chromatography, precipitation and ion exchange process. 
     After the step of purifying the product stream, the polymer composite material  2  can be further homogeneously dispersed. For example, the polymer composite material  2  can be homogeneously dispersed by at least one of a homogenous stirrer, ultrasonic grinder, high pressure homogenizer and ball mill. 
     Another embodiment of the instant disclosure provides another polymer composite material and method for manufacturing the same. Please refer to  FIG. 10  and  FIG. 11 .  FIG. 10  is the structural schematic view of the polymer composite material of this embodiment, and  FIG. 11  is the flow chart of the method for manufacturing the polymer composite material. 
     Specifically, compared to the embodiment shown in  FIG. 5  and  FIG. 6 , the poly(3,4-ethylenedioxythiophene) unit  211 , the polystyrene sulfonate unit  212  and the carbon nanomaterial  22  are connected in a different manner to form the polymer composite material  2 . As shown in  FIG. 10 , the polystyrene sulfonate unit  212  is connected between the carbon nanomaterial  22  and the poly(3,4-ethylenedioxythiophene) unit  211 , and the polystyrene sulfonate unit  212  is connected to the polystyrene sulfonate unit  212  through a polymerization process. The method for manufacturing the polymer composite material of the present embodiment is described below. 
     As shown in  FIG. 11 , the method for manufacturing the polymer composite material comprises mixing the carbon nanomaterial  22  and polystyrene sulfonate for forming a carbon nanomaterial modified by polystyrene sulfonate (S 201 ); adding 3,4-ethylenedioxythiophene into a solution comprising the carbon nanomaterial modified by polystyrene sulfonate (S 203 ); and initiating a polymerization reaction to allow a reaction between 3,4-ethylenedioxythiophene and the carbon nanomaterial modified by polystyrene sulfonate in the solution for forming a product stream comprising the polymer composite material (S 205 ). 
     Please refer to  FIG. 10 . In the polymer composite material  2  manufactured by the method described above, the polystyrene sulfonate unit  212  is connected between the carbon nanomaterial  22  and a poly(3,4-ethylenedioxythiophene) unit  211 , and the polystyrene sulfonate unit  212  is bonded to the poly(3,4-ethylenedioxythiophene) unit  211  through a polymerization reaction. Based on the weight of the polymer composite material, the content of the carbon nanomaterial  22  is from 0.01-1.5 wt. %. 
     Specifically, step S 201  is for forming the carbon nanomaterial modified with PSS. In the embodiment shown in  FIG. 10  and  FIG. 11 , the carbon nanomaterial  22  is carbon nanotubes. However, the type of the carbon nanomaterial  22  is described in the previous embodiments and can be carbon nanotubes, carbon nanospheres, graphenes, carbon freak or any combination thereof. The carbon nanotubes shown in  FIG. 10  can be formed by a thermal chemical vapor deposition process. 
     Before performing step S 201 , the carbon nanomaterial  22  (carbon nanotubes, CNT) can be surface-modified. In the present embodiment, the carbon nanotubes are treated with the mixture of concentrated sulfuric acid and nitric acid (HNO 3 :H 2 SO 4 =3:1, v/v) for bonding carboxylic groups on the surface of the carbon nanotubes, thereby forming CNT-COOH. Next, the carboxylic groups on the surface of the carbon nanotubes react with thionyl choloride (SOCl 2 ) for forming carbon nanotubes modified with thinoyl chloride (CNT-COCl). The CNT-COCl is reflux by 2-hydroxyethtl-2′-bromoisobutyrate and toluene to synthesis carbon nanotubes with bromide groups (CNT-Br). 
     After the activation process mentioned above, the activated carbon nanotubes (CNT-Br) are mixed with polystyrene sulfonate  212 . Specifically, the polystyrene sulfonate  212  can be provided by sodium polystyrene sulfonate. For example, the reaction between the CNT-Br and the sodium polystyrene sulfonate can be carried out in a N, N-dimethylformamide solution with the copper bromide and PMDTA (N,N,N′,N′,N″-pentamethyldiethylenetriamine) as reaction additive. The reaction temperature in step S 201  can be, for example, 120° C., and the reaction time can be about 30 hours. After the reaction is completed, the product can be separated by centrifugation or filtration, thereby obtained the carbon nanomaterial (carbon nanotube) modified by PSS. 
     In step S 203 , 3,4-ethylenedioxythiophene is added into the solution comprising the carbon nanomaterial modified by PSS. For example, the solvent for dissolving the carbon nanomaterial modified by PSS is water. 
     In step S 205 , initiating a polymerization reaction to allow the carbon nanomaterial modified by PSS and the 3,4-ethylenedioxythiophene in the solution for forming a product stream comprising the polymer composite material  2 . After the polymerization reaction is completed, the polymer composite material  2  comprises the polystyrene sulfonate unit  212 , the poly(3,4-ethylenedioxythiophene) unit  211  and the carbon nanomaterial  22 . The polymerization reaction can be carried out by chemical oxidative method under the presence of 3,4-ethylenedioxythiophene  211 ′ and polystyrene sulfonate. Ammonium persulfate (APS) can be added during the polymerization reaction, and mechanical stirring can be applied. For example, the product stream comprising the polymer composite material  2  can be formed by mechanical stirring the solution for 48 hours under room temperature. 
     The structure of the polymer composite material  2  formed by polymerization process is shown in  FIG. 10 . Since the carbon nanotube is activated before performing step S 201 , the activated carbon nanotube is bonded to the polystyrene sulfonate unit  212  through the modified functional groups on the surface thereof. In other words, in the embodiments of the instant disclosure, the carbon nanomaterial  22  does not have to directly bond to the polystyrene sulfonate unit  212 . However, the instant disclosure is not limited thereto. In other words, the carbon nanomaterial  22  can be directly bonded to the polystyrene sulfonate unit  212 . 
     As mentioned before, the polymer composite material  2  manufactured by the method mentioned can be directly used as the material for the cathode of the capacitor. Alternatively, after step S 203 , the product stream can be further purified for separating the polymer composite material  2 . After the purifying step, the polymer composite material  2  can further be homogeneously dispersed. The details for performing purification and homogeneously dispersion are described in the previous embodiments and are not described herein. 
     In addition, the instant disclosure further provides a method for manufacturing capacitor package structure, comprising: providing at least a capacitor in which the cathode of the capacitor comprises the polymer composite material manufactured by the method mentioned above; and packaging the capacitor by a package structure. A positive electrode pin and a negative electrode pin electrically connected to the capacitor are exposed from the package structure. 
     Please refer to  FIG. 2  and  FIG. 4 .  FIG. 2  is a sectional view of one of the capacitor packaging provided by the embodiments of the instant disclosure; and  FIG. 4  is a side schematic view of another capacitor package structure provided by the embodiments of the instant disclosure. The capacitor  1  can be the capacitor unit  42  in the stacked type solid electrolytic capacitor  4 , or the wound type component  31  of the wound type solid electrolytic capacitor  3 . The package structure can be the package  43  in the stacked type solid electrolytic capacitor  4 , or the packaging component  32  in the wound type solid electrolytic capacitor  3 . The details of the above components are described above regarding the capacitor package structure. 
     In summary, the effectiveness of the instant disclosure is that the polymer composite material  2  of the instant disclosure comprises a carbon nanomaterial  22  of specific content and thus has excellent electric property. Therefore, the solid electrolytic capacitor comprising the polymer composite  2  has improved conductivity, improved thermal stability, improved polymer impregnating rate, improved capacitance, reduced equivalent series resistance, reduced loss factor and reduced leak current. In addition, the method of manufacturing the polymer composite material  2  of the instant disclosure has reduced manufacturing cost and hence, the overall manufacturing cost of the solid electrolytic capacitor is reduced. 
     The above-mentioned descriptions represent merely the exemplary embodiment of the present disclosure, without any intention to limit the scope of the instant disclosure thereto. Various equivalent changes, alterations or modifications based on the claims of the instant disclosure are all consequently viewed as being embraced by the scope of the instant disclosure.