TWI575012B - Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor - Google Patents
Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor Download PDFInfo
- Publication number
- TWI575012B TWI575012B TW104109207A TW104109207A TWI575012B TW I575012 B TWI575012 B TW I575012B TW 104109207 A TW104109207 A TW 104109207A TW 104109207 A TW104109207 A TW 104109207A TW I575012 B TWI575012 B TW I575012B
- Authority
- TW
- Taiwan
- Prior art keywords
- weight
- structural unit
- supercapacitor
- electrode
- resin composition
- Prior art date
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Description
本發明是有關於一種超級電容器電極用樹脂組成物、超級電容器電極用漿料、超級電容器電極以及超級電容器。特別是關於一種超級電容器電極用樹脂組成物，其所製備的超級電容器電極用漿料可以製作出電極層與集電體之間密著性佳的超級電容器電極、超級電容器電極用漿料、超級電容器電極，以及具有所述超級電容器電極的超級電容器。 The present invention relates to a resin composition for a supercapacitor electrode, a slurry for a supercapacitor electrode, a supercapacitor electrode, and a supercapacitor. In particular, regarding a resin composition for a supercapacitor electrode, the supercapacitor electrode slurry prepared by the method can produce a supercapacitor electrode having excellent adhesion between an electrode layer and a current collector, a slurry for a supercapacitor electrode, and a super a capacitor electrode, and a supercapacitor having the supercapacitor electrode.
超級電容器(supercapacitor,SC)，又稱為電雙層電容器(electrical double layer capacitor,EDLC)，其比一般電池有較高的能量密度，且具有可快速充放電與高循環使用壽命等優點，因此廣泛地用於能源儲存領域。 Supercapacitor (SC), also known as electrical double layer capacitor (EDLC), which has higher energy density than general batteries, and has the advantages of fast charge and discharge and high cycle life. Widely used in the field of energy storage.
超級電容器是以電雙層方式將電能儲存於電極上的電化學裝置。超級電容器能量貯存及釋放皆來自靜電荷吸附所形成的 電雙層結構。由於在這樣的電雙層結構反覆充放電的過程中，幾乎不會產生一般電池在電化學反應過程中對於電解液以及電極的損耗，所以具有優異的可逆電量以及高循環使用壽命。然而，在超級電容器的電極的製程中，經過捲繞步驟，因此容易造成集電體上的電極層剝落，而電容器的儲能效率不佳。 A supercapacitor is an electrochemical device that stores electrical energy on an electrode in an electrical double layer manner. The energy storage and release of supercapacitors are all formed by electrostatic charge adsorption. Electric double layer structure. Since in the process of repeatedly charging and discharging such an electric double layer structure, the loss of the electrolyte and the electrode in the electrochemical reaction process of the general battery is hardly generated, so that it has excellent reversible electric power and high cycle life. However, in the process of the electrode of the supercapacitor, after the winding step, the electrode layer on the current collector is easily peeled off, and the energy storage efficiency of the capacitor is not good.
因此，如何改善電極層與集電體之間密著性，實為目前此領域技術人員亟欲解決的問題。 Therefore, how to improve the adhesion between the electrode layer and the current collector is a problem that those skilled in the art are currently trying to solve.
有鑑於此，本發明提供一種超級電容器電極用樹脂組成物，及其所製備的超級電容器電極用漿料，可以製作出電極層與集電體之間密著性佳的超級電容器電極。 In view of the above, the present invention provides a resin composition for a supercapacitor electrode and a slurry for a supercapacitor electrode prepared thereby, and a supercapacitor electrode having excellent adhesion between an electrode layer and a current collector can be produced.
本發明提供一種超級電容器電極用樹脂組成物，其包括聚合物。聚合物包括式(1)所示的第一結構單元以及除了第一結構單元以外的第二結構單元。以聚合物為100重量%計，第一結構單元的含量為65重量%至95重量%，第二結構單元的含量為5重量%至35重量%。另外，聚合物的平均粒徑為290奈米至490奈米。 The present invention provides a resin composition for a supercapacitor electrode comprising a polymer. The polymer includes the first structural unit represented by the formula (1) and the second structural unit other than the first structural unit. The content of the first structural unit is from 65% by weight to 95% by weight based on 100% by weight of the polymer, and the content of the second structural unit is from 5% by weight to 35% by weight. Further, the average particle diameter of the polymer is from 290 nm to 490 nm.
式(1)中，R1為氫原子或甲基，R2為碳數為4至10的烷基。 In the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 4 to 10 carbon atoms.
在本發明的一實施例中，上述的第一結構單元為70重量%至95重量%。 In an embodiment of the invention, the first structural unit is 70% by weight to 95% by weight.
在本發明的一實施例中，上述的第一結構單元為75重量%至90重量%。 In an embodiment of the invention, the first structural unit is 75 wt% to 90 wt%.
在本發明的一實施例中，上述的聚合物的重量平均分子量為20,000至40,000。 In an embodiment of the invention, the above polymer has a weight average molecular weight of from 20,000 to 40,000.
在本發明的一實施例中，上述的第二結構單元包括醯胺系結構單元、乙烯性不飽和羧酸結構單元、乙烯性不飽和羧酸酯結構單元、芳香族乙烯基結構單元以及丙烯腈系結構單元。 In an embodiment of the invention, the second structural unit comprises a guanamine-based structural unit, an ethylenically unsaturated carboxylic acid structural unit, an ethylenically unsaturated carboxylic acid ester structural unit, an aromatic vinyl structural unit, and an acrylonitrile. Department of structural units.
在本發明的一實施例中，上述的超級電容器電極用樹脂組成物，其中醯胺系結構單元的含量為1重量%至7重量%、乙烯性不飽和羧酸結構單元的含量為1重量%至7重量%、乙烯性不飽和羧酸酯結構單元的含量為1重量%至7重量%、芳香族乙烯基結構單元的含量為1重量%至15重量%、丙烯腈系結構單元的含量為1重量%至3重量%。 In an embodiment of the present invention, the resin composition for a supercapacitor electrode, wherein the content of the guanamine-based structural unit is from 1% by weight to 7% by weight, and the content of the ethylenically unsaturated carboxylic acid structural unit is 1% by weight. The content of the ethylenically unsaturated carboxylate structural unit is from 1% by weight to 7% by weight, the content of the aromatic vinyl structural unit is from 1% by weight to 15% by weight, and the content of the acrylonitrile-based structural unit is 7% by weight or less 1% by weight to 3% by weight.
在本發明的一實施例中，上述的聚合物是經乳化聚合反應而製得。 In an embodiment of the invention, the above polymer is obtained by emulsion polymerization.
在本發明的一實施例中，上述的超級電容器電極用樹脂組成物，更包括水。 In an embodiment of the invention, the resin composition for a supercapacitor electrode described above further includes water.
本發明另提供一種超級電容器電極用漿料，其包括上述 的超級電容器電極用樹脂組成物以及活性物質。 The present invention further provides a slurry for a supercapacitor electrode, comprising the above The resin composition of the supercapacitor electrode and the active material.
本發明還提供一種超級電容器電極，其包括集電體以及位於集電體的表面上的電極層，其中電極層是由上述超級電容器電極用漿料而製得。 The present invention also provides a supercapacitor electrode comprising a current collector and an electrode layer on a surface of the current collector, wherein the electrode layer is obtained from the slurry for the supercapacitor electrode described above.
本發明還提供一種超級電容器，其包括：兩個電極以及位於這些電極之間的電解質，其中這些電極中的至少一者為上述的超級電容器電極。 The present invention also provides a supercapacitor comprising: two electrodes and an electrolyte between the electrodes, wherein at least one of the electrodes is the supercapacitor electrode described above.
基於上述，含有特定聚合物的超級電容器電極用樹脂組成物所製備的超級電容器電極用漿料可以製作出電極層與集電體之間密著性佳的超級電容器電極。藉此，應用於超級電容器時，可以有效提升電容器的儲能效率。 Based on the above-described slurry for a supercapacitor electrode prepared by using a resin composition for a supercapacitor electrode of a specific polymer, a supercapacitor electrode having excellent adhesion between the electrode layer and the current collector can be produced. Therefore, when applied to a supercapacitor, the energy storage efficiency of the capacitor can be effectively improved.
為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 The above described features and advantages of the present invention will be more apparent from the following description.
100‧‧‧捲繞型超級電容器 100‧‧‧Winding supercapacitors
110‧‧‧主體部 110‧‧‧ Main body
110a‧‧‧圓柱面 110a‧‧‧Cylindrical surface
110b‧‧‧底面 110b‧‧‧ bottom
110c‧‧‧頂面 110c‧‧‧ top surface
112‧‧‧正極 112‧‧‧ positive
112a、112c、116a、116c‧‧‧電極層 112a, 112c, 116a, 116c‧‧‧ electrode layers
112b、116b‧‧‧集電體 112b, 116b‧‧‧ Collector
114‧‧‧電解質 114‧‧‧ Electrolytes
116‧‧‧負極 116‧‧‧negative
120‧‧‧導線 120‧‧‧ wire
130‧‧‧封裝殼體 130‧‧‧Package housing
140‧‧‧封口元件 140‧‧‧ Sealing elements
H‧‧‧貫孔 H‧‧‧Tongkong
L‧‧‧積層結構 L‧‧‧ laminated structure
S1‧‧‧隔膜 S1‧‧‧ diaphragm
S2‧‧‧隔膜 S2‧‧‧ diaphragm
圖1A為依照本發明的一實施例的捲繞型超級電容器的***圖。 1A is an exploded view of a wound type supercapacitor in accordance with an embodiment of the present invention.
圖1B為依照本發明的一實施例的捲繞型超級電容器的內部示意圖。 1B is a schematic diagram of the interior of a wound type supercapacitor in accordance with an embodiment of the present invention.
圖2為沿著圖1B中的I-I’剖面的剖視示意圖。 Fig. 2 is a schematic cross-sectional view taken along line I-I' of Fig. 1B.
本發明提供一種超級電容器電極用樹脂組成物，其包括聚合物。 The present invention provides a resin composition for a supercapacitor electrode comprising a polymer.
聚合物包括式(1)所示的第一結構單元以及除了第一結構單元以外的第二結構單元。 The polymer includes the first structural unit represented by the formula (1) and the second structural unit other than the first structural unit.
式(1)中，R1為氫原子或甲基，R2為碳數為4至10的烷基。 In the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 4 to 10 carbon atoms.
第一結構單元源自於式(2)所示的第一單體。 The first structural unit is derived from the first monomer represented by the formula (2).
式(2)中，R1及R2與式(1)中的R1及R2同義，在此不另行贅述。 In the formula (2), R 1 and R 2 have the same meanings as R 1 and R 2 in the formula (1), and are not described herein.
第一單體的具體例包括但不限於丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸正戊酯、丙烯酸異戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸2,2-二乙基己酯等丙烯酸烷基酯；甲基丙烯酸 正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸正戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2,2-二乙基己酯等甲基丙烯酸烷基酯，或上述化合物的組合。 Specific examples of the first monomer include, but are not limited to, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 2,2-diethyl acrylate Alkyl acrylate such as hexyl hexyl ester; methacrylic acid N-butyl ester, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, 2,2-diethyl methacrylate An alkyl methacrylate such as hexyl hexyl ester or a combination of the above compounds.
第一單體可單獨使用一種也可組合多種來使用。 The first monomers may be used singly or in combination of two or more.
第一單體的具體例較佳為丙烯酸正丁酯、丙烯酸2-乙基己酯，或上述化合物的組合。 Specific examples of the first monomer are preferably n-butyl acrylate, 2-ethylhexyl acrylate, or a combination of the above compounds.
以聚合物為100重量%計，第一結構單元的含量為65重量%至95重量%，較佳為70重量%至95重量%，更佳為75重量%至90重量%。當第一結構單元的含量為65重量%至95重量%時，超級電容器電極的電極層與集電體之間密著性佳。 The content of the first structural unit is from 65% by weight to 95% by weight, preferably from 70% by weight to 95% by weight, more preferably from 75% by weight to 90% by weight, based on 100% by weight of the polymer. When the content of the first structural unit is from 65% by weight to 95% by weight, the adhesion between the electrode layer of the supercapacitor electrode and the current collector is good.
第二結構單元源自於第二單體。第二結構單元包括醯胺系結構單元、乙烯性不飽和羧酸結構單元、乙烯性不飽和羧酸酯結構單元、芳香族乙烯基結構單元以及丙烯腈系結構單元。第二單體包括醯胺系單體、乙烯性不飽和羧酸單體、乙烯性不飽和羧酸酯單體、芳香族乙烯基單體以及丙烯腈系單體。 The second structural unit is derived from the second monomer. The second structural unit includes a guanamine-based structural unit, an ethylenically unsaturated carboxylic acid structural unit, an ethylenically unsaturated carboxylic acid ester structural unit, an aromatic vinyl structural unit, and an acrylonitrile-based structural unit. The second monomer includes a guanamine-based monomer, an ethylenically unsaturated carboxylic acid monomer, an ethylenically unsaturated carboxylic acid ester monomer, an aromatic vinyl monomer, and an acrylonitrile-based monomer.
醯胺系結構單元源自於醯胺系單體。醯胺系單體的具體例包括但不限於丙烯醯胺(acrylamide)、甲基丙烯醯胺、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、N,N-二甲基丙烯醯胺(N,N-dimethylacrylamide)、N,N-二甲基甲基丙烯醯胺(N,N-dimethylmethacrylamide)，或上述化合物的組合。醯胺系單體可單獨使用一種也可組合多種來使用。醯胺系單體的具體例較佳為丙烯醯胺或甲基丙烯醯胺，或上述化合物的組合。以聚合物 為100重量%計，醯胺系結構單元的含量較佳為1重量%至7重量%，更佳為2重量%至6重量%，最佳為2重量%至5重量%。 The guanamine-based structural unit is derived from a guanamine-based monomer. Specific examples of the amide-based monomer include, but are not limited to, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-di N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, or a combination of the above compounds. The guanamine-based monomers may be used singly or in combination of two or more. A specific example of the amide-based monomer is preferably acrylamide or methacrylamide, or a combination of the above compounds. Polymer The content of the guanamine-based structural unit is preferably from 1% by weight to 7% by weight, more preferably from 2% by weight to 6% by weight, most preferably from 2% by weight to 5% by weight, based on 100% by weight.
乙烯性不飽和羧酸結構單元源自於乙烯性不飽和羧酸單體。乙烯性不飽和羧酸單體的具體例包括但不限於丙烯酸、甲基丙烯酸、順丁烯二酸、巴豆酸、衣康酸、反丁烯二酸，或上述化合物的組合。乙烯性不飽和羧酸單體可單獨使用一種也可組合多種來使用。乙烯性不飽和羧酸單體的具體例較佳為包括丙烯酸、甲基丙烯酸、衣康酸，或上述化合物的組合。以聚合物為100重量%計，乙烯性不飽和羧酸結構單元的含量較佳為1重量%至7重量%，更佳為2重量%至6重量%，最佳為2重量%至5重量%。 The ethylenically unsaturated carboxylic acid structural unit is derived from an ethylenically unsaturated carboxylic acid monomer. Specific examples of the ethylenically unsaturated carboxylic acid monomer include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, or a combination of the above compounds. The ethylenically unsaturated carboxylic acid monomers may be used singly or in combination of two or more. Specific examples of the ethylenically unsaturated carboxylic acid monomer preferably include acrylic acid, methacrylic acid, itaconic acid, or a combination of the above compounds. The content of the ethylenically unsaturated carboxylic acid structural unit is preferably from 1% by weight to 7% by weight, more preferably from 2% by weight to 6% by weight, most preferably from 2% by weight to 5% by weight based on 100% by weight of the polymer. %.
乙烯性不飽和羧酸酯結構單元源自於乙烯性不飽和羧酸酯單體。乙烯性不飽和羧酸酯單體的具體例包括但不限於丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯等的丙烯酸烷基酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯等的甲基丙烯酸烷基酯：順丁烯二酸二甲酯、順丁烯二酸二乙酯等的順丁烯二酸烷基酯；衣康酸二甲酯等的衣康酸烷基酯；反丁烯二酸單甲酯、反丁烯二酸單乙酯、反丁烯二酸二甲酯、反丁烯二酸二乙酯等的反丁烯二酸烷基酯，或上述化合物的組合。乙烯性不飽和羧酸酯單體可單獨使用一種也可組合多種來使用。乙烯性不飽和羧酸酯單體的具體例較佳為包括甲基丙烯酸甲酯、丙烯酸甲酯，或上述化合物的組合。以聚合物為100重量%計，乙烯性不飽和羧酸酯結構單元的含量較佳為1重量%至7重量%，更佳為2重量%至6重量%，最佳為2重量% 至5重量%。 The ethylenically unsaturated carboxylic acid ester structural unit is derived from an ethylenically unsaturated carboxylic acid ester monomer. Specific examples of the ethylenically unsaturated carboxylic acid ester monomer include, but are not limited to, alkyl acrylate such as methyl acrylate, ethyl acrylate or propyl acrylate; methacrylic acid such as methyl methacrylate or ethyl methacrylate; Alkyl ester: alkyl maleate such as dimethyl maleate or diethyl maleate; alkyl itaconate such as dimethyl itaconate; An alkyl fumarate such as monomethyl diacid, monoethyl fumarate, dimethyl fumarate or diethyl fumarate, or a combination of the above compounds. The ethylenically unsaturated carboxylic acid ester monomers may be used singly or in combination of two or more. Specific examples of the ethylenically unsaturated carboxylic acid ester monomer preferably include methyl methacrylate, methyl acrylate, or a combination of the above compounds. The content of the ethylenically unsaturated carboxylic acid structural unit is preferably from 1% by weight to 7% by weight, more preferably from 2% by weight to 6% by weight, most preferably 2% by weight based on 100% by weight of the polymer. Up to 5% by weight.
芳香族乙烯基結構單元源自於芳香族乙烯基單體。芳香族乙烯基單體的具體例包括但不限於苯乙烯、α-甲基苯乙烯、甲基-α-甲基苯乙烯、乙烯基甲苯、二乙烯基苯，或上述化合物的組合。芳香族乙烯基單體可單獨使用一種也可組合多種來使用。芳香族乙烯基單體的具體例較佳為苯乙烯或α-甲基苯乙烯，或上述化合物的組合。以聚合物為100重量%計，芳香族乙烯基結構單元的含量較佳為1重量%至15重量%，更佳為3重量%至13重量%，最佳為5重量%至11重量%。 The aromatic vinyl structural unit is derived from an aromatic vinyl monomer. Specific examples of the aromatic vinyl monomer include, but are not limited to, styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, divinylbenzene, or a combination of the above compounds. The aromatic vinyl monomers may be used singly or in combination of two or more. A specific example of the aromatic vinyl monomer is preferably styrene or α-methylstyrene, or a combination of the above compounds. The content of the aromatic vinyl structural unit is preferably from 1% by weight to 15% by weight, more preferably from 3% by weight to 13% by weight, most preferably from 5% by weight to 11% by weight based on 100% by weight of the polymer.
丙烯腈系結構單元源自於丙烯腈系單體。丙烯腈系單體的具體例包括但不限於丙烯腈(acrylonitrile)、α-甲基丙烯腈(methacrylonitrile)，或上述化合物的組合。丙烯腈系單體可單獨使用一種也可組合多種來使用。丙烯腈系單體的具體例較佳為丙烯腈。以聚合物為100重量%計，丙烯腈系結構單元的含量較佳為1重量%至3重量%，更佳為1重量%至2.5重量%，最佳為1.3重量%至2.2重量%。 The acrylonitrile-based structural unit is derived from an acrylonitrile-based monomer. Specific examples of the acrylonitrile-based monomer include, but are not limited to, acrylonitrile, α-methacrylonitrile, or a combination of the above compounds. The acrylonitrile-based monomers may be used singly or in combination of two or more. A specific example of the acrylonitrile-based monomer is preferably acrylonitrile. The content of the acrylonitrile-based structural unit is preferably from 1% by weight to 3% by weight, more preferably from 1% by weight to 2.5% by weight, most preferably from 1.3% by weight to 2.2% by weight, based on 100% by weight of the polymer.
以聚合物為100重量%計，當醯胺系結構單元、乙烯性不飽和羧酸結構單元、乙烯性不飽和羧酸酯結構單元、芳香族乙烯基結構單元，以及丙烯腈系結構單元的含量在前述範圍內時，超級電容器電極用樹脂組成物製作出的超級電容器電極的電極層與集電體之間密著性較佳。 The content of the guanamine-based structural unit, the ethylenically unsaturated carboxylic acid structural unit, the ethylenically unsaturated carboxylic acid ester structural unit, the aromatic vinyl structural unit, and the acrylonitrile-based structural unit is 100% by weight of the polymer. When it is in the above range, the adhesion between the electrode layer of the supercapacitor electrode produced by the resin composition for a supercapacitor electrode and the current collector is preferable.
以聚合物為100重量%計，第二結構單元的含量為5重量 %至35重量%。較佳為5重量%至30重量%，更佳為10重量%至25重量%。 The content of the second structural unit is 5 weights based on 100% by weight of the polymer. % to 35% by weight. It is preferably from 5% by weight to 30% by weight, more preferably from 10% by weight to 25% by weight.
聚合物的平均粒徑為290奈米至490奈米，較佳為300奈米至450奈米。當聚合物的平均粒徑小於290奈米時，超級電容器電極用樹脂組成物製作出的超級電容器電極的電極層與集電體之間密著性不佳。另外，就合成觀點而言，平均粒徑大於490奈米的聚合物難以獲得。 The polymer has an average particle diameter of from 290 nm to 490 nm, preferably from 300 nm to 450 nm. When the average particle diameter of the polymer is less than 290 nm, the adhesion between the electrode layer of the supercapacitor electrode and the current collector produced by the resin composition for the supercapacitor electrode is not good. Further, from the viewpoint of synthesis, a polymer having an average particle diameter of more than 490 nm is difficult to obtain.
聚合物的重量平均分子量較佳為20,000至40,000，更佳為25,000至35,000。當聚合物的重量平均分子量在上述範圍內時，超級電容器電極用樹脂組成物製作出的超級電容器電極的電極層與集電體之間密著性較佳。 The weight average molecular weight of the polymer is preferably from 20,000 to 40,000, more preferably from 25,000 to 35,000. When the weight average molecular weight of the polymer is within the above range, the adhesion between the electrode layer of the supercapacitor electrode and the current collector produced by the resin composition for the supercapacitor electrode is preferable.
聚合物可在水、乳化劑、聚合起始劑的存在下，使第一單體及第二單體經乳化聚合反應而製得。第一單體及第二單體的具體例已在前文說明，在此不另行贅述。另外，以合成聚合物的單體混合物的使用量為100重量%計，其第一單體及第二單體的含量約與聚合物第一結構單元及第二結構單元的含量相當，在此不另行贅述。 The polymer can be obtained by emulsion polymerization of the first monomer and the second monomer in the presence of water, an emulsifier, and a polymerization initiator. Specific examples of the first monomer and the second monomer have been described above and will not be further described herein. In addition, the content of the first monomer and the second monomer in the monomer mixture of the synthetic polymer is about 100% by weight, which is equivalent to the content of the first structural unit and the second structural unit of the polymer. No further details will be given.
水例如是去離子水、超純水、離子交換水、逆滲透水(Reverse Osmosis Water)或蒸餾水。以合成聚合物的單體混合物的使用量為100重量份計，水的使用量可為100重量份至1,000重量份。 The water is, for example, deionized water, ultrapure water, ion exchanged water, reverse osmosis water or distilled water. The amount of water used may be from 100 parts by weight to 1,000 parts by weight based on 100 parts by weight of the monomer mixture of the synthetic polymer.
乳化劑的具體例包括但不限於陰離子型表面活性劑，例 如高級醇的硫酸酯鹽、烷基苯磺酸鹽(如十二烷基苯磺酸鈉)、烷基二苯醚二磺酸鹽、脂肪族磺酸鹽、脂肪族羧酸鹽；非離子型表面活性劑，例如聚乙二醇烷基酯型、烷基苯基醚型、烷基醚；或上述乳化劑的組合。乳化劑的具體例較佳為磺化琥珀酸二環己酯鈉鹽(Sodium dicyclohexyl sulfosuccinate，商品名MA-80)。以合成聚合物的單體混合物的使用量為100重量份計，乳化劑的使用量可為0.5重量份至2重量份。 Specific examples of the emulsifier include, but are not limited to, anionic surfactants, for example Such as higher alcohol sulfate salt, alkylbenzenesulfonate (such as sodium dodecylbenzenesulfonate), alkyl diphenyl ether disulfonate, aliphatic sulfonate, aliphatic carboxylate; nonionic a surfactant such as a polyethylene glycol alkyl ester type, an alkylphenyl ether type, an alkyl ether; or a combination of the above emulsifiers. A specific example of the emulsifier is preferably sodium dicyclohexyl sulfosuccinate (trade name: MA-80). The emulsifier may be used in an amount of from 0.5 part by weight to 2 parts by weight based on 100 parts by weight of the monomer mixture of the synthetic polymer.
聚合起始劑可為自由基聚合起始劑。聚合起始劑的具體例包括但不限於過硫酸鉀、過硫酸鈉、過硫酸銨等的水溶性聚合起始劑；油溶性聚合起始劑，例如過氧化氫異丙苯、過氧化苯甲醯、第三丁基過氧化氫、乙醯化過氧化氫、過氧化氫二異丙基苯、1,1,3,3-四甲基丁基過氧化氫；或上述聚合起始劑的組合。聚合起始劑的具體例較佳為過硫酸銨。以合成聚合物的單體混合物的使用量為100重量份計，聚合起始劑的使用量可為0.01重量份至5重量份。 The polymerization initiator may be a radical polymerization initiator. Specific examples of the polymerization initiator include, but are not limited to, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, etc.; oil-soluble polymerization initiators such as cumene hydroperoxide , benzamidine peroxide, t-butyl hydroperoxide, acetonitrile hydrogen peroxide, diisopropylbenzene hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide; or A combination of polymerization initiators. A specific example of the polymerization initiator is preferably ammonium persulfate. The polymerization initiator may be used in an amount of from 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the monomer mixture of the synthetic polymer.
乳化聚合反應也可以在其他添加劑的存在下進行。其他添加劑可以列舉如防老化劑、防腐劑、分散劑、增黏劑、或上述其他添加劑的組合。 The emulsion polymerization can also be carried out in the presence of other additives. Other additives may, for example, be an anti-aging agent, a preservative, a dispersing agent, a tackifier, or a combination of the other additives mentioned above.
乳化聚合反應並沒有特別限定，可以使用批次聚合、半批次聚合、種子聚合(seed polymerization)等。此外，對於各種成分的添加方法也沒有特別限定，可以使用一次添加方法、分次添加方法、連續添加方法、或自動添加(power feeding)法等。 The emulsion polymerization reaction is not particularly limited, and batch polymerization, semi-batch polymerization, seed polymerization, or the like can be used. Further, the method of adding the various components is not particularly limited, and a single addition method, a fractional addition method, a continuous addition method, or a power feeding method can be used.
乳化聚合反應的溫度可為40至100℃，較佳為50至90℃。乳化聚合反應的反應時間可為2至12小時，較佳為3至8小時。 The temperature of the emulsion polymerization may be from 40 to 100 ° C, preferably from 50 to 90 ° C. The reaction time of the emulsion polymerization reaction may be from 2 to 12 hours, preferably from 3 to 8 hours.
經乳化聚合反應後，即可獲得含有聚合物以及水的溶液，該溶液可再經過減壓濃縮而獲得固體含量為20重量%至50重量%的超級電容器電極用樹脂組成物。亦即，超級電容器電極用樹脂組成物，除了包括聚合物之外，可更包括合成聚合物所使用的水。 After the emulsion polymerization, a solution containing a polymer and water can be obtained, and the solution can be further concentrated under reduced pressure to obtain a resin composition for a supercapacitor electrode having a solid content of 20% by weight to 50% by weight. That is, the resin composition for a supercapacitor electrode may further include water used for the synthetic polymer in addition to the polymer.
本發明另提供一種超級電容器電極用漿料，其包括上述的超級電容器電極用樹脂組成物以及活性物質。此外，若需要，超級電容器電極用漿料可更包括腐蝕劑、導電輔助劑、增黏劑、分散劑、穩定化劑等至少一種添加劑以及額外添加的水。 The present invention further provides a slurry for a supercapacitor electrode comprising the above-described resin composition for a supercapacitor electrode and an active material. In addition, the slurry for the supercapacitor electrode may further include at least one additive such as an etchant, a conductive auxiliary, a tackifier, a dispersant, a stabilizer, and additionally added water, if necessary.
活性物質的具體例包括但不限於導電性碳質材料，例如天然石墨、人造石墨或活性碳。人造石墨例如是將石油、煤炭瀝青或焦炭等經石墨化處理者。導電性高分子例如多并苯(polyacene)系有機半導體、聚乙炔、聚對伸苯基，或上述碳化物的組合。 Specific examples of the active material include, but are not limited to, conductive carbonaceous materials such as natural graphite, artificial graphite or activated carbon. The artificial graphite is, for example, a graphitized person such as petroleum, coal pitch or coke. The conductive polymer is, for example, a polyacene organic semiconductor, a polyacetylene, a polyparaphenylene group, or a combination of the above carbides.
腐蝕劑只要可以部分腐蝕後述集電體的表面，而使集電體的表面粗糙化之外，沒有其他的限制。腐蝕劑的具體例包括但不限於甲酸、乙酸、草酸、丙二酸、蘋果酸、酒石酸、琥珀酸或 或丙酸等的有機酸；或鹽酸、磷酸或硫酸等的無機酸。 The etchant has no other limitation as long as it can partially etch the surface of the current collector described above and roughen the surface of the current collector. Specific examples of the etchant include, but are not limited to, formic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid or Or an organic acid such as propionic acid; or an inorganic acid such as hydrochloric acid, phosphoric acid or sulfuric acid.
導電輔助劑的具體例包括但不限於乙炔黑或科琴黑(Ketjenblack)等之碳黑；氣相法碳纖維等之奈米碳纖；奈米碳管、石墨微粉等之導電性碳，或上述碳化物的組合。 Specific examples of the conductive auxiliary agent include, but are not limited to, carbon black such as acetylene black or Ketjenblack; carbon nanofibers such as fumed carbon fibers; conductive carbon such as carbon nanotubes and graphite fine powder, or carbonization described above. a combination of things.
增黏劑的具體例包括但不限於羧甲基纖維素、甲基纖維素、羥甲基纖維素、乙基纖維素、聚乙烯醇、聚丙烯酸(鹽)、氧化澱粉、磷酸化澱粉、酪蛋白，或上述增黏劑的組合。增黏劑的具體例較佳為甲基纖維素。 Specific examples of the tackifier include, but are not limited to, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, and cheese. Protein, or a combination of the above tackifiers. A specific example of the tackifier is preferably methyl cellulose.
分散劑的具體例包括但不限於六偏磷酸鈉、三聚磷酸鈉、焦磷酸鈉、聚丙烯酸鈉等。 Specific examples of the dispersing agent include, but are not limited to, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium polyacrylate, and the like.
穩定化劑的具體例包括但不限於非離子型表面活性劑、陰離子型表面活性劑，或其組合。 Specific examples of the stabilizer include, but are not limited to, a nonionic surfactant, an anionic surfactant, or a combination thereof.
水可用於提升漿料的均勻度。水的具體例與合成聚合物所使用的具體例相同，在此不另行贅述。 Water can be used to increase the uniformity of the slurry. Specific examples of the water are the same as those used in the case of the synthetic polymer, and are not described herein.
製備超級電容器電極用漿料的方法沒有特別的限制，只要可將超級電容器電極用樹脂組成物以及活性物質混合即可。具體而言，混合超級電容器電極用樹脂組成物以及活性物質的方法例如是以電磁攪拌器進行攪拌或以機械攪拌器進行攪拌。在本發明的超級電容器電極用漿料中，基於活性物質100重量份，超級電容器電極用樹脂組成物的使用量為1重量份至40重量份，較佳為5重量份至30重量份。超級電容器電極用漿料的固體含量為20重量%至35重量%。 The method for preparing the slurry for a supercapacitor electrode is not particularly limited as long as the resin composition for the supercapacitor electrode and the active material can be mixed. Specifically, the method of mixing the resin composition for a supercapacitor electrode and the active material is, for example, stirring with a magnetic stirrer or stirring with a mechanical stirrer. In the slurry for a supercapacitor electrode of the present invention, the resin composition for a supercapacitor electrode is used in an amount of from 1 part by weight to 40 parts by weight, based on 100 parts by weight of the active material, preferably from 5 parts by weight to 30 parts by weight. The slurry for the supercapacitor electrode has a solid content of 20% by weight to 35% by weight.
本發明另提供一種超級電容器電極，其包括集電體以及位於集電體的表面上的電極層，其中電極層是由上述的超級電容器電極用漿料而製得。 The present invention further provides a supercapacitor electrode comprising a current collector and an electrode layer on a surface of the current collector, wherein the electrode layer is obtained from the slurry for a supercapacitor electrode described above.
超級電容器電極是藉由將如上述的超級電容器電極用漿料經塗布於集電體的上表面與下表面的至少一者，並經乾燥等處理步驟而形成。 The supercapacitor electrode is formed by applying a slurry for a supercapacitor electrode as described above to at least one of an upper surface and a lower surface of a current collector, and drying or the like.
集電體例如是鋁、鈦、鉭、鐵、銅、鎳或不鏽鋼等金屬材料。金屬材料可為片狀(金屬箔)、膜狀或網狀。 The current collector is, for example, a metal material such as aluminum, titanium, tantalum, iron, copper, nickel or stainless steel. The metal material may be in the form of a sheet (metal foil), a film or a mesh.
將超級電容器電極用漿料經塗布於集電體的方法可以使用刮刀棒法、浸漬法、直接輥法、凹版印刷法、擠壓法、刷塗法、逆轉輥法、或氣刀法等方法。 The method of applying the slurry for a supercapacitor electrode to a current collector can be performed by a doctor blade method, a dipping method, a direct roll method, a gravure printing method, an extrusion method, a brush coating method, a reverse roll method, or an air knife method. .
乾燥的方法可使用放置乾燥、送風乾燥機、溫風乾燥機、紅外線加熱器、遠紅外線加熱器等。乾燥溫度通常為50℃以上。 The drying method may be a dry drying, a blower dryer, a warm air dryer, an infrared heater, a far infrared heater or the like. The drying temperature is usually 50 ° C or more.
本發明的超級電容器電極用樹脂組成物、超級電容器電極用漿料以及超級電容器電極，可應用於各種公知的超級電容器中。舉例來說，如捲繞型超級電容器、積層型超級電容器或紐扣型超級電容器。利用本發明的超級電容器電極用樹脂組成物以及超級電容器電極用漿料因電極層與集電體之間密著性佳而可有效 提升電容器的儲能效率。 The resin composition for a supercapacitor electrode, the slurry for a supercapacitor electrode, and the supercapacitor electrode of the present invention can be applied to various known supercapacitors. For example, a wound type super capacitor, a laminated type super capacitor or a button type super capacitor. The resin composition for a supercapacitor electrode of the present invention and the slurry for a supercapacitor electrode can be effectively used because of good adhesion between the electrode layer and the current collector. Improve the energy storage efficiency of the capacitor.
圖1A為依照本發明的一實施例的捲繞型超級電容器的***圖。圖1B為依照本發明的一實施例的捲繞型超級電容器的內部示意圖。請同時參照圖1A及圖1B。捲繞型超級電容器100包括主體部110、兩條導線120、封裝殼體130以及封口元件140。導線120的材料例如是金、銀、銅、鎳或不鏽鋼等金屬。封裝殼體130的材料例如是鋁、鐵、銅、鎳或不鏽鋼等金屬。封口元件140例如是由橡膠、鐵氟龍或塑膠片。 1A is an exploded view of a wound type supercapacitor in accordance with an embodiment of the present invention. 1B is a schematic diagram of the interior of a wound type supercapacitor in accordance with an embodiment of the present invention. Please refer to FIG. 1A and FIG. 1B at the same time. The wound supercapacitor 100 includes a body portion 110, two wires 120, a package housing 130, and a sealing member 140. The material of the wire 120 is, for example, a metal such as gold, silver, copper, nickel or stainless steel. The material of the package housing 130 is, for example, a metal such as aluminum, iron, copper, nickel or stainless steel. The sealing element 140 is for example made of rubber, Teflon or plastic sheet.
主體部110為圓柱體。主體部110具有圓柱面110a、底面110b以及頂面110c，其中底面110b與頂面110c位於圓柱面110a的相對兩側。主體部110是由包括正極112及負極116的積層結構L經捲繞而製得。兩條導線120分別與正極112及負極116電性連接。封裝殼體130包覆主體部110的圓柱面110a以及底面110b。封口元件140位於主體部110的頂面110c上，且具有兩個貫孔H。兩條導線120分別穿過封口元件140的兩個貫孔H而向外部電性連接。 The body portion 110 is a cylinder. The main body portion 110 has a cylindrical surface 110a, a bottom surface 110b, and a top surface 110c, wherein the bottom surface 110b and the top surface 110c are located on opposite sides of the cylindrical surface 110a. The main body portion 110 is obtained by winding a laminated structure L including the positive electrode 112 and the negative electrode 116. The two wires 120 are electrically connected to the positive electrode 112 and the negative electrode 116, respectively. The package housing 130 covers the cylindrical surface 110a and the bottom surface 110b of the main body portion 110. The sealing member 140 is located on the top surface 110c of the body portion 110 and has two through holes H. The two wires 120 are electrically connected to the outside through the two through holes H of the sealing member 140, respectively.
圖2為沿著圖1B中的I-I’剖面的剖視示意圖。積層結構L由左而右依序積層為正極112、隔膜S1、電解質114、負極116以及隔膜S2。電解質114位於正極112與負極116之間。隔膜S1位於正極112與電解質114之間。隔膜S2位於負極116的相反於電解質114的一側，亦即負極116位於電解質114與隔膜S2之間。 Fig. 2 is a schematic cross-sectional view taken along line I-I' of Fig. 1B. The laminated structure L is sequentially laminated from left to right into a positive electrode 112, a separator S1, an electrolyte 114, a negative electrode 116, and a separator S2. The electrolyte 114 is located between the positive electrode 112 and the negative electrode 116. The separator S1 is located between the positive electrode 112 and the electrolyte 114. The separator S2 is located on the side of the negative electrode 116 opposite to the electrolyte 114, that is, the negative electrode 116 is located between the electrolyte 114 and the separator S2.
正極112包括電極層112a、集電體112b以及電極層112c，其中集電體112b位於電極層112a與電極層112c之間。電極層112c位於隔膜S1旁。負極116包括電極層116a、集電體116b以及電極層116c，其中集電體116b位於電極層116a與電極層116c之間。電極層116a位於電解質114旁。正極112與負極116中的至少一者為上述的超級電容器電極。就密著性的觀點而言，正極112與負極116較佳是皆為上述的超級電容器電極。在另一實施例中，電極層112a、電極層112c、電極層116a以及電極層116c中的至少一者亦為含有上述的超級電容器電極用樹脂組成物。 The positive electrode 112 includes an electrode layer 112a, a current collector 112b, and an electrode layer 112c, wherein the current collector 112b is located between the electrode layer 112a and the electrode layer 112c. The electrode layer 112c is located beside the diaphragm S1. The anode 116 includes an electrode layer 116a, a current collector 116b, and an electrode layer 116c, wherein the current collector 116b is located between the electrode layer 116a and the electrode layer 116c. Electrode layer 116a is located next to electrolyte 114. At least one of the positive electrode 112 and the negative electrode 116 is the above-described supercapacitor electrode. From the viewpoint of adhesion, the positive electrode 112 and the negative electrode 116 are preferably the above-described supercapacitor electrodes. In another embodiment, at least one of the electrode layer 112a, the electrode layer 112c, the electrode layer 116a, and the electrode layer 116c is also a resin composition for the supercapacitor electrode described above.
電解質114的選用並沒有特別限定，也能使用公知的超級電容器電解液，只要不影響超級電容器電極上的電極層即可。電解質114例如是鋰鹽或銨鹽等電解質溶於有機溶劑所形成的非水性電解液；1-乙基-3-甲基-咪唑二氰胺(1-ethyl-3-methylimidazolium dicyanamide)、1-丁基-3,5-二甲基-吡啶溴(1-butyl-3,5-dimethylpyridinium bromide)或1-丁基-3-甲基-咪唑六氟磷酸鹽(1-butyl-3-methylimidazolium hexafluorophosphate)等室溫離子液體等。在非水性電解液中，鋰鹽例如是LiPF6、LiBF4、LiAsF6、LiSbF6、LiC(SO2CF3)3、LiN(SO2CF3)2或上述之組合。銨鹽例如是三乙基單甲基四氟硼酸銨、四乙基四氟硼酸銨、四乙基六氟磷酸銨或上述之組合。有機溶劑例如是γ-丁基內酯、碳酸乙烯酯(ethylene carbonate，EC)、碳酸丙烯酯、碳酸丁烯酯、碳酸二乙酯(diethyl carbonate，DEC)、 乙酸丙酯(propyl acetate，PA)、碳酸二甲酯(dimethyl carbonate，DMC)、碳酸甲乙酯(ethylmethyl carbonate，EMC)、環丁碸類化合物、乙腈或上述之組合。電解質114的具體例較佳為三乙基單甲基四氟硼酸銨的碳酸丙烯酯溶液。 The selection of the electrolyte 114 is not particularly limited, and a known supercapacitor electrolyte can be used as long as it does not affect the electrode layer on the supercapacitor electrode. The electrolyte 114 is, for example, a non-aqueous electrolyte solution in which an electrolyte such as a lithium salt or an ammonium salt is dissolved in an organic solvent; 1-ethyl-3-methylimidazolium dicyanamide, 1- Butyl-3,5-dimethylpyridinium bromide or 1-butyl-3-methylimidazolium hexafluorophosphate ) Room temperature ionic liquid, etc. In the non-aqueous electrolyte solution, the lithium salt is, for example, LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 CF 3 ) 2 or a combination thereof. The ammonium salt is, for example, triethylammonium monomethyltetrafluoroborate, tetraethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate or a combination thereof. The organic solvent is, for example, γ-butyl lactone, ethylene carbonate (EC), propylene carbonate, butylene carbonate, diethyl carbonate (DEC), propyl acetate (PA). , dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), cyclobutyl hydrazine, acetonitrile or a combination thereof. A specific example of the electrolyte 114 is preferably a propylene carbonate solution of triethylmonomethylammonium tetrafluoroborate.
隔膜S1、隔膜S2的選用沒有特別限制，可使用公知或市售的隔膜。隔膜例如是絕緣材料、玻璃纖維或纖維素，而絕緣材料可為聚乙烯(PE)、聚丙烯(PP)、紙漿等聚烯烴製成的微孔膜或不織布。 The selection of the diaphragm S1 and the diaphragm S2 is not particularly limited, and a known or commercially available separator can be used. The separator may be, for example, an insulating material, glass fiber or cellulose, and the insulating material may be a microporous film or a non-woven fabric made of polyolefin such as polyethylene (PE), polypropylene (PP), or pulp.
在下文中，單體混合物中的各種單體的比例約與所合成出的聚合物中的各結構單元比例相同。 Hereinafter, the ratio of the various monomers in the monomer mixture is about the same as the ratio of each structural unit in the synthesized polymer.
在耐壓性的反應器中，置入250重量份的去離子水、0.95重量份的磺化琥珀酸二環己酯鈉鹽(作為乳化劑，商品名MA-80)以及100重量份的單體混合物，其中以單體混合物為100重量%計，丙烯酸2-乙基己酯(2-EHA)為67重量%；丙烯醯胺(以下簡稱為AM)為5重量%；甲基丙烯酸(MAA)為5重量%；甲基丙烯酸甲酯(MMA)為5重量%；苯乙烯(SM)為15重量%；丙烯腈(AN)為3重量%。接著，於升溫至70℃後，加入1重量 份的過硫酸銨(APS)作為聚合起始劑，並且進行反應5小時。反應結束後進行減壓濃縮，即可獲得實施例1的固體含量為30重量%的超級電容器電極用樹脂組成物。超級電容器電極用樹脂組成物中所含有的聚合物的平均粒徑、重量平均分子量如表2。另外，平均粒徑、重量平均分子量的量測方法如後述。 In a pressure-resistant reactor, 250 parts by weight of deionized water, 0.95 parts by weight of sodium dicyclohexyl sulfosuccinate (as emulsifier, trade name MA-80) and 100 parts by weight of a single part were placed. a mixture of 2-ethylhexyl acrylate (2-EHA) of 67% by weight; acrylamide (hereinafter abbreviated as AM) of 5% by weight; methacrylic acid (MAA) ) was 5% by weight; methyl methacrylate (MMA) was 5% by weight; styrene (SM) was 15% by weight; and acrylonitrile (AN) was 3% by weight. Then, after raising the temperature to 70 ° C, add 1 weight A portion of ammonium persulfate (APS) was used as a polymerization initiator, and the reaction was carried out for 5 hours. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a resin composition for a supercapacitor electrode having a solid content of 30% by weight in Example 1. The average particle diameter and weight average molecular weight of the polymer contained in the resin composition for a supercapacitor electrode are shown in Table 2. Further, the method of measuring the average particle diameter and the weight average molecular weight will be described later.
將2重量份甲基纖維素(作為增黏劑)、16.7重量份的超級電容器電極用樹脂組成物以及93重量份的活性碳(作為活性物質)加入254重量份的去離子水中，並混合攪拌均勻，即可獲得實施例1的固體含量為27重量%的漿料。 2 parts by weight of methyl cellulose (as a tackifier), 16.7 parts by weight of a resin composition for a supercapacitor electrode, and 93 parts by weight of activated carbon (as an active material) were added to 254 parts by weight of deionized water, and mixed and stirred. Uniformly, a slurry having a solid content of 27% by weight of Example 1 was obtained.
以刮刀棒法將漿料均勻塗佈於鋁箔(作為集電體)上，漿料厚度為200μm，並將鋁箔置於烘箱中。在溫度為80℃下烘烤30分鐘，以乾燥漿料。然後，對鋁箔進行滾壓，以製成厚度約100μm、寬度約10cm、長度約30cm的實施例1的電極。將所製得的電極進行評價，評價方式如後述，並且其結果如表2所示。 The slurry was uniformly coated on an aluminum foil (as a current collector) by a doctor bar method, the thickness of the slurry was 200 μm, and the aluminum foil was placed in an oven. Bake at a temperature of 80 ° C for 30 minutes to dry the slurry. Then, the aluminum foil was rolled to prepare an electrode of Example 1 having a thickness of about 100 μm, a width of about 10 cm, and a length of about 30 cm. The obtained electrode was evaluated, and the evaluation method was as described later, and the results are shown in Table 2.
利用捲繞機，將上述製作的電極與隔膜(纖維素)一同進行捲繞，以形成主體部，並將主體部接上導線。將主體部、圓筒狀的鋁製封裝殼體以及橡膠製的封口元件真空乾燥後，在乾燥室中，將主體部***鋁製封裝殼體中。接著，注入電解液，其中電解液為溶有三乙基單甲基四氟硼酸銨的碳酸丙烯酯溶液。然 後，以封口元件進行封閉，即可製得實施例1的超級電容器。 The electrode prepared above was wound together with a separator (cellulose) by a winder to form a main body portion, and the main body portion was connected to a wire. The main body portion, the cylindrical aluminum package case, and the rubber sealing member were vacuum-dried, and then the main body portion was inserted into the aluminum package case in the drying chamber. Next, an electrolyte solution in which the electrolyte solution is a propylene carbonate solution in which triethylmonomethylammonium tetrafluoroborate is dissolved is injected. Of course Thereafter, the supercapacitor of Example 1 was obtained by sealing with a sealing member.
實施例2至實施例8的超級電容器電極用樹脂組成物、漿料、電極及超級電容器以與實施例1相同的步驟來製備。惟不同之處在於：改變超級電容器電極用樹脂組成物的成分及其用量(如表2所示)，其中表2中簡稱所對應的化合物如表1所示。將所製得的超級電容器電極用樹脂組成物以及電極進行評價，其結果如表2所示。 The resin composition, slurry, electrode, and supercapacitor for the supercapacitor electrode of Example 2 to Example 8 were prepared in the same manner as in Example 1. The only difference is that the composition of the resin composition for the supercapacitor electrode and the amount thereof (as shown in Table 2) are changed, and the compounds corresponding to the abbreviations in Table 2 are shown in Table 1. The obtained supercapacitor electrode was evaluated for the resin composition and the electrode, and the results are shown in Table 2.
比較例1至比較例8的超級電容器電極用樹脂組成物、漿料、電極及超級電容器以與實施例1相同的步驟來製備。惟不同之處在於：改變超級電容器電極用樹脂組成物的成分及其用量(如表3所示)，其中表3中簡稱所對應的化合物如表1所示。將所製得的超級電容器電極用樹脂組成物以及電極進行評價，其結果如表3所示。 The resin composition for a supercapacitor electrode of Comparative Example 1 to Comparative Example 8, a slurry, an electrode, and a supercapacitor were prepared in the same manner as in Example 1. The only difference is that the composition of the resin composition for the supercapacitor electrode and the amount thereof (as shown in Table 3) are changed, and the compounds corresponding to the abbreviations in Table 3 are shown in Table 1. The obtained supercapacitor electrode was evaluated for the resin composition and the electrode, and the results are shown in Table 3.
將所製得之超級電容器電極用樹脂組成物，以雷射粒徑分析儀(MALVERN公司製，型號：nano-s90)的動態光散射法測量聚合物的平均粒徑。 The resin composition for the supercapacitor electrode thus obtained was measured for the average particle diameter of the polymer by a dynamic light scattering method using a laser particle size analyzer (manufactured by MALVERN, model: nano-s90).
重量平均分子量(Mw)是利用已知市售標準聚苯乙烯作成之檢量線求得，以具示差曲折率偵測及光散射偵測兩項功能的凝膠透析層析儀(GPC，沃特世(Waters)公司製造)測定。 The weight average molecular weight (Mw) is obtained by using a calibration line made of a commercially available standard polystyrene, and is a gel dialysis chromatograph (GPC, Wo, which has the functions of differential tortuosity detection and light scattering detection). Measured by Waters Corporation.
取1cm×10cm的電極。接著，對電極進行彎折，使其一端環繞於直徑為1mm的滾棒。之後，在電極彎折的情況下，使滾棒自電極的一端滾至另外一端(稱為彎折1次)。來回彎折10次後，並觀察鋁箔上的電極層脫附或從鋁箔上剝落的情況。評價基準如下所示。 Take an electrode of 1 cm x 10 cm. Next, the electrode was bent so that one end thereof was wrapped around a roller having a diameter of 1 mm. Thereafter, in the case where the electrode is bent, the roller is rolled from one end of the electrode to the other end (referred to as bending once). After bending back and forth 10 times, the electrode layer on the aluminum foil was desorbed or peeled off from the aluminum foil. The evaluation criteria are as follows.
○：電極的表面平滑，密著性佳。 ○: The surface of the electrode was smooth and the adhesion was good.
×：電極的表面出現裂痕或電極層從鋁箔表面剝落，表示密著性不佳。 ×: A crack occurred on the surface of the electrode or the electrode layer peeled off from the surface of the aluminum foil, indicating that the adhesion was poor.
請參照表2及表3，與第一結構單元的含量為65重量%至95重量%的實施例1至實施例8相比，第一結構單元的含量為65重量%以下的比較例2、3、5、6的密著性不佳。由此可見，第一結構單元的含量為65重量%至95重量%時，超級電容器電極中的電極層與集電體之間密著性佳；第一結構單元的含量小於65重量%時，超級電容器電極中的電極層與集電體之間密著性不佳。 Referring to Tables 2 and 3, Comparative Example 2 in which the content of the first structural unit is 65% by weight or less is compared with Examples 1 to 8 in which the content of the first structural unit is 65% by weight to 95% by weight. The adhesion of 3, 5, and 6 is not good. It can be seen that when the content of the first structural unit is from 65% by weight to 95% by weight, the adhesion between the electrode layer and the current collector in the supercapacitor electrode is good; when the content of the first structural unit is less than 65% by weight, The adhesion between the electrode layer and the current collector in the supercapacitor electrode is poor.
與聚合物的平均粒徑為290奈米至490奈米的實施例1至實施例8相比，聚合物的平均粒徑小於290奈米的比較例1、2、4、7、8的密著性不佳。由此可見，聚合物的平均粒徑為290奈米至490奈米時，超級電容器電極中的電極層與集電體之間密著性佳；聚合物的平均粒徑小於290奈米時，超級電容器電極中的電極層與集電體之間密著性不佳。另外，平均粒徑大於490奈米的聚合物難以合成。 The density of Comparative Examples 1, 2, 4, 7, and 8 having an average particle diameter of the polymer of less than 290 nm was compared with Example 1 to Example 8 in which the average particle diameter of the polymer was from 290 nm to 490 nm. Poor sex. It can be seen that when the average particle diameter of the polymer is from 290 nm to 490 nm, the adhesion between the electrode layer and the current collector in the supercapacitor electrode is good; when the average particle diameter of the polymer is less than 290 nm, The adhesion between the electrode layer and the current collector in the supercapacitor electrode is poor. In addition, polymers having an average particle diameter of more than 490 nm are difficult to synthesize.
綜上所述，本發明提出一種超級電容器電極用樹脂組成物。在超級電容器電極用樹脂組成物中，藉由控制第一結構單元的含量為65重量%至95重量%以及聚合物的平均粒徑為290奈米至490奈米，而使得當超級電容器電極用樹脂組成物應用於超級電容器電極時，超級電容器電極中的電極層與集電體之間密著性良好。因此，應用於超級電容器時，可以有效提升電容器的儲能效率。 As described above, the present invention proposes a resin composition for a supercapacitor electrode. In the resin composition for a supercapacitor electrode, by controlling the content of the first structural unit to be 65% by weight to 95% by weight and the average particle diameter of the polymer being 290 nm to 490 nm, it is made for the supercapacitor electrode When the resin composition is applied to a supercapacitor electrode, the adhesion between the electrode layer and the current collector in the supercapacitor electrode is good. Therefore, when applied to a supercapacitor, the energy storage efficiency of the capacitor can be effectively improved.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.
112‧‧‧正極 112‧‧‧ positive
112a、112c、116a、116c‧‧‧電極層 112a, 112c, 116a, 116c‧‧‧ electrode layers
112b、116b‧‧‧集電體 112b, 116b‧‧‧ Collector
114‧‧‧電解質 114‧‧‧ Electrolytes
116‧‧‧負極 116‧‧‧negative
L‧‧‧積層結構 L‧‧‧ laminated structure
S1‧‧‧隔膜 S1‧‧‧ diaphragm
S2‧‧‧隔膜 S2‧‧‧ diaphragm
Claims (9)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104109207A TWI575012B (en) | 2015-03-23 | 2015-03-23 | Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor |
| CN201510510431.7A CN105985481B (en) | 2015-03-23 | 2015-08-19 | Resin composition for supercapacitor electrode, slurry, electrode, and supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104109207A TWI575012B (en) | 2015-03-23 | 2015-03-23 | Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201634562A TW201634562A (en) | 2016-10-01 |
| TWI575012B true TWI575012B (en) | 2017-03-21 |
Family
ID=57040468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104109207A TWI575012B (en) | 2015-03-23 | 2015-03-23 | Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105985481B (en) |
| TW (1) | TWI575012B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125971A (en) * | 2007-09-20 | 2008-02-20 | 谌丽莉 | Coating with mosquito, fly and insect driving function and preparation method thereof |
| TWI356072B (en) * | 2006-08-29 | 2012-01-11 | Unitika Ltd | Binder for forming an electrode, slurry using such |
| CN104109205A (en) * | 2013-10-28 | 2014-10-22 | 纪军 | Monoclonal antibody, antigen and gene, and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4281118B2 (en) * | 1997-11-14 | 2009-06-17 | 日本ゼオン株式会社 | Binder composition for battery, slurry for battery electrode, electrode for lithium secondary battery, and lithium secondary battery |
| US6773838B2 (en) * | 2000-09-04 | 2004-08-10 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery and negative electrode for the same |
| CN101156264B (en) * | 2005-04-07 | 2011-05-25 | Lg化学株式会社 | Binder with good rate property and long cycleability for lithium secondary battery |
| JP5760945B2 (en) * | 2011-10-24 | 2015-08-12 | 東洋インキＳｃホールディングス株式会社 | Secondary battery electrode forming composition, secondary battery electrode, and secondary battery |
-
2015
- 2015-03-23 TW TW104109207A patent/TWI575012B/en not_active IP Right Cessation
- 2015-08-19 CN CN201510510431.7A patent/CN105985481B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI356072B (en) * | 2006-08-29 | 2012-01-11 | Unitika Ltd | Binder for forming an electrode, slurry using such |
| CN101125971A (en) * | 2007-09-20 | 2008-02-20 | 谌丽莉 | Coating with mosquito, fly and insect driving function and preparation method thereof |
| CN104109205A (en) * | 2013-10-28 | 2014-10-22 | 纪军 | Monoclonal antibody, antigen and gene, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105985481B (en) | 2018-06-26 |
| TW201634562A (en) | 2016-10-01 |
| CN105985481A (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6311269B2 (en) | Adhesive for lithium ion secondary battery, separator for lithium ion secondary battery, and lithium ion secondary battery | |
| JP5626336B2 (en) | Lithium ion secondary battery | |
| US9171675B2 (en) | Electrical storage device, lithium ion capacitor and negative electrode for lithium ion capacitor | |
| JP6273956B2 (en) | Binder for secondary battery porous membrane, slurry composition for secondary battery porous membrane, porous membrane for secondary battery, and secondary battery | |
| US11028209B2 (en) | Conductive resin composition for electrodes, electrode composition, electrode using same and lithium ion battery | |
| JP6327251B2 (en) | Porous membrane slurry composition for lithium ion secondary battery, separator for lithium ion secondary battery, electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| WO2014002937A1 (en) | Method for producing resin film for non-aqueous electrolyte secondary battery and resin film for non-aqueous electrolyte secondary battery | |
| JP2015028842A (en) | Adhesive agent for lithium ion secondary batteries, lithium ion secondary battery separator, and lithium ion secondary battery | |
| KR20120094003A (en) | Binder particles for electrochemical element | |
| JP2010218793A (en) | Lithium ion secondary battery and method of manufacturing the same | |
| KR20190125329A (en) | Conductive material dispersion liquid for electrochemical device electrodes, slurry composition for electrochemical device electrodes and production method thereof, electrode for electrochemical device, and electrochemical device | |
| WO2019107463A1 (en) | Conductive material paste for electrochemical elements, slurry composition for electrochemical element positive electrodes and method for producing same, positive electrode for electrochemical elements, and electrochemical element | |
| KR20160140888A (en) | Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus | |
| JP2012238488A (en) | Electrode binder, electrode, and lithium ion secondary battery including the electrode | |
| CN114008825A (en) | Composition for electrochemical device, positive electrode mixture, positive electrode structure, and secondary battery | |
| JP4969734B2 (en) | Secondary battery negative electrode binder and secondary battery electrode composition | |
| JP6236964B2 (en) | Porous membrane composition for lithium ion secondary battery, separator for lithium ion secondary battery, electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP2015070245A (en) | Binder composition for electrochemical capacitors, slurry composition for electrochemical capacitors, electrode for electrochemical capacitors, and electrochemical capacitor | |
| KR20160113587A (en) | Electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| TW201843870A (en) | Collector for electricity storage devices, method for producing same, and coating liquid used in production of same | |
| JP5562688B2 (en) | Lithium ion capacitor manufacturing method and positive electrode manufacturing method | |
| TWI575012B (en) | Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor | |
| JP6340826B2 (en) | Secondary battery porous membrane slurry, manufacturing method, secondary battery porous membrane, and secondary battery | |
| TWI575011B (en) | Resin composition for electrode of supercapacitor, slurry, electrode and supercapacitor | |
| WO2010150902A1 (en) | Electrode for lithium ion secondary battery, binder for the electrode, and lithium ion secondary battery equipped with the electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |