TWI552421B - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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TWI552421B
TWI552421B TW103103225A TW103103225A TWI552421B TW I552421 B TWI552421 B TW I552421B TW 103103225 A TW103103225 A TW 103103225A TW 103103225 A TW103103225 A TW 103103225A TW I552421 B TWI552421 B TW I552421B
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secondary battery
lithium secondary
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TW201444160A (en
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俞成勳
姜有宣
李敬美
朴秦賢
石正敦
梁斗景
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Ｌｇ化學股份有限公司
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Description

鋰二次電池 Lithium secondary battery

本發明係關於一種鋰二次電池，其包括陰極；陽極；分隔器；和凝膠聚合物電解質，更特別地，係關於一種鋰二次電池，其中陽極包含以矽(Si)為基礎的陽極活性材料，凝膠聚合物電解質係藉由聚合包括具有能夠鍵結至金屬離子的官能基之單體之組成物而形成，和電池的充電電壓在3.0伏特至5.0伏特的範圍內。 The present invention relates to a lithium secondary battery comprising a cathode; an anode; a separator; and a gel polymer electrolyte, and more particularly, to a lithium secondary battery in which the anode comprises a ruthenium (Si)-based anode The active material, the gel polymer electrolyte is formed by polymerizing a composition including a monomer having a functional group capable of bonding to a metal ion, and the charging voltage of the battery is in the range of 3.0 volts to 5.0 volts.

近來，電子裝置、電子產品、資訊和通信工業中的可攜、微小化、質輕和高性能之趨勢迅速成長。據此，高性能鋰二次電池被用來作為這些可攜式電子裝置的能源，且其需求迅速提高。二次電池，其可藉充電和放電重覆使用，為用於資訊和通信、電動自行車或電動載具之可攜式電子裝置的能源之必要者。特別地，由於這些產品的性能取決於作為關鍵組件的電池，所以消費者對於高容量電池的需求提高。 Recently, the trend of portability, miniaturization, light weight and high performance in the electronic device, electronic products, information and communication industries has grown rapidly. Accordingly, high-performance lithium secondary batteries are used as an energy source for these portable electronic devices, and their demand is rapidly increasing. Secondary batteries, which can be reused by charging and discharging, are essential for the energy of portable electronic devices for information and communication, electric bicycles or electric vehicles. In particular, since the performance of these products depends on batteries as a key component, consumer demand for high-capacity batteries has increased.

通常，已知電池安全性之改良依序為液態電 解質、凝膠聚合物電解質、和固態聚合物電解質，但電池性能卻以相同順序降低。 In general, it is known that the improvement of battery safety is in the order of liquid electricity. Desolvation, gel polymer electrolyte, and solid polymer electrolyte, but battery performance is reduced in the same order.

液態電解質，特別地，鹽溶於非水性有機溶劑中之離子導電性有機液態電解質，為用於電化學裝置(如使用電化學反應的典型電池和電雙層電容器)的電解質主要使用者。但是，當使用液態電解質時，電極材料會退化且有機溶劑易揮發。安全性有限，如因為常溫和電池本身的溫度升高而導致燃燒。 A liquid electrolyte, in particular, an ion-conductive organic liquid electrolyte in which a salt is dissolved in a non-aqueous organic solvent, is a main user of an electrolyte for an electrochemical device such as a typical battery using an electrochemical reaction and an electric double-layer capacitor. However, when a liquid electrolyte is used, the electrode material is degraded and the organic solvent is volatile. There is limited safety, such as burning due to the normal temperature and the temperature of the battery itself.

已經知道固態聚合物電解質因為電池性能欠佳而尚未被商品化。 Solid polymer electrolytes have not been known to be commercially available due to poor battery performance.

由於凝膠聚合物電解質具有極佳的電化學安全性，所以具有極佳的電化學安定性，可以持續維持電池的厚度。此外，由於凝膠相的固有黏著性，電極和電解質之間的接觸極佳，可製造薄膜型電池。因此，擴大各種凝膠聚合物電解質之開發。 Since the gel polymer electrolyte has excellent electrochemical safety, it has excellent electrochemical stability and can continuously maintain the thickness of the battery. Further, due to the intrinsic adhesion of the gel phase, the contact between the electrode and the electrolyte is excellent, and a thin film type battery can be manufactured. Therefore, the development of various gel polymer electrolytes has been expanded.

凝膠聚合物電解質中，由於鋰離子的尺寸小，不僅較容易直接移動，且因為圖1說明的跳躍現象(hopping phenomenon)，所以，鋰離子容易在電解質液中移動。 In the gel polymer electrolyte, since the size of lithium ions is small, not only is it easy to move directly, but because of the hopping phenomenon illustrated in Fig. 1, lithium ions easily move in the electrolyte solution.

當金屬離子溶解時，金屬離子在陽極中還原成金屬態而阻斷陽極的反應點。當新金屬沈澱在陽極表面上時，電解質液在金屬表面上製造新的固態電解質界面(SEI)層，並因此，持續消耗電解質液。陽極中的SEI層的厚度會持續提高而提高電阻，鋰二次電池的壽命特性會 降低。因此，須改良前述限制。 When the metal ions are dissolved, the metal ions are reduced to a metallic state in the anode to block the reaction point of the anode. When a new metal precipitates on the surface of the anode, the electrolyte liquid creates a new solid electrolyte interface (SEI) layer on the metal surface and, therefore, continues to consume the electrolyte liquid. The thickness of the SEI layer in the anode will continue to increase and the resistance will be increased, and the life characteristics of the lithium secondary battery will reduce. Therefore, the aforementioned limitations must be improved.

本發明提供一種鋰二次電池，其藉由防止溶解的金屬離子自陰極移動至陽極或降低移動速率而減少金屬於陽極上之沉澱，並因此，不僅改良電池壽命，電池於一般和高電壓的容量特性亦極佳。 The present invention provides a lithium secondary battery which reduces precipitation of a metal on an anode by preventing dissolved metal ions from moving from a cathode to an anode or lowering a moving rate, and thus, not only improves battery life, but also improves battery life in general and high voltage. The capacity characteristics are also excellent.

根據本發明之特點，提供一種鋰二次電池，其包括陰極；陽極；分隔器；和凝膠聚合物電解質。 According to a feature of the present invention, there is provided a lithium secondary battery comprising a cathode; an anode; a separator; and a gel polymer electrolyte.

其中i)該陽極包含以矽(Si)為基礎的陽極活性材料， ii)該凝膠聚合物電解質係藉由聚合包括具有能夠鍵結至金屬離子的官能基之單體之組成物而形成，和 iii)該電池的充電電壓在3.0伏特至5.0伏特的範圍內。 Where i) the anode comprises an anode active material based on cerium (Si), Ii) the gel polymer electrolyte is formed by polymerizing a composition including a monomer having a functional group capable of bonding to a metal ion, and Iii) The charging voltage of the battery is in the range of 3.0 volts to 5.0 volts.

根據本發明的另一特點，提供一種製造鋰二次電池之方法，該方法包括將包括陰極、陽極、介於陰極和陽極之間的分隔器之電極組合品***電池殼中；和將用於凝膠聚合物電解質之組成物注入電池殼中並聚合該組成物以形成凝膠聚合物電解質，其中該用於聚合物電解質之組成物包含電解質溶液溶劑；可被離子化的鋰鹽；聚合反 應引發劑；和具有能夠鍵結至金屬離子之官能基的單體。 According to another feature of the present invention, there is provided a method of manufacturing a lithium secondary battery, the method comprising: inserting an electrode assembly including a cathode, an anode, a separator interposed between a cathode and an anode, into a battery can; and a composition of the gel polymer electrolyte is injected into the battery can and polymerized to form a gel polymer electrolyte, wherein the composition for the polymer electrolyte contains an electrolyte solution solvent; a lithium salt which can be ionized; An initiator; and a monomer having a functional group capable of bonding to a metal ion.

根據本發明之具體實施例之鋰二次電池藉由防止溶解的金屬離子自陰極移動至陽極或降低移動速率而減少金屬於陽極上之沉澱，並因此，不僅改良電池壽命，電池於一般和高電壓的容量特性亦極佳。 A lithium secondary battery according to a specific embodiment of the present invention reduces precipitation of a metal on an anode by preventing dissolved metal ions from moving from a cathode to an anode or lowering a moving rate, and thus, not only improves battery life, but also improves battery life. The capacity characteristics of the voltage are also excellent.

圖1說明當使用凝膠聚合物電解質時，鋰離子的移動原理；圖2為根據典型的電解質液和根據本發明之具體實施例的凝膠聚合物電解質之使用，比較金屬沉澱於陽極上的程度。 1 illustrates the principle of movement of lithium ions when a gel polymer electrolyte is used; and FIG. 2 is a comparison of the use of a typical electrolyte liquid and a gel polymer electrolyte according to a specific embodiment of the present invention to compare metal precipitation on an anode. degree.

圖3為說明實例1至4和比較例1至4中製得的鋰二次電池於4.3伏特的高電壓之容量的圖。 3 is a graph illustrating the capacity of a lithium secondary battery prepared in Examples 1 to 4 and Comparative Examples 1 to 4 at a high voltage of 4.3 volts.

下文中，將更詳細地描述本發明以更清楚地瞭解本發明。 Hereinafter, the present invention will be described in more detail to more clearly understand the present invention.

將瞭解說明書和申請專利範圍中所用的詞彙或名詞不應以一般使用的辭典中所定義的意義闡釋。將進一步瞭解詞彙或名詞應基於本發明者可合宜地界定詞彙或名詞以最佳地解釋本發明之原則，以具有與本發明的相關 技術和技術構思之背景中的意義一致的意思加以闡釋。 It will be understood that the words or nouns used in the specification and the scope of the patent application should not be interpreted in the meanings defined in the commonly used dictionary. It will be further understood that the vocabulary or noun should be based on the inventor's right to define a vocabulary or noun to best explain the principles of the present invention to have relevance to the present invention. The meaning of the meaning in the context of technical and technical ideas is explained.

本發明之鋰二次電池包括包括陰極；陽極；分隔器；和凝膠聚合物電解質，其中i)該陽極包含以矽(Si)為基礎的陽極活性材料，ii)該凝膠聚合物電解質係藉由聚合包括具有能夠鍵結至金屬離子的官能基之單體之組成物而形成，和iii)該電池的充電電壓在3.0伏特至5.0伏特的範圍內。 A lithium secondary battery of the present invention includes a cathode; an anode; a separator; and a gel polymer electrolyte, wherein i) the anode contains an anode active material based on cerium (Si), and ii) the gel polymer electrolyte system Formed by polymerizing a composition comprising a monomer having a functional group capable of bonding to a metal ion, and iii) charging voltage of the battery is in the range of 3.0 volts to 5.0 volts.

在根據本發明之具體實施例之鋰二次電池的電解質中，組成物，作為用於凝膠聚合物電解質之組成物，包括電解質溶液溶劑、可被離子化的鋰鹽、聚合反應引發劑、和具有可鍵結至金屬離子的官能基之單體(作為可藉聚合反應形成凝膠聚合物之單體)。 In the electrolyte of the lithium secondary battery according to the specific embodiment of the present invention, the composition, as a composition for the gel polymer electrolyte, includes an electrolyte solution solvent, an ionizable lithium salt, a polymerization initiator, And a monomer having a functional group bondable to a metal ion (as a monomer which can form a gel polymer by polymerization).

該具有官能基的單體係丙烯腈或以丙烯酸酯為基礎的單體，較佳地，該官能基包含選自由經C1-C5烷基或鹵素取代或未經彼等取代之下列結構-CN、和、或其二或更多者之混合物所組成之群組中之任一者。 The single-system acrylonitrile or acrylate-based monomer having a functional group, preferably, the functional group comprises the following structure selected from the group consisting of C 1 -C 5 alkyl or halogen substituted or not substituted -CN, with Or any of the group consisting of a mixture of two or more thereof.

根據本發明之具體實施例，該具有官能基的單體之代表例為選自由以下化合物或其二或更多者之混合物所組成之群組中之任一者： According to a specific embodiment of the present invention, a representative example of the monomer having a functional group is any one selected from the group consisting of the following compounds or a mixture of two or more thereof:

(1)丙烯酸2-氰乙酯； (1) 2-cyanoethyl acrylate;

(2)丙烯酸2-氰基乙氧基乙酯； (2) 2-cyanoethoxyethyl acrylate;

(3)丙烯腈； (3) acrylonitrile;

(4)(E)-3-(吡啶-2-基)-丙烯酸乙酯； (4) (E)-3-(pyridin-2-yl)-ethyl acrylate;

(5)(E)-3-(4-吡啶基)-2-丙烯酸乙酯； (5) ethyl (E)-3-(4-pyridyl)-2-acrylate;

(6)2-丙烯酸，3,3’-[2,2’-聯吡啶]-4,4’-二基雙-，二甲酯； (6) 2-acrylic acid, 3,3'-[2,2'-bipyridyl]-4,4'-diylbis-, dimethyl ester;

(7)2-丙烯酸，2-[2,2’-聯吡啶]-6-基乙酯；(8)2-丙烯酸，2-[2,2’-聯吡啶]-5-基乙酯；(9)2-丙烯酸，2-[2,2’-聯吡啶]-4-基乙酯；(10)2-丙烯酸，1,1’-[[2,2’-聯吡啶]-4,4’-二基雙(伸甲基)]酯；(11)2-丙烯酸，1,10-啡啉-2,9-二基雙(伸甲基)酯；(12)2-丙烯酸，3-(1,10-啡啉-2-基)-，苯基甲酯；和(13)2-丙烯酸，2-[[(1-側氧基-2-丙烯基)氧基]甲基]-2-[(1,10-啡啉-5-基甲氧基)甲基]-1,3-丙二酯。 (7) 2-acrylic acid, 2-[2,2'-bipyridyl]-6-ylethyl ester; (8) 2-acrylic acid, 2-[2,2'-bipyridyl]-5-ylethyl ester; (9) 2-acrylic acid, 2-[2,2'-bipyridyl]-4-ylethyl ester; (10) 2-acrylic acid, 1,1'-[[2,2'-bipyridyl]-4, 4'-diylbis(methyl)]ester; (11)2-acrylic acid, 1,10-morpholine-2,9-diylbis(methyl)ester; (12)2-acrylic acid, 3 -(1,10-morpholin-2-yl)-, phenylmethyl ester; and (13) 2-acrylic acid, 2-[[(1-o-oxy-2-propenyl)oxy]methyl] -2-[(1,10-morpholine-5-ylmethoxy)methyl]-1,3-propanediester.

這些化合物中，特別可以使用選自由丙烯酸2-氰乙酯、丙烯酸2-氰基乙氧基乙酯、丙烯腈、和(E)-3-(吡啶-2-基)丙烯酸乙酯、或其二或更多者之混合物所組成之群組中之任一者。 Among these compounds, particularly selected from the group consisting of 2-cyanoethyl acrylate, 2-cyanoethoxyethyl acrylate, acrylonitrile, and ethyl (E)-3-(pyridin-2-yl)acrylate, or Any of a group consisting of a mixture of two or more.

根據本發明之具體實施例，由於該具有官能基的單體包括在單體中之官能基，該官能基可以安定地固定於凝膠聚合物電解質的凝膠結構中。 According to a specific embodiment of the present invention, since the functional group-containing monomer includes a functional group in the monomer, the functional group can be stably fixed in the gel structure of the gel polymer electrolyte.

例如，在藉由分別將氰基和丙烯酸基加至用於凝膠聚合物電解質(凝膠電解質液)的組成物中並聚合而形成錯合物的情況中，錯合物本身在用於凝膠聚合物電解質的組成物中移動，而於陽極發生還原反應且有金屬沉澱。但是，根據本發明之具體實施例，在使用丙烯酸2-氰乙酯作為該具有官能基的單體的情況中，由於氰基含括於 該具有官能基的單體中，氰基本身不會在凝膠結構中移動。 For example, in the case where a cyano group and an acrylic group are respectively added to a composition for a gel polymer electrolyte (gel electrolyte liquid) and polymerized to form a complex, the complex itself is used for coagulation. The composition of the gel polymer electrolyte moves, and a reduction reaction occurs at the anode and a metal precipitates. However, according to a specific embodiment of the present invention, in the case where 2-cyanoethyl acrylate is used as the monomer having a functional group, since the cyano group is included In the monomer having a functional group, cyanide does not substantially move in the gel structure.

即，根據本發明之具體實施例，如圖2所示者，在用於凝膠聚合物電解質的組成物中使用該具有官能基的單體的情況中，該具有官能基的單體與自陰極溶解的金屬離子鍵結而減少金屬於陽極上之沉澱，此不同於使用典型的電解質液的情況(其中，自陰極溶出的金屬離子沉澱於陽極上)。因此，可改良鋰二次電池的充電和放電效率並展現良好的循環特性。此外，在包括具有官能基的單體之用於凝膠聚合物電解質的組成物用於鋰二次電池的情況中，可改良一般和高電壓範圍的容量特性。 That is, according to a specific embodiment of the present invention, as shown in FIG. 2, in the case of using the monomer having a functional group in the composition for a gel polymer electrolyte, the monomer having a functional group and self The metal ions in the cathode are bonded to reduce the precipitation of the metal on the anode, which is different from the case of using a typical electrolyte solution in which metal ions eluted from the cathode are precipitated on the anode. Therefore, the charging and discharging efficiency of the lithium secondary battery can be improved and good cycle characteristics can be exhibited. Further, in the case where a composition for a gel polymer electrolyte including a monomer having a functional group is used for a lithium secondary battery, capacity characteristics in a general and high voltage range can be improved.

本說明書中所謂的“一般電壓”是指鋰二次電池的充電電壓在3.0伏特至低於4.3伏特的範圍內，而“高電壓”是指充電電壓在4.3伏特至5.0伏特的範圍內的情況。 The term "general voltage" as used in the specification means that the charging voltage of the lithium secondary battery is in the range of 3.0 volts to less than 4.3 volts, and the "high voltage" refers to the case where the charging voltage is in the range of 4.3 volts to 5.0 volts. .

以該組成物總重計，所包括之該具有官能基的單體含量為0.1重量%至10重量%，例如，0.5重量%至5重量%。在該具有官能基的單體的量低於0.1重量%的情況中，膠凝困難，並因此，未展現凝膠聚合物電解質的特性。在該單體的量高於10重量%的情況中，因為單體過量而造成電阻提高，並因此，電池性能降低。 The monomer having a functional group is included in an amount of from 0.1% by weight to 10% by weight, for example, from 0.5% by weight to 5% by weight based on the total weight of the composition. In the case where the amount of the monomer having a functional group is less than 0.1% by weight, gelation is difficult, and therefore, the characteristics of the gel polymer electrolyte are not exhibited. In the case where the amount of the monomer is more than 10% by weight, the electric resistance is increased due to the excess of the monomer, and thus, the battery performance is lowered.

根據本發明之具體實施例，組成物亦進一步包括具有2至6個丙烯酸基的單體，且該單體為支鏈單體。 According to a particular embodiment of the invention, the composition further comprises a monomer having from 2 to 6 acrylic groups, and the monomer is a branched monomer.

支鏈單體，例如，為選自由四丙烯酸二三羥甲基丙烷酯、五丙烯酸二季戊四醇酯、和六丙烯酸二季戊四醇酯、或其二或更多者之混合物所組成之群組中之任一者。 The branched monomer is, for example, selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate, or a mixture of two or more thereof. One.

以該組成物總重計，所包括之該支鏈單體含量為0.1重量%至10重量%，例如，0.5重量%至5重量%。 The branched monomer content is from 0.1% by weight to 10% by weight, for example, from 0.5% by weight to 5% by weight, based on the total weight of the composition.

根據本發明之具體實施例，在組成物進一步包括支鏈單體的情況中，該具有官能基的單體和該支鏈單體可混合並於30℃至100℃的溫度範圍內反應2分鐘至12小時以製造可聚合的單體。此情況中，該具有官能基的單體對該支鏈單體之含量比(重量比)，例如，在1：0.1至1：10的範圍內。但本發明不限於此。 According to a specific embodiment of the present invention, in the case where the composition further includes a branched monomer, the functional group-containing monomer and the branched monomer may be mixed and reacted in a temperature range of 30 ° C to 100 ° C for 2 minutes. It took 12 hours to produce a polymerizable monomer. In this case, the content ratio (weight ratio) of the monomer having a functional group to the branched monomer is, for example, in the range of 1:0.1 to 1:10. However, the invention is not limited thereto.

含括於本發明之組成物中之可離子化的鋰鹽，例如，可為選自由LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、LiN(CF3SO2)2、CF3SO3Li、LiC(CF3SO2)3、和LiC4BO8、或其二或更多者之混合物所組成之群組中之任一者。但本發明不限於此。 The ionizable lithium salt included in the composition of the present invention may be, for example, selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN(C 2 F 5 SO 2 ) 2 , LiN. Any of the group consisting of (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC(CF 3 SO 2 ) 3 , and LiC 4 BO 8 , or a mixture of two or more thereof. However, the invention is not limited thereto.

典型上用於鋰二次電池之電解質液中的任何電解質溶液溶劑可以無限制地作為本發明中使用的電解質溶液溶劑，且例如，醚、酯、醯胺、直鏈碳酸酯、或環狀碳酸酯可以單獨或以其二或更多者之混合物的形式使用。 Any of the electrolyte solution solvents typically used in the electrolyte liquid of the lithium secondary battery may be used as the electrolyte solution solvent used in the present invention without limitation, and for example, an ether, an ester, a guanamine, a linear carbonate, or a cyclic carbonic acid. The esters may be used singly or in the form of a mixture of two or more thereof.

這些材料中，基本上含括環狀碳酸酯、直鏈碳酸酯、或其混合物(碳酸酯混合物)。環狀碳酸酯的特定 例子可為選自由碳酸伸乙酯(EC)、碳酸伸丙酯(PC)、碳酸1,2-伸丁酯、碳酸2,3-伸丁酯、碳酸1,2-伸戊酯、碳酸2,3-伸戊酯、碳酸伸乙烯酯、和其鹵化物、或其二或更多者之混合物所組成之群組中之任一者。直鏈碳酸酯的特定例子亦可為選自由碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸乙酯甲酯(EMC)、碳酸甲酯丙酯(MPC)、和碳酸乙酯丙酯(EPC)、或其二或更多者之混合物所組成之群組中之任一者。但本發明不限於此。 Among these materials, substantially include a cyclic carbonate, a linear carbonate, or a mixture thereof (carbonate mixture). Cyclic carbonate specific Examples may be selected from the group consisting of ethyl acetate (EC), propyl carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-carbenyl carbonate, carbonic acid 2 Any of the group consisting of 3-amyl ester, carbonic acid vinyl ester, and halides thereof, or a mixture of two or more thereof. Specific examples of the linear carbonate may also be selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), and methyl propyl carbonate. Any of the group consisting of (MPC), and ethyl propyl carbonate (EPC), or a mixture of two or more thereof. However, the invention is not limited thereto.

特別地，由於碳酸伸丙酯和碳酸伸乙酯(作為以碳酸酯為基礎的電解質溶液溶劑中之環狀碳酸酯)係高黏度的有機溶劑並具有高介電常數，所以碳酸伸丙酯和碳酸伸乙酯易使得電解質液中的鋰鹽解離。因此，可使用碳酸伸丙酯和碳酸伸乙酯。由於前述環狀碳酸酯與低黏度、低介電常數的直鏈碳酸酯(如碳酸乙酯甲酯、碳酸二乙酯、和碳酸二甲酯)以適當比例混合會製造導電性高的電解質液，所以可以使用，例如，碳酸伸丙酯和碳酸伸乙酯。 In particular, since propylene carbonate and ethyl carbonate (as a cyclic carbonate in a carbonate-based electrolyte solution solvent) are high-viscosity organic solvents and have a high dielectric constant, propyl carbonate and Carbonic acid ethyl ester readily dissociates the lithium salt in the electrolyte solution. Therefore, propyl carbonate and ethyl carbonate can be used. Since the above-mentioned cyclic carbonate is mixed with a low-viscosity, low-dielectric linear carbonate such as ethyl methyl carbonate, diethyl carbonate, and dimethyl carbonate in an appropriate ratio, a highly conductive electrolyte solution is produced. Therefore, it is possible to use, for example, propyl carbonate and ethyl carbonate.

選自由乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、γ-丁內酯、γ-戊內酯、γ-己內酯、σ-戊內酯、和ε-己內酯、或其二或更多者之混合物所組成之群組中之任一者亦可作為電解質溶液溶劑中的酯。但本發明不限於此。 Selected from methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, and ε Any of the group consisting of caprolactone, or a mixture of two or more thereof, may also be used as the ester in the solvent of the electrolyte solution. However, the invention is not limited thereto.

本發明中，此技術已知的典型聚合反應引發 劑可作為聚合反應引發劑。 In the present invention, typical polymerization reactions known in the art are initiated The agent can be used as a polymerization initiator.

該聚合反應引發劑的非限制例可為有機過氧化物或氫過氧化物，如苄醯過氧化物、乙醯過氧化物、二月桂醯過氧化物、二三級丁基過氧化物、過氧基-2-乙基己酸三級丁酯、枯基過氧化氫、和氫過氧化物，和偶氮基化合物，如2,2’-偶氮基雙(2-氰基丁烷)、2,2’-偶氮基雙(甲基丁腈)、2,2’-偶氮基雙(異-丁腈)(AIBN)、和2,2’-偶氮基雙(二甲基戊腈)(AMVN)。但本發明不限於此。 Non-limiting examples of the polymerization initiator may be organic peroxides or hydroperoxides such as benzammonium peroxide, acetamidine peroxide, dilaurin peroxide, di-tertiary butyl peroxide, Tert-butyl peroxy-2-ethylhexanoate, cumyl hydroperoxide, and hydroperoxide, and azo compounds such as 2,2'-azobis(2-cyanobutane) ), 2,2'-azobis(methylbutyronitrile), 2,2'-azobis(iso-butyronitrile) (AIBN), and 2,2'-azobis(dimethyl) A valeronitrile) (AMVN). However, the invention is not limited thereto.

聚合反應引發劑可藉熱而在電池中解離，用於非限制例，於30℃至100℃的溫度，或可於室溫(5℃至30℃)解離而形成自由基，且可藉自由基聚合反應與可聚合的單體反應而形成凝膠聚合物電解質。 The polymerization initiator can be dissociated in the battery by heat, and can be used for non-limiting examples, at a temperature of 30 ° C to 100 ° C, or can be dissociated at room temperature (5 ° C to 30 ° C) to form free radicals, and freely The base polymerization reacts with the polymerizable monomer to form a gel polymer electrolyte.

以該組成物總重計，該聚合反應引發劑的用量為0.01重量%至2重量%。聚合反應引發劑的量大於2重量%時，在用於凝膠聚合物電解質之組成物注入電池的期間內，膠凝過於迅速，或者會留下未反應的引發劑而在之後對電池性能造成負面影響。反之，聚合反應引發劑的量低於0.01重量%時，無法順利地膠凝。 The polymerization initiator is used in an amount of from 0.01% by weight to 2% by weight based on the total weight of the composition. When the amount of the polymerization initiator is more than 2% by weight, gelation is excessively rapid during the injection of the composition for the gel polymer electrolyte into the battery, or an unreacted initiator may remain and the battery performance may be caused thereafter. Negative impact. On the other hand, when the amount of the polymerization initiator is less than 0.01% by weight, gelation cannot be smoothly performed.

除了前述組份以外，根據本發明之組成物可以選擇性地包括此技術已知的其他添加劑。 In addition to the foregoing components, the compositions according to the present invention may optionally include other additives known in the art.

根據本發明之具體實施例，本發明亦提供一種製造鋰二次電池之方法，其包括：將包括陰極、陽極、介於陰極和陽極之間的分隔器之電極組合品***電池殼中；和將用於凝膠聚合物電解質之組成物注入電池殼中並 聚合該組成物以形成凝膠聚合物電解質，其中該用於凝膠聚合物電解質之組成物包含電解質溶液溶劑；可被離子化的鋰鹽；聚合反應引發劑；和具有能夠鍵結至金屬離子之官能基的單體。根據此技術已知的典型方法，根據本發明之具體實施例之凝膠聚合物電解質係藉由聚合該用於凝膠聚合物電解質之前述組成物而形成。例如，凝膠聚合物電解質可藉用於凝膠聚合物電解質之組成物在二次電池中之原處聚合反應而形成。 According to a specific embodiment of the present invention, the present invention also provides a method of manufacturing a lithium secondary battery, comprising: inserting an electrode assembly including a cathode, an anode, and a separator interposed between a cathode and an anode into a battery can; and Injecting the composition for the gel polymer electrolyte into the battery can and Polymerizing the composition to form a gel polymer electrolyte, wherein the composition for the gel polymer electrolyte comprises an electrolyte solution solvent; a lithium salt that can be ionized; a polymerization initiator; and having a bond capable of bonding to the metal ion a functional monomer. According to a typical method known in the art, a gel polymer electrolyte according to a specific embodiment of the present invention is formed by polymerizing the aforementioned composition for a gel polymer electrolyte. For example, the gel polymer electrolyte can be formed by a polymerization reaction of a composition of a gel polymer electrolyte in situ in a secondary battery.

根據本發明之例示具體實施例，該方法可包括(a)將由陰極、陽極、介於陰極和陽極之間的分隔器形成之電極組合品***電池殼中；和(b)將用於凝膠聚合物電解質之組成物注入電池殼中並聚合該組成物以形成電解質。 According to an exemplary embodiment of the present invention, the method may include (a) inserting an electrode assembly formed of a cathode, an anode, a separator interposed between the cathode and the anode into the battery can; and (b) using the gel The composition of the polymer electrolyte is injected into the battery can and the composition is polymerized to form an electrolyte.

在鋰二次電池中之原處聚合反應可藉熱聚合反應進行。此情況中，所須聚合時間在約2分鐘至12小時的範圍內，而熱聚合反應溫度在30℃至100℃的範圍內。 The in situ polymerization in a lithium secondary battery can be carried out by thermal polymerization. In this case, the polymerization time required is in the range of about 2 minutes to 12 hours, and the thermal polymerization temperature is in the range of 30 ° C to 100 ° C.

完成藉聚合反應之膠凝時，形成凝膠聚合物電解質。特定言之，形成凝膠聚合物，其中可聚合的單體藉聚合反應彼此交聯，且藉此形成的凝膠聚合物均勻地以液態電解質液浸滲，其中，電解質鹽在電解質溶液溶劑中解離。 Upon completion of gelation by polymerization, a gel polymer electrolyte is formed. Specifically, a gel polymer is formed in which polymerizable monomers are cross-linked to each other by polymerization, and the gel polymer formed thereby is uniformly impregnated with a liquid electrolyte solution in which an electrolyte salt is in an electrolyte solution solvent Dissociation.

本發明之鋰二次電池的電極可藉此技術已知的典型方法製造。例如，黏合劑、導電劑、和分散劑，必 要時，及溶劑與電極活性材料混合並攪拌以製造漿料，及之後以此漿料塗覆金屬電流收集器表面並壓製。之後，藉由乾燥此金屬電流收集器而製得電極。 The electrode of the lithium secondary battery of the present invention can be produced by a typical method known in the art. For example, binders, conductive agents, and dispersants must When necessary, the solvent is mixed with the electrode active material and stirred to prepare a slurry, and then the metal current collector surface is coated with the slurry and pressed. Thereafter, an electrode is produced by drying the metal current collector.

本發明中，任何化合物可以無限制地作為陰極中的陰極活性材料，只要其可於一般電壓或高電壓使用且可逆地插置/脫離鋰即可。 In the present invention, any compound can be used as the cathode active material in the cathode without limitation as long as it can be used at a general voltage or a high voltage and reversibly interposed/decoupled from lithium.

根據本發明之具體實施例，於一般電壓可使用的陰極活性材料，例如，包括選自由LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiNi1-yCoyO2(0y<1)、LiCo1-yMnyO2(0y<1)、LiNi1-yMnyO2(0y<1)、和Li(NiaCobMnc)O2(0<a,b,c1、a+b+c=1)、或其二或更多者之混合物所組成之群組中之任一者。但本發明不限於此。除了以上氧化物以外，亦可含括硫化物、硒化物、和鹵化物。 According to a specific embodiment of the present invention, a cathode active material usable at a general voltage, for example, includes a material selected from the group consisting of LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiNi 1-y Co y O 2 (0) y<1), LiCo 1-y Mn y O 2 (0 y<1), LiNi 1-y Mn y O 2 (0 y<1), and Li(Ni a Co b Mn c )O 2 (0<a,b,c 1. Any of a group of a+b+c=1), or a mixture of two or more thereof. However, the invention is not limited thereto. In addition to the above oxides, sulfides, selenides, and halides may also be included.

根據本發明之另一具體實施例之鋰二次電池中，可用於高電壓的陰極活性材料包括選自由尖晶石鋰過渡金屬氧化物(其具有六角形層狀塊鹽結構和高容量特性、橄欖石結構、立方體結構)、V2O5、TiS、和MoS、或其二或更多者之混合物所組成之群組中之任一者。 In a lithium secondary battery according to another embodiment of the present invention, a cathode active material usable for a high voltage includes a lithium transition metal oxide selected from a spinel having a hexagonal layered salt structure and high capacity characteristics, Any of the group consisting of an olivine structure, a cubic structure, V 2 O 5 , TiS, and MoS, or a mixture of two or more thereof.

特定言之，陰極活性材料，例如，可包括選自由化學式1至3之化合物、或其二或更多者之混合物所組成之群組中之任一者。 Specifically, the cathode active material, for example, may include any one selected from the group consisting of the compounds of Chemical Formulas 1 to 3, or a mixture of two or more thereof.

<化學式1> Li[LixNiaCobMnc]O2(其中0<x0.3，0.3c0.7，0<a+b<0.5，和x+a+b+c=1)；<化學式2>LiMn2-xMxO4(其中M為選自由鎳(Ni)、鈷(Co)、鐵(Fe)、磷(P)、硫(S)、鋯(Zr)、鈦(Ti)、和鋁(Al)所組成之群組中之一或多種元素，而0<x2)；<化學式3>Li1+aCoxM1-xAX4(其中M為選自由Al、鎂(Mg)、Ni、Co、錳(Mn)、Ti、鎵(Ga)、銅(Cu)、釩(V)、鈮(Nb)、Zr、鈰(Ce)、銦(In)、鋅(Zn)、和釔(Y)所組成之群組中之一或多種元素，X為選自由氧(O)、氟(F)、和氮(N)所組成之群組中之一或多種元素，A為P、S或其混合元素，0a0.2，而0.5x1)。 <Chemical Formula 1> Li[Li x Ni a Co b Mn c ]O 2 (where 0<x 0.3, 0.3 c 0.7,0<a+b<0.5, and x+a+b+c=1); <Chemical Formula 2>LiMn 2-x M x O 4 (wherein M is selected from nickel (Ni), cobalt (Co), One or more elements of the group consisting of iron (Fe), phosphorus (P), sulfur (S), zirconium (Zr), titanium (Ti), and aluminum (Al), and 0 < x 2); <Chemical Formula 3> Li 1+a Co x M 1-x AX 4 (wherein M is selected from the group consisting of Al, magnesium (Mg), Ni, Co, manganese (Mn), Ti, gallium (Ga), copper ( One or more elements of the group consisting of Cu), vanadium (V), niobium (Nb), Zr, cerium (Ce), indium (In), zinc (Zn), and yttrium (Y), X is selected One or more elements in the group consisting of free oxygen (O), fluorine (F), and nitrogen (N), A is P, S or a mixed element thereof, 0 a 0.2, and 0.5 x 1).

該陰極活性材料符合化學式1中的0.4c0.7，和0.2a+b<0.5，且包括選自由LiNi0.5Mn1.5O4、LiCoPO4、和LiFePO4、或其二或更多者之混合物所組成之群組中之任一者。 The cathode active material conforms to 0.4 in Chemical Formula 1. c 0.7, and 0.2 a+b<0.5, and includes any one selected from the group consisting of LiNi 0.5 Mn 1.5 O 4 , LiCoPO 4 , and LiFePO 4 , or a mixture of two or more thereof.

根據本發明之具體實施例之鋰二次電池的陽極中，該以Si為基礎的陽極活性材料包括可在此技術中作為陽極活性材料的Si。例如，該陽極活性材料包括選自由單獨Si；藉Si和碳質材料之機械熔合而形成的Si-C複合物；藉Si和金屬之機械熔合而形成的複合物；碳-Si奈 米複合物；Si氧化物(SiOx，1x2)；和經碳塗覆的Si或Si氧化物；或其二或更多者之混合物所組成之群組中之任一者。Si-C複合物中的碳質材料為選自由天然石墨、人造石墨、中間相碳微球(MCMB)、碳纖維、和碳黑、或其二或更多者之混合物所組成之群組中之任一者。使用Si-C複合物時，該Si-C複合物中之矽(Si)對碳(C)的比在40重量份：60重量份至80重量份：20重量份的範圍內。由於SiO或SiO2，作為Si氧化物，藉由在與鋰反應的期間內，形成Li2O和矽酸鋰作為惰性相，所以可在紓緩Si體積變化中扮演緩衝的角色，所以SiO或SiO2亦改良容量特性。此外，在藉Si和金屬之機械熔合而形成的複合物中，金屬為選自由Ti、V、鉻(Cr)、Mn、Fe、Co、Ni、Cu、Zr、Nb、鉬(Mo)、鉭(Ta)、鎢(W)、鉿(Hf)、錸(Re)、銀(Ag)、金(Au)、Al、Zn、錫(Sn)、銻(Sb)、和其組合所組成之群組中之任一者。 In the anode of the lithium secondary battery according to the specific embodiment of the present invention, the Si-based anode active material includes Si which can be used as an anode active material in the art. For example, the anode active material includes a Si-C composite selected from the group consisting of Si alone; mechanical fusion by Si and a carbonaceous material; a composite formed by mechanical fusion of Si and metal; carbon-Si nanocomposite ;Si oxide (SiO x ,1 x 2); and any of the group consisting of carbon coated Si or Si oxide; or a mixture of two or more thereof. The carbonaceous material in the Si-C composite is selected from the group consisting of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), carbon fibers, and carbon black, or a mixture of two or more thereof. Either. When the Si-C composite is used, the ratio of cerium (Si) to carbon (C) in the Si-C composite is in the range of 40 parts by weight: 60 parts by weight to 80 parts by weight: 20 parts by weight. Since SiO or SiO 2 , as the Si oxide, Li 2 O and lithium niobate are formed as an inert phase during the reaction with lithium, so that it can play a buffering role in relieving the volume change of Si, so SiO or SiO 2 also improves the capacity characteristics. Further, in the composite formed by mechanical fusion of Si and metal, the metal is selected from the group consisting of Ti, V, chromium (Cr), Mn, Fe, Co, Ni, Cu, Zr, Nb, molybdenum (Mo), yttrium. a group consisting of (Ta), tungsten (W), hafnium (Hf), yttrium (Re), silver (Ag), gold (Au), Al, Zn, tin (Sn), bismuth (Sb), and combinations thereof Any of the groups.

根據本發明之具體實施例之鋰二次電池的陽極之以Si為基礎的陽極活性材料中，可以進一步包括以碳為基礎的材料，如石墨。 The Si-based anode active material of the anode of the lithium secondary battery according to the specific embodiment of the present invention may further include a carbon-based material such as graphite.

混合和攪拌陽極或陰極活性材料、黏合劑、溶劑和導電劑及必要時典型使用的分散劑而製造漿料。之後，藉由以此漿料塗覆電流收集器及壓製經塗覆的電流收集器而製得陽極或陰極。 The slurry is prepared by mixing and stirring an anode or a cathode active material, a binder, a solvent, and a conductive agent, and a dispersant which is typically used, if necessary. Thereafter, an anode or a cathode is prepared by coating a current collector with the slurry and pressing the coated current collector.

各種類型的黏合劑聚合物，如偏二氟乙烯-六氟丙烯共聚物(PVDF-co-HEP)、聚偏二氟乙烯、聚丙烯 腈、聚甲基丙烯酸甲酯、聚乙烯醇、羧甲基纖維素(CMC)、澱粉、羥丙基纖維素、再生的纖維素、聚乙烯基吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、聚丙烯酸酯、乙烯-丙烯-二烯單體(EPDM)、磺化的EPDM、苯乙烯-丁二烯橡膠(SBR)、氟橡膠、和各種共聚物等，可作為黏合劑。 Various types of binder polymers, such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride, polypropylene Nitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, Polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, and various copolymers can be used as a binder.

典型的多孔材料聚合物膜亦可作為典型的分隔器，例如，自以聚烯烴為基礎的聚合物(如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物，和乙烯/甲基丙烯酸酯共聚物)製造的多孔聚合物膜，可以單獨使用或積層作為分隔器。此外，可以使用典型的多孔非梭織物，例如，高熔點玻璃纖維或聚對酞酸伸乙酯纖維形成的非梭織物。但本發明不限於此。 Typical porous polymer membranes can also be used as typical separators, for example, from polyolefin-based polymers (eg, ethylene homopolymers, propylene homopolymers, ethylene/butene copolymers, ethylene/hexene copolymers). A porous polymer film made of an ethylene/methacrylate copolymer can be used alone or as a separator. Further, a typical porous non-woven fabric, for example, a high-melting glass fiber or a non-woven fabric of polyethylene terephthalate fibers can be used. However, the invention is not limited thereto.

未特別限制本發明之鋰二次電池的形狀，且例如，可為使用罐的圓筒型、稜鏡型、囊袋型、或硬幣型。 The shape of the lithium secondary battery of the present invention is not particularly limited, and may be, for example, a cylindrical type, a sputum type, a pouch type, or a coin type using a can.

下文中，將根據特定實例，詳細說明本發明。然而，本發明可以許多不同的形式體現且不應限於文中所提出的具體實施例。更確切言之，提出這些具體實施例而使得此揭示完全和完整，且將本發明之觀點的範圍完整傳達至嫻於此技術者。 Hereinafter, the present invention will be described in detail based on specific examples. However, the invention may be embodied in many different forms and should not be limited to the specific embodiments set forth herein. Rather, these specific embodiments are presented so that this disclosure will be thorough and complete.

實例 Instance

下文中，將根據實例和實驗例，更詳係地描 述本發明。但本發明不限於此。 In the following, it will be described in more detail based on examples and experimental examples. The invention is described. However, the invention is not limited thereto.

實例1 Example 1 <用於凝膠聚合物電解質之組成物之製造> <Manufacture of a composition for a gel polymer electrolyte>

藉由將LiPF6溶於非水性電解質溶液溶劑(其組成中，碳酸伸乙酯(EC)對碳酸乙酯甲酯(EMC)的體積比為1：2)中，使得LiPF6濃度為1M，而製得電解質液。藉由添加以100重量份電解質液計為5重量份可聚合的單體(2.5重量份丙烯酸2-氰乙酯和2.5重量份四丙烯酸二三羥甲基丙烷酯)和0.25重量份過氧基-2-乙基己酸三級丁酯(作為聚合反應引發劑)，製得用於凝膠聚合物電解質之組成物。 The LiPF 6 concentration is 1 M by dissolving LiPF 6 in a solvent of a non-aqueous electrolyte solution in which the volume ratio of ethyl carbonate (EC) to ethyl methyl carbonate (EMC) is 1:2. And the electrolyte solution is prepared. 5 parts by weight of a polymerizable monomer (2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate) and 0.25 parts by weight of peroxy group by adding 100 parts by weight of the electrolyte liquid A ternary butyl 2-ethylhexanoate (as a polymerization initiator) was used to prepare a composition for a gel polymer electrolyte.

<硬幣型二次電池之製造> <Manufacture of coin type secondary battery> 陰極之製造 Cathode manufacturing

藉由將94重量%Li[Li0.29Ni0.14Co0.11Mn0.46]O2作為陰極活性材料、3重量%碳黑作為導電劑、和3重量%偏二氟乙烯(PVdF)作為黏合劑添加至作為溶劑的N-甲基-2-吡咯烷酮(NMP)中，製得陰極混合物漿料。作為陰極電流收集器之約20微米厚的鋁(Al)薄膜經此陰極混合物漿料塗覆並乾燥，之後，Al薄膜經滾壓而製得陰極。 By adding 94% by weight of Li[Li 0.29 Ni 0.14 Co 0.11 Mn 0.46 ]O 2 as a cathode active material, 3% by weight of carbon black as a conductive agent, and 3% by weight of vinylidene fluoride (PVdF) as a binder, A cathode mixture slurry was prepared in a solvent of N-methyl-2-pyrrolidone (NMP). An approximately 20 micrometer thick aluminum (Al) film as a cathode current collector was coated with the cathode mixture slurry and dried, after which the Al film was rolled to obtain a cathode.

陽極之製造 Manufacture of anode

經碳塗覆的SiO和石墨以10：90的重量比混合作為陽極活性材料。此陽極活性材料、作為導電劑的碳黑、SBR、和CMC以94：2：2：2的重量比混合。藉此製得的混合物置於蒸餾水(作為溶劑)中並混合以製造均勻的陽極漿料。 The carbon-coated SiO and graphite were mixed as a anode active material in a weight ratio of 10:90. This anode active material, carbon black as a conductive agent, SBR, and CMC were mixed at a weight ratio of 94:2:2:2. The mixture thus obtained was placed in distilled water (as a solvent) and mixed to produce a uniform anode slurry.

作為陽極電流收集器之約10微米厚的銅(Cu)薄膜經此陽極漿料塗覆，乾燥，和壓製，之後，對此Cu薄膜沖壓而製得陽極。 Approximately 10 micrometers thick copper (Cu) film as an anode current collector was coated, dried, and pressed through the anode slurry, after which the anode was formed by stamping the Cu film.

電池之製造 Battery manufacturing

使用陰極、陽極、和聚丙烯/聚乙烯/聚丙烯(PP/PE/PP)之三層形成的分隔器組裝電池，製得之用於凝膠聚合物電解質之組成物注入組裝的電池中。之後，藉由使該組裝的電池在氮氣氛中於80℃加熱2分鐘至30分鐘而製得硬幣型二次電池。 The battery was assembled using a separator formed of a cathode, an anode, and a polypropylene/polyethylene/polypropylene (PP/PE/PP) three-layer separator, and the composition for the gel polymer electrolyte was injected into the assembled battery. Thereafter, a coin-type secondary battery was produced by heating the assembled battery at 80 ° C for 2 minutes to 30 minutes in a nitrogen atmosphere.

實例2 Example 2

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，使用丙烯酸2-羥基乙氧基乙酯代替丙烯酸2-氰乙酯。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the composition for the gel polymer electrolyte of Example 1, 2-hydroxyethoxyethyl acrylate was used instead of 2-cyanoethyl acrylate. .

實例3 Example 3

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，使用丙烯腈代替丙烯酸2-氰乙酯。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the composition for the gel polymer electrolyte of Example 1, acrylonitrile was used instead of 2-cyanoethyl acrylate.

實例4 Example 4

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，使用(E)-3-(吡啶-2-基)丙烯酸乙酯代替丙烯酸2-氰乙酯。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the composition for the gel polymer electrolyte of Example 1, ethyl (E)-3-(pyridin-2-yl)acrylate was used. Instead of 2-cyanoethyl acrylate.

比較例1 Comparative example 1

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，未使用可聚合的單體和聚合反應引發劑。 A coin-type secondary battery was fabricated in the same manner as in Example 1, but in the production of the composition for the gel polymer electrolyte of Example 1, no polymerizable monomer and polymerization initiator were used.

比較例2 Comparative example 2

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，單獨使用5重量份的四丙烯酸二三羥甲基丙烷酯代替使用5重量份可聚合的單體(其藉由混合2.5重量份丙烯酸2-氰乙酯和2.5重量份四丙烯酸二三羥甲基丙烷酯而製得)。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the composition for the gel polymer electrolyte of Example 1, 5 parts by weight of ditrimethylolpropane tetraacrylate was used instead. 5 parts by weight of a polymerizable monomer obtained by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate.

比較例3 Comparative example 3

以與實例1相同的方式製造硬幣型二次電池，但在實例1之用於凝膠聚合物電解質的組成物的製造中，單獨使用5重量份的五丙烯酸二季戊四醇酯代替使用5重量份可聚合的單體(其藉由混合2.5重量份丙烯酸2-氰乙酯和2.5重量份四丙烯酸二三羥甲基丙烷酯而製得)。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the composition for the gel polymer electrolyte of Example 1, 5 parts by weight of dipentaerythritol pentaacrylate was used instead of 5 parts by weight. A polymerized monomer obtained by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate.

比較例4 Comparative example 4

以與實例1相同的方式製造硬幣型二次電池，但在實例1之陽極的製造中，單獨使用石墨代替使用陽極活性材料(經碳塗覆的SiO和石墨之混合物)。 A coin-type secondary battery was fabricated in the same manner as in Example 1, except that in the production of the anode of Example 1, graphite was used alone instead of using an anode active material (a mixture of carbon-coated SiO and graphite).

實驗例 Experimental example

實例1至4和比較例1至4中製造的鋰二次電池(電池容量：4.5毫安培小時)於55℃於0.7C的恆定電流充電至4.3伏特。之後，鋰二次電池於4.3伏特的恆定電壓充電，當充電電流達0.225毫安培時中止充電。電池靜置10分鐘之後，電池於0.5C的恆定電流放電至3.0伏特的電壓。重覆充電和放電至40次循環及之後測定電池容量。其結果示於圖3。 The lithium secondary batteries (battery capacity: 4.5 mAh) manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were charged to 4.3 volts at a constant current of 0.7 C at 55 °C. Thereafter, the lithium secondary battery was charged at a constant voltage of 4.3 volts, and the charging was stopped when the charging current reached 0.225 mA. After the battery was allowed to stand for 10 minutes, the battery was discharged at a constant current of 0.5 C to a voltage of 3.0 volts. The charging and discharging were repeated until 40 cycles and then the battery capacity was measured. The result is shown in Fig. 3.

特定言之，如圖3所示者，至第5次循環，實例1至4和比較例1至4的電池容量彼此幾乎類似。但是，比較例1至4的容量在約第10次循環之後開始降低且在第20次循環中快速降低。反之，相較於比較例1至4，實例1至4的容量變化斜率相當小，且特別地，甚至 於在第40次循環中，實例1至4所展現的容量為比較例1至4之容量的2至4倍或更高。 Specifically, as shown in FIG. 3, the battery capacities of Examples 1 to 4 and Comparative Examples 1 to 4 were almost similar to each other up to the 5th cycle. However, the capacities of Comparative Examples 1 to 4 began to decrease after about the 10th cycle and rapidly decreased in the 20th cycle. On the contrary, the slopes of the capacity changes of Examples 1 to 4 were rather small compared to Comparative Examples 1 to 4, and in particular, even In the 40th cycle, the capacities exhibited by Examples 1 to 4 were 2 to 4 times or more of the capacities of Comparative Examples 1 to 4.

因此，瞭解在4.3伏特的高電壓充電，在49次循環之後，相較於比較例1至4中製造的電池之情況，實例1至4中製造的電池之放電容量獲明顯改良。 Therefore, understanding of the high voltage charging at 4.3 volts, after 49 cycles, the discharge capacity of the batteries fabricated in Examples 1 to 4 was significantly improved as compared with the case of the batteries fabricated in Comparative Examples 1 to 4.

工業應用性 Industrial applicability

由於根據本發明之具體實施例之鋰二次電池不僅改良電池的壽命，亦於一般和高電壓皆具有極佳的容量特性，所以其適用於二次電池。 Since the lithium secondary battery according to the embodiment of the present invention not only improves the life of the battery, but also has excellent capacity characteristics in both general and high voltage, it is suitable for a secondary battery.

Claims (14)

一種鋰二次電池，其包含：陰極；陽極；分隔器；和凝膠聚合物電解質，其中該陽極包含以矽(Si)為基礎的陽極活性材料，該凝膠聚合物電解質係藉由聚合包括具有能夠鍵結至金屬離子的官能基之單體之組成物而形成，該電池的充電電壓在3.0伏特至5.0伏特的範圍內，該具有官能基的單體係以丙烯酸酯為基礎的單體，及該官能基包含選自由經C1-C5烷基或鹵素取代或未經彼等取代之下列結構-CN、和、或其二或更多者之混合物所組成之群組中之任一者。 A lithium secondary battery comprising: a cathode; an anode; a separator; and a gel polymer electrolyte, wherein the anode comprises an anode active material based on cerium (Si), the gel polymer electrolyte being included by polymerization Formed with a composition of a monomer capable of bonding to a functional group of a metal ion having a charging voltage in the range of 3.0 volts to 5.0 volts, the single system acrylate-based monomer having a functional group And the functional group comprises the following structure -CN selected from the group consisting of C 1 -C 5 alkyl or halogen substituted or not substituted with Or any of the group consisting of a mixture of two or more thereof. 如申請專利範圍第1項之鋰二次電池，其中該陽極活性材料包含選自由單獨Si；藉Si和碳質材料之機械熔合而形成的Si-C複合物；藉Si和金屬之機械熔合而形成的複合物；碳-Si奈米複合物；Si氧化物；和經碳塗覆的Si或Si氧化物；或其二或更多者之混合物所組成之群組中之任一者。 The lithium secondary battery of claim 1, wherein the anode active material comprises a Si-C composite selected from the group consisting of Si alone; mechanical fusion of Si and a carbonaceous material; mechanical fusion by Si and metal Any of the group of composites formed; a carbon-Si nanocomposite; an Si oxide; and a carbon-coated Si or Si oxide; or a mixture of two or more thereof. 如申請專利範圍第2項之鋰二次電池，其中該Si-C複合物中之矽(Si)對碳(C)的比在40重量份：60重量份至 80重量份：20重量份的範圍內。 The lithium secondary battery of claim 2, wherein the ratio of cerium (Si) to carbon (C) in the Si-C composite is 40 parts by weight: 60 parts by weight to 80 parts by weight: in the range of 20 parts by weight. 如申請專利範圍第2項之鋰二次電池，其中該碳質材料為選自由天然石墨、人造石墨、中間相碳微球(MCMB)、碳纖維、和碳黑、或其二或更多者之混合物所組成之群組中之任一者。 A lithium secondary battery according to claim 2, wherein the carbonaceous material is selected from the group consisting of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), carbon fibers, and carbon black, or two or more thereof. Any of the groups of mixtures. 如申請專利範圍第1項之鋰二次電池，其中該具有該官能基的單體為選自由以下化合物或其二或更多者之混合物所組成之群組中之任一者：(1)丙烯酸2-氰乙酯；(2)丙烯酸2-氰基乙氧基乙酯；(3)(E)-3-(吡啶-2-基)-丙烯酸乙酯；(4)(E)-3-(4-吡啶基)-2-丙烯酸乙酯；(5)2-丙烯酸，3,3’-[2,2’-聯吡啶]-4,4’-二基雙-，二甲酯；(6)2-丙烯酸，2-[2,2’-聯吡啶]-6-基乙酯；(7)2-丙烯酸，2-[2,2’-聯吡啶]-5-基乙酯；(8)2-丙烯酸，2-[2,2’-聯吡啶]-4-基乙酯；(9)2-丙烯酸，1,1’-[[2,2’-聯吡啶]-4,4’-二基雙(伸甲基)]酯；(10)2-丙烯酸，1,10-啡啉-2,9-二基雙(伸甲基)酯；(11)2-丙烯酸，3-(1,10-啡啉-2-基)-，苯基甲酯；和(12)2-丙烯酸，2-[[(1-側氧基-2-丙烯基)氧基]甲基]-2-[(1,10-啡啉-5-基甲氧基)甲基]-1,3-丙二酯。 A lithium secondary battery according to claim 1, wherein the monomer having the functional group is any one selected from the group consisting of the following compounds or a mixture of two or more thereof: (1) 2-cyanoethyl acrylate; (2) 2-cyanoethoxyethyl acrylate; (3) (E)-3-(pyridin-2-yl)-ethyl acrylate; (4) (E)-3 -(4-pyridyl)-2-ethyl acrylate; (5) 2-acrylic acid, 3,3'-[2,2'-bipyridyl]-4,4'-diyl bis-, dimethyl ester; (6) 2-acrylic acid, 2-[2,2'-bipyridyl]-6-ylethyl ester; (7) 2-acrylic acid, 2-[2,2'-bipyridyl]-5-ylethyl ester; (8) 2-acrylic acid, 2-[2,2'-bipyridyl]-4-ylethyl ester; (9) 2-acrylic acid, 1,1'-[[2,2'-bipyridyl]-4, 4'-diylbis(methyl)]ester; (10) 2-acrylic acid, 1,10-morpholine-2,9-diylbis(methyl)ester; (11)2-acrylic acid, 3 -(1,10-morpholin-2-yl)-, phenylmethyl ester; and (12) 2-acrylic acid, 2-[[(1-o-oxy-2-propenyl)oxy]methyl] -2-[(1,10-morpholine-5-ylmethoxy)methyl]-1,3-propanediester. 如申請專利範圍第1項之鋰二次電池，其中該組成 物包含電解質溶液溶劑、可被離子化的鋰鹽、聚合反應引發劑、和具有可鍵結至金屬離子的官能基之單體。 Such as the lithium secondary battery of claim 1 of the patent scope, wherein the composition The material comprises an electrolyte solution solvent, a lithium salt which can be ionized, a polymerization initiator, and a monomer having a functional group bondable to the metal ion. 如申請專利範圍第6項之鋰二次電池，其中該組成物進一步包含具有2至6個丙烯酸基的單體，且該單體為選自由四丙烯酸二三羥甲基丙烷酯、五丙烯酸二季戊四醇酯、和六丙烯酸二季戊四醇酯、或其二或更多者之混合物所組成之群組的支鏈單體。 The lithium secondary battery of claim 6, wherein the composition further comprises a monomer having 2 to 6 acrylic groups, and the monomer is selected from the group consisting of ditrimethylolpropane tetraacrylate and pentaacrylic acid. A branched monomer of the group consisting of pentaerythritol ester, and dipentaerythritol hexaacrylate, or a mixture of two or more thereof. 如申請專利範圍第6項之鋰二次電池，其中以該組成物總重計，所包括之該具有該官能基的單體含量為0.1重量%至10重量%。 A lithium secondary battery according to claim 6, wherein the content of the monomer having the functional group is from 0.1% by weight to 10% by weight based on the total weight of the composition. 如申請專利範圍第7項之鋰二次電池，其中以該組成物總重計，所包括之該支鏈單體含量為0.1重量%至10重量%。 A lithium secondary battery according to claim 7, wherein the branched monomer content is from 0.1% by weight to 10% by weight based on the total weight of the composition. 如申請專利範圍第7項之鋰二次電池，其中該具有官能基的單體對該支鏈單體之含量比(重量比)在1：0.1至1：10的範圍內。 The lithium secondary battery of claim 7, wherein the content ratio of the functional group-containing monomer to the branched monomer is in the range of 1:0.1 to 1:10. 如申請專利範圍第1項之鋰二次電池，其中用於該陰極的陰極活性材料為選自由化學式1至3之化合物、或其二或更多者之混合物所組成之群組中之任一者：<化學式1>Li[LixNiaCobMnc]O2(其中0<x0.3，0.3c0.7，0<a+b<0.5，和x+a+b+c=1)；<化學式2>LiMn2-xMxO4(其中M為選自由鎳(Ni)、鈷(Co)、鐵 (Fe)、磷(P)、硫(S)、鋯(Zr)、鈦(Ti)、和鋁(Al)所組成之群組中之一或多種元素，而0<x2)；<化學式3>Li1+aCoxM1-xAX4(其中M為選自由Al、鎂(Mg)、Ni、Co、錳(Mn)、Ti、鎵(Ga)、銅(Cu)、釩(V)、鈮(Nb)、Zr、鈰(Ce)、銦(In)、鋅(Zn)、和釔(Y)所組成之群組中之一或多種元素，X為選自由氧(O)、氟(F)、和氮(N)所組成之群組中之一或多種元素，A為P、S或其混合元素，0a0.2，而0.5x1)。 A lithium secondary battery according to claim 1, wherein the cathode active material for the cathode is any one selected from the group consisting of compounds of Chemical Formulas 1 to 3, or a mixture of two or more thereof. : <Chemical Formula 1>Li[Li x Ni a Co b Mn c ]O 2 (where 0<x 0.3, 0.3 c 0.7,0<a+b<0.5, and x+a+b+c=1); <Chemical Formula 2>LiMn 2-x M x O 4 (wherein M is selected from nickel (Ni), cobalt (Co), One or more elements of the group consisting of iron (Fe), phosphorus (P), sulfur (S), zirconium (Zr), titanium (Ti), and aluminum (Al), and 0 < x 2); <Chemical Formula 3> Li 1+a Co x M 1-x AX 4 (wherein M is selected from the group consisting of Al, magnesium (Mg), Ni, Co, manganese (Mn), Ti, gallium (Ga), copper ( One or more elements of the group consisting of Cu), vanadium (V), niobium (Nb), Zr, cerium (Ce), indium (In), zinc (Zn), and yttrium (Y), X is selected One or more elements in the group consisting of free oxygen (O), fluorine (F), and nitrogen (N), A is P, S or a mixed element thereof, 0 a 0.2, and 0.5 x 1). 如申請專利範圍第1項之鋰二次電池，其中用於該陰極的陰極活性材料為選自由LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiNi1-yCoyO2(0y<1)、LiCo1-yMnyO2(0y<1)、LiNi1-yMnyO2(0y<1)、和Li(NiaCobMnc)O2(0<a,b,c1、a+b+c=1)、或其二或更多者之混合物所組成之群組中之任一者。 A lithium secondary battery according to claim 1, wherein the cathode active material for the cathode is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiNi 1-y Co y O 2 (0) y<1), LiCo 1-y Mn y O 2 (0 y<1), LiNi 1-y Mn y O 2 (0 y<1), and Li(Ni a Co b Mn c )O 2 (0<a,b,c 1. Any of a group of a+b+c=1), or a mixture of two or more thereof. 一種製造如申請專利範圍第1項之鋰二次電池之方法，該方法包含：將包括陰極、陽極、設置於陰極和陽極之間的分隔器之電極組合品***電池殼中；和將用於凝膠聚合物電解質之組成物注入電池殼中並聚合該組成物以形成凝膠聚合物電解質，其中該用於凝膠聚合物電解質之組成物包含電解質溶液溶劑；可被離子化的鋰鹽；聚合反應引發劑；和具有能夠鍵結至金屬離子之官能基的單體。 A method of manufacturing a lithium secondary battery according to claim 1, the method comprising: inserting an electrode assembly including a cathode, an anode, a separator disposed between a cathode and an anode, into a battery can; and a composition of the gel polymer electrolyte is injected into the battery can and polymerized to form a gel polymer electrolyte, wherein the composition for the gel polymer electrolyte comprises an electrolyte solution solvent; a lithium salt that can be ionized; a polymerization initiator; and a monomer having a functional group capable of bonding to a metal ion. 如申請專利範圍第13項之方法，其中該聚合反應係在30℃至100℃的溫度範圍內進行。 The method of claim 13, wherein the polymerization is carried out at a temperature ranging from 30 ° C to 100 ° C.
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