TWI622208B - Positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery - Google Patents
Positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本發明之課題在於提供具有扁平狀的捲繞電極體，且高容量，充放電循環特性及生產性良好之非水電解質二次電池，以及能構成前述非水電解質二次電池之正極。 An object of the present invention is to provide a nonaqueous electrolyte secondary battery having a flat wound electrode body, high capacity, excellent charge and discharge cycle characteristics and productivity, and a positive electrode which can constitute the nonaqueous electrolyte secondary battery.
本發明之解決手段為一種非水電解質二次電池正極，其係使用於具有將正極、負極及隔板予以重疊而捲繞成渦捲狀且橫剖面成為扁平狀的捲繞電極體，充電之上限電壓經設定在4.3V以上之非水電解質二次電池，其特徵為：具有金屬製的集電體與形成在前述集電體之兩面上的含有正極活性物質、導電助劑及黏著劑之正極合劑層，前述集電體係厚度為11μm以下，且拉伸強度為2.5N/mm以上，前述正極合劑層含有偏二氟乙烯-氯三氟乙烯共聚物作為前述黏著劑；及一種非水電解質二次電池，其具備具有前述正極的扁平狀捲繞電極體、與非水電解質，充電之上限電壓經設定在4.3V以上。 The solution of the present invention is a non-aqueous electrolyte secondary battery positive electrode, which is used in a wound electrode body in which a positive electrode, a negative electrode, and a separator are stacked and wound into a spiral shape and has a flat cross section. A nonaqueous electrolyte secondary battery having an upper limit voltage of 4.3 V or more, characterized in that it has a metal current collector and a positive electrode active material, a conductive auxiliary agent, and an adhesive which are formed on both surfaces of the current collector. a positive electrode mixture layer having a thickness of 11 μm or less and a tensile strength of 2.5 N/mm or more, wherein the positive electrode mixture layer contains a vinylidene fluoride-chlorotrifluoroethylene copolymer as the adhesive; and a nonaqueous electrolyte The secondary battery includes a flat wound electrode body having the positive electrode described above and a nonaqueous electrolyte, and the upper limit voltage of charging is set to 4.3 V or more.
Description
本發明關於具有扁平狀的捲繞電極體，且高容量，充放電循環特性及生產性良好之非水電解質二次電池，以及能構成前述非水電解質二次電池之正極。 The present invention relates to a nonaqueous electrolyte secondary battery having a flat wound electrode body and having high capacity, excellent charge and discharge cycle characteristics and productivity, and a positive electrode capable of constituting the nonaqueous electrolyte secondary battery.
近年來，隨著行動電話、筆記型個人電腦等的攜帶式電子機器之發達、或電動汽車之實用化等，而變成需要求小型輕量且高容量的非水電解質二次電池。 In recent years, with the development of portable electronic devices such as mobile phones and notebook personal computers, or the practical use of electric vehicles, there has been a demand for small, lightweight, high-capacity nonaqueous electrolyte secondary batteries.
作為如此謀求小型化‧輕量化的非水電解質二次電池，例如可舉出一邊使正極與負極隔著隔板疊合，一邊捲繞成渦捲狀，更且將橫剖面成為扁平狀所成形的扁平狀捲繞電極體，收納在方形(方筒形)的外裝罐或以金屬層合薄膜所構成之層合薄膜外裝體般的薄型外裝體內之構造。 In the non-aqueous electrolyte secondary battery which is reduced in size and size, for example, a positive electrode and a negative electrode are stacked in a spiral shape while being laminated via a separator, and a cross section is formed into a flat shape. The flat wound electrode body is housed in a rectangular (square tube) outer can or a thin outer casing such as a laminated film outer casing made of a metal laminated film.
然而，於如前述之扁平狀捲繞電極體中，在其彎曲部(尤其最內周的彎曲部)中，容易發生正極的合劑層(包含正極活性物質的合劑層)之裂紋或集電體之破損，因此於所製造的多數之電池中，亦包含因前述的裂紋或破損而可靠性低者，有電池的生產效率的降低等之虞。 However, in the flat wound electrode body as described above, cracks or current collectors of the mixture layer (the mixture layer containing the positive electrode active material) of the positive electrode easily occur in the bent portion (especially the bent portion of the innermost periphery). Since it is damaged, in many of the batteries to be manufactured, the reliability is low due to the crack or breakage described above, and the production efficiency of the battery is lowered.
接受如此的情況，亦開發出抑制扁平狀捲繞電極體中的正極之合劑層的裂紋之技術。專利文獻1中提案使用由偏二氟乙烯或氯三氟乙烯等之單體所形成之含氟原子的高分子材料於合劑層之黏著劑，使前述合劑層的彈性係數成為特定值，同時使集電體的拉伸強度成為特定值，而提高正極的彎曲性之技術。 In response to such a situation, a technique for suppressing cracks in the mixture layer of the positive electrode in the flat wound electrode body has also been developed. Patent Document 1 proposes to use an adhesive of a fluorine atom-containing polymer material formed of a monomer such as vinylidene fluoride or chlorotrifluoroethylene in a mixture layer, and to make the elastic modulus of the mixture layer a specific value. A technique in which the tensile strength of a current collector becomes a specific value and the bendability of the positive electrode is improved.
又，專利文獻2中顯示藉由以正極合劑層所含有的黏著劑之拉伸彈性模數、與此正極合劑層中的黏著劑之體積比例成為特定的關係之方式進行調整，而抑制前述裂紋之發生，得到能提高非水電解質二次電池的可靠性、生產性及負荷特性之正極。 Further, in Patent Document 2, it is shown that the above-mentioned crack is suppressed by adjusting the tensile elastic modulus of the adhesive contained in the positive electrode mixture layer and the volume ratio of the adhesive in the positive electrode mixture layer in a specific relationship. When this occurs, a positive electrode capable of improving the reliability, productivity, and load characteristics of the nonaqueous electrolyte secondary battery is obtained.
再者，專利文獻3中顯示關於能相當於前述含氟原子的高分子材料之偏二氟乙烯-氯三氟乙烯共聚物，藉由將其使用於正極或負極之黏著劑，可提高正極合劑層或負極合劑層的離子傳導性，藉此可提高非水電解質二次電池之充放電循環特性等。 Further, Patent Document 3 discloses a vinylidene fluoride-chlorotrifluoroethylene copolymer which is a polymer material which can correspond to the above-mentioned fluorine atom, and can be used as an adhesive for a positive electrode or a negative electrode to improve a positive electrode mixture. The ion conductivity of the layer or the negative electrode mixture layer can improve the charge and discharge cycle characteristics and the like of the nonaqueous electrolyte secondary battery.
[專利文獻1]特開2005-56743號公報 [Patent Document 1] JP-A-2005-56743
[專利文獻2]特開2012-28158號公報 [Patent Document 2] JP-A-2012-28158
[專利文獻3]特開2004-87325號公報 [Patent Document 3] JP-A-2004-87325
可是近年來，對於非水電解質二次電池之高容量化的要求，由於比以往還提高充電時的上限電壓，而檢討欲對應於此者。然而，另一方面，若提高非水電解質二次電池的充電電壓，則正極活性物質劣化，亦有引起非水電解質二次電池的充放電循環特性之降低等問題。 In recent years, in order to increase the capacity of the non-aqueous electrolyte secondary battery, the upper limit voltage during charging has been increased more than in the past, and the review is intended to correspond to this. On the other hand, when the charging voltage of the nonaqueous electrolyte secondary battery is increased, the positive electrode active material is deteriorated, and the charge/discharge cycle characteristics of the nonaqueous electrolyte secondary battery are lowered.
本發明係鑒於前述情事而完成者，其目的在於提供具有扁平狀的捲繞電極體，且高容量，充放電循環特性及生產性良好之非水電解質二次電池，以及能構成前述非水電解質二次電池之正極。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a nonaqueous electrolyte secondary battery having a flat wound electrode body and having high capacity, good charge and discharge cycle characteristics and productivity, and capable of constituting the aforementioned nonaqueous electrolyte. The positive electrode of the secondary battery.
能夠達成前述目的之本發明之非水電解質二次電池用正極，係使用於具有將正極、負極及隔板予以重疊而捲繞成渦捲狀且橫剖面成為扁平狀的捲繞電極體(以下亦稱為「扁平狀捲繞電極體」)與非水電解質，充電之上限電壓經設定在4.3V以上之非水電解質二次電池，其特徵為：具有金屬製的集電體與形成在前述集電體之兩面上的含有正極活性物質、導電助劑及黏著劑之正極合劑層，前述集電體係厚度為11μm以下，且拉伸強度為2.5N/mm以上，前述正極合劑層含有偏二氟乙烯-氯三氟乙烯共聚物作為前述黏著劑。 The positive electrode for a non-aqueous electrolyte secondary battery of the present invention which is capable of achieving the above-described object is used in a wound electrode body in which a positive electrode, a negative electrode, and a separator are stacked and wound into a spiral shape and have a flat cross section. Also referred to as a "flat-wound electrode body" and a non-aqueous electrolyte, a non-aqueous electrolyte secondary battery having a charge upper limit voltage of 4.3 V or more is characterized in that it has a metal current collector and is formed in the foregoing a positive electrode mixture layer containing a positive electrode active material, a conductive auxiliary agent, and an adhesive on both surfaces of the current collector, wherein the thickness of the current collecting system is 11 μm or less, and the tensile strength is 2.5 N/mm or more, and the positive electrode mixture layer contains two A fluoroethylene-chlorotrifluoroethylene copolymer is used as the aforementioned adhesive.
又，本發明之非水電解質二次電池，係將正極、負極及隔板予以重疊而捲繞成渦捲狀且橫剖面成為扁平狀的捲 繞電極體與非水電解質者，其特徵為：前述正極係本發明之非水電解質二次電池用正極，充電之上限電壓經設定在4.3V以上。 Moreover, the nonaqueous electrolyte secondary battery of the present invention is a roll in which a positive electrode, a negative electrode, and a separator are stacked and wound into a spiral shape and have a flat cross section. In the electrode assembly and the non-aqueous electrolyte, the positive electrode is a positive electrode for a non-aqueous electrolyte secondary battery of the present invention, and the upper limit voltage of charging is set to 4.3 V or more.
依照本發明，可提供具有扁平狀的捲繞電極體，且高容量，充放電循環特性及生產性良好之非水電解質二次電池，以及能構成前述非水電解質二次電池之正極。 According to the present invention, it is possible to provide a nonaqueous electrolyte secondary battery having a flat wound electrode body and high capacity, excellent charge and discharge cycle characteristics and productivity, and a positive electrode which can constitute the nonaqueous electrolyte secondary battery.
1‧‧‧正極 1‧‧‧ positive
2‧‧‧負極 2‧‧‧negative
3‧‧‧隔板 3‧‧‧Baffle
圖1係示意地表示本發明的非水電解質二次電池之一例的部分縱截面圖。 Fig. 1 is a partial longitudinal sectional view showing an example of a nonaqueous electrolyte secondary battery of the present invention.
圖2係圖1之斜視圖。 Figure 2 is a perspective view of Figure 1.
圖3係用於實施例及比較例的非水電解質二次電池之正極中的正極合劑層與集電體之剝離強度之測定方法之說明圖。 3 is an explanatory view showing a method of measuring the peel strength of the positive electrode mixture layer and the current collector in the positive electrode of the nonaqueous electrolyte secondary battery of the examples and the comparative examples.
本發明之非水電解質二次電池用正極(以下僅稱「正極」)，係具有將含有正極活性物質、導電助劑及黏著劑之正極合劑層形成在金屬製的集電體之兩面上之構造。 The positive electrode for a non-aqueous electrolyte secondary battery of the present invention (hereinafter referred to simply as "positive electrode") has a positive electrode mixture layer containing a positive electrode active material, a conductive auxiliary agent, and an adhesive on both sides of a metal current collector. structure.
本發明之正極的集電體係其厚度為11μm以下，較佳為10μm以下。本發明之正極具備如此薄的集電體，藉 此，於非水電解質二次電池的內容積之中，盡可能地減小正極集電體所占有之比例。因此，於使用本發明的正極所形成之非水電解質二次電池(本發明之非水電解質二次電池)中，可進一步增多非水電解質對內部的導入量。 The current collecting system of the positive electrode of the present invention has a thickness of 11 μm or less, preferably 10 μm or less. The positive electrode of the present invention has such a thin current collector, Therefore, in the internal volume of the nonaqueous electrolyte secondary battery, the ratio occupied by the positive electrode current collector is reduced as much as possible. Therefore, in the nonaqueous electrolyte secondary battery (the nonaqueous electrolyte secondary battery of the present invention) formed using the positive electrode of the present invention, the amount of introduction of the nonaqueous electrolyte into the interior can be further increased.
於使用本發明的正極所形成之非水電解質二次電池中，藉由將充電之上限電壓設定在4.3V以上，而謀求高容量化。然而，因此非水電解質二次電池在充電狀態下正極之電位變非常高，發生非水電解質的氧化分解，由於正極中的電解液不足，分解生成物堆積於正極中所含有的正極活性物質之表層，或粒子間的離子傳導路徑減少，此等係成為電池的充放電循環特性降低之原因。 In the nonaqueous electrolyte secondary battery formed using the positive electrode of the present invention, the upper limit voltage of charging is set to 4.3 V or more, thereby increasing the capacity. However, in the non-aqueous electrolyte secondary battery, the potential of the positive electrode becomes extremely high in the charged state, and oxidative decomposition of the non-aqueous electrolyte occurs, and the decomposition product is accumulated in the positive electrode active material contained in the positive electrode due to insufficient electrolyte solution in the positive electrode. The surface layer or the ion conduction path between the particles is reduced, which is a cause of a decrease in the charge and discharge cycle characteristics of the battery.
因此，若為使用本發明之正極，已增多非水電解質對內部之導入量的非水電解質二次電池，則可抑制前述問題之發生，抑制充放電循環特性之降低。 Therefore, in the nonaqueous electrolyte secondary battery in which the amount of introduction of the nonaqueous electrolyte to the inside is increased by using the positive electrode of the present invention, the occurrence of the above problem can be suppressed, and the deterioration of the charge and discharge cycle characteristics can be suppressed.
如專利文獻3中所示，已知VDF-CTFE係有助於非水電解質二次電池的充放電循環特性提高，但於使用本發明的正極所形成之非水電解質二次電池，即本發明之非水電解質二次電池中，除了僅在正極合劑層的黏著劑中使用VDF-CTFE而造成的作用，加上藉由前述非水電解質量之增加所造成的作用發揮相乘的機能，故可一邊將充電之上限電壓設定在4.3V以上而謀求高容量化，一邊確保良好的充放電循環特性。 As shown in Patent Document 3, it is known that VDF-CTFE contributes to improvement of charge/discharge cycle characteristics of a nonaqueous electrolyte secondary battery, but the nonaqueous electrolyte secondary battery formed using the positive electrode of the present invention, that is, the present invention In the non-aqueous electrolyte secondary battery, in addition to the effect of using VDF-CTFE only in the adhesive of the positive electrode mixture layer, and the function of multiplication by the increase in the amount of the non-aqueous electrolyte, the function of multiplication is exhibited. It is possible to ensure a high charge capacity while setting the upper limit voltage of the charge to be 4.3 V or more, and to ensure good charge and discharge cycle characteristics.
然而，若如前述地減薄正極的集電體，則由於其強度變小，在形成扁平狀捲繞電極體之際，集電體的破損容易 發生，非水電解質二次電池之生產性降低。 However, if the current collector of the positive electrode is thinned as described above, the strength of the current collector is reduced, and the current collector is easily broken when the flat wound electrode body is formed. When this occurs, the productivity of the nonaqueous electrolyte secondary battery is lowered.
於是，於本發明之正極中，使用偏二氟乙烯-氯三氟乙烯共聚物(VDF-CTFE)於正極合劑層之黏著劑。 Thus, in the positive electrode of the present invention, an adhesive of a vinylidene fluoride-chlorotrifluoroethylene copolymer (VDF-CTFE) on the positive electrode mixture layer was used.
於與非水電解質二次電池用之正極有關的正極合劑層之黏著劑中，多使用聚偏二氟乙烯(PVDF)。由於此PVDF係在與正極活性物質中所含有的鹼成分(正極活性物質的原料之未反應物，或正極活性物質的合成時之副生成物等)之共存下發生脫HF反應而進行交聯形成，正極合劑層容易變硬。若使用具有硬的正極合劑層之正極來形成扁平狀捲繞電極體，則由於在其捲繞時集電體所負荷的應力變大，若如前述地使用薄、強度小之集電體，則容易發生破損。 Polyvinylidene fluoride (PVDF) is often used in the adhesive of the positive electrode mixture layer relating to the positive electrode for a nonaqueous electrolyte secondary battery. The PVDF is crosslinked by a dehydrogenation reaction in the presence of an alkali component (an unreacted material of a raw material of a positive electrode active material or a by-product of synthesis of a positive electrode active material) in the presence of a positive electrode active material. Formed, the positive electrode mixture layer is easily hardened. When a flat-shaped wound electrode body is formed using a positive electrode having a hard positive electrode mixture layer, the stress applied to the current collector at the time of winding is increased, and if a thin, low-strength current collector is used as described above, It is prone to breakage.
然而，於VDF-CTFE之情況中，即使於與鹼成分的共存下發生脫HF反應，也藉由來自氯三氟乙烯的構造單位之作用而停止前述反應。因此，藉由使用VDF-CTFE於黏著劑，正極合劑層的柔軟性升高，故即使如前述地使用薄的集電體，也可抑制扁平狀捲繞電極體之形成時集電體之破損，提高非水電解質二次電池之生產性，而且可抑制因集電體之破損而可能發生的容量等之電池特性的降低，故亦可提高非水電解質二次電池的可靠性。 However, in the case of VDF-CTFE, even if a dehydrogenation reaction occurs in the coexistence with an alkali component, the above reaction is stopped by the action of a structural unit derived from chlorotrifluoroethylene. Therefore, since the flexibility of the positive electrode mixture layer is increased by using the VDF-CTFE in the adhesive, even if a thin current collector is used as described above, the damage of the current collector at the time of formation of the flat wound electrode body can be suppressed. In addition, the productivity of the nonaqueous electrolyte secondary battery can be improved, and the battery characteristics such as the capacity which may occur due to breakage of the current collector can be suppressed, so that the reliability of the nonaqueous electrolyte secondary battery can be improved.
於正極合劑層之黏著劑中，可僅使用VDF-CTFE，也可將其以外的黏著劑與VDF-CTFE併用。作為可與VDF-CTFE併用的黏著劑之具體例，例如可舉出由包含選自由丙烯腈、丙烯酸酯(丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸2乙基己酯等)及甲基丙烯酸酯(甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等)所成之群組中的至少1種單體之2種以上的單體所形成之共聚物；氫化氰橡膠；PVDF；偏二氟乙烯-四氟乙烯共聚物(VDF-TFE)；偏二氟乙烯-六氟丙烯-四氟乙烯共聚物(VDF-HFP-TFE)等。即使為在鹼共存下容易形成交聯構造的PVDF，當與VDF-CTFE併用時，也由於VDF-CTFE中之來自氯三氟乙烯的構造單位之作用，而抑制交聯構造之形成，故可維持正極合劑層的柔軟性。 In the adhesive of the positive electrode mixture layer, only VDF-CTFE may be used, or an adhesive other than the VDF-CTFE may be used in combination. Specific examples of the adhesive which can be used in combination with VDF-CTFE include, for example, acrylonitrile, acrylate (methyl acrylate, ethyl acrylate, acrylic acid). Two kinds of at least one monomer in the group of methacrylate (methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.) Copolymer formed by the above monomers; hydrogenated cyanohydrin; PVDF; vinylidene fluoride-tetrafluoroethylene copolymer (VDF-TFE); vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer (VDF-HFP) -TFE) and so on. Even PVDF which is easy to form a crosslinked structure in the presence of a base, when used in combination with VDF-CTFE, inhibits the formation of a crosslinked structure due to the action of a structural unit derived from chlorotrifluoroethylene in VDF-CTFE. The flexibility of the positive electrode mixture layer is maintained.
正極合劑層中的黏著劑之含量，從可良好地黏合正極合劑層中的正極活性物質或導電助劑，防止此等從正極合劑層的脫離，更良好地提高使用此正極的電池之可靠性之觀點來看，較佳為1質量%以上。惟，正極合劑層中的黏著劑之量若過多，則正極活性物質之量或導電助劑之量變少，有高容量化的效果變小之虞。因此，正極合劑層中的黏著劑之含量較佳為1.6質量%以下。 The content of the adhesive in the positive electrode mixture layer is such that the positive electrode active material or the conductive auxiliary agent in the positive electrode mixture layer can be well bonded, and the detachment from the positive electrode mixture layer is prevented, and the reliability of the battery using the positive electrode is more improved. From the viewpoint of the above, it is preferably 1% by mass or more. When the amount of the binder in the positive electrode mixture layer is too large, the amount of the positive electrode active material or the amount of the conductive auxiliary agent is small, and the effect of increasing the capacity is small. Therefore, the content of the adhesive in the positive electrode mixture layer is preferably 1.6% by mass or less.
又，於正極的黏著劑中併用VDF-CTEF與其它的黏著劑時，從更良好地確保因VDF-CTFE之使用所造成的前述效果之觀點來看，黏著劑全量中的VDF-CTFE之比例較佳為20質量%以上，更佳為50質量%以上。再者，由於可在正極合劑層之黏著劑中僅使用VDF-CTFE，黏著劑全量中的VDF-CTFE之比例的合適上限值為100質量%。 Further, when VDF-CTEF and other adhesives are used in combination with the adhesive of the positive electrode, the ratio of VDF-CTFE in the total amount of the adhesive is better from the viewpoint of ensuring the aforementioned effects due to the use of VDF-CTFE. It is preferably 20% by mass or more, and more preferably 50% by mass or more. Further, since only VDF-CTFE can be used for the adhesive of the positive electrode mixture layer, a suitable upper limit of the ratio of VDF-CTFE in the total amount of the adhesive is 100% by mass.
於本發明之正極的正極活性物質中，使用以往已知之作為非水電解質二次電池用的正極活性物質使用者，例如 可吸藏‧放出鋰離子之活性物質。作為如此的正極活性物質之具體例，例如可舉出Li1+xMO2(-0.1<x<0.1，M：Co、Ni、Mn、Al、Mg等)所示之層狀構造之含鋰的過渡金屬氧化物、LiMn2O4或其元素的一部分經其它元素取代之尖晶石構造的鋰錳氧化物、LiMPO4(M：Co、Ni、Mn、Fe等)所示之橄欖石型化合物等。作為前述層狀構造之含鋰的過渡金屬氧化物之具體例，除了LiCoO2等，還可例示至少包含Co、Ni及Mn之氧化物(LiMn1/3Ni1/3Co1/3O2、LiMn5/12Ni5/12Co1/6O2、LiNi3/5Mn1/5Co1/5O2等)等。特別地，非水電解質二次電池係在其使用之前，以比通常還高的終止電壓進行充電時，為了提高高電壓充電之狀態下的正極活性物質之安定性，前述例示之各種活性物質較佳為更包含安定化元素。作為如此的安定化元素，例如可舉出Mg、Al、Ti、Zr、Mo、Sn等。 In the positive electrode active material of the positive electrode of the present invention, a conventionally known positive electrode active material for a nonaqueous electrolyte secondary battery can be used, for example, an active material capable of occluding and releasing lithium ions. Specific examples of such a positive electrode active material include lithium in a layered structure represented by Li 1+x MO 2 (-0.1<x<0.1, M: Co, Ni, Mn, Al, Mg, etc.). a transition metal oxide, LiMn 2 O 4 or a part thereof, a lithium manganese oxide having a spinel structure substituted with other elements, and an olivine type represented by LiMPO 4 (M: Co, Ni, Mn, Fe, etc.) Compounds, etc. Specific examples of the lithium-containing transition metal oxide having the layered structure include an oxide containing at least Co, Ni, and Mn (LiMn 1/3 Ni 1/3 Co 1/3 O 2 ) in addition to LiCoO 2 or the like. LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiNi 3/5 Mn 1/5 Co 1/5 O 2 , etc.). In particular, when the nonaqueous electrolyte secondary battery is charged at a termination voltage higher than usual before use, the above-exemplified various active materials are more preferable in order to improve the stability of the positive electrode active material in a state of high voltage charging. Jiawei also contains stability elements. Examples of such a stabilizer element include Mg, Al, Ti, Zr, Mo, Sn, and the like.
於本發明之正極的導電助劑中，例如較佳為使用天然石墨(鱗片狀石墨等)、人造石墨等石墨類，乙炔黑、廚黑、槽黑、爐黑、燈黑、熱黑等碳黑類，碳纖維等碳材料，以及亦可使用金屬纖維等導電性纖維類，氟化碳，鋁等之金屬粉末類，氧化鋅；鈦酸鉀等導電性晶鬚類，氧化鈦等導電性金屬氧化物，聚伸苯基衍生物等有機導電性材料等。 In the conductive auxiliary agent of the positive electrode of the present invention, for example, graphite such as natural graphite (flaky graphite) or artificial graphite, and carbon such as acetylene black, kitchen black, channel black, furnace black, lamp black, and hot black are preferably used. Carbon materials such as black and carbon fiber, and conductive fibers such as metal fibers, metal powders such as fluorinated carbon and aluminum, zinc oxide, conductive whiskers such as potassium titanate, and conductive metals such as titanium oxide. An organic conductive material such as an oxide or a polyphenylene derivative.
於製作正極時，可採用使用N-甲基-2-吡咯啶酮(NMP)等之溶劑使前述包含正極活性物質、導電助劑及 黏著劑等的正極合劑均勻地分散，調製糊狀或漿體狀的組成物(黏著劑亦可溶解在溶劑中)，將此組成物塗佈於正極集電體表面上，進行乾燥，視需要藉由加壓處理而調整正極合劑層之厚度或密度之方法。惟，本發明之正極的製作方法係不受前述方法所限定，亦可採用其它的方法。 When the positive electrode is produced, the above-mentioned positive electrode active material, conductive auxiliary agent, and the like may be used by using a solvent such as N-methyl-2-pyrrolidone (NMP). The positive electrode mixture such as an adhesive is uniformly dispersed to prepare a paste-like or slurry-like composition (the adhesive may be dissolved in a solvent), and the composition is applied onto the surface of the positive electrode current collector to be dried, as needed. A method of adjusting the thickness or density of the positive electrode mixture layer by pressure treatment. However, the method for producing the positive electrode of the present invention is not limited to the above method, and other methods may be employed.
本發明之正極的集電體係如前述，其厚度為11μm以下，較佳為10μm以下。本發明中，由於使用VDF-CTFE作為正極合劑層的黏著劑，即使為具有如此厚度的集電體之正極，也可抑制在作為扁平狀捲繞電極體時的集電體之破損。然而，正極的集電體之強度若過小，因VDF-CTFE之使用所導致的破損之抑制作用係有變不充分之虞。因此，於本發明之正極中，除了在正極合劑層之黏著劑中使用VDF-CTFE，還有在集電體中使用其拉伸強度為2.5N/mm以上、較佳2.7N/mm以上者，而良好地抑制在作為扁平狀捲繞電極體時的集電體之破損。再者，正極之集電體的拉伸強度較佳為3.9N/mm以下。 The current collecting system of the positive electrode of the present invention has a thickness of 11 μm or less, preferably 10 μm or less, as described above. In the present invention, the VDF-CTFE is used as the adhesive for the positive electrode mixture layer, and even in the case of the positive electrode having the current collector having such a thickness, the current collector in the case of the flat wound electrode body can be prevented from being damaged. However, if the strength of the current collector of the positive electrode is too small, the suppression of the damage due to the use of VDF-CTFE may be insufficient. Therefore, in the positive electrode of the present invention, in addition to the use of VDF-CTFE in the adhesive of the positive electrode mixture layer, the tensile strength of the current collector is preferably 2.5 N/mm or more, preferably 2.7 N/mm or more. In addition, damage of the current collector when it is a flat wound electrode body is favorably suppressed. Further, the tensile strength of the current collector of the positive electrode is preferably 3.9 N/mm or less.
本說明書所言之集電體的拉伸強度，係在前處理中自集電體切出15mm×250mm之矩形而成為試驗片，對此試驗片，使用夾具間距離為100mm之拉伸試驗機(今田製作所公司製「SDT-52型」)，以十字頭速度10mm/分鐘進行試驗而得之值。 The tensile strength of the current collector described in the present specification is a test piece obtained by cutting a rectangle of 15 mm × 250 mm from the current collector in the pretreatment, and a tensile tester using a distance between the clamps of 100 mm is used for the test piece. ("SDT-52 type" manufactured by Ida Manufacturing Co., Ltd.), which was tested at a crosshead speed of 10 mm/min.
作為具有如前述之拉伸強度的集電體，例如可舉出以下者。 Examples of the current collector having the tensile strength as described above include the following.
作為正極之集電體的材質，宜主成分為鋁之鋁合金。 鋁合金係鋁的純度為99.0質量%以上，作為其它的添加成分，例如宜含有Si≦0.6質量%、Fe≦0.7質量%、Cu≦0.25質量%、Mn≦1.5質量%、Mg≦1.3質量%、Zn≦0.25質量%。可使用如此材質所構成的箔、薄膜作為集電體。 As a material of the current collector of the positive electrode, an aluminum alloy whose main component is aluminum is preferable. The purity of the aluminum alloy-based aluminum is 99.0% by mass or more, and as the other additive component, for example, Si≦ 0.6% by mass, Fe≦ 0.7% by mass, Cu≦0.25% by mass, Mn≦1.5% by mass, and Mg≦1.3% by mass are preferably contained. Zn≦0.25 mass%. A foil or a film made of such a material can be used as a current collector.
再者，集電體若過薄，則難以確保前述之拉伸強度，故其厚度較佳為6μm以上。 Further, if the current collector is too thin, it is difficult to secure the above tensile strength, and therefore the thickness thereof is preferably 6 μm or more.
正極中的正極合劑層之厚度較佳為每一面30~80μm。又，於正極合劑層中，從成為更高容量之觀點來看，填充率較佳為75%以上。惟，正極合劑層之填充率若過高，則正極合劑層中之空孔變過少，非水電解質(非水電解液)對正極合劑層中的浸透性有降低之虞，故其填充率較佳為83%以下。正極合劑層之填充率係藉由下述式求得。 The thickness of the positive electrode mixture layer in the positive electrode is preferably 30 to 80 μm per side. Further, in the positive electrode mixture layer, the filling ratio is preferably 75% or more from the viewpoint of higher capacity. However, if the filling ratio of the positive electrode mixture layer is too high, the pores in the positive electrode mixture layer become too small, and the permeability of the nonaqueous electrolyte (nonaqueous electrolyte) to the positive electrode mixture layer is lowered, so that the filling ratio is higher. Good is below 83%. The filling ratio of the positive electrode mixture layer was determined by the following formula.
填充率(%)=100×(正極合劑層之實際密度/正極合劑層之理論密度) Filling rate (%) = 100 × (actual density of positive electrode mixture layer / theoretical density of positive electrode mixture layer)
算出正極合劑層之填充率用的前述式中之所謂的「正極合劑層之理論密度」，就是由正極合劑層的各構成成分之密度與含量所算出之密度(作為正極合劑層中空孔不存在者所求之密度)，所謂的「正極合劑層之實際密度」，就是藉由以下之方法測定者。首先，自正極切取1cm×1cm之大小，用測微計測定厚度(l1)，用精密天秤測定質量 (m1)。其次，削掉正極合劑層，僅取出集電體，與正極同樣地測定該集電體之厚度(lc)與質量(mc)。自所得之厚度與質量，藉由以下之式求得正極合劑層之實際密度(dca)(前述之厚度的單位為cm，質量之單位為g)。 The so-called "the theoretical density of the positive electrode mixture layer" in the above formula for calculating the filling ratio of the positive electrode mixture layer is the density calculated from the density and content of each component of the positive electrode mixture layer (the hollow hole is not present as the positive electrode mixture layer). The density of the "positive density of the positive electrode mixture layer" is measured by the following method. First, a size of 1 cm × 1 cm was cut out from the positive electrode, the thickness (l 1 ) was measured with a micrometer, and the mass (m 1 ) was measured with a precision balance. Next, the positive electrode mixture layer was scraped off, and only the current collector was taken out, and the thickness (l c ) and mass (m c ) of the current collector were measured in the same manner as the positive electrode. From the obtained thickness and mass, the actual density ( dca ) of the positive electrode mixture layer was determined by the following formula (the unit of the aforementioned thickness is cm, and the unit of mass is g).
dca=(m1-mc)/(l1-lc) d ca =(m 1 -m c )/(l 1 -l c )
正極合劑層中的黏著劑以外的各成分之含量，係正極活性物質較佳為94~98質量%，導電助劑較佳為1~5質量%。 The content of each component other than the adhesive in the positive electrode mixture layer is preferably 94 to 98% by mass, and the conductive auxiliary agent is preferably 1 to 5% by mass.
本發明之非水電解質二次電池，只要是具備具有本發明的非水電解質二次電池用正極之扁平狀捲繞電極體與非水電解質，充電之上限電壓可設定在4.3V以上者即可，其它構成及構造係沒有特別的限制，可使用以往已知之非水電解質二次電池中採用的各構成及構造。 In the non-aqueous electrolyte secondary battery of the present invention, as long as the flat-packed electrode body and the non-aqueous electrolyte having the positive electrode for a non-aqueous electrolyte secondary battery of the present invention are provided, the upper limit voltage of charging can be set to 4.3 V or more. Other configurations and structures are not particularly limited, and various configurations and structures used in conventionally known nonaqueous electrolyte secondary batteries can be used.
作為負極，例如可舉出在集電體的單面或兩面上形成含有負極活性物質的負極合劑層者。負極合劑層係除了負極活性物質，還含有黏著劑或視需要的導電助劑，例如可藉由於包含負極活性物質及黏著劑(更且導電助劑)等的混合物(負極合劑)中，添加適當的溶劑，充分地混煉，將所得之含負極合劑的組成物(漿體等)塗佈在集電體表面上，進行乾燥，成為所欲之厚度而形成。 Examples of the negative electrode include those in which a negative electrode mixture layer containing a negative electrode active material is formed on one surface or both surfaces of a current collector. The negative electrode mixture layer contains an adhesive or an optional conductive auxiliary agent in addition to the negative electrode active material, and may be appropriately added by, for example, a mixture (negative electrode mixture) containing a negative electrode active material and an adhesive (and a conductive auxiliary agent). The solvent is sufficiently kneaded, and the obtained negative electrode mixture-containing composition (slurry or the like) is applied onto the surface of the current collector, dried, and formed into a desired thickness.
作為負極活性物質，例如可舉出天然石墨(鱗片狀石墨)、人造石墨、膨脹石墨等之石墨材料；將瀝青煅燒而得之焦炭等之易石墨化性碳質材料；將糠醇樹脂(PFA)或聚對伸苯基(PPP)及酚樹脂低溫焙燒而得之非晶質碳 等的難石墨化性碳質材料；於石墨材料之表面上擔持非晶質碳或樹脂等之表面處理碳材料等之碳材料。又，除了碳材料，鋰或含鋰的化合物亦可作為負極活性物質使用。作為含鋰的化合物，可舉出Li-Al等之鋰合金、或含有與Si、Sn等之與鋰可合金化的元素之合金。再者，亦可使用Sn氧化物或Si氧化物等之氧化物系材料。負極合劑層中的負極活性物質之含量，例如較佳為97~99質量%。 Examples of the negative electrode active material include graphite materials such as natural graphite (flaky graphite), artificial graphite, and expanded graphite; and easily graphitizable carbonaceous materials such as coke obtained by calcining pitch; and phenol resin (PFA). Or amorphous carbon obtained by low temperature calcination of polyparaphenylene (PPP) and phenolic resin A non-graphitizable carbonaceous material such as a carbonaceous material such as a surface-treated carbon material such as amorphous carbon or a resin is supported on the surface of the graphite material. Further, in addition to the carbon material, lithium or a lithium-containing compound can also be used as the negative electrode active material. Examples of the lithium-containing compound include a lithium alloy such as Li-Al or an alloy containing an element which can be alloyed with lithium such as Si or Sn. Further, an oxide-based material such as a Sn oxide or an Si oxide can also be used. The content of the negative electrode active material in the negative electrode mixture layer is, for example, preferably from 97 to 99% by mass.
若使用表面處理碳材料作為負極活性物質，則由於可防止與非水電解質的過剩反應而較佳。 When a surface-treated carbon material is used as the negative electrode active material, it is preferable because it can prevent excessive reaction with the nonaqueous electrolyte.
負極活性物質若使用特別是在石墨材料的表面上擔持有非晶質碳，平均粒徑為8~18μm之比較小粒子的碳材料，則可提高非水電解質對負極合劑層中的浸透性而較佳。其理由雖然未確定，但判斷若為比較小粒子的碳材料，則在對負極進行加壓處理時，由於負極合劑層中所形成的空孔之大小被均一化，而非水電解液變容易浸透。又，此種石墨係鋰離子的受容性(相對於總充電容量，恆定電流充電容量之比例)高，藉由使用此石墨作為負極活性物質，可提供充放電循環特性優異之非水電解質二次電池。 When the negative electrode active material is made of a relatively small particle carbon material having an average particle diameter of 8 to 18 μm on the surface of the graphite material, the permeability of the nonaqueous electrolyte to the negative electrode mixture layer can be improved. Better. Although the reason is not determined, if it is judged that it is a carbon material of a relatively small particle, when the negative electrode is subjected to a pressure treatment, the size of the pores formed in the negative electrode mixture layer is uniform, and the non-aqueous electrolyte becomes easy. Soaked. Further, the graphite-based lithium ion has high acceptability (ratio of constant charge capacity to total charge capacity), and by using this graphite as a negative electrode active material, it is possible to provide a non-aqueous electrolyte which is excellent in charge and discharge cycle characteristics. battery.
再者，本說明書中所言之前述碳材料的平均粒徑，例如使用雷射散射粒度分布計(例如，日機裝股份有限公司製Microtrac粒度分布測定裝置「HRA9320」)，於不將前述碳材料溶解或膨潤的介質中，使前述碳材料分散，自所測定的粒度分布之小粒子求得積分體積的體積基準之累 計分率中的50%直徑之值(d50)中位徑。 In addition, the average particle diameter of the carbon material described in the present specification is, for example, a laser scattering particle size distribution meter (for example, Microtrac particle size distribution measuring apparatus "HRA9320" manufactured by Nikkiso Co., Ltd.), and the carbon is not used. In the medium in which the material is dissolved or swollen, the carbon material is dispersed, and the median diameter of the value (d 50 ) of the 50% diameter in the cumulative fraction of the volume basis of the integrated volume is obtained from the small particles of the measured particle size distribution.
導電助劑只要是電子傳導性材料，則沒有特別的限定，亦可不使用。作為導電助劑之具體例，可舉出乙炔黑，廚黑，槽黑、爐黑、燈黑、熱黑等碳黑類，碳纖維等碳材料，以及亦可使用金屬纖維等導電性纖維類，氟化碳，銅、鎳等金屬粉末類，聚伸苯基衍生物等有機導電性材料等，可單獨1種使用此等，也可併用2種以上。於此等之中，特佳為乙炔黑、廚黑或碳纖維。惟，於負極使用導電助劑時，為了高容量化，負極合劑層中的導電助劑之含量較佳為10質量%以下。 The conductive auxiliary agent is not particularly limited as long as it is an electron conductive material, and may not be used. Specific examples of the conductive auxiliary agent include carbon black such as acetylene black, kitchen black, channel black, furnace black, lamp black, and heat black, carbon materials such as carbon fiber, and conductive fibers such as metal fibers. The carbon fluoride, a metal powder such as copper or nickel, or an organic conductive material such as a polyphenylene derivative may be used alone or in combination of two or more. Among them, acetylene black, kitchen black or carbon fiber is particularly preferred. When the conductive auxiliary agent is used for the negative electrode, the content of the conductive auxiliary agent in the negative electrode mixture layer is preferably 10% by mass or less in order to increase the capacity.
作為負極合劑層之黏著劑，可為熱塑性樹脂、熱硬化性樹脂之任一者。具體地，例如可使用與本發明之正極的黏著劑相同之材料、或苯乙烯丁二烯橡膠(SBR)、乙烯-丙烯酸共聚物或該共聚物的Na+離子交聯體、乙烯-甲基丙烯酸共聚物或該共聚物之Na+離子交聯體、乙烯-丙烯酸甲酯共聚物或該共聚物之Na+離子交聯體、乙烯-甲基丙烯酸甲酯共聚物或該共聚物之Na+離子交聯體等，可單獨1種使用彼等之材料，也可併用2種以上。 The adhesive for the negative electrode mixture layer may be either a thermoplastic resin or a thermosetting resin. Specifically, for example, the same material as the adhesive of the positive electrode of the present invention, or styrene butadiene rubber (SBR), ethylene-acrylic acid copolymer or Na + ion crosslinked body of the copolymer, ethylene-methyl group can be used. Acrylic copolymer or Na + ion crosslinker of the copolymer, ethylene methyl acrylate copolymer or Na + ion crosslinker of the copolymer, ethylene methyl methacrylate copolymer or Na + of the copolymer The ion-crosslinking body or the like may be used alone or in combination of two or more.
於前述之中，特佳為PVDF、SBR、乙烯-丙烯酸共聚物或該共聚物之Na+離子交聯體、乙烯-甲基丙烯酸共聚物或該共聚物之Na+離子交聯體、乙烯-丙烯酸甲酯共聚物或該共聚物之Na+離子交聯體、乙烯-甲基丙烯酸甲酯共聚物或該共聚物之Na+離子交聯體。負極合劑層中的黏著劑之含量例如較佳為1~5質量%。 Among the foregoing, particularly preferred are PVDF, SBR, ethylene-acrylic acid copolymer or Na + ion crosslinker of the copolymer, ethylene-methacrylic acid copolymer or Na + ion crosslinker of the copolymer, ethylene - A methyl acrylate copolymer or a Na + ion crosslinker of the copolymer, an ethylene methyl methacrylate copolymer or a Na + ion crosslinker of the copolymer. The content of the adhesive in the negative electrode mixture layer is preferably, for example, 1 to 5% by mass.
負極合劑層之厚度(於集電體之兩面上形成有負極合劑層時，其每一面之厚度)較佳為30~80μm。 The thickness of the negative electrode mixture layer (the thickness of each surface when the negative electrode mixture layer is formed on both surfaces of the current collector) is preferably 30 to 80 μm.
作為用於負極之集電體，只要在非水電解質二次電池內，實質上化學安定的電子傳導體，則沒有特別的限定。作為構成該集電體之材料，除了例如使用不銹鋼、鎳或其合金、銅或其合金、鈦或其合金、碳、導電性樹脂等以外，以及使用使碳或鈦處理銅或不銹鋼之表面者等。於此等之中，特佳為銅及銅合金。此等之材料亦可將表面氧化而使用。又，較佳為藉由表面處理而將凹凸賦予集電體表面。作為集電體之形狀，可舉出箔，以及薄膜、薄片、網、經穿孔者、拉氏體、多孔質體、發泡體、纖維群之成形體等。集電體之厚度係沒有特別的限定，但例如較佳為5~50μm。 The current collector for the negative electrode is not particularly limited as long as it is a chemically stable electron conductor in the nonaqueous electrolyte secondary battery. As the material constituting the current collector, in addition to, for example, stainless steel, nickel or an alloy thereof, copper or an alloy thereof, titanium or an alloy thereof, carbon, a conductive resin, or the like, and a surface of copper or stainless steel treated with carbon or titanium are used. Wait. Among them, copper and copper alloys are particularly preferred. These materials can also be used by oxidizing the surface. Further, it is preferable to impart unevenness to the surface of the current collector by surface treatment. Examples of the shape of the current collector include a foil, a film, a sheet, a mesh, a perforator, a Larsite, a porous body, a foam, and a molded body of a fiber group. The thickness of the current collector is not particularly limited, but is preferably, for example, 5 to 50 μm.
作為非水電解質，例如可使用藉由在下述的非水系溶劑中溶解鋰鹽而調製之溶液(非水電解液)。 As the nonaqueous electrolyte, for example, a solution (nonaqueous electrolyte solution) prepared by dissolving a lithium salt in a nonaqueous solvent described below can be used.
作為溶劑，例如可將碳酸伸乙酯(EC)、碳酸伸丙酯(PC)、碳酸伸丁酯(BC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲基乙酯(MEC)、γ-丁內酯(γ-BL)、1,2-二甲氧基乙烷(DME)、四氫呋喃(THF)、2-甲基四氫呋喃、二甲亞碸(DMSO)、1,3-二氧戊環、甲醯胺、二甲基甲醯胺(DMF)、二氧戊環、乙腈、硝基甲烷、甲酸甲酯、醋酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊環衍生物、環丁碸、3-甲基-2-唑啉酮、碳酸伸丙酯衍生物、四氫呋喃衍生物、二乙基醚、1,3-丙 烷磺內酯等之非質子性有機溶劑以單獨1種或作為混合有2種以上之混合溶劑使用。 As the solvent, for example, ethyl carbonate (EC), propyl carbonate (PC), butyl carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl carbonate B can be used. Ester (MEC), γ-butyrolactone (γ-BL), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, dimethyl hydrazine (DMSO), 1 , 3-dioxolane, formamide, dimethylformamide (DMF), dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, Dioxolane derivatives, cyclobutane, 3-methyl-2- The aprotic organic solvent such as the oxazolinone, the propylene carbonate derivative, the tetrahydrofuran derivative, the diethyl ether or the 1,3-propane sultone is used alone or in combination of two or more kinds of mixed solvents. .
作為非水電解液之無機離子鹽，例如可舉出由LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、LiCF3SO3、LiCF3CO2、Li2C2F4(SO3)2、LiN(CF3SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≧2)、LiN(RfOSO2)2[此處Rf為氟烷基]等之鋰鹽中選出的至少1種。此等之鋰鹽在非水電解液中之濃度，較佳為0.6~1.8mol/l，更佳為0.9~1.6mol/l。 Examples of the inorganic ion salt of the nonaqueous electrolytic solution include LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ). 2 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiC n F 2n+1 SO 3 (n≧2), LiN(RfOSO 2 ) 2 [where Rf is fluoroalkyl], etc. At least one selected from the group consisting of lithium salts. The concentration of the lithium salt in the nonaqueous electrolytic solution is preferably from 0.6 to 1.8 mol/l, more preferably from 0.9 to 1.6 mol/l.
在使用於非水電解質二次電池的非水電解質中，以充放電循環特性的進一步改善或使高溫儲存性或過充電防止等之安全性提高為目的，亦可適宜添加碳酸伸乙烯酯、碳酸乙烯基伸乙酯、酸酐、磺酸酯、二腈、1,3-丙烷磺內酯、二苯基二硫化物、環己基苯、聯苯、氟苯、第三丁基苯等之添加劑(亦包含此等的衍生物)。 In the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery, for the purpose of further improving the charge-discharge cycle characteristics or improving the safety of high-temperature storage property or overcharge prevention, it is also possible to suitably add a vinyl carbonate carbonate or a carbonic acid. Additives such as vinyl ethyl ester, acid anhydride, sulfonate, dinitrile, 1,3-propane sultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, t-butylbenzene, etc. Contains such derivatives).
再者，於非水電解質二次電池之非水電解質中，亦可使用在前述的非水電解液中添加聚合物等之眾所周公知的凝膠化劑而凝膠化者(凝膠狀電解質)。 In addition, in the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery, a gelling agent known as a polymer or the like may be added to the non-aqueous electrolyte solution described above, and gelled (gel-like) may be used. Electrolyte).
於本發明之非水電解質二次電池內，在前述正極與前述負極之間配置含有前述非水電解質之隔板。作為隔板，較佳為使用具有大的離子透過度及指定之機械強度的絕緣性微多孔性薄膜。又，在一定溫度以上(例如100~140℃)藉由構成材料的熔融而孔閉塞，具有提高電阻之機能者(即，具有關閉機能者)。 In the nonaqueous electrolyte secondary battery of the present invention, a separator containing the nonaqueous electrolyte is disposed between the positive electrode and the negative electrode. As the separator, an insulating microporous film having a large ion permeability and a specified mechanical strength is preferably used. Further, the hole is closed by melting of the constituent material at a constant temperature or higher (for example, 100 to 140 ° C), and the function of improving the electric resistance (that is, having a shutdown function) is provided.
作為如此的隔板之具體例，可舉出以具有耐有機溶劑性及疏水性之聚乙烯、聚丙烯等聚烯烴系聚合物、或玻璃纖維等材料所構成的薄片(多孔質薄片)、不織布或織布；以接著劑固定有前述例示的聚烯烴系聚合物之微粒子的多孔質體等。 Specific examples of such a separator include a sheet (porous sheet) composed of a polyolefin-based polymer such as polyethylene or polypropylene having organic solvent resistance and hydrophobicity, or a material such as glass fiber, and a non-woven fabric. Or a woven fabric; a porous body or the like in which the fine particles of the polyolefin-based polymer exemplified above are fixed with an adhesive.
隔板之孔徑較佳為自正負極所脫離的正負極之活性物質、導電助劑及黏著劑等不通過之程度，例如宜為0.01~1μm。隔板之厚度一般為8~30μm，但於本發明中較佳為設定為10~20μm。又，隔板之空孔率係按照構成材料或厚度來決定，但一般為30~80%。 The pore diameter of the separator is preferably such that the active material of the positive and negative electrodes, the conductive auxiliary agent, and the adhesive which are separated from the positive and negative electrodes do not pass, and is, for example, preferably 0.01 to 1 μm. The thickness of the separator is generally 8 to 30 μm, but in the present invention, it is preferably set to 10 to 20 μm. Further, the porosity of the separator is determined according to the constituent material or thickness, but is generally 30 to 80%.
於本發明之電池中，使用如前述將本發明之正極與前述之負極，隔著前述隔板疊合而捲繞成渦捲狀，進行壓垮等而使橫剖面成為扁平狀之扁平狀捲繞電極體。 In the battery of the present invention, the positive electrode of the present invention and the negative electrode described above are stacked in a spiral shape by laminating the separator, and the flat cross section having a flat cross section is formed by pressing or the like. Wrap around the electrode body.
而且，於本發明之電池中，由於使用扁平狀捲繞電極體，可將能使電池薄型化的方形(方筒形)之外裝罐使用於外裝體。又，於本發明之電池中，亦可使用由在金屬層的單面或兩面上形成有樹脂層之層合薄膜所成之外裝體。 Further, in the battery of the present invention, since the flat wound electrode body is used, a square (square tubular) canned which can make the battery thinner can be used for the outer casing. Further, in the battery of the present invention, an outer casing formed of a laminated film in which a resin layer is formed on one surface or both surfaces of a metal layer may be used.
本發明之非水電解質二次電池係將充電之上限電壓設定為4.3V以上來使用，如此地藉由比通常還高地設定充電之上限電壓而謀求高容量化，同時即使長期重複使用，也可安定地發揮優異的特性。再者，非水電解質二次電池的充電之上限電壓較佳為4.7V以下。 In the non-aqueous electrolyte secondary battery of the present invention, the upper limit voltage of the charging is set to be 4.3 V or higher, and the upper limit voltage of charging is set higher than usual to increase the capacity, and the battery can be stabilized even after repeated use for a long period of time. The ground exerts excellent characteristics. Further, the upper limit voltage of the charging of the nonaqueous electrolyte secondary battery is preferably 4.7 V or less.
本發明之非水電解質二次電池係可適用於與習知的非水電解質二次電池同樣之用途。 The nonaqueous electrolyte secondary battery of the present invention can be applied to the same use as a conventional nonaqueous electrolyte secondary battery.
以下，以實施例為基礎來詳細說明本發明。惟，下述實施例係不限制本發明。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the invention.
混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：96.9質量份、導電助劑之乙炔黑：1.5質量份及黏著劑之VDF-CTFE：1.6質量份而成為正極合劑，於此正極合劑中加入溶劑之NMP，使用M Technique公司製之「Cleamix CLM0.8(商品名)」以旋轉數：10000min-1進行30分鐘處理，而成為糊狀的混合物。於此混合物中再加入溶劑之NMP，以旋轉數：10000min-1進行15分鐘處理，調製含正極合劑的組成物。 LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 mixed with a positive electrode active material: 96.9 parts by mass, acetylene black of a conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of an adhesive: 1.6 parts by mass to form a positive electrode mixture, and the positive electrode mixture The NMP to which the solvent was added was treated with "Cleamix CLM 0.8 (trade name)" manufactured by M Technique Co., Ltd. for 30 minutes at a number of revolutions of 10000 min -1 to obtain a paste-like mixture. Further, NMP in a solvent was added to the mixture, and the mixture was treated at a number of revolutions of 10,000 min -1 for 15 minutes to prepare a composition containing a positive electrode mixture.
將前述之含正極合劑的組成物塗佈於集電體的鋁合金箔(1100，厚度：10.0μm，拉伸強度：2.5N/mm)之兩面，在120℃施予12小時真空乾燥，更施予加壓處理，而製作在集電體之兩面上具有厚度為61μm的正極合劑層之正極。由前述方法所求得之加壓處理後的正極合劑層之密度(實際密度)為3.75g/cm3，填充率為76%。 The composition containing the positive electrode mixture described above was applied to both sides of an aluminum alloy foil (1100, thickness: 10.0 μm, tensile strength: 2.5 N/mm) of a current collector, and vacuum-dried at 120 ° C for 12 hours. A positive electrode having a positive electrode mixture layer having a thickness of 61 μm on both surfaces of the current collector was produced by applying a pressure treatment. The density (actual density) of the positive electrode mixture layer after pressurization obtained by the above method was 3.75 g/cm 3 and the filling ratio was 76%.
使用水，混合天然石墨：97.5質量%(平均粒徑： 19.3μm)、SBR：1.5質量%、及羧甲基纖維素(增黏劑)：1質量%，調製漿體狀之含負極合劑的組成物。將此含負極合劑的組成物塗佈於集電體的銅箔(厚度：86μm)之兩面，在120℃施予12小時真空乾燥，更施予加壓處理，而製作在集電體之兩面上具有厚度為73μm的負極合劑層之負極。 Using water, mixed natural graphite: 97.5 mass% (average particle size: 19.3 μm), SBR: 1.5% by mass, and carboxymethylcellulose (tackifier): 1% by mass, and a slurry-containing composition containing a negative electrode mixture was prepared. The composition containing the negative electrode mixture was applied to both surfaces of a copper foil (thickness: 86 μm) of a current collector, vacuum-dried at 120 ° C for 12 hours, and further subjected to a pressure treatment to be formed on both sides of the current collector. A negative electrode having a negative electrode mixture layer having a thickness of 73 μm was used.
將前述之正極與負極隔著隔板(厚度為14μm，透氣度為300秒/100cm3之聚乙烯製多孔膜)疊合，捲繞成渦捲狀後，以橫剖面成為扁平狀之方式進行壓垮，而製作扁平狀捲繞電極體。 The positive electrode and the negative electrode described above were laminated with a separator (a porous film made of polyethylene having a thickness of 14 μm and a gas permeability of 300 sec/100 cm 3 ), wound into a spiral shape, and then flattened in a cross section. The flat electrode-shaped electrode body was produced by pressing.
於碳酸甲基乙酯、碳酸二乙酯與碳酸伸乙酯之混合溶劑(體積比2：1：3)中，以1.2mol/l之濃度溶解LiPF6，於其中加入碳酸伸乙烯酯：2質量%、碳酸乙烯基伸乙酯：1質量%，調製非水電解液(非水電解質)。 In a mixed solvent of methyl ethyl carbonate, diethyl carbonate and ethyl carbonate (volume ratio of 2:1:3), LiPF 6 was dissolved at a concentration of 1.2 mol/l, and ethylene carbonate was added thereto: 2 Mass%, vinyl carbonate ethyl ester: 1% by mass, and a nonaqueous electrolyte (nonaqueous electrolyte) was prepared.
於外部尺寸為厚度4.0mm、寬度34mm、高度50mm之鋁合金製的方形電池殼中***前述之電極體，進行引線體之焊接，同時將鋁合金製的蓋板焊接於電池殼之開口端部。然後，自設於蓋板的注入口，注入前述的非水電解 液，靜置1小時後，封閉注入口，得到圖1所示之構造且圖2所示之外觀的角形非水電解質二次電池。 The electrode body is inserted into a square battery case made of an aluminum alloy having an outer dimension of 4.0 mm, a width of 34 mm, and a height of 50 mm, and the lead body is welded, and the aluminum alloy cover is welded to the open end of the battery case. . Then, the non-aqueous electrolysis is injected into the injection port of the cover plate. After leaving the solution for 1 hour, the injection port was closed to obtain an angular nonaqueous electrolyte secondary battery having the structure shown in Fig. 1 and having the appearance shown in Fig. 2.
圖1係其部分截面圖，正極1與負極2係隔著隔板3而捲繞成渦捲狀後，加壓成扁平狀，而形成扁平狀捲繞電極體6，與非水電解質一起被收納在方形(方筒形)的外裝罐4中。惟，於圖1中為了避免繁雜化，在正極1或負極2之製作時所使用的作為集電體之金屬箔或非水電解液等係未圖示。 Fig. 1 is a partial cross-sectional view showing a positive electrode 1 and a negative electrode 2 wound in a spiral shape via a separator 3, and then pressed into a flat shape to form a flat wound electrode body 6, which is combined with a nonaqueous electrolyte. It is housed in a square (square tube) outer can 4 . In order to avoid complication, the metal foil or the non-aqueous electrolyte used as the current collector used in the production of the positive electrode 1 or the negative electrode 2 is not shown in FIG.
電池殼4係以鋁合金製構成電池的外裝體者，此外裝罐4兼任正極端子。而且，於電池殼4之底部上配置由聚乙烯薄片所成之絕緣體5，從由正極1、負極2及隔板3所構成的扁平狀捲繞電極體6，拉出連接於正極1及負極2的各自一端之正極引線體7與負極引線體8。又，於封閉電池殼4之開口部的鋁合金製封口用蓋板9上，隔著聚丙烯製的絕緣墊圈10，安裝不銹鋼製的端子11，於此端子11上隔著絕緣體12，安裝不銹鋼製的引線板13。 The battery case 4 is an outer casing of a battery made of an aluminum alloy, and the can 4 is also a positive electrode terminal. Further, an insulator 5 made of a polyethylene sheet is placed on the bottom of the battery can 4, and the flat wound electrode body 6 composed of the positive electrode 1, the negative electrode 2, and the separator 3 is pulled out and connected to the positive electrode 1 and the negative electrode. The positive electrode lead body 7 and the negative electrode lead body 8 at the respective ends of 2. Further, a stainless steel terminal 11 is attached to the aluminum alloy sealing cover 9 that closes the opening of the battery can 4 via a polypropylene insulating gasket 10, and the insulator 11 is placed on the terminal 11 with stainless steel interposed therebetween. The lead plate 13 is made.
然後，將此蓋板9***電池殼4之開口部，藉由焊接兩者之接合部，而封閉電池殼4之開口部，密閉電池內部。又，於圖1之電池中，在蓋板9中設置非水電解質注入口14，於此非水電解質注入口14中***封閉構件之狀態下，例如藉由雷射焊接等而焊接封閉，確保電池之密閉性。再者，於蓋板9中設置裂開式通氣口15，作為在電池的溫度上升時將內部氣體排出至外部之機構。 Then, the cover 9 is inserted into the opening of the battery can 4, and the opening of the battery can 4 is closed by welding the joint portions of the battery case 4 to seal the inside of the battery. Further, in the battery of Fig. 1, the non-aqueous electrolyte injection port 14 is provided in the cover plate 9, and the non-aqueous electrolyte injection port 14 is inserted into the sealing member, and is welded and sealed by, for example, laser welding. The tightness of the battery. Further, a split vent 15 is provided in the cover plate 9 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises.
於此實施例1的電池中，藉由將正極引線體7直接焊 接於蓋板9，電池殼4與蓋板9具有正極端子之機能，藉由將負極引線體8焊接於引線板13，經由該引線板13而使負極引線體8與端子11導通，端子11具有負極端子之機能，但取決於電池殼4之材質等，亦有其正負變相反之情況。 In the battery of the first embodiment, the positive electrode lead body 7 is directly welded. The battery case 4 and the cover plate 9 are connected to the cover plate 9, and the negative electrode lead body 8 is soldered to the lead plate 13, and the negative electrode lead body 8 and the terminal 11 are electrically connected via the lead plate 13, and the terminal 11 is connected. It has the function of the negative terminal, but depending on the material of the battery case 4, etc., there are cases where the positive and negative changes are reversed.
圖2係示意地顯示前述圖1中所示的電池之外觀的斜視圖，此圖2之目的係顯示前述電池為角形電池，於該圖1中概略地顯示電池，僅圖示電池之構成構件中的特定者。又，於圖1中，電極體之內周側的部分係不成為截面。 2 is a perspective view schematically showing the appearance of the battery shown in FIG. 1, and the purpose of this FIG. 2 is to show that the battery is an angular battery, and the battery is schematically shown in FIG. 1, and only the constituent members of the battery are shown. Specific in the middle. Further, in Fig. 1, the portion on the inner peripheral side of the electrode body does not have a cross section.
除了混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：97.1質量份、導電助劑之乙炔黑：1.5質量份、以及黏著劑之VDF-CTFE：1.0質量份及PVDF：0.4質量份而成為正極合劑，除了使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 : 97.1 parts by mass of the positive electrode active material, acetylene black of the conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of the adhesive: 1.0 part by mass and PVDF: 0.4 parts by mass. A positive electrode mixture-containing composition was prepared in the same manner as in Example 1 except that the positive electrode mixture was used.
然後，除了使用前述之含正極合劑的組成物以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Example 1 except that the positive electrode mixture-containing composition was used, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
除了混合正極活性物質之 LiCo0.98Al0.008Mg0.008Ti0.004O2：97.3質量份、導電助劑之乙炔黑：1.5質量份、以及黏著劑之VDF-CTFE：0.6質量份及PVDF：0.6質量份而成為正極合劑，使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 mixed with a positive electrode active material: 97.3 parts by mass, acetylene black of a conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of an adhesive: 0.6 parts by mass and PVDF: 0.6 parts by mass. A positive electrode mixture-containing composition was prepared in the same manner as in Example 1 except that the positive electrode mixture was used.
然後，除了使用前述之含正極合劑的組成物以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Example 1 except that the positive electrode mixture-containing composition was used, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
除了混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：97.5質量份、導電助劑之乙炔黑：1.5質量份、以及黏著劑之VDF-CTFE：0.2質量份及PVDF：0.8質量份而成為正極合劑，使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 : 97.5 parts by mass of the positive electrode active material, acetylene black of the conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of the adhesive: 0.2 parts by mass and PVDF: 0.8 parts by mass. A positive electrode mixture-containing composition was prepared in the same manner as in Example 1 except that the positive electrode mixture was used.
然後，除了使用前述之含正極合劑的組成物以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Example 1 except that the positive electrode mixture-containing composition was used, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
除了混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：96.9質量份、導電助劑之乙炔黑：1.5質量份、以及黏著劑之VDF-CTFE：0.4質量份及PVDF：1.2質量份而成為正極合劑，使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 : 96.9 parts by mass of the positive electrode active material, acetylene black of the conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of the adhesive: 0.4 parts by mass and PVDF: 1.2 parts by mass. A positive electrode mixture-containing composition was prepared in the same manner as in Example 1 except that the positive electrode mixture was used.
然後，除了使用前述之含正極合劑的組成物以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Example 1 except that the positive electrode mixture-containing composition was used, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
除了混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：97.3質量份、導電助劑之乙炔黑：1.5質量份及黏著劑之VDF-CTFE：1.2質量份而成為正極合劑，使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 : 97.3 parts by mass of a positive electrode active material, acetylene black of a conductive auxiliary agent: 1.5 parts by mass, and VDF-CTFE of an adhesive: 1.2 parts by mass, a positive electrode mixture is used, and the positive electrode is used. A composition containing a positive electrode mixture was prepared in the same manner as in Example 1 except for the mixture.
然後，除了使用前述之含正極合劑的組成物，且將厚度為8.0μm且拉伸強度為2.5N/mm之鋁合金箔(3003)使用於集電體以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Example 1 except that the above-described composition containing the positive electrode mixture was used, and an aluminum alloy foil (3003) having a thickness of 8.0 μm and a tensile strength of 2.5 N/mm was used for the current collector. An angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that this positive electrode was used.
將與實施例1中作為負極活性物質使用者相同之天然石墨、與在天然石墨之表面上擔持有非晶質碳的平均粒徑為10μm之表面處理碳材料，以1：1之質量比混合而得到混合物。使用水，混合此混合物(負極活性物質)：97.5質量%、SBR：1.5質量%、及羧甲基纖維素(增黏劑)：1質量%，調製漿體狀之含負極合劑的組成物。將此含負極合劑的組成物，與實施例1同樣地，塗佈於集電 體之銅箔(厚度：86μm)之兩面，在120℃施予12小時真空乾燥，更施予加壓處理，而製作在集電體之兩面上具有厚度為73μm的負極合劑層之負極。 The natural graphite similar to the user of the negative electrode active material in Example 1 and the surface-treated carbon material having an average particle diameter of 10 μm on the surface of the natural graphite, having a mass ratio of 1:1, in a mass ratio of 1:1 Mix to give a mixture. The mixture (negative electrode active material) was mixed with water: 97.5 mass%, SBR: 1.5 mass%, and carboxymethylcellulose (tackifier): 1 mass%, and a slurry-containing negative electrode mixture-containing composition was prepared. The composition containing the negative electrode mixture was applied to current collection in the same manner as in Example 1. Both sides of the body copper foil (thickness: 86 μm) were vacuum dried at 120 ° C for 12 hours, and further subjected to a pressure treatment to prepare a negative electrode having a negative electrode mixture layer having a thickness of 73 μm on both faces of the current collector.
然後，除了使用前述之負極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the above-described negative electrode was used.
比較例1 Comparative example 1
除了將正極之集電體變更成厚度為15.0μm且拉伸強度為3.8N/mm之鋁合金箔(1100)以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 A positive electrode was produced in the same manner as in Example 1 except that the current collector of the positive electrode was changed to an aluminum alloy foil (1100) having a thickness of 15.0 μm and a tensile strength of 3.8 N/mm, and Example 1 was used except that the positive electrode was used. An angular nonaqueous electrolyte secondary battery was produced in the same manner.
除了混合正極活性物質之LiCo0.98Al0.008Mg0.008Ti0.004O2：96.9質量份、導電助劑之乙炔黑：1.5質量份及黏著劑之PVDF：1.6質量份而成為正極合劑，使用此正極合劑以外，與實施例1同樣地調製含正極合劑的組成物。 In addition to the positive electrode active material, LiCo 0.98 Al 0.008 Mg 0.008 Ti 0.004 O 2 : 96.9 parts by mass, acetylene black of the conductive auxiliary agent: 1.5 parts by mass, and PVDF of the adhesive: 1.6 parts by mass to form a positive electrode mixture, and the positive electrode mixture is used. The composition containing the positive electrode mixture was prepared in the same manner as in Example 1.
然後，除了使用前述之含正極合劑的組成物以外，與比較例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 Then, a positive electrode was produced in the same manner as in Comparative Example 1, except that the positive electrode mixture-containing composition was used, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
除了將正極之集電體變更成厚度為10.0μm且拉伸強 度為2.2N/mm之鋁合金箔(AIN30)以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 In addition to changing the current collector of the positive electrode to a thickness of 10.0 μm and strong tensile force An anode was produced in the same manner as in Example 1 except that the positive electrode was used in the same manner as in Example 1 except that the aluminum foil having a degree of 2.2 N/mm (AIN30) was used. An angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1.
除了使用與比較例2所調製者相同之含正極合劑的組成物以外，與實施例1同樣地製作正極，除了使用此正極以外，與實施例1同樣地製作角形非水電解質二次電池。 An anode was produced in the same manner as in Example 1 except that the positive electrode mixture-containing composition was used in the same manner as in the example 2, and an angular nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
表1中顯示使用於實施例及比較例之非水電解質二次電池的正極中之黏著劑之構成、正極合劑層之密度(實際密度)及填充率，表2中顯示集電體之構成、及注入於此等非水電解質二次電池中的非水電解液之量。表2中，非水電解液之量表示以比較例1的電池之量作為100時之相對值(質量基準)。 Table 1 shows the structure of the adhesive used in the positive electrode of the nonaqueous electrolyte secondary battery of the examples and the comparative examples, the density (actual density) of the positive electrode mixture layer, and the filling ratio. Table 2 shows the composition of the current collector. And the amount of the nonaqueous electrolyte injected into the nonaqueous electrolyte secondary battery. In Table 2, the amount of the nonaqueous electrolytic solution indicates the relative value (mass basis) when the amount of the battery of Comparative Example 1 was taken as 100.
對於實施例及比較例之非水電解質二次電池、以及用於此等電池之正極，進行下述之各評價。 The following evaluations were performed on the nonaqueous electrolyte secondary batteries of the examples and the comparative examples, and the positive electrodes used in the batteries.
將正極之兩面塗佈部分(於集電體之兩面上形成有正極合劑層之部分)在長度方向中切出5cm，在寬度方向中切出4cm，而成為試驗片，將自此試驗片長尺側之末端起15mm之位置，於與捲繞電極體製作時之折彎方向相同之方向中折彎。在試驗片之折彎地方均勻地施加200gf的荷重後，用拉伸試驗機(今田製作所公司製「SDT-52型」)之夾具夾住已打開的試驗片之兩端來固定，以十字頭速度50mm/分鐘進行拉伸試驗，將試驗片之折彎地方斷裂時的強度當作折彎強度。由於此折彎強度愈大，愈可良好地抑制在扁平狀捲繞電極體之形成時正極集電體之破損，而可評價能更提高非水電解質二次電池之生產性。 The coated portion on both sides of the positive electrode (the portion in which the positive electrode mixture layer was formed on both surfaces of the current collector) was cut 5 cm in the longitudinal direction, and 4 cm was cut in the width direction to become a test piece, and the test piece was long. The end of the side is bent at a position of 15 mm in the same direction as the bending direction when the wound electrode body is produced. After uniformly applying a load of 200 gf to the bent portion of the test piece, the ends of the opened test piece were clamped by a jig of a tensile tester ("SDT-52 type" manufactured by Ida Seisakusho Co., Ltd.) to fix the cross head. The tensile test was carried out at a speed of 50 mm/min, and the strength at which the bent portion of the test piece was broken was taken as the bending strength. As the bending strength is increased, the damage of the positive electrode current collector at the time of formation of the flat wound electrode body can be satisfactorily suppressed, and the productivity of the nonaqueous electrolyte secondary battery can be improved.
將正極之兩面塗佈部分在長度方向中切出10cm，在寬度方向中切出1cm，將所得之試料接著於雙面膠帶(NICHIBAN公司製「Nicetack NW-15」)之一面上，將雙面膠帶的另一面如圖3中所示地接著於90°剝離試驗機(TESTER產業公司製「TE-3001」)之試料設置面100。將前述的試料(正極1)之與接著於試料設置面100之側呈相反側之端部，以90°剝離試驗機的夾具101夾住，在 相對於試料設置面100而言90°之角度，以剝離速度50mm/min，在長度方向(圖中箭號之方向)中拉伸試料1，而剝離正極合劑層與集電體，測定當時的強度。由於此剝離強度愈大，亦可良好地抑制正極活性物質或導電助劑從正極合劑層之脫落，而可評價能形成可靠性更高的電池。 The coated portions on both sides of the positive electrode were cut out 10 cm in the longitudinal direction, and 1 cm in the width direction, and the obtained sample was placed on one side of a double-sided tape (Nicetack NW-15, manufactured by NICHIBAN Co., Ltd.). The other side of the tape was placed on the sample setting surface 100 of the 90° peeling tester ("TE-3001" manufactured by TESTER Industries, Inc.) as shown in Fig. 3 . The sample (positive electrode 1) and the end opposite to the side of the sample setting surface 100 were sandwiched by a jig 101 of a 90° peeling tester. The sample 1 was stretched in the longitudinal direction (direction of the arrow in the figure) at an angle of 90° with respect to the sample setting surface 100 at a peeling speed of 50 mm/min, and the positive electrode mixture layer and the current collector were peeled off, and the measurement was performed at that time. strength. As the peel strength is increased, the positive electrode active material or the conductive auxiliary agent can be favorably suppressed from falling off from the positive electrode mixture layer, and it is possible to evaluate a battery having higher reliability.
對於實施例及比較例之各電池，在室溫下以0.2C的恆定電流充電至4.35V為止後，以恆定電壓充電直到總充電時間成為8小時為止，繼續在室溫下以0.2C進行恆定電流放電直到電池電壓成為3.3V為止，求得當時的放電容量。再者，對於實施例1之電池，除了將充電時之上限電壓設定為4.2V以外，亦進行與前述相同條件下的放電容量測定。 Each of the batteries of the examples and the comparative examples was charged at a constant current of 0.2 C to 4.35 V at room temperature, and then charged at a constant voltage until the total charging time became 8 hours, and continued to be constant at 0.2 C at room temperature. The current was discharged until the battery voltage became 3.3 V, and the current discharge capacity was obtained. Further, in the battery of Example 1, the discharge capacity measurement under the same conditions as described above was also carried out except that the upper limit voltage at the time of charging was set to 4.2 V.
對於實施例及比較例之各電池，除了將環境溫度設定為45℃以外，將於與前述放電容量測定時相同之條件下進行恆定電流-恆定電壓充電及恆定電流放電之一連串操作當作1循環，重複多數的此等，求得放電容量為第1循環的放電容量之60%以上的循環數。再者，對於實施例1之電池，除了將充電時的上限電壓設定為4.2V以外，亦進行與前述相同條件下的循環數測定。 For each of the batteries of the examples and the comparative examples, a series of constant current-constant voltage charging and constant current discharging were performed as one cycle under the same conditions as those in the above-described discharge capacity measurement except that the ambient temperature was set to 45 °C. The majority of these were repeated, and the number of cycles in which the discharge capacity was 60% or more of the discharge capacity of the first cycle was determined. Further, in the battery of Example 1, the cycle number measurement under the same conditions as described above was also performed except that the upper limit voltage at the time of charging was set to 4.2 V.
表3中顯示前述之各評價結果。於表3中，各非水電解質二次電池之放電容量及充放電循環特性評價時之循環數，皆顯示以比較例1的電池之結果作為100時之相對值。又，表3中，對於實施例1及比較例1之非水電解質二次電池，將充電時的上限電壓設定為4.2V而求得的放電容量及充放電循環特性評價時之循環數，各自作為參考例1、參考例2顯示。 Table 3 shows the results of the respective evaluations described above. In Table 3, the discharge capacity of each of the nonaqueous electrolyte secondary batteries and the number of cycles in the evaluation of the charge and discharge cycle characteristics showed relative values when the result of the battery of Comparative Example 1 was taken as 100. In the non-aqueous electrolyte secondary battery of the first embodiment and the comparative example 1, the discharge capacity and the number of cycles in the evaluation of the charge/discharge cycle characteristics were determined by setting the upper limit voltage at the time of charging to 4.2 V. It is shown as Reference Example 1 and Reference Example 2.
如表3中所示，集電體之厚度及拉伸強度為適當，且具有於正極合劑層之黏著劑中使用VDF-CTFE之正極的實 施例1~7之非水電解質二次電池，與將充電之上限電壓設定為4.2V之參考例的情況比較下，係放電容量大，可達成高容量化。又，使用於實施例1~7的電池之正極，係折彎強度及剝離強度大，使用此等之正極的實施例1~7之電池，可說生產性及可靠性亦良好。 As shown in Table 3, the thickness and tensile strength of the current collector are appropriate, and the positive electrode of VDF-CTFE is used in the adhesive of the positive electrode mixture layer. In the case of the reference example in which the upper limit voltage of the charging is set to 4.2 V, the discharge capacity is large, and the capacity can be increased. Further, the positive electrodes of the batteries of Examples 1 to 7 were excellent in bending strength and peeling strength, and the batteries of Examples 1 to 7 using the positive electrodes described above were excellent in productivity and reliability.
又，實施例1~7之非水電解質二次電池，由於將充電之上限電壓設定為4.35V，與將此設定在4.2V的參考例1~2之情況比較下，雖然充放電循環特性評價時之循環數少，但若與以和實施例1~7之電池相同的上限電壓所充電之比較例1~4的電池比較下，則循環數多，可確保更良好之充放電循環特性。特別地，將在石墨的表面上擔持有非晶質碳之小粒徑的碳材料使用於負極活性物質之實施例7的電池，與其它實施例的電池比較下，亦充放電循環特性優異。 Further, in the nonaqueous electrolyte secondary batteries of Examples 1 to 7, the upper limit voltage of the charging was set to 4.35 V, and the charge/discharge cycle characteristics were evaluated in comparison with the case of the reference examples 1 to 2 set at 4.2 V. In the case of the batteries of Comparative Examples 1 to 4 which were charged with the same upper limit voltage as those of the batteries of Examples 1 to 7, the number of cycles was large, and the charge/discharge cycle characteristics were further improved. In particular, the battery of Example 7 in which a carbon material having a small particle diameter of amorphous carbon is supported on the surface of graphite is used for the negative electrode active material, and is excellent in charge and discharge cycle characteristics as compared with the battery of the other examples. .
即，具有集電體厚的正極之比較例1的電池，及具有集電體厚且在正極合劑層之黏著劑中不使用VDF-CTFE的正極之比較例2之電池，與實施例之電池比較下，係充放電循環特性評價時之循環數少，充放電循環特性差。 In other words, the battery of Comparative Example 1 having a positive electrode having a thick collector and the battery of Comparative Example 2 having a positive electrode and a positive electrode of VDF-CTFE in the adhesive of the positive electrode mixture layer, and the battery of the example In comparison, the number of cycles in the evaluation of the charge-discharge cycle characteristics was small, and the charge-discharge cycle characteristics were poor.
又，具有集電體之拉伸強度小的正極之比較例3之電池，及具有在正極合劑層之黏著劑中不使用VDF-CTFE的正極之比較例4之電池，與實施例之電池比較下，係放電容量小，且充放電循環特性評價時之循環數少，充放電循環特性差。再者，使用於比較例3及比較例4之電池的正極，由於折彎強度小，此等之電池可說是生產性差。 Further, a battery of Comparative Example 3 having a positive electrode having a small tensile strength of a current collector, and a battery of Comparative Example 4 having a positive electrode without using VDF-CTFE in the adhesive of the positive electrode mixture layer were compared with the battery of the example. In the following, the discharge capacity was small, and the number of cycles in the evaluation of the charge and discharge cycle characteristics was small, and the charge and discharge cycle characteristics were poor. Further, in the positive electrodes of the batteries used in Comparative Example 3 and Comparative Example 4, since the bending strength was small, such batteries were inferior in productivity.
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