TW201336145A - Nonaqueous electrolyte secondary battery including a capture member - Google Patents
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- TW201336145A TW201336145A TW102102124A TW102102124A TW201336145A TW 201336145 A TW201336145 A TW 201336145A TW 102102124 A TW102102124 A TW 102102124A TW 102102124 A TW102102124 A TW 102102124A TW 201336145 A TW201336145 A TW 201336145A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
Description
本發明係關於一種非水電解質二次電池(nonaqueous electrolyte secondary battery),特別是關於一種非水電解質二次電池之充放電循環特性之改善者。本申請案係基於日本專利申請:日本專利特願2012-009346號而主張優先權。 The present invention relates to a nonaqueous electrolyte secondary battery, and more particularly to an improvement in charge and discharge cycle characteristics of a nonaqueous electrolyte secondary battery. The present application claims priority based on Japanese Patent Application No. 2012-009346.
鋰離子二次電池等二次電池現在被廣泛用作行動機器用電源。特別是與已知之鎳-鎘蓄電池或鎳-氫蓄電池相比,鋰離子二次電池為高能量密度,因此作為電動汽車或電力貯存等大型電源用途亦受到期待。 Secondary batteries such as lithium ion secondary batteries are now widely used as power sources for mobile devices. In particular, lithium ion secondary batteries have high energy density as compared with known nickel-cadmium batteries or nickel-hydrogen batteries, and are therefore expected to be used as large power sources such as electric vehicles and electric power storage.
鋰離子二次電池伴隨著使用而放電,因此必需於放電後進行充電。如此,鋰離子二次電池於使用中反覆充放電。有電池容量伴隨著該充放電循環而減少之性質,且將其稱為「充放電循環特性」之劣化。特別是於高溫時其傾向明顯。 A lithium ion secondary battery is discharged in accordance with use, and therefore it is necessary to perform charging after discharging. Thus, the lithium ion secondary battery is repeatedly charged and discharged during use. There is a property that the battery capacity is reduced in accordance with the charge and discharge cycle, and this is called deterioration of "charge and discharge cycle characteristics". Especially at high temperatures, its tendency is obvious.
因此,例如於專利文獻1中,為了抑制高溫時充放電循環特性之劣化,而使捕捉電池內部所產生之鋰離子以外之陽離子或氟化物離子等雜質離子的捕捉物質保持於隔片之表面、正極或負極之表面或內部中,藉此抑制成為電池劣化之原因之陽離子或氟化物離子向負極活性物質粒子進行附著的情況。作為上述捕捉物質之例,於專利文獻1中,可列舉比表面積為1000 m2/g或孔隙體積為0.1 cc/g以上之活性碳,亦可列舉鹼土類金屬之氧化物。 Therefore, for example, in Patent Document 1, in order to suppress deterioration of charge/discharge cycle characteristics at a high temperature, a trapping substance that traps impurity ions such as cations or fluoride ions other than lithium ions generated inside the battery is held on the surface of the separator. In the surface or inside of the positive electrode or the negative electrode, cation or fluoride ions which cause deterioration of the battery are prevented from adhering to the negative electrode active material particles. As an example of the above-mentioned capture material, Patent Document 1 includes activated carbon having a specific surface area of 1000 m 2 /g or a pore volume of 0.1 cc/g or more, and an oxide of an alkaline earth metal.
專利文獻1:日本專利特開2000-77103號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2000-77103
然而,於專利文獻1所記載之結構中,選擇於高於碳之電位(以下電位為「較高、較低」時,將於正電位之方向上變大時稱為「較高」,將於負電位之方向上變大時稱為「較低」)下動作之負極活性物質作為電極材料的情形時,有如下問題:即便使用上述之捕捉物質,亦難以獲得陽離子或氟化物離子等雜質離子於到達負極前被捕捉物質捕捉到之效果。 However, in the configuration described in Patent Document 1, when the potential is higher than the carbon (the potential is "higher or lower", it will be called "higher" when it is increased in the direction of the positive potential, and will be referred to as "higher". When the negative electrode active material which operates under the negative potential in the direction of the negative potential is referred to as "electrode material", there is a problem that it is difficult to obtain impurities such as cations or fluoride ions even if the above-described capturing substance is used. The effect that the ions are captured by the trapping substance before reaching the negative electrode.
又,如專利文獻1之記載所述,若使用比表面積較大之活性碳,則於將包含電極活性物質、活性碳、溶劑之混練物塗佈於集電體上時,伴隨著活性碳之溶劑吸收量之增大,混練物之黏度變得容易上升,而塗佈作業性下降。又,使鹼土類金屬之氧化物保持於負極中之情形時,有如下之虞:因氧化物為絕緣體,故使負極活性物質之導電性能下降,而電極之每單位重量之電池容量下降。 Further, as described in Patent Document 1, when activated carbon having a large specific surface area is used, when a kneaded material containing an electrode active material, activated carbon, or a solvent is applied to a current collector, it is accompanied by activated carbon. As the amount of solvent absorption increases, the viscosity of the kneaded material tends to rise, and the coating workability decreases. Further, when the oxide of the alkaline earth metal is held in the negative electrode, the oxide is an insulator, so that the conductivity of the negative electrode active material is lowered, and the battery capacity per unit weight of the electrode is lowered.
鑒於上述情況,本發明者發現,藉由使包含於特定之電位下動作之金屬之捕捉體存在於電池中,可獲得充放電循環特性優異之非水電解質二次電池,以致完成本發明。進而發現藉由捕捉體之存在而抑制氣體產生的效果,以致完成本發明。 In view of the above, the present inventors have found that a non-aqueous electrolyte secondary battery excellent in charge and discharge cycle characteristics can be obtained by allowing a trapping body of a metal which is operated at a specific potential to exist in a battery, so that the present invention has been completed. Further, it was found that the effect of suppressing gas generation by the presence of the trapping body was completed, so that the present invention was completed.
本發明之非水電解質二次電池具有正極、負極、及介於正極與負極之間之非水電解質層,且於不接觸上述正極、上述負極中任一個之狀態,且與非水電解質接觸之狀態下,使包含氧化還原電位為負極動作電位以下之金屬、金屬間化合物或合金的捕捉體介於正極與負極 之間。 The nonaqueous electrolyte secondary battery of the present invention has a positive electrode, a negative electrode, and a nonaqueous electrolyte layer interposed between the positive electrode and the negative electrode, and is in contact with the nonaqueous electrolyte without contacting the positive electrode or the negative electrode. In the state, a trap containing a metal, an intermetallic compound or an alloy having an oxidation-reduction potential equal to or lower than the negative electrode potential is interposed between the positive electrode and the negative electrode. between.
根據該結構,捕捉體之氧化還原電位為負極之動作電位以下,因此可獲得如下非水電解質二次電池,其自正極向負極移動中之雜質離子於到達負極前變得容易被捕捉體捕捉到,從而即便反覆進行充放電循環亦可降低電池特性之劣化。再者,將「不接觸上述正極、上述負極中任一個之狀態」設為必需條件之原因在於:防止電池內經由捕捉體之電極彼此之短路,並且防止上述捕捉體與上述正極、或上述捕捉體與上述負極之間所形成之局部電池的產生。 According to this configuration, since the oxidation-reduction potential of the trap is equal to or lower than the operating potential of the negative electrode, the following non-aqueous electrolyte secondary battery can be obtained, and the impurity ions moving from the positive electrode to the negative electrode are easily caught by the capturing body before reaching the negative electrode. Therefore, deterioration of battery characteristics can be reduced even if the charge and discharge cycle is repeated. In addition, the reason why the "state in which neither the positive electrode and the negative electrode are not contacted" is required is to prevent short-circuiting between the electrodes in the battery via the capturing body, and to prevent the above-described capturing body from the above positive electrode or the above-described capturing. The generation of a local battery formed between the body and the above negative electrode.
作為捕捉體所含有之金屬,較佳為選定鹼金屬、鹼金屬間化合物或合金。鹼金屬之氧化還原電位為-3 V左右之較大值,而可高效率地獲得上述之雜質離子捕捉效果。 As the metal contained in the capturing body, an alkali metal, an alkali intermetallic compound or an alloy is preferably selected. The oxidation-reduction potential of the alkali metal is a large value of about -3 V, and the above-described impurity ion trapping effect can be obtained with high efficiency.
鹼金屬亦可為鋰或鈉。 The alkali metal can also be lithium or sodium.
作為捕捉體所含有之金屬,亦可選定鹼土類金屬、鹼土類金屬間化合物或合金。鹼土類金屬之氧化還原電位亦為接近-3 V之值,而可容易地獲得上述之雜質離子捕捉效果。 As the metal contained in the capturing body, an alkaline earth metal or an alkaline earth metal compound or alloy may be selected. The oxidation-reduction potential of the alkaline earth metal is also close to -3 V, and the above-described impurity ion trapping effect can be easily obtained.
作為於非水電解質二次電池中配置捕捉體之形態,亦可使捕捉體分散配置於非水電解質溶液中。又,成為隔片之多孔質膜介於正極與負極之間之情形時,亦可使捕捉體存在於多孔質膜中。亦可將捕捉體配置於凝膠狀之非水電解質中。於任一情形時,均可藉由捕捉體而高效率地捕捉自正極向負極移動之雜質離子,而提高充放電循環特性,且抑制氣體之產生。 As a form in which the capturing body is disposed in the nonaqueous electrolyte secondary battery, the capturing body may be dispersed and disposed in the nonaqueous electrolyte solution. Further, when the porous film of the separator is interposed between the positive electrode and the negative electrode, the trap may be present in the porous film. The trap can also be placed in a gel-like non-aqueous electrolyte. In either case, the impurity ions moving from the positive electrode to the negative electrode can be efficiently captured by the trap to improve the charge-discharge cycle characteristics and suppress the generation of gas.
較佳為,於負極中使用以標準氫電極基準計,於-2.7 V以上-1.0 V以下動作之負極活性物質。若使用此種負極活性物質,則例如於使用鋰金屬作為捕捉體之情形時,可以相對於鋰金屬之氧化還原電位(-3 V),0.3 V以上2.0 V以下之電位差而動作。 Preferably, a negative electrode active material which operates at -2.7 V or more to 1.0 V or less based on a standard hydrogen electrode is used for the negative electrode. When such a negative electrode active material is used, for example, when lithium metal is used as the trapping body, it is possible to operate with a potential difference of 0.3 V or more and 2.0 V or less with respect to the oxidation-reduction potential (-3 V) of lithium metal.
特佳為,於構成負極之負極活性物質中使用鋰鈦氧化物或鈦氧 化物。 Particularly preferably, lithium titanium oxide or titanium oxide is used in the negative electrode active material constituting the negative electrode. Compound.
又,較佳為,於構成正極之正極活性物質中使用鋰錳氧化物或鋰錳氧化物之錳之一部分被異種金屬或異種物質取代之材料。 Moreover, it is preferable to use a material in which a part of manganese of lithium manganese oxide or lithium manganese oxide is replaced with a dissimilar metal or a heterogeneous substance in the positive electrode active material constituting the positive electrode.
本發明中上述或進而其他之優點、特徵及效果係參照隨附圖式,藉由如下所述之實施形態之說明而明確。 The above and other advantages, features, and advantages of the invention will be apparent from the description of the embodiments described herein.
1‧‧‧非水電解質二次電池 1‧‧‧Non-aqueous electrolyte secondary battery
2‧‧‧正極用集電體 2‧‧‧ Positive current collector
4‧‧‧負極用集電體 4‧‧‧ Current collector for negative electrode
3‧‧‧非水電解質層 3‧‧‧Non-aqueous electrolyte layer
5‧‧‧正極活性物質 5‧‧‧ positive active material
6‧‧‧負極活性物質 6‧‧‧Negative active material
7a、7b‧‧‧隔片 7a, 7b‧‧‧ spacer
8‧‧‧絕緣密封材 8‧‧‧Insulation sealing material
9‧‧‧捕捉體 9‧‧‧ Capture
10‧‧‧框 10‧‧‧ box
21‧‧‧恆定電流驅動源 21‧‧‧ Constant current drive source
22‧‧‧繼電器開關 22‧‧‧Relay switch
23‧‧‧電壓檢測部 23‧‧‧Voltage Detection Department
24‧‧‧充放電控制部 24‧‧‧Charge and Discharge Control Department
圖1係表示本發明之實施形態之非水電解質二次電池1之結構的剖面圖。 Fig. 1 is a cross-sectional view showing the structure of a nonaqueous electrolyte secondary battery 1 according to an embodiment of the present invention.
圖2係圖1之非水電解質二次電池1之分解立體圖。 Fig. 2 is an exploded perspective view of the nonaqueous electrolyte secondary battery 1 of Fig. 1.
圖3係表示將捕捉體9形成為複數個細長之箔狀,而格子狀地嵌入框10之內部之例的立體圖。 Fig. 3 is a perspective view showing an example in which the trap body 9 is formed in a plurality of elongated foil shapes and embedded in the inside of the frame 10 in a lattice shape.
圖4係表示將捕捉體9形成為複數個細長之箔狀,而網狀地編入框10之內部之例的平面圖。 Fig. 4 is a plan view showing an example in which the trap body 9 is formed in a plurality of elongated foil shapes and meshed into the inside of the frame 10.
圖5係實施充放電循環試驗之裝置之概略電路圖。 Fig. 5 is a schematic circuit diagram of a device for performing a charge and discharge cycle test.
圖6係表示相對於充放電循環數,繪製實施例1與比較例1之電池容量維持率而成之圖表。 Fig. 6 is a graph showing the battery capacity retention ratios of Example 1 and Comparative Example 1 with respect to the number of charge and discharge cycles.
以下,對本發明之實施形態進行說明。再者,本發明之範圍係藉由申請專利範圍而表示,且意圖包含與申請專利範圍均等之意思及範圍內之全部變更。 Hereinafter, embodiments of the present invention will be described. The scope of the present invention is defined by the scope of the claims, and is intended to include all modifications within the meaning and scope of the claims.
圖1係表示本發明之實施形態之非水電解質二次電池1之內部結構的剖面圖,圖2係分解立體圖。非水電解質二次電池1具有正極用集電體2、負極用集電體4、介於正極與負極之間之非水電解質層3。正極用集電體2與負極用集電體4相互對向,且以從俯視來看重疊之方式進行配置。於正極用集電體2之對向於負極用集電體4之面上形成有正 極活性物質5,於負極用集電體4之對向於正極用集電體2之面上形成有負極活性物質6。將正極用集電體2與正極活性物質5之集合體稱為「正極」,將負極用集電體4與負極活性物質6之集合體稱為「負極」。 Fig. 1 is a cross-sectional view showing the internal structure of a nonaqueous electrolyte secondary battery 1 according to an embodiment of the present invention, and Fig. 2 is an exploded perspective view. The nonaqueous electrolyte secondary battery 1 includes a current collector for a positive electrode 2, a current collector 4 for a negative electrode, and a nonaqueous electrolyte layer 3 interposed between a positive electrode and a negative electrode. The current collector 2 for the positive electrode and the current collector 4 for the negative electrode face each other and are arranged to overlap each other in plan view. The positive electrode current collector 2 is formed on the surface of the current collector 4 for the negative electrode. In the polar active material 5, the negative electrode active material 6 is formed on the surface of the current collector 4 for the negative electrode facing the positive electrode current collector 2. The aggregate of the positive electrode current collector 2 and the positive electrode active material 5 is referred to as a "positive electrode", and the aggregate of the negative electrode current collector 4 and the negative electrode active material 6 is referred to as a "negative electrode".
多孔質膜狀之隔片7a、7b以2層構成介於正極活性物質5與負極活性物質6之間。承擔鋰離子等離子傳導之非水電解質溶液含浸於隔片7a、7b之內部、隔片7a與正極活性物質5之間的空隙、及隔片7b與負極活性物質6之間之空隙中。 The porous film-shaped separators 7a and 7b are interposed between the positive electrode active material 5 and the negative electrode active material 6 in two layers. The nonaqueous electrolyte solution which is subjected to lithium ion plasma conduction is impregnated into the inside of the separators 7a and 7b, the space between the separator 7a and the positive electrode active material 5, and the space between the separator 7b and the negative electrode active material 6.
又,為了防止鄰接之電極彼此之接觸,來自外部之水分、氧等之浸透,而以密封正極用集電體2之周邊部與負極用集電體4之周邊部之間的方式形成有框狀之絕緣密封材8。 In addition, in order to prevent the adjacent electrodes from coming into contact with each other, moisture or oxygen from the outside penetrates, and a frame is formed so as to seal the peripheral portion of the positive electrode current collector 2 and the peripheral portion of the negative electrode current collector 4. Insulating sealing material 8.
於該非水電解質二次電池1中,具有如下結構:於不接觸正極用集電體2與負極用集電體4中任一個之狀態,且與非水電解質接觸之狀態下,使鹼金屬、鹼金屬間化合物或合金、或鹼土類金屬、鹼土類金屬間化合物或鹼土類金屬之合金介於正極用集電體2與負極用集電體4之間。於本說明書中,將該鹼金屬、鹼金屬間化合物或合金、或鹼土類金屬、鹼土類金屬間化合物或鹼土類金屬之合金稱為「捕捉體」9。作為鹼金屬之例,可列舉鋰、鈉、鉀。作為鹼土類金屬之例,可列舉鎂、鈣。 In the non-aqueous electrolyte secondary battery 1, the alkali metal, the alkali metal, and the non-aqueous electrolyte are not in contact with each other in a state in which they are not in contact with the current collector 2 for the positive electrode and the current collector 4 for the negative electrode. An alkali metal compound or alloy, or an alkaline earth metal, an alkaline earth metal compound or an alkaline earth metal alloy is interposed between the positive electrode current collector 2 and the negative electrode current collector 4. In the present specification, the alkali metal, the alkali metal compound or alloy, or the alkaline earth metal, the alkaline earth metal compound or the alkaline earth metal alloy is referred to as a "capture body" 9. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium.
以下,對構成本發明之非水電解質二次電池1之各要素進行詳細地說明。 Hereinafter, each element constituting the nonaqueous electrolyte secondary battery 1 of the present invention will be described in detail.
用來於非水電解質二次電池1中具備本發明之捕捉體9的結構並無限定,例如亦可將捕捉體9形成為複數個粒子,而分散配置於非水電解質溶液中。如此,將捕捉體9形成為複數個粒子而分散配置於非水電解質溶液中之情形時,1個粒子不可同時接觸雙方之電極。 The configuration of the non-aqueous electrolyte secondary battery 1 including the capturing body 9 of the present invention is not limited. For example, the capturing body 9 may be formed into a plurality of particles and dispersed in a non-aqueous electrolyte solution. As described above, when the capturing body 9 is formed into a plurality of particles and dispersed in the nonaqueous electrolyte solution, one particle cannot simultaneously contact both electrodes.
各個粒子之形狀亦可為球、橢圓體、圓柱體、針狀體、長方 體、多面體等。長方體之情形時,其尺寸比並無限定,因此亦可為板片、箔片之形狀。將粒子分散配置於非水電解質溶液中之情形時,粒子之體積密度較佳為:相對於非水電解質溶液為100體積份,較佳為2體積份以上20體積份以下之範圍。若高於該範圍,則抑制電解質溶液及離子之運動,若低於該範圍,則捕捉雜質之功能下降,故而均欠佳。 The shape of each particle can also be a sphere, an ellipsoid, a cylinder, a needle, and a rectangular shape. Body, polyhedron, etc. In the case of a rectangular parallelepiped, the size ratio is not limited, and therefore it may be in the shape of a sheet or a foil. When the particles are dispersed and disposed in the nonaqueous electrolyte solution, the bulk density of the particles is preferably 100 parts by volume, preferably 2 parts by volume or more and 20 parts by volume or less with respect to the nonaqueous electrolyte solution. When it is higher than this range, the movement of the electrolyte solution and ions is suppressed, and if it is less than this range, the function of trapping impurities is lowered, and thus it is not preferable.
又,捕捉體9亦可為如下結構:如圖2、圖3所示,準備框10,將捕捉體9形成為複數個細長之箔狀,並以於相同方向上進行排列之方式格子狀地嵌入框10之內部,且連框10一起插入複數個隔片7a、7b之間而進行配置。只要隔片7a、7b之層數為2層以上則無限定。例如可於2層之隔片7a、7b之間插入1層面狀的捕捉體9,亦可分別於3層之隔片之間插入2層之面狀的捕捉體9。 Further, the capturing body 9 may have a configuration in which the frame 10 is prepared as shown in FIGS. 2 and 3, and the capturing body 9 is formed in a plurality of elongated foil shapes and arranged in a lattice pattern in the same direction. The inside of the frame 10 is embedded, and the frame 10 is inserted together between a plurality of spacers 7a, 7b for arrangement. There is no limitation as long as the number of layers of the spacers 7a and 7b is two or more. For example, one layer of the capturing body 9 may be inserted between the two layers of the spacers 7a and 7b, or two layers of the planar capturing body 9 may be inserted between the three layers of the spacers.
捕捉體9之形狀較佳設為進行俯視而呈格子狀、網狀等有間隙之形狀。然而,若形成為沒有間隙之實體平面狀,則阻礙運送電荷之物質的輸送,故而欠佳。 The shape of the capturing body 9 is preferably a shape having a gap such as a lattice shape or a mesh shape in plan view. However, if it is formed in a planar shape without a gap, the conveyance of the substance carrying the electric charge is hindered, which is not preferable.
圖3係表示形成為格子狀之捕捉體9之結構的立體圖。格子之形狀並無限定,可為於縱橫兩個方向上延伸之格子,亦可為如圖3所示,僅於一個方向上排列之格子。 Fig. 3 is a perspective view showing the structure of the trap body 9 formed in a lattice shape. The shape of the lattice is not limited, and may be a lattice extending in both the longitudinal and lateral directions, or may be a lattice arranged in only one direction as shown in FIG.
圖4係表示形成為網狀之捕捉體9之結構的立體圖。該情形之網之形狀亦無限定,可為如圖4所示般,將縱向之捕捉體9與橫向之捕捉體9編成直角之網,亦可為以形成直角以外之角度之方式進行編織而成者。 Fig. 4 is a perspective view showing the structure of the trap body 9 formed in a mesh shape. The shape of the mesh in this case is not limited, and the meshing body 9 and the horizontal capturing body 9 may be formed into a net at right angles as shown in FIG. 4, or may be knitted at an angle other than a right angle. Adult.
構成格子或網之各棒或長條體之形狀之剖面亦可為圓、橢圓、長方形、多邊形。剖面為長方形之情形時,其尺寸比並無限定,因此亦可為板狀或箔狀。然而,若棒或長條體之厚度t過厚,則於形成電池時由於來自上下之壓縮而導致電池之進一步壓延產生,因此為了防 止該壓延,厚度t較佳為設為100 μm以下。 The cross-section of the shape of each of the rods or strips constituting the lattice or the net may be a circle, an ellipse, a rectangle, or a polygon. When the cross section is a rectangular shape, the dimensional ratio is not limited, and therefore it may be in the form of a plate or a foil. However, if the thickness t of the rod or the elongated body is too thick, further compression of the battery occurs due to compression from the upper and lower sides when the battery is formed, so in order to prevent This rolling is preferably performed, and the thickness t is preferably set to 100 μm or less.
將俯視棒或長條體時相對於整體之空隙之面積比定義為捕捉體9之開孔率S。 The area ratio of the gap with respect to the whole when the rod or the elongated body is viewed in plan is defined as the opening ratio S of the capturing body 9.
若將俯視棒或長條體時之寬度設為w,將排列間距設為p,則捕捉體9之開孔率S於圖3之縱格子的情形時,可以S=(p-w)/p進行計算。於圖4之網狀之情形時,可以S=(p-w)2/p2進行計算。例如圖3之縱格子之情形時,若設為寬度w=1 mm、排列間距p=10 mm,則成為開孔率S=0.9。 When the width of the rod or the elongated body is set to w and the arrangement pitch is set to p, the opening ratio S of the capturing body 9 is in the case of the vertical lattice of FIG. 3, and can be performed by S=(pw)/p. Calculation. In the case of the mesh of Fig. 4, the calculation can be performed with S = (p - w) 2 / p2. For example, in the case of the vertical lattice of Fig. 3, if the width w = 1 mm and the arrangement pitch p = 10 mm, the opening ratio S = 0.9.
開孔率S較佳為以成為0.7~0.98之範圍之方式進行選定。若開孔率S小於上述範圍,則變得阻礙運送電荷之物質的輸送,若開孔率S大於上述範圍,則捕捉雜質之功能下降,故而均欠佳。 The opening ratio S is preferably selected so as to be in the range of 0.7 to 0.98. When the opening ratio S is smaller than the above range, the conveyance of the substance that transports the electric charge is hindered, and if the opening ratio S is larger than the above range, the function of trapping impurities is lowered, and thus it is not preferable.
將該等棒狀或長條狀之捕捉體9網狀地或格子狀地排列於框10中。由於將捕捉體9安裝於框10上,故捕捉體9之操作變得便利,而電池之組裝變容易。 The rod-shaped or strip-shaped traps 9 are arranged in a mesh or grid shape in the frame 10. Since the capturing body 9 is attached to the frame 10, the operation of the capturing body 9 is facilitated, and assembly of the battery becomes easy.
框10之材質必需為不與非水電解質溶液反應之物質,只要滿足其,則材質為任意。例如可列舉:使不鏽鋼等具有強度之材料成形而製作之框、使鹼金屬、鹼金屬間化合物或合金成形而製作之框、使鹼土類金屬、鹼土類金屬間化合物或鹼土類金屬之合金成形而製作之框。若使用不鏽鋼等,則可容易地確保強度,而操作變便利。若使用鹼金屬或鹼土類金屬進行製作,則可使其框本身具有與捕捉體9相同之捕捉作用。 The material of the frame 10 must be a substance that does not react with the non-aqueous electrolyte solution, and the material is arbitrary as long as it is satisfied. For example, a frame formed by molding a material having strength such as stainless steel, a frame formed by molding an alkali metal, an alkali intermetallic compound or an alloy, and an alloy of an alkaline earth metal, an alkaline earth intermetallic compound or an alkaline earth metal may be used. And the box for making. When stainless steel or the like is used, strength can be easily ensured, and handling becomes convenient. When it is produced using an alkali metal or an alkaline earth metal, the frame itself can have the same capturing action as the capturing body 9.
框10之寬度較佳為3 mm~5 mm。若小於3 mm,則操作變困難,若大於5 mm,則有框10本身遮住正極或負極,而阻礙運送電荷之物質之輸送之虞。又,存在隔片7a、7b變得過大之可能性。再者,框10之形狀並不限定於如圖3、圖4般之四角之框,只要為具有支持捕捉體9之任何結構之構件,則其形狀為任意。例如亦可為圓環狀之框。 又,亦可為「U」「C」之字狀等具有局部開口之結構之構件。 The width of the frame 10 is preferably from 3 mm to 5 mm. If it is less than 3 mm, the operation becomes difficult. If it is larger than 5 mm, the frame 10 itself blocks the positive electrode or the negative electrode, and hinders the conveyance of the substance carrying the electric charge. Moreover, there is a possibility that the spacers 7a, 7b become too large. Further, the shape of the frame 10 is not limited to the frame of the four corners as shown in FIGS. 3 and 4, and the shape is arbitrary as long as it is a member having any structure supporting the capturing body 9. For example, it may be a ring-shaped frame. Further, it may be a member having a structure having a partial opening such as a shape of "U" or "C".
又,亦可代替將捕捉體9設置於框10中,而將作為捕捉體9之鹼金屬、鹼金屬間化合物或合金;或鹼土類金屬、鹼土類金屬間化合物或合金形成為厚度t之板狀,且為了獲得特定之開孔率S,而利用打孔於其上開孔圓形、橢圓形、三角形、四角形、或多邊形等孔。 Further, instead of providing the capturing body 9 in the frame 10, an alkali metal, an alkali intermetallic compound or alloy as the capturing body 9, or an alkaline earth metal, an alkaline earth intermetallic compound or alloy may be formed into a plate having a thickness t. In order to obtain a specific opening ratio S, a hole having a circular shape, an elliptical shape, a triangular shape, a quadrangular shape, or a polygonal shape on which the hole is punched is used.
使捕捉體9自粒子成形之情形時,為了使成形容易,而亦可使用黏合劑。作為黏合劑,並無特別限定,但例如可使用選自由聚偏二氟乙烯(PVdF,poly vinylidene fluoride)、聚四氟乙烯(PTFE,polytetrafluorethylene)、苯乙烯-丁二烯橡膠、聚醯亞胺及該等之衍生物所組成之群中之至少1種。 When the capturing body 9 is formed from particles, a binder may be used in order to facilitate molding. The binder is not particularly limited, and for example, it can be selected from the group consisting of poly(vinylidene fluoride) (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, and polyimine. And at least one of the group consisting of the derivatives.
又,本發明之捕捉體9亦可為如上所述,鹼金屬、鹼金屬間化合物或合金;或鹼土類金屬、鹼土類金屬間化合物或合金之「單體」,但亦可為單體以外之如下所述之結構。即,亦可為利用異種金屬或異種物質之基材而構成粒子、格子、網、打孔前之板等,於該異種金屬或異種物質基材之表面上,藉由塗佈、鍍敷、蒸鍍、濺鍍等方法而將鹼金屬、鹼金屬間化合物或合金、或鹼土類金屬、鹼土類金屬間化合物或合金形成為薄膜狀者。鍍敷之方法為電解鍍敷、非電解鍍敷等而不受限定。此處所謂異種金屬或異種物質係指鹼金屬、鹼金屬間化合物或合金、或鹼土類金屬、鹼土類金屬問化合物或合金以外的金屬或物質。 Further, the capturing body 9 of the present invention may be an "alkali metal, an alkali intermetallic compound or an alloy" or an "alkali" of an alkaline earth metal or an alkaline earth intermetallic compound or alloy as described above, but may be a monomer The structure described below. That is, it is also possible to form a particle, a lattice, a mesh, a plate before punching, or the like by using a substrate of a dissimilar metal or a different substance, and apply coating, plating, or the like on the surface of the dissimilar metal or dissimilar material substrate. An alkali metal, an alkali intermetallic compound or alloy, or an alkaline earth metal, an alkaline earth metal compound or an alloy is formed into a film shape by a method such as vapor deposition or sputtering. The plating method is not limited by electrolytic plating, electroless plating, or the like. Here, the dissimilar metal or the heterogeneous substance means an alkali metal, an alkali intermetallic compound or alloy, or an alkali earth metal, an alkaline earth metal compound or a metal or a substance other than the alloy.
再者,作為本發明之實施形態之非水電解質二次電池1之結構的變更例,若正極.負極間未直接接觸,則未必必需使用獨立之隔片7a、7b。即,亦可考慮沒有隔片7a、7b之結構。該情形時,為了防止正極、負極之接觸,只要使用凝膠狀者作為非水電解質即可。如此,使用凝膠狀之非水電解質之情形時,於本發明之捕捉體9係形成為複數個粒子時,則係分散配置於凝膠狀之非水電解質之內部。又,於插 入配置面狀之捕捉體9之情形時,以不與正極、負極中任一個接觸之方式插入配置於凝膠狀之非水電解質的內部。 Further, a modified example of the configuration of the nonaqueous electrolyte secondary battery 1 according to the embodiment of the present invention is a positive electrode. If the negative electrodes are not in direct contact, it is not necessary to use separate spacers 7a, 7b. That is, it is also conceivable that the structure of the spacers 7a and 7b is not provided. In this case, in order to prevent contact between the positive electrode and the negative electrode, a gel-like one may be used as the non-aqueous electrolyte. When a gel-like nonaqueous electrolyte is used as described above, when the capturing body 9 of the present invention is formed into a plurality of particles, it is dispersed and disposed inside the gel-like nonaqueous electrolyte. Also, insert In the case where the planar capturing body 9 is placed, it is inserted into the inside of the gel-like nonaqueous electrolyte so as not to be in contact with either the positive electrode or the negative electrode.
本發明之非水電解質二次電池所使用之負極至少由負極活性物質或負極活性物質與集電體所構成。負極活性物質亦可根據需要而含有導電助材及黏合劑。 The negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a negative electrode active material or a negative electrode active material and a current collector. The negative electrode active material may contain a conductive auxiliary material and a binder as needed.
較佳為使用以標準氫電極基準計,於-2.7 V以上-1.0 V以下動作之材料作為負極活性物質。此種材料並無特別限定,例如可使用選自由氧化鉬、氧化鈮、氧化錳、鋰錳氧化物、氧化鈦、鋰鈦氧化物等含過渡金屬之氧化物;氮化鎳、氮化錳、氮化鐵等過渡金屬氮化物;硫化鎳、硫化錳等過渡金屬硫化物;磷化鎳、磷化錳、磷化鐵等磷化物及磷單體;氟化鐵、氟化鎳等氟化物;與鹼金屬及/或鹼土類金屬作成合金之金屬所組成之群中的至少1種。 It is preferable to use a material which operates from -2.7 V or more to 1.0 V or less based on a standard hydrogen electrode as a negative electrode active material. The material is not particularly limited, and for example, an oxide containing a transition metal such as molybdenum oxide, cerium oxide, manganese oxide, lithium manganese oxide, titanium oxide or lithium titanium oxide; nickel nitride or manganese nitride may be used. Transition metal nitrides such as iron nitride; transition metal sulfides such as nickel sulfide and manganese sulfide; phosphide and phosphorus monomers such as nickel phosphide, manganese phosphide, and iron phosphide; fluorides such as iron fluoride and nickel fluoride; At least one of the group consisting of a metal alloyed with an alkali metal and/or an alkaline earth metal.
形成本發明之負極時,亦可使用黏合劑。黏合劑並無特別限定,例如可使用選自由聚偏二氟乙烯(PVdF)、聚四氟乙烯(PTFE)、苯乙烯-丁二烯橡膠、聚醯亞胺及該等之衍生物所組成之群中的至少1種。就負極之製作容易性而言,較佳為使黏合劑溶解或分散於非水溶劑或水中。非水溶劑並無特別限定,可列舉:N-甲基-2-吡咯啶酮(NMP,N-methyl-2-pyrrolidone)、二甲基甲醯胺、二甲基乙醯胺、甲基乙基酮、乙酸甲酯、乙酸乙酯、及四氫呋喃等。亦可於該等中加入分散劑、增黏劑。 When the negative electrode of the present invention is formed, a binder can also be used. The binder is not particularly limited, and for example, it may be selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimine, and the like. At least one of the groups. In terms of ease of production of the negative electrode, it is preferred to dissolve or disperse the binder in a nonaqueous solvent or water. The nonaqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP, N-methyl-2-pyrrolidone), dimethylformamide, dimethylacetamide, and methyl ethyl bromide. Ketone, methyl acetate, ethyl acetate, tetrahydrofuran, and the like. A dispersing agent or a tackifier may also be added to the materials.
於本發明中,負極所含有之黏合劑之量相對於負極活性物質100重量份,較佳為1重量份以上30重量份以下,更佳為1重量份以上15重量份以下。若為該範圍,則可維持負極活性物質與導電助材之接著性,而充分地獲得與集電體之接著性。 In the present invention, the amount of the binder contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less based on 100 parts by weight of the negative electrode active material. When it is this range, the adhesiveness with a electrically-conductive material can be maintained, and the adhesiveness with a collector can be fully acquired.
本發明之負極亦可根據需要而含有導電助材。作為導電助材, 並無特別限定,較佳為碳材料及/或金屬微粒子。作為碳材料,例如可列舉:天然石墨、人造石墨、氣相成長碳纖維、奈米碳管、乙炔黑、科琴黑、及爐黑等。作為金屬微粒子,例如可列舉:銅、鋁、鎳及包含該等中至少1種之合金。又,亦可為對無機材料之微粒子實施了鍍敷者。該等碳材料及金屬微粒子可使用1種,亦可使用2種以上。 The negative electrode of the present invention may also contain a conductive auxiliary material as needed. As a conductive aid, It is not particularly limited, and is preferably a carbon material and/or a metal fine particle. Examples of the carbon material include natural graphite, artificial graphite, vapor-grown carbon fiber, carbon nanotube, acetylene black, ketjen black, and furnace black. Examples of the metal fine particles include copper, aluminum, nickel, and an alloy containing at least one of these. Further, it is also possible to apply a plating to the fine particles of the inorganic material. These carbon materials and metal fine particles may be used alone or in combination of two or more.
本發明中,負極所含有之導電助材之量相對於負極活性物質100重量份,較佳為1重量份以上30重量份以下,更佳為1重量份以上15重量份以下。若為該範圍,則確保負極之導電性。 In the present invention, the amount of the conductive auxiliary material contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less based on 100 parts by weight of the negative electrode active material. If it is this range, the electrical conductivity of a negative electrode is ensured.
本發明之非水電解質二次電池之負極所使用之集電體的材料例如可列舉:銅、鋁、鎳及包含該等中至少1種之合金或具有導電性之高分子。作為形狀,例如可列舉:箔狀、網狀、穿孔狀、擴展狀、或發泡結構體。 The material of the current collector used for the negative electrode of the nonaqueous electrolyte secondary battery of the present invention is, for example, copper, aluminum, nickel, and an alloy containing at least one of these or a polymer having conductivity. Examples of the shape include a foil shape, a mesh shape, a perforated shape, an expanded shape, and a foamed structure.
此處,所謂網狀,係指使金屬或導電性高分子之纖維為織布或不織布者。纖維之粗細較佳為50 μm以上2000 μm以下。未達50 μm之情形時,集電體之強度較弱,因此有於使活性物質混合物擔載於集電體上時,集電體容易破損之傾向。另一方面,使用粗於2000 μm之纖維之情形時,有如下傾向:於設置下述之空隙度中,網眼變得過大,從而利用網之活性物質混合物之保持變困難。 Here, the term "mesh" means that the fibers of the metal or the conductive polymer are woven or non-woven. The thickness of the fiber is preferably 50 μm or more and 2000 μm or less. When the amount of the current collector is less than 50 μm, the strength of the current collector is weak. Therefore, when the active material mixture is carried on the current collector, the current collector tends to be broken. On the other hand, when a fiber thicker than 2000 μm is used, there is a tendency that the mesh becomes too large in the provision of the following void ratio, and the retention of the active material mixture by the mesh becomes difficult.
所謂穿孔狀,係指於板上開有圓形、四角形、或六角形等孔者,且包含金屬者為穿孔金屬。空隙度係對應開孔率,而開孔率係根據孔徑與骨架之比率、孔之形狀、及孔之排列而決定。孔之形狀並無特別限定,但就開孔率上升之觀點而言,較佳為圓孔60°鋸齒型、方孔鋸齒.並列型。 The term "perforated" means that a hole having a circular shape, a quadrangular shape, or a hexagonal shape is formed on the plate, and the metal is a perforated metal. The void ratio corresponds to the open porosity, and the open porosity is determined by the ratio of the pore diameter to the skeleton, the shape of the pores, and the arrangement of the pores. The shape of the hole is not particularly limited, but from the viewpoint of an increase in the opening ratio, it is preferably a circular hole 60° sawtooth type or square hole sawtooth. Parallel type.
所謂擴展狀,係指於板上切鋸齒狀切口,進行延長而成為網狀者,且包含金屬者為擴展金屬。空隙度係對應開孔率,而開孔率係根據孔徑與骨架之比率、孔之形狀、及孔之排列而決定。 The term "expanded" refers to a zigzag slit cut in a plate, which is elongated to form a mesh, and includes a metal as an expanded metal. The void ratio corresponds to the open porosity, and the open porosity is determined by the ratio of the pore diameter to the skeleton, the shape of the pores, and the arrangement of the pores.
所謂發泡結構體,係指如海綿般骨架成為三維網狀者,且其孔連續。結構係由孔徑及孔隙率所決定。連續孔之形狀或孔徑並無特別限定,但較佳為具有高比表面積之結構。 The term "foamed structure" means a skeleton having a three-dimensional network such as a sponge, and the pores thereof are continuous. The structure is determined by the pore size and porosity. The shape or pore diameter of the continuous pores is not particularly limited, but is preferably a structure having a high specific surface area.
本發明之集電體所使用之金屬只要於負極動作電壓間穩定即可,若動作電位為-2.3 V以下,則較佳為銅及其合金,若於-2.3 V以上,則較佳為鋁及其合金。 The metal used in the current collector of the present invention may be stabilized between the operating voltages of the negative electrode. When the operating potential is -2.3 V or less, copper and its alloy are preferable, and if it is -2.3 V or more, aluminum is preferable. And its alloys.
本發明之負極係例如藉由使包含負極活性物質、導電助材、及黏合劑之負極混合物擔載於集電體上而製作,但就製造方法之容易性而言,較佳為如下方法:利用負極活性物質、導電助材、黏合劑及溶劑而製作漿料,將獲得之漿料填充及塗佈於集電體之孔隙部及其外面,之後去除溶劑,藉此製作負極。又,亦可不使負極活性物質、導電助材及黏合劑之混合物分散於溶劑中,而直接擔載於集電體上。 The negative electrode of the present invention is produced by, for example, supporting a negative electrode mixture containing a negative electrode active material, a conductive auxiliary material, and a binder on a current collector. However, in terms of easiness of the production method, the following method is preferred: A slurry is prepared by using a negative electrode active material, a conductive auxiliary material, a binder, and a solvent, and the obtained slurry is filled and applied to the pore portion of the current collector and the outside thereof, and then the solvent is removed to prepare a negative electrode. Further, the negative electrode active material, the conductive auxiliary material, and the binder may be directly supported on the current collector without being dispersed in a solvent.
製作漿料之情形時,並無特別限定,但就可均勻地混合負極活性物質、導電助材、黏合劑、及溶劑而言,較佳為使用球磨機、行星式攪拌機、噴射磨機、薄膜旋轉型攪拌器。漿料之製作並無特別限定,亦可於混合負極活性物質、導電助材、及黏合劑後加入溶劑而進行製作,亦可將負極活性物質、導電助材、黏合劑、及溶劑一起進行混合而製作。 In the case of producing a slurry, it is not particularly limited, but it is preferable to use a ball mill, a planetary mixer, a jet mill, or a film rotation in order to uniformly mix the negative electrode active material, the conductive auxiliary material, the binder, and the solvent. Type agitator. The preparation of the slurry is not particularly limited, and it may be carried out by adding a solvent after mixing the negative electrode active material, the conductive auxiliary material, and the binder, or may mix the negative electrode active material, the conductive auxiliary material, the binder, and the solvent together. And making.
漿料之固形物成分濃度較佳為30 wt%以上80 wt%以下。未達30 wt%之情形時,有漿料之黏度過低之傾向,另一方面,高於80 wt%之情形時,有漿料之黏度過高之傾向,因此有下述之電極之形成變得困難之情形。 The solid content concentration of the slurry is preferably from 30% by weight to 80% by weight. When the amount is less than 30% by weight, the viscosity of the slurry tends to be too low. On the other hand, when it is higher than 80% by weight, the viscosity of the slurry tends to be too high, so that the following electrode is formed. It becomes a difficult situation.
漿料所使用之溶劑較佳為非水溶劑或水。非水溶劑並無特別限定,例如可列舉:N-甲基-2-吡咯啶酮(NMP)、二甲基甲醯胺、二甲基乙醯胺、甲基乙基酮、乙酸甲酯、乙酸乙酯、及四氫呋喃等。又,亦可於該等中加入分散劑、增黏劑。 The solvent used for the slurry is preferably a nonaqueous solvent or water. The nonaqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, and methyl acetate. Ethyl acetate, tetrahydrofuran, and the like. Further, a dispersing agent or a tackifier may be added to the materials.
向集電體上擔載負極混合物之方法並無特別限定,例如較佳為如下方法:藉由刮漿刀、模嘴塗機、缺角輪塗佈機等塗佈漿料後去除溶劑之方法;藉由噴霧附著於集電體上後去除溶劑之方法;使集電體含浸於漿料中後去除溶劑之方法。去除溶劑之方法為使用烘箱或真空烘箱之乾燥,其簡單且較佳。作為環境,可列舉室溫、或設為高溫之空氣、惰性氣體、真空狀態等。負極之形成可於形成下述之正極前,亦可於形成下述之正極後。於未使負極活性物質、導電助材及黏合劑之混合物分散於溶劑中之情形時,就可均勻地混合負極活性物質、導電助材、及黏合劑而言,較佳為於使用球磨機、行星式攪拌機、噴射磨機、薄膜旋轉型攪拌器而製作混合物後擔載於集電體上。作為使混合物擔載於集電體上之方法,並無特別限定,較佳為將混合物填滿於集電體中後進行壓製之方法。壓製亦可進行加熱。又,亦可於製作負極後,使用輥壓製機等而壓縮負極。電極之壓縮可於形成上述之正極前,亦可於形成上述之正極後。 The method of supporting the negative electrode mixture on the current collector is not particularly limited, and for example, a method of removing the solvent by coating the slurry by a doctor blade, a die coater, a notch coater or the like is preferred. A method of removing a solvent by spraying on a current collector, and a method of removing the solvent after immersing the current collector in the slurry. The method of removing the solvent is drying using an oven or a vacuum oven, which is simple and preferred. Examples of the environment include room temperature, air at a high temperature, an inert gas, and a vacuum state. The formation of the negative electrode may be performed before the formation of the positive electrode described below, or after the formation of the positive electrode described below. When the mixture of the negative electrode active material, the conductive auxiliary material, and the binder is not dispersed in the solvent, the negative electrode active material, the conductive auxiliary material, and the binder can be uniformly mixed, preferably using a ball mill or a planet. The mixture was prepared by a mixer, a jet mill, and a film rotary agitator, and then carried on a current collector. The method of supporting the mixture on the current collector is not particularly limited, and a method in which the mixture is filled in the current collector and then pressed is preferably used. Pressing can also be carried out. Further, after the negative electrode is produced, the negative electrode may be compressed using a roll press or the like. The compression of the electrode may be performed before the formation of the positive electrode described above, or after the formation of the positive electrode described above.
本發明之非水電解質二次電池所使用之正極係至少由正極混合物、或正極混合物與集電體所構成。正極混合物至少含有正極活性物質及黏合劑,且根據需要而含有導電助材。 The positive electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a positive electrode mixture, or a positive electrode mixture and a current collector. The positive electrode mixture contains at least a positive electrode active material and a binder, and contains a conductive auxiliary material as needed.
正極活性物質並無特別限定,可使用動作電位以標準氫電極基準計為-0.2 V以上2.2 V以下之選擇自由含有鹼金屬及/或鹼土類金屬之複合氧化物、複合氮化物、複合氟化物、複合硫化物、複合硒化物等所組成之群中的至少1種。 The positive electrode active material is not particularly limited, and a composite oxide, a composite nitride, and a complex fluoride containing an alkali metal and/or an alkaline earth metal can be used in an operation potential of -0.2 V or more and 2.2 V or less based on a standard hydrogen electrode. At least one of a group consisting of a composite sulfide, a composite selenide, and the like.
亦可於正極活性物質中使用黏合劑。可以相同之方式應用上述負極混合物所使用之黏合劑所例示者。就正極之製作容易性而言,較佳為使黏合劑溶解或分散於非水溶劑或水中。非水溶劑可以相同之方式應用上述非水溶劑所例示者。亦可於該等中加入分散劑、增黏劑。 It is also possible to use a binder in the positive electrode active material. The exemplified by the binder used in the above negative electrode mixture can be applied in the same manner. In terms of ease of production of the positive electrode, it is preferred to dissolve or disperse the binder in a nonaqueous solvent or water. The nonaqueous solvent can be exemplified by the application of the above nonaqueous solvent in the same manner. A dispersing agent or a tackifier may also be added to the materials.
亦可根據需要,於本發明之正極中含有導電助材。作為導電助材,並無特別限定,較佳為碳材料或金屬微粒子。作為碳材料,可例示與可含於上述負極中之碳材料相同者。作為金屬微粒子,例如可列舉鋁及鋁合金。又,亦可為對無機材料之微粒子實施了鍍敷者。該等碳材料及金屬微粒子可使用1種,亦可使用2種以上。 A conductive auxiliary material may be contained in the positive electrode of the present invention as needed. The conductive auxiliary material is not particularly limited, and is preferably a carbon material or metal fine particles. As the carbon material, the same as the carbon material which can be contained in the above negative electrode can be exemplified. Examples of the metal fine particles include aluminum and an aluminum alloy. Further, it is also possible to apply a plating to the fine particles of the inorganic material. These carbon materials and metal fine particles may be used alone or in combination of two or more.
本發明中,正極所含有之導電助材之量相對於正極活性物質100重量份,較佳為1重量份以上30重量份以下,更佳為1重量份以上15重量份以下。若為該範圍,則確保正極之導電性。又,可維持與黏合劑之接著性,而充分地獲得與集電體之接著性。另一方面,使用多於30重量份之導電助材的情形時,有導電助材所佔體積增大,而能量密度下降之傾向。 In the present invention, the amount of the conductive auxiliary material contained in the positive electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less based on 100 parts by weight of the positive electrode active material. If it is this range, the electroconductivity of a positive electrode is ensured. Further, the adhesion to the binder can be maintained, and the adhesion to the current collector can be sufficiently obtained. On the other hand, in the case where more than 30 parts by weight of the electrically conductive auxiliary material is used, there is a tendency that the volume of the electrically conductive auxiliary material increases and the energy density decreases.
本發明之非水電解質二次電池之正極所使用之集電體可以相同之方式應用用於上述負極活性物質之集電體所例示者及箔狀者。 The current collector used for the positive electrode of the nonaqueous electrolyte secondary battery of the present invention can be applied to the current collector and the foil of the negative electrode active material in the same manner.
本發明之正極例如藉由將正極活性物質、導電助材、及黏合劑之正極活性物質擔載於集電體上而製作,但就製作方法之容易性而言,較佳為如下方法:利用正極活性物質、導電助材、黏合劑及溶劑製作漿料,並將獲得之漿料填充及塗佈於集電體之空孔部及其外面,之後去除溶劑,藉此製作正極。又,亦可不使正極活性物質、導電助材及黏合劑之混合物分散於溶劑中,而直接擔載於集電體上。 The positive electrode of the present invention is produced by supporting a positive electrode active material, a conductive auxiliary material, and a positive electrode active material of a binder on a current collector, for example, but the ease of the production method is preferably as follows: A slurry is prepared by using a positive electrode active material, a conductive auxiliary material, a binder, and a solvent, and the obtained slurry is filled and applied to the pore portion of the current collector and the outside thereof, and then the solvent is removed to prepare a positive electrode. Further, the positive electrode active material, the conductive auxiliary material, and the binder may be directly supported on the current collector without being dispersed in a solvent.
即便於正極之製作中,亦可以相同之方式應用上述負極之製作中漿料的製作法、漿料之固形物成分濃度、用於漿料之溶劑、向集電體上之活性物質層之擔載方法、電極之壓縮。 That is, in the production of the positive electrode, the method for preparing the slurry in the production of the above negative electrode, the solid content concentration of the slurry, the solvent for the slurry, and the active material layer on the current collector may be applied in the same manner. Loading method, compression of the electrode.
本發明之非水電解質二次電池中正極之電容與負極的電容之比較佳為滿足下述式(1)。 In the nonaqueous electrolyte secondary battery of the present invention, the capacitance of the positive electrode and the capacitance of the negative electrode are preferably in accordance with the following formula (1).
0.7≦B/A≦1.3 (1) 0.7≦B/A≦1.3 (1)
其中,式(1)中,A表示正極每1 cm2之電容,B表示負極每1 cm2之電容。 In the formula (1), A represents a capacitance per 1 cm 2 of the positive electrode, and B represents a capacitance per 1 cm 2 of the negative electrode.
B/A未達0.7之情形時,有過充電時負極之電位成為鹼金屬及/或鹼土類金屬之析出電位的情形,另一方面,B/A大於1.3之情形時,有未參與電池反應之負極活性物質較多,因此引起副反應之情形。 When the B/A is less than 0.7, the potential of the negative electrode becomes the precipitation potential of the alkali metal and/or alkaline earth metal during charging. On the other hand, when the B/A is greater than 1.3, there is no participation in the battery reaction. Since there are many negative electrode active materials, a side reaction is caused.
本發明之非水電解質二次電池中正極與負極之面積比並無特別限定,較佳為滿足下述式(2)。 The area ratio of the positive electrode to the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, and it is preferable to satisfy the following formula (2).
1≦D/C≦1.2 (2) 1≦D/C≦1.2 (2)
(其中,C表示正極之面積,D表示負極之面積) (where C is the area of the positive electrode and D is the area of the negative electrode)
D/C未達1之情形時,例如於上述之B/A=1之情形時,有因負極之容量變得小於正極,故於過充電時負極之電位成為鹼金屬及/或鹼土類金屬之析出電位之虞。另一方面,D/C大於1.2之情形時,有因未與正極接觸之部分之負極較大,故未參與電池反應之負極活性物質引起副反應之情形。正極及負極之面積之控制並無特別限定,例如可藉由於塗佈漿料時控制塗佈寬度而進行。 When the D/C is less than 1, for example, in the case of the above B/A=1, since the capacity of the negative electrode becomes smaller than the positive electrode, the potential of the negative electrode becomes an alkali metal and/or an alkaline earth metal at the time of overcharge. The potential of the precipitation potential. On the other hand, when D/C is larger than 1.2, there is a case where a negative electrode which is not in contact with the positive electrode is large, and a negative electrode active material which does not participate in the battery reaction causes a side reaction. The control of the area of the positive electrode and the negative electrode is not particularly limited, and can be carried out, for example, by controlling the coating width when the slurry is applied.
作為本發明之非水電解質二次電池所使用之隔片,可列舉多孔質材料或不織布等。作為隔片之材質,較佳為不溶解於構成電解液之有機溶劑中者,具體而言,可列舉聚乙烯或聚丙烯之類之聚烯烴系聚合物;聚對苯二甲酸乙二酯之類之聚酯系聚合物;纖維素或改性纖維素、玻璃之類之無機材料。 The separator used for the nonaqueous electrolyte secondary battery of the present invention may, for example, be a porous material or a nonwoven fabric. The material of the separator is preferably not dissolved in the organic solvent constituting the electrolytic solution, and specific examples thereof include a polyolefin-based polymer such as polyethylene or polypropylene; and polyethylene terephthalate. Polyester-based polymers; cellulose or modified inorganic materials such as cellulose and glass.
隔片之厚度較佳為1~500 μm。若未達1 μm,則有由於隔片之機械強度不足而導致斷裂,從而內部短路之傾向。另一方面,厚於500 μm之情形時,有由於電池之內部電阻與正極負極之電極間距離增大而導致電池之負荷特性下降的傾向。更佳之厚度為10~50 μm。 The thickness of the separator is preferably from 1 to 500 μm. If it is less than 1 μm, there is a tendency that the mechanical strength of the separator is insufficient to cause breakage and internal short circuit. On the other hand, when it is thicker than 500 μm, there is a tendency that the load characteristics of the battery are lowered due to an increase in the internal resistance of the battery and the distance between the electrodes of the positive and negative electrodes. A more preferable thickness is 10 to 50 μm.
本發明之非水電解質二次電池所使用之隔片與負極之面積比並 無特別限定,較佳為滿足下述式(3)。 The ratio of the area of the separator to the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention It is not particularly limited, and it is preferable to satisfy the following formula (3).
1≦F/E≦1.5 (3) 1≦F/E≦1.5 (3)
(其中,E表示負極之面積,F表示隔片之面積) (where E is the area of the negative electrode and F is the area of the spacer)
F/E未達1之情形時,有正極與負極接觸之情形,大於1.5之情形時,有外部所需要之體積變大,而電池之能量密度下降之情形。 When the F/E is less than 1, there is a case where the positive electrode is in contact with the negative electrode, and when it is larger than 1.5, the volume required for the external portion becomes large, and the energy density of the battery decreases.
本發明之非水電解質二次電池所使用之非水電解質溶液並無特別限定,可使用於非水溶劑中溶解有溶質之電解液;使於非水溶劑中溶解有溶質之電解液含浸於高分子中而成之凝膠電解質等。 The nonaqueous electrolyte solution used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, and an electrolyte solution in which a solute is dissolved in a nonaqueous solvent can be used; and an electrolyte in which a solute is dissolved in a nonaqueous solvent is impregnated high. a gel electrolyte formed in a molecule.
作為非水溶劑,較佳為含有環狀之非質子性溶劑及/或鏈狀之非質子性溶劑。作為環狀之非質子性溶劑,例示有環狀碳酸酯、環狀酯、環狀碸及環狀醚等。作為鏈狀之非質子性溶劑,例示有鏈狀碳酸酯、鏈狀羧酸酯及鏈狀醚等。又,除該等以外,亦可使用乙腈等通常用作非水電解質溶液之溶劑的溶劑。更具體而言,可使用碳酸二甲酯、碳酸甲基乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲基丙酯、碳酸乙二酯、碳酸氟乙二酯、碳酸丙二酯、碳酸丁二酯、四氫呋喃、γ-丁內酯、1,2-二甲氧基乙烷、環丁碸、二氧戊環、丙酸甲酯等。該等溶劑可使用1種,亦可混合2種以上而使用,但就溶解下述溶質之容易性、鋰離子之傳導性之高度而言,較佳為使用混合有2種以上之溶劑。又,亦可使用使電解液滲入高分子中之凝膠狀電解質。 The nonaqueous solvent preferably contains a cyclic aprotic solvent and/or a chain aprotic solvent. Examples of the cyclic aprotic solvent include a cyclic carbonate, a cyclic ester, a cyclic oxime, and a cyclic ether. Examples of the chain-shaped aprotic solvent include a chain carbonate, a chain carboxylate, and a chain ether. Further, in addition to these, a solvent which is usually used as a solvent for a nonaqueous electrolyte solution such as acetonitrile can also be used. More specifically, dimethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, Butylene carbonate, tetrahydrofuran, γ-butyrolactone, 1,2-dimethoxyethane, cyclobutyl hydrazine, dioxolane, methyl propionate, and the like. These solvents may be used alone or in combination of two or more. However, in terms of the ease of dissolving the following solutes and the conductivity of lithium ions, it is preferred to use a mixture of two or more solvents. Further, a gel electrolyte in which an electrolyte solution is infiltrated into a polymer can also be used.
溶質並無特別限定,但就溶解於溶劑中之容易性而言,較佳為例如LiClO4、LiBF4、LiPF6、LiAsF6、LiCF3SO3、LiBOB(Lithium Bis(Oxalato)Borate)、LiN(SO2CF3)2等鋰鹽;NaClO4、NaBF4、NaPF6等鈉鹽;Mg[AlCl2(C4H9)(C2H5)]2、C6H5MgCl、C6H5MgBr等鎂鹽。電解液所含有之溶質之濃度較佳為0.5 mol/L以上2.0 mol/L以下。若未達0.5 mol/L,則有所需之離子傳導性未顯現之情形,另一方面,若高於 2.0 mol/L,則有溶質未進一步溶解之情形,又,黏度增大而負荷特性下降。於非水電解質溶液中,亦可含有微量之阻燃劑、穩定劑等。 The solute is not particularly limited, but in terms of ease of dissolution in a solvent, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBOB (Lithium Bis (Oxalato) Borate), LiN are preferable. a lithium salt such as (SO 2 CF 3 ) 2 ; a sodium salt such as NaClO 4 , NaBF 4 or NaPF 6 ; Mg[AlCl 2 (C 4 H 9 )(C 2 H 5 )] 2 , C 6 H 5 MgCl, C 6 Magnesium salt such as H 5 MgBr. The concentration of the solute contained in the electrolyte is preferably 0.5 mol/L or more and 2.0 mol/L or less. If it is less than 0.5 mol/L, the required ion conductivity is not observed. On the other hand, if it is higher than 2.0 mol/L, the solute is not further dissolved, and the viscosity is increased and the load characteristics are increased. decline. The non-aqueous electrolyte solution may also contain a trace amount of a flame retardant, a stabilizer, and the like.
非水電解質溶液之量並無特別限定,較佳為每電池容量1 Ah,0.1 mL以上。未達0.1 mL之情形時,有伴隨著電極反應之鋰離子之傳導未趕上,而所需之電池性能未顯現之情形。非水電解質溶液亦可預先含於正極、負極及隔片中,亦可於捲繞或積層於正極側與負極側之間配置有隔片者後進行添加。 The amount of the nonaqueous electrolyte solution is not particularly limited, but is preferably 1 Ah or 0.1 mL per battery capacity. In the case of less than 0.1 mL, the conduction of lithium ions accompanying the electrode reaction did not catch up, and the required battery performance did not appear. The non-aqueous electrolyte solution may be contained in the positive electrode, the negative electrode, and the separator in advance, or may be added after being wound or laminated between the positive electrode side and the negative electrode side.
再者,如上所述,作為非水電解質,只要可防止正極、負極之接觸,則不限定於非水電解質溶液。亦可使用凝膠狀之非水電解質。使用凝膠狀者之情形時,電解質可含浸於正極及負極中,亦可為僅存在於正極.負極間之狀態。 In addition, as described above, the nonaqueous electrolyte is not limited to the nonaqueous electrolyte solution as long as the contact between the positive electrode and the negative electrode can be prevented. A gel-like non-aqueous electrolyte can also be used. In the case of using a gel, the electrolyte may be impregnated in the positive electrode and the negative electrode, or may be present only in the positive electrode. The state between the negative electrodes.
本發明之非水電解質二次電池之正極及負極根據電池之連接構成,可為於板狀之集電體之兩面上形成相同電極之形態,亦可為於集電體之一面上形成正極,於另一面上形成負極之形態,即,雙極性電極。設為雙極性型之情形時,為防止經由集電體之正極與負極之液界,而將導電材料及/或絕緣材料配置於正極與負極之間。又,為雙極性電極之情形時,於鄰接之雙極性電極之正極側與負極側之間配置隔片,於各正極側與負極側對向之層內,為防止液界,而於正極及負極之周邊部配置絕緣密封材。 The positive electrode and the negative electrode of the nonaqueous electrolyte secondary battery of the present invention may be configured by forming a battery on both sides of a plate-shaped current collector, or may form a positive electrode on one surface of the current collector. The form of the negative electrode, that is, the bipolar electrode, is formed on the other side. In the case of the bipolar type, a conductive material and/or an insulating material is disposed between the positive electrode and the negative electrode in order to prevent liquid boundary from passing through the positive electrode and the negative electrode of the current collector. Further, in the case of a bipolar electrode, a separator is disposed between the positive electrode side and the negative electrode side of the adjacent bipolar electrode, and the liquid crystal is prevented from being formed in the layer facing each of the positive electrode side and the negative electrode side. An insulating sealing material is disposed on the peripheral portion of the negative electrode.
本發明之非水電解質二次電池可於捲繞或積層複數個積層體後利用層壓薄膜進行封裝,亦可利用角形、橢圓形、圓筒形、圓片形、按鈕形、片形之金屬罐進行封裝。亦可具備用來釋出於封裝中產生之氣體等之機構。又,亦可具備自電池外部注入用來恢復劣化之該非水電解質二次電池之功能之捕捉體9的機構。積層體之積層數可積層至顯現所需之電池容量為止。 The nonaqueous electrolyte secondary battery of the present invention can be packaged by laminating film after winding or laminating a plurality of laminated bodies, and can also be made of a metal such as an angular shape, an elliptical shape, a cylindrical shape, a disk shape, a button shape or a sheet shape. The can is packaged. It is also possible to have a mechanism for releasing gas generated in the package or the like. Further, a mechanism for injecting the capturing body 9 for recovering the function of the nonaqueous electrolyte secondary battery which deteriorates from the outside of the battery may be provided. The number of layers of the laminate can be layered until the desired battery capacity is developed.
本發明之非水電解質二次電池可藉由連接複數個而製成電池組。本發明之電池組可藉由根據所需之大小、容量、電壓而適當串聯、並聯地進行連接而製作。又,為了確認各電池之充電狀態、提高安全性,較佳為於電池組上附上控制電路。 The nonaqueous electrolyte secondary battery of the present invention can be fabricated into a battery by connecting a plurality of them. The battery pack of the present invention can be produced by connecting in series and in parallel according to the required size, capacity, and voltage. Further, in order to confirm the state of charge of each battery and improve safety, it is preferable to attach a control circuit to the battery pack.
以如下所述之方式製作Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池。 A Li 4 Ti 5 O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery was fabricated in the manner described below.
利用文獻("Zero-Strain Insertion Material of Li[Li1/3Ti5/3]04 for Rechargeable Lithium Cells" J.Electrochem.Soc.,Volume142,Issue5,pp.1431-1435(1995))所記載之方法製作負極活性物質之Li4Ti5O12。 A negative electrode was produced by the method described in the literature ("Zero-Strain Insertion Material of Li[Li1/3Ti5/3]04 for Rechargeable Lithium Cells" J. Electrochem. Soc., Volume 142, Issue 5, pp. 1431-1435 (1995)). Li 4 Ti 5 O 12 of the active substance.
即,首先以鈦與鋰之莫耳比成為5:4之方式混合二氧化鈦與氫氧化鋰,繼而藉由於氮氣環境下於800℃下加熱該混合物12小時而製作負極活性物質。 Namely, titanium dioxide and lithium hydroxide were first mixed in such a manner that the molar ratio of titanium to lithium was 5:4, and then the mixture was heated at 800 ° C for 12 hours under a nitrogen atmosphere to prepare a negative electrode active material.
將該負極活性物質100重量份、導電助材(乙炔黑)3.2重量份、及PVdF黏合劑(KF7305,KUREHA化學公司製造)(固形物成分濃度5 wt%,NMP溶液)固形物成分3.2重量份進行混合而製作漿料。將該漿料塗佈於鋁金屬網(LW×SW=8×4)上後,於150℃下進行真空乾燥,藉此製作負極。上述LW表示「網之長邊(long way of mesh)」,SW表示「網之短邊(short way of mesh)」。 100 parts by weight of the negative electrode active material, 3.2 parts by weight of a conductive auxiliary material (acetylene black), and 3.2 parts by weight of a PVdF binder (KF7305, manufactured by Kureha Chemical Co., Ltd.) (solid content concentration: 5 wt%, NMP solution) The mixture was mixed to prepare a slurry. This slurry was applied onto an aluminum metal mesh (LW × SW = 8 × 4), and then vacuum-dried at 150 ° C to prepare a negative electrode. The above LW stands for "long way of mesh" and SW stands for "short way of mesh".
利用文獻("Lithium Aluminum Manganese Oxide Having Spinel-Framework Structure for Long-Life Lithium-Ion Batteries" Electrochemical and Solid-State Letters Volume9,Issue12,Pages A557(2006))所記載之方法製作正極活性物質之Li1.1Al0.1Mn1.8O4。 Li 1.1 Al of the positive electrode active material was produced by the method described in the literature ("Lithium Aluminum Manganese Oxide Having Spinel-Framework Structure for Long-Life Lithium-Ion Batteries" Electrochemical and Solid-State Letters Volume 9, Issue 12, Pages A557 (2006)). 0.1 Mn 1.8 O 4 .
即,製備二氧化錳、碳酸鋰、氫氧化鋁、及硼酸之水分散液, 並利用噴霧乾燥法而製作混合粉末。此時,二氧化錳、碳酸鋰及氫氧化鋁之量係以鋰、鋁及錳之莫耳比成為1.1:0.1:1.8之方式進行製備。繼而,於空氣環境下於900℃下加熱該混合粉末12小時,之後再次於650℃下加熱24小時。最後,利用95℃之水清洗該粉末後進行乾燥,藉此製作正極活性物質。 That is, an aqueous dispersion of manganese dioxide, lithium carbonate, aluminum hydroxide, and boric acid is prepared. The mixed powder was prepared by a spray drying method. At this time, the amounts of manganese dioxide, lithium carbonate, and aluminum hydroxide were prepared so that the molar ratio of lithium, aluminum, and manganese was 1.1:0.1:1.8. Then, the mixed powder was heated at 900 ° C for 12 hours in an air atmosphere, and then heated again at 650 ° C for 24 hours. Finally, the powder was washed with water at 95 ° C and then dried to prepare a positive electrode active material.
將該正極活性物質100重量份、導電助材(乙炔黑)3.2重量份、及聚偏二氟乙烯(PVdF)黏合劑(KF7305,KUREHA化學公司製造)(固形物成分濃度5 wt%,NMP溶液)固形物成分3.2重量份進行混合而製作漿料。將該漿料塗佈於鋁金屬網(LW×SW=8×4)上後,於150℃下進行真空乾燥,藉此製作正極。 100 parts by weight of the positive electrode active material, 3.2 parts by weight of a conductive auxiliary material (acetylene black), and a polyvinylidene fluoride (PVdF) binder (KF7305, manufactured by Kureha Chemical Co., Ltd.) (solid content concentration: 5 wt%, NMP solution) 3.2 parts by weight of the solid content component was mixed to prepare a slurry. This slurry was applied onto an aluminum metal mesh (LW × SW = 8 × 4), and then vacuum dried at 150 ° C to prepare a positive electrode.
將所製作之負極或正極設為作用極。作為其對極,將鋰金屬之板狀者衝壓成與作用極相同之面積。以作用極/隔片(Celgard # 2500,Celgard公司製造)/對極之順序積層於層壓電池內,並於碳酸乙二酯/碳酸二甲酯=3/7體積%之非水溶劑中加入溶解有1 moL/L之LipF4者0.5 mL而製作半電池。將該半電池於25℃下放置一天,之後連接於充放電試驗裝置(HJ1005SD8;北斗電工公司製造)上。於25℃、1 mA下對該半電池反覆恆定電流放電5次,而將第5次之結果設為負極或正極之容量。 The produced negative electrode or positive electrode was set as a working electrode. As the counter electrode, the plate metal of the lithium metal is punched into the same area as the working electrode. Laminated in a laminated battery in the order of the working electrode/separator (Celgard # 2500, manufactured by Celgard) / counter electrode, and added to a nonaqueous solvent of ethylene carbonate / dimethyl carbonate = 3 / 7 vol% A half-cell was prepared by dissolving 0.5 mL of LipF 4 in 1 mol/L. The half-cell was allowed to stand at 25 ° C for one day, and then connected to a charge and discharge test apparatus (HJ1005SD8; manufactured by Hokuto Electric Co., Ltd.). The half-cell was repeatedly discharged at a constant current of 5 times at 25 ° C and 1 mA, and the result of the fifth time was set as the capacity of the negative electrode or the positive electrode.
於最初,以獲得之正極/隔片/獲得之負極之順序進行積層。就隔片而言,使用2片纖維素不織布(25 μm、55 cm2)。於2片之纖維素不織布之間,配置使鋰金屬壓接於與隔片之外縁同型之不鏽鋼框(框寬度5 mm,厚度0.3 mm)上而成者作為捕捉體。鋰金屬之形狀係將寬度1 mm之細長之鋰金屬之薄板以5 mm的間距縱格子狀地排列於不鏽鋼框中者。繼而,使鋁板振動焊接於電池之兩端之正極及負極上後,放入 袋狀之鋁層壓片中。於乾燥環境下注入非水電解液(碳酸乙二酯/碳酸二甲酯=3/7 vol%、LiPF6 1 mol/L)4 mL後,一面進行減壓一面進行密封,藉此製作非水電解質二次電池。將以上述製作之非水電解質二次電池稱為「電池」(以下之實施例、比較例中相同)。 Initially, the layers were obtained in the order of the obtained positive electrode/separator/obtained negative electrode. For the separator, two sheets of cellulose non-woven fabric (25 μm, 55 cm 2 ) were used. Between the two sheets of cellulose non-woven fabric, a lithium metal was placed under pressure to a stainless steel frame (frame width 5 mm, thickness 0.3 mm) which is the same as the separator, and was used as a trap. The shape of the lithium metal is such that a thin sheet of elongated lithium metal having a width of 1 mm is arranged in a lattice shape at a pitch of 5 mm in a stainless steel frame. Then, the aluminum plate was vibrated and welded to the positive electrode and the negative electrode at both ends of the battery, and then placed in a bag-shaped aluminum laminate. After injecting 4 mL of a non-aqueous electrolyte (ethylene carbonate / dimethyl carbonate = 3/7 vol%, LiPF 6 1 mol / L) in a dry environment, the mixture was sealed while decompressing, thereby producing a non-aqueous solution. Electrolyte secondary battery. The nonaqueous electrolyte secondary battery produced as described above is referred to as "battery" (the same in the following examples and comparative examples).
於實施例1中,代替不鏽鋼框而使用混合鋰金屬與聚偏二氟乙烯(PVdF)後進行成形而製成與不鏽鋼框同型者,除此以外,以與實施例1相同之方式製作非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池)。 In the first embodiment, a non-aqueous material was produced in the same manner as in Example 1 except that instead of a stainless steel frame, a mixed lithium metal and polyvinylidene fluoride (PVdF) were used and molded to have the same shape as that of the stainless steel frame. Electrolyte secondary battery (Li 4 Ti 5 O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery).
於實施例1中,代替不鏽鋼框而使用鎂金屬框,並將捕捉體之材質設為鎂金屬,除此以外,以與實施例1相同之方式製作非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池)。 A nonaqueous electrolyte secondary battery (Li 4 Ti 5 ) was produced in the same manner as in Example 1 except that a magnesium metal frame was used instead of the stainless steel frame, and the material of the capturing body was changed to magnesium metal. O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery).
於實施例1中,使用TiO2(B)作為負極活性物質,除此以外,以與實施例1相同之方式製作非水電解質二次電池(TiO2(B)/Li1.1Al0.1Mn1.8O4電池)。負極材料之TiO2(B)係利用文獻(Materias Research Bulletin,Vol.15,pp.1129-1133(1980)所記載之方法進行製作。 A nonaqueous electrolyte secondary battery (TiO 2 (B) / Li 1.1 Al 0.1 Mn 1.8 O) was produced in the same manner as in Example 1 except that TiO 2 (B) was used as the negative electrode active material in Example 1. 4 batteries). The TiO 2 (B) of the negative electrode material was produced by the method described in the literature (Materias Research Bulletin, Vol. 15, pp. 1129-1133 (1980).
於實施例1中,使用NaNi0.5Mn0.5O2作為正極活性物質,使用鈉金屬作為壓接於不鏽鋼框上之金屬,並使用含有鈉離子之電解液(PC,NaPF6,1.0 mol/L),除此以外,以與實施例1相同之方式製作非水電解質二次電池(Li4Ti5O12/NaNi0.5Mn0.5O2電池)。正極材料之NaNi0.5Mn0.5O2係利用文獻(ECS Transactions,volume 16,issue 42,pp.43-55(2009))所記載之方法進行製作。 In Example 1, NaNi 0.5 Mn 0.5 O 2 was used as a positive electrode active material, sodium metal was used as a metal bonded to a stainless steel frame, and an electrolyte containing sodium ions (PC, NaPF 6 , 1.0 mol/L) was used. A nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 /NaNi 0.5 Mn 0.5 O 2 battery) was produced in the same manner as in Example 1 except the above. The NaNi 0.5 Mn 0.5 O 2 system of the positive electrode material was produced by the method described in the literature (ECS Transactions, volume 16, issue 42, pp. 43-55 (2009)).
於實施例1中,將包含聚環氧乙烷(PEO,polyethylene oxide)之固體電解質與LiPF6之碳酸丙二酯溶液之電解液的混合物浸漬於獲得之正極及負極中,藉由熱壓製進行硬化而製成正極板及負極板。於上述電解液之混合物中分散鋰金屬微粒子(直徑900 nm)作為捕捉體,並藉由熱硬化而製成電解質層。以正極板/電解質層/負極板之順序貼合該等,藉此構成電極群,以與實施例1相同之方式將該電極群封入鋁層壓片中,藉此製作非水電解質二次電池(Li4Ti5O12/捕捉體分散PEO/Li1.1Al0.1Mn1.8O4電池)。 In the first embodiment, a mixture of a solid electrolyte containing polyethylene oxide (PEO) and a solution of a propylene carbonate solution of LiPF 6 is immersed in the obtained positive electrode and negative electrode by hot pressing. It is hardened to form a positive electrode plate and a negative electrode plate. Lithium metal fine particles (900 nm in diameter) were dispersed as a trap in the mixture of the above electrolytes, and an electrolyte layer was formed by thermal hardening. The positive electrode plate/electrolyte layer/negative electrode plate was laminated in this order to form an electrode group, and the electrode group was sealed in an aluminum laminate in the same manner as in Example 1, thereby producing a nonaqueous electrolyte secondary battery. (Li 4 Ti 5 O 12 / capture body dispersion PEO/Li 1.1 Al 0.1 Mn 1.8 O 4 battery).
於實施例1中,不插入捕捉體(壓接於不鏽鋼框上之鋰金屬),除此以外,以與實施例1相同之方式製作非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池)。 A nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 /Li) was produced in the same manner as in Example 1 except that the capturing body (lithium metal bonded to the stainless steel frame) was not inserted in the first embodiment. 1.1 Al 0.1 Mn 1.8 O 4 battery).
於實施例4中,不插入捕捉體(壓接於不鏽鋼框上之鋰金屬),除此以外,以與實施例4相同之方式製作非水電解質二次電池(TiO2(B)/Li1.1Al0.1Mn1.8O4電池)。 A nonaqueous electrolyte secondary battery (TiO 2 (B)/Li 1.1 was produced in the same manner as in Example 4 except that the capturing body (lithium metal bonded to the stainless steel frame) was not inserted in Example 4. Al 0.1 Mn 1.8 O 4 battery).
於實施例5中,不插入捕捉體(壓接於不鏽鋼框上之鋰金屬),除此以外,以與實施例5相同之方式製作非水電解質二次電池(Li4Ti5O12/NaNi0.5Mn0.5O2電池)。 A nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 /NaNi) was produced in the same manner as in Example 5 except that the capturing body (lithium metal bonded to the stainless steel frame) was not inserted. 0.5 Mn 0.5 O 2 battery).
於實施例6中,不分散鋰金屬微粒子,除此以外,以與實施例6相同之方式獲得非水電解質二次電池(Li4Ti5O12/PEO/Li1.1Al0.1Mn1.8O4電池)。 A nonaqueous electrolyte secondary battery (Li 4 Ti 5 O 12 /PEO/Li 1.1 Al 0.1 Mn 1.8 O 4 battery) was obtained in the same manner as in Example 6 except that lithium metal fine particles were not dispersed in Example 6. ).
於圖5中表示概略,設置恆定電流驅動源21、檢測電池之端子電壓V之電壓檢測部23、驅動繼電器開關22之充放電控制部24,並根據電壓檢測部23所檢測之端子電壓V,藉由充放電控制部24而驅動繼電器開關22,從而切換流過電池之固定之電流I的方向。即,若端子電壓V低於上限電壓V1,則向對電池進行充電之方向流過電流,若超過下限電壓V2,則切換電流之方向而放電。但是設為V2>V1。上述固定之電流I係設定對具有上述<負極及正極之容量測定>中測定之容量的電池進行恆定電流放電,於恰好1小時內結束放電而獲得之電流值(將其稱為「1小時率之電流值」)。以上述方式反覆充放電特定次數,而測定電池容量減少何種程度。所謂「電池容量」係指自開始電池之放電直至放電結束之時間T乘以電流I而成之值「TI」。循環初期,電池之內部電阻較小,電池容量(TI值)較大,但若反覆循環,則電池容量變小,而於短時間內結束放電。因電流I之值固定,故可認為電池容量與放電時間T成比例。 As shown in FIG. 5, the constant current drive source 21, the voltage detecting unit 23 for detecting the terminal voltage V of the battery, and the charge and discharge control unit 24 for driving the relay switch 22 are provided, and based on the terminal voltage V detected by the voltage detecting unit 23, The relay switch 22 is driven by the charge and discharge control unit 24 to switch the direction of the fixed current I flowing through the battery. In other words, when the terminal voltage V is lower than the upper limit voltage V1, a current flows in a direction in which the battery is charged, and when the lower limit voltage V2 is exceeded, the direction of the current is switched and discharged. But set to V2>V1. The fixed current I is a current value obtained by performing constant current discharge on a battery having the capacity measured in the above-described <capacity measurement of the negative electrode and the positive electrode, and ending the discharge in exactly one hour (referred to as "1 hour rate". Current value"). The charge and discharge were repeated for a specific number of times in the above manner, and the degree of reduction in battery capacity was measured. The term "battery capacity" refers to a value "TI" obtained by multiplying the time T from the start of discharge of the battery to the end of discharge by the current I. At the beginning of the cycle, the internal resistance of the battery is small, and the battery capacity (TI value) is large. However, if the cycle is repeated, the battery capacity becomes small, and the discharge is terminated in a short time. Since the value of the current I is fixed, it can be considered that the battery capacity is proportional to the discharge time T.
對於實施例1~4、實施例6、比較例1~2、比較例4,分別測定使用充放電試驗裝置(HJ1005SD8;北斗電工公司製造)而反覆充放電250次後之電池容量維持率,因此示於表1。又,對於實施例5、比較例3,分別測定反覆充放電100次後之電池容量維持率,因此示於表 1。此處所謂「電池容量維持率」係指「反覆特定次充放電後之電池容量」除以「充放電循環試驗第1次循環之電池容量」而獲得之數值(單位%)。又,除測定電池容量維持率以外,於該測定之前後,將電池浸漬於碳酸乙二酯中,而測定增加之體積的差,並將其設為氣體產生量。將氣體產生量之測定結果一併記載於表1中(單位mL)。 In Examples 1 to 4, Example 6, Comparative Example 1 to 2, and Comparative Example 4, the battery capacity retention rate after the charge and discharge test device (HJ1005SD8; manufactured by Hokuto Electric Co., Ltd.) was used for 250 times of charge and discharge was measured. Shown in Table 1. Further, in Example 5 and Comparative Example 3, the battery capacity retention ratio after repeated charge and discharge 100 times was measured, and thus it is shown in the table. 1. Here, the "battery capacity retention rate" means a value (unit: %) obtained by dividing "the battery capacity after repeated specific charge and discharge" by the "battery capacity of the first cycle of the charge and discharge cycle test". Further, in addition to the measurement of the battery capacity retention rate, the battery was immersed in ethylene carbonate after the measurement, and the difference in volume was measured, and this was set as the gas generation amount. The measurement results of the gas generation amount are collectively shown in Table 1 (unit: mL).
比較例1之非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池)於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。電池容量隨著每次循環而平緩地減少,而第250次循環時之容量維持率為初期之89%。伴隨著充放電循環之氣體產生量為8.76 mL。 The nonaqueous electrolyte secondary battery of Comparative Example 1 (Li 4 Ti 5 O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery) was subjected to a current value of 60 ° C, an upper limit voltage of 3.4 V, a lower limit voltage of 0 V, and a one hour rate. 250 cycles of testing. The battery capacity gradually decreased with each cycle, and the capacity retention rate at the 250th cycle was 89% of the initial period. The gas generation amount accompanying the charge and discharge cycle was 8.76 mL.
又,實施例1及實施例2之非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池,捕捉體=鋰金屬)亦於60℃、上限電壓3.4V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。電池容量隨著每次循環而平緩地減少,而第250次循環時之容量維持率分別為初期之94%、92%。伴隨著充放電循環之氣體產生量分別為4.30 mL、5.44 mL。 Further, the nonaqueous electrolyte secondary batteries (Li 4 Ti 5 O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery, capturing body = lithium metal) of Examples 1 and 2 were also at 60 ° C and an upper limit voltage of 3.4 V. The cycle voltage test was performed at a lower limit voltage of 0 V and a current value of 1 hour. The battery capacity was gradually reduced with each cycle, and the capacity retention rate at the 250th cycle was 94% and 92%, respectively. The gas generation amount accompanying the charge and discharge cycle was 4.30 mL and 5.44 mL, respectively.
於圖6中表示相對於充放電循環數,對實施例1與比較例1之各電池容量維持率進行繪製而成之圖表。可知充放電循環數越增加,電池容量維持率越減少,但與比較例1相比,實施例1之電池容量維持率之下降率較低。根據上述情況可知,藉由將鹼金屬之捕捉體配置於電池內而提高充放電循環特性。又,根據表1所示之結果可知抑制伴隨著充放電循環之氣體產生。 Fig. 6 is a graph showing the battery capacity retention ratios of Example 1 and Comparative Example 1 plotted against the number of charge and discharge cycles. It was found that the battery charge retention rate decreased as the number of charge/discharge cycles increased, but the decrease rate of the battery capacity retention rate of Example 1 was lower than that of Comparative Example 1. According to the above, it is understood that the charge and discharge cycle characteristics are improved by disposing the trapezing body of the alkali metal in the battery. Further, from the results shown in Table 1, it was found that the generation of gas accompanying the charge and discharge cycle was suppressed.
實施例3之非水電解質二次電池(Li4Ti5O12/Li1.1Al0.1Mn1.8O4電池,鎂金屬框)亦於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。容量隨著每次循環而平緩地減少,而第250次循環時之容量維持率為初期之91%。又,起因於充放電循環之氣體 產生量為6.22 mL。根據上述情況可知,藉由將鹼土類金屬配置於電池內而提高充放電循環特性,且抑制氣體產生。 The nonaqueous electrolyte secondary battery of Example 3 (Li 4 Ti 5 O 12 /Li 1.1 Al 0.1 Mn 1.8 O 4 battery, magnesium metal frame) was also at 60 ° C, the upper limit voltage was 3.4 V, the lower limit voltage was 0 V, and the hour rate was 250 cycles of the current were performed. The capacity was gradually reduced with each cycle, and the capacity retention rate at the 250th cycle was 91% of the initial period. Further, the amount of gas generated due to the charge and discharge cycle was 6.22 mL. According to the above, it is understood that the alkaline earth metal is disposed in the battery to improve the charge/discharge cycle characteristics and suppress the generation of gas.
比較例2之非水電解質二次電池(TiO2(B)/Li1.1Al0.1Mn1.8O4電池)於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。容量隨著每次循環而平緩地減少,而第250次循環時之容量維持率為初期之66%。又,起因於充放電循環之氣體產生量為10.78 mL。 The nonaqueous electrolyte secondary battery of Comparative Example 2 (TiO 2 (B) / Li 1.1 Al 0.1 Mn 1.8 O 4 battery) was subjected to 250 at 60 ° C, an upper limit voltage of 3.4 V, a lower limit voltage of 0 V, and a current value of 1 hour. Secondary cycle test. The capacity was gradually reduced with each cycle, and the capacity retention rate at the 250th cycle was 66% of the initial period. Further, the amount of gas generated due to the charge and discharge cycle was 10.78 mL.
又,實施例4之非水電解質二次電池(TiO2(B)/Li1.1Al0.1Mn1.8O4電池,捕捉體=鋰金屬)亦於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。容量隨著每次循環而平緩地減少,而第250次循環時之容量維持率為初期之75%。又,起因於充放電循環之氣體產生量為5.60 mL。根據上述情況可知,藉由將鹼金屬配置於電池內而提高充放電循環特性,且抑制氣體產生。 Further, the nonaqueous electrolyte secondary battery of Example 4 (TiO 2 (B)/Li 1.1 Al 0.1 Mn 1.8 O 4 battery, trapping body = lithium metal) was also at 60 ° C, the upper limit voltage was 3.4 V, and the lower limit voltage was 0 V. A 250 cycle test was performed at a current value of 1 hour. The capacity gradually decreases with each cycle, and the capacity retention rate at the 250th cycle is 75% of the initial period. Further, the amount of gas generated due to the charge and discharge cycle was 5.60 mL. According to the above, it is understood that the charge and discharge cycle characteristics are improved by disposing the alkali metal in the battery, and gas generation is suppressed.
比較例3之非水電解質二次電池(Li4Ti5O12/NaNi0.5Mn0.5O2電池)於25℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行100次循環試驗。第100次循環時之容量維持率為初期之61%。又,起因於充放電循環之氣體產生量為17.78 mL。 The nonaqueous electrolyte secondary battery of Comparative Example 3 (Li 4 Ti 5 O 12 /NaNi 0.5 Mn 0.5 O 2 battery) was subjected to 100 times at a current value of 25 ° C, an upper limit voltage of 3.4 V, a lower limit voltage of 0 V, and a one hour rate. Cycle test. The capacity retention rate at the 100th cycle was 61% of the initial period. Further, the amount of gas generated due to the charge and discharge cycle was 17.78 mL.
實施例5之非水電解質二次電池(Li4Ti5O12/NaNi0.5Mn0.5O2電池,捕捉體=鈉金屬)亦於25℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行100次循環試驗。第100次循環時之容量維持率為初期之71%,且起因於充放電循環之氣體產生量為10.32 mL,根據上述情況可知,藉由將鹼金屬配置於電池內而提高充放電循環特性,且抑制氣體產生。 The nonaqueous electrolyte secondary battery of Example 5 (Li 4 Ti 5 O 12 /NaNi 0.5 Mn 0.5 O 2 battery, capturing body = sodium metal) was also at 25 ° C, the upper limit voltage was 3.4 V, the lower limit voltage was 0 V, and the hour rate was 100 cycles of the current were performed. The capacity retention rate at the 100th cycle was 71% at the initial stage, and the gas generation amount due to the charge and discharge cycle was 10.32 mL. From the above, it was found that the charge and discharge cycle characteristics were improved by disposing the alkali metal in the battery. And suppress gas generation.
關於比較例4之非水電解質二次電池(Li4Ti5O12/PEO/Li1.1Al0.1Mn1.8O4電池),係於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。第250次循環時之容量維持率為初期之85%。 又,起因於充放電循環之氣體產生量為4.12 mL。 The nonaqueous electrolyte secondary battery of Comparative Example 4 (Li 4 Ti 5 O 12 /PEO/Li 1.1 Al 0.1 Mn 1.8 O 4 battery) was at 60 ° C, an upper limit voltage of 3.4 V, a lower limit voltage of 0 V, and a 1 hour rate. 250 cycles of the current were performed. The capacity retention rate at the 250th cycle was 85% of the initial period. Further, the amount of gas generated due to the charge and discharge cycle was 4.12 mL.
關於實施例6之非水電解質二次電池(Li4Ti5O12/捕捉體分散PEO/Li1.1Al0.1Mn1.8O4電池),係亦於60℃、上限電壓3.4 V、下限電壓0 V、1小時率之電流值下進行250次循環試驗。第250次循環時之容量維持率為初期之89%,且起因於充放電循環之氣體產生量為2.26 mL,根據上述情況可知,藉由於固體電解質中分散捕捉體而提高充放電循環特性,且抑制起因於充放電循環之氣體產生。 The nonaqueous electrolyte secondary battery of Example 6 (Li 4 Ti 5 O 12 / capture body dispersed PEO/Li 1.1 Al 0.1 Mn 1.8 O 4 battery) was also at 60 ° C, the upper limit voltage was 3.4 V, and the lower limit voltage was 0 V. The cycle test was carried out at a current value of 1 hour. The capacity retention rate at the 250th cycle was 89% at the initial stage, and the gas generation amount due to the charge and discharge cycle was 2.26 mL. From the above, it was found that the charge and discharge cycle characteristics were improved by dispersing the trap in the solid electrolyte. The generation of gas due to the charge and discharge cycle is suppressed.
1‧‧‧非水電解質二次電池 1‧‧‧Non-aqueous electrolyte secondary battery
2‧‧‧正極用集電體 2‧‧‧ Positive current collector
4‧‧‧負極用集電體 4‧‧‧ Current collector for negative electrode
3‧‧‧非水電解質層 3‧‧‧Non-aqueous electrolyte layer
5‧‧‧正極活性物質 5‧‧‧ positive active material
6‧‧‧負極活性物質 6‧‧‧Negative active material
7a、7b‧‧‧隔片 7a, 7b‧‧‧ spacer
8‧‧‧絕緣密封材 8‧‧‧Insulation sealing material
9‧‧‧捕捉體 9‧‧‧ Capture
10‧‧‧框 10‧‧‧ box
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