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"Secondary Battery, Electronic Device, Electric Power Tool, Electrical Vehicle, And Electric Power Storage System"

Abstract: A secondary battery capable of suppressing resistance rise even after repeated charge and discharge is provided. The secondary battery includes a cathode, an anode, and an electrolytic solution. The anode contains titanium-containing lithium composite as an anode active material, and the electrolytic solution contains cyclic disulfonic acid anhydride.

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Patent Information

Application #
Filing Date
16 March 2012
Publication Number
34/2015
Publication Type
INA
Invention Field
ELECTRONICS
Status
Email
remfry-sagar@remfry.com
Parent Application

Applicants

SONY CORPORATION
1-7-1 KONAN, MINATO-KU, TOKYO, JAPAN

Inventors

1. ATSUMICHI KAWASHIMA
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
2. HIROSHI IMOTO
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
3. TOMOYUKI SHIRATSUCHI
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
4. TAKUMA SAKAMOTO
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
5. NAOTO UEDA
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
6. ATSUSHI NISHIMOTO
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
7. TADAHIKO KUBOTO
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN
8. MASAYUKI IHARA
SONY ENERGY DEVICES CORPORATION, 1-1 SHIMOSUGISHITA TAKAHURA HIWADA-MACHI, KORIYAMA-SHI, FUKUSHIMA, JAPAN

Specification

BACKGROUND [0001] The present technology relates to secondary batteries including a cathode, an anode, and an electrolytic solution, electronic devices using the same, electric power tools using the same, electrical vehicles using the same, and electric power storage systems using the same. [0002] In recent years, electronic devices represented by a mobile phone and a Personal Digital Assistant (PDA) have been widely used, and it has been strongly demanded to further reduce their size and weight and to achieve their long life. Accordingly, as a power source for the electronic devices, a battery, in particular, a small and light-weight secondary battery capable of providing a high energy density has been developed. In recent years, it has been considered to apply such a secondary battery not only to the foregoing electronic devices but also to various applications represented by an electric power tool such as an electrical drill, an electrical vehicle such as an electrical automobile, and an electric power storage system such as a home electrical power server. [0003] As the secondary batteries, secondary batteries using various charge and discharge principles have been widely proposed. Specially, lithium ion secondary batteries using insertion and extraction of lithium ions are considered promising, since the lithium ion secondary batteries are able to provide a higher energy density than that of lead batteries, nickel cadmium batteries and the like. [0004] The secondary batteries include a cathode, an anode, and an electrolytic solution. The cathode and the anode respectively contain a cathode active material and 2 an anode active material that insert and extract lithium ions. In the secondary battery, in order to obtain a high battery capacity, a lithium-containing compound such as LiCo02 is used as a cathode active material, and a carbon material such as graphite is used as an anode active material. [0005] In the secondary battery using the carbon material as an anode active material, the anode active material is easily reacted with an electrolytic solution at the time of charge and discharge, and therefore decomposition reaction of the electrolytic solution tends to be promoted. In this case, since the surface of the anode is covered with a decomposed matter or the like of the electrolytic solution. Therefore, when charge and discharge are repeated, resistance of the anode is easily increased. [0006] Therefore, it has been proposed to use, as an anode active material, a low reactive titanium-containing lithium composite oxide instead of the high reactive carbon material (for example, see Japanese Unexamined Patent Application Publication No. 06-275263). The titanium-containing lithium composite oxide is an oxide containing Li, Ti, and other metal element as an element, and has a spinel type crystal structure. SUMMARY [0007] By using the titanium-containing lithium composite oxide as an anode active material, decomposition reaction of the electrolytic solution resulting from reactivity of the anode is inhibited. However, in this case, decomposition reaction of the electrolytic solution resulting from reactivity of the cathode is not inhibited. Therefore, in the case where the lithium-containing compoimd providing a high capacity is used as a cathode active material, after repeated charge and discharge, resistance of the cathode 3 is easily increased resulting from decomposition reaction of the electrolytic solution. Accordingly, resistance of the entire battery is still increased. [0008] It is desirable to provide a secondary battery, an electronic device, an electric power tool, an electrical vehicle, and an electric power storage system capable of suppressing resistance rise even after repeated charge and discharge. [0009] According to an embodiment of the present technology, there is provided a secondary battery including a cathode, an anode, and an electrolytic solution. The anode contains one or more of titanium-containing lithium composite oxides expressed by the following Formula 1 to Formula 3 as an anode active material. The electrolytic solution contains one cyclic disulfonic acid anhydride expressed by the following Formula 4 or cyclic disulfonic acid anhydride expressed by the following Formula 5 or both. Formula 1 Li[LixMl (1.3x)/2Ti(3+x)/2]O4 ... (1) [0010] In the formula. Ml is one or more of Mg, Ca, Cu, Zn, and Sr, and x satisfies 0 [0028] FIG. 1 and FIG. 2 illustrate a cross sectional configuration of a secondary battery in the embodiment of this technology. FIG. 2 illustrates an enlarged part of a spirally wound electrode body 20 illustrated in FIG 1. [Whole Configuration of Secondary Battery] [0029] The secondary battery herein described is, for example, a lithium ion secondary battery in which the battery capacity is obtained by insertion and extraction of lithium ions, and is what we call a cylindrical type secondary battery. The secondary battery contains the spirally wound electrode body 20 and a pair of insulating plates 12 and 13 inside a battery can 11 in the shape of an approximately hollow cylinder. In the spirally wound electrode body 20, a cathode 21 and an anode 22 are layered with a separator 23 in between and are spirally wound. [0030] The battery can 11 has a hollow structure in which one end of the battery 7 can 11 is closed and the other end thereof is opened. The battery can 11 is made of, for example, Fe, Al, an alloy thereof or the like. Plating of Ni or the like may be provided on the surface of the battery can 11. The pair of insulating plates 12 and 13 is arranged to sandwich the spirally wound electrode body 20 in between from the upper and the lower sides, and to extend perpendicularly to the spirally wound periphery face. [0031] At the open end of the battery can 11, a battery cover 14, a safety valve mechanism 15, and a PTC (Positive Temperature Coefiicient) device 16 are attached by being caulked with a gasket 17. Thereby, the battery can 11 is hermetically sealed. The battery cover 14 is made of, for example, a material similar to that of the battery can 11. The safety valve mechanism 15 and the PTC device 16 are provided inside the battery cover 14. The safety valve mechanism 15 is electrically cormected to the battery cover 14 through the PTC device 16. In the safety valve mechanism 15, when the internal pressure becomes a certain level or more by internal short circuit, external heating or the like, a disk plate 15A inverts to cut the electric cormection between the battery cover 14 and the spirally wound electrode body 20. The PTC device 16 prevents abnormal heat generation resulting from a large current. In the PTC device 16, as temperature rises, the resistance is increased. The gasket 17 is made of, for example, an insulating material. The surface of Ihe gasket 17 may be coated with asphalt. [0032] In the center of the spirally wound electrode body 20, a center pin 24 may be inserted. For example, a cathode lead 25 made of a conductive material such as Al is cormected to the cathode 21. For example, an anode lead 26 made of a conductive material such as Ni is cormected to the anode 22. The cathode lead 25 is, for example, welded to the safety valve mechanism 15, and is electrically cormected to the battery 8 cover 14. The anode lead 26 is, for example, welded to the battery can 11, and is electrically connected to the battery can 11. [Cathode] [0033] In the cathode 21, for example, a cathode active material layer 21B is provided on a single face or both faces of a cathode current collector 21 A. The cathode current collector 21A is made of, for example, a conductive material such as Al, Ni, and stainless steel. [0034] The cathode active material layer 21B contains, as a cathode active material, one or more cathode materials inserting and extracting lithium ions. According to needs, the cathode active material layer 2IB may contain other material such as a cathode binder and a cathode electrical conductor. [0035] As the cathode material, a lithium-containing compound is preferable, since thereby a high energy density is obtained. Examples of the lithium-containing compound include a composite oxide containing Li and a transition metal element as an element and a phosphate compound containing Li and a transition metal element as an element. Specially, it is preferable that the transition metal element be one or more of Co, Ni, Mn, and Fe, since thereby a higher voltage is obtained. The chemical formula thereof is expressed by, for example, LixMI02 or LiyMIIP04. In the formula, MI and Mil represent one or more transition metal elements. Values of x and y vary according to the charge and discharge state, and are generally in the range of 0.05 [0109] FIG. 4 illustrates an exploded perspective configuration of another 32 secondary battery in the embodiment of this technology. FIG. 5 illustrates an enlarged cross section taken along line V-V of a spirally wovmd electrode body 30 illustrated in FIG 4. In the following description, the elements of the cylindrical type secondary battery described above will be used as needed. [Whole Structure of Secondary Battery] [0110] The secondary battery herein described is what we call a laminated film type lithium ion secondary battery. In the secondary battery, the spirally wound electrode body 30 is contained in a film package member 40. In the spirally wound electrode body 30, a cathode 33 and an anode 34 are layered with a separator 35 and an electrolyte layer 36 in between and are spirally wound. A cathode lead 31 is attached to the cathode 33, and an anode lead 32 is attached to the anode 34. The outermost peripheral portion of the spirally wound electrode body 30 is protected by a protective tape 37. [0111] The cathode lead 31 and the anode lead 32 are, for example, respectively led out fi-om inside to outside of the package member 40 in the same direction. The cathode lead 31 is made of, for example, a conductive material such as Al, and the anode lead 32 is made of, for example, a conducive material such as Cu, Ni, and stainless steel. These materials are in the shape of, for example, a thin plate or mesh. [0112] The package member 40 is a laminated film in which, for example, a fiision bonding layer, a metal layer, and a surface protective layer are layered in this order. In the laminated film, for example, the respective outer edges of the fusion bonding layer of two films are bonded to each other by fusion bonding, an adhesive or the like so that the fusion bonding layer and the spirally wound electrode body 30 are opposed to each other. Examples of the fiision bonding layer include a film made of polyethylene, 33 polypropylene or the like. Examples of the metal layer include an Al foil. Examples of the surface protective layer include a film made of nylon, polyethylene terephthalate or the like. [0113] Specially, as the package member 40, an aluminum laminated film in which a polyethylene film, an alimiinum foil, and a nylon film are layered in this order is preferable. However, the package member 40 may be made of a laminated film havmg other laminated structure, a polymer film such as polypropylene, or a metal film. [0114] An adhesive film 41 to protect fi-om entering of outside air is inserted between the package member 40 and the cathode lead 31/the anode lead 32. The adhesive film 41 is made of a material having contact characteristics with respect to the cathode lead 31 and the anode lead 32. Examples of such a material include, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, ■ and modified polypropylene. [0115] In the cathode 33, for example, a cathode active material layer 33B is provided on both faces of a cathode current collector 33A. In the anode 34, for example, an anode active material layer 34B is provided on both faces of an anode current collector 34A. The structures of the cathode current collector 33 A, the cathode active material layer 33B, the anode current collector 34A, and the anode active material layer 34B are respectively similar to the structures of the cathode current collector 21 A, the cathode active material layer 2IB, the anode current collector 22A, and the anode active material layer 22B. Therefore, the anode active material layer 34B contains the titanium-containing lithium composite oxide as an anode active material. Further, the structure of the separator 35 is similar to the structure of the separator 23. 34 [0116] In the electrolyte layer 36, an electrolytic solution is held by a polymer compoimd. The electrolyte layer 36 may contain other material such as an additive according to needs. The electrolyte layer 36 is what we call a gel electrolyte. The gel electrolyte is preferable, since high ion conductivity (for example, 1 mS/cm or more at room temperature) is obtained and liquid leakage of the electrolytic solution is prevented. [0117] Examples of the polymer compound include one or more of the following polymer materials. That is, examples thereof include polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, and polyvinyl fluoride. Further, examples thereof include polyvinyl acetate, polyvinyl alcohol, polymethacrylic acid methyl, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, and polycarbonate. Further examples thereof include a copolymer of vinylidene fluoride and hexafluoropropylene. Specially, polyvinylidene fluoride or the copolymer of vinylidene fluoride and hexafluoropropylene is preferable, and polyvinylidene fluoride is more preferable, since such a polymer compoimd is electrochemically stable. [0118] The composition of the electrolytic solution is similar to the composition of the cylindrical type secondary battery, and the electrolytic solution contains a solvent, an electrolyte salt, and a cyclic disulfonic acid anhydride. However, in the electrolyte layer 36 as the gel electrolyte, a solvent of the electrolytic solution means a wide concept including not only a liquid solvent but also a material having ion conductivity capable of dissociating the electrolyte salt. Therefore, in the case where the polymer compoimd having ion conductivity is used, the polymer compound is also included in 35 the solvent. [0119] Instead of the gel electrolyte layer 36, the electrolytic solution may be directly used. In this case, the separator 35 is impregnated with the electrolytic solution. [Operation of Secondary Battery] [0120] In the secondary battery, for example, at the time of charge, lithium ions extracted from the cathode 33 are inserted in the anode 34 through the electrolyte layer 36. In addition, at the time of discharge, for example, lithium ions extracted from the anode 34 are inserted in the cathode 33 through the electrolyte layer 36. [Manufacturing Method of Secondary Battery] [0121] The secondary battery including the gel elecfrolyte layer 36 is manufactured, for example, by the following three procedures. [0122] In the first procedure, the cathode 33 and the anode 34 are formed by a formation procedure similar to that of the cathode 21 and the anode 22. In this case, the cathode 33 is formed by forming the cathode active material layer 33B on both faces of the cathode current collector 33A, and the anode 34 is formed by forming the anode active material layer 34B on both faces of the anode current collector 34A. Subsequently, a precursor solution containing an elecfrolytic solution, a polymer compoimd, an organic solvent and the like is prepared. After that, the cathode 33 and the anode 34 are coated with the precursor solution to form the gel electrolyte layer 36. Subsequently, the cathode lead 31 is attached to the cathode current collector 33A by welding method or the like and the anode lead 32 is attached to the anode current collector 34A by welding method or the like. Subsequently, the cathode 33 and the 36 anode 34 provided with the electrolyte layer 36 are layered with the separator 35 in between and are spirally wound to form the spirally wound electrode body 30. After that, the protective tape 37 is adhered to the outermost periphery thereof. Subsequently, after the spirally wound electrode body 30 is sandwiched between two pieces of film-like package members 40, outer edges of the package members 40 are contacted by thermal fusion bonding method or the like to enclose the spirally wound electrode body 30 into the package members 40. In this case, the adhesive films 41 are inserted between the cathode lead 31, the anode lead 32 and the package member 40. [0123] In the second procedure, the cathode lead 31 is attached to the cathode 33, and the anode lead 32 is attached to the anode 34. Subsequently, the cathode 33 and the anode 34 are layered with the separator 35 in between and are spirally wound to form a spirally wound body as a precursor of the spirally wound electrode body 30. After that, the protective. tape 37 is adhered to the outermost periphery thereof Subsequently, after the spirally wovmd body is sandwiched between two pieces of the film-like package members 40, the outermost peripheries except for one side are bonded by thermal fusion bonding method or the like to obtain a pouched state, and the spirally wound body is contained in the pouch-like package member 40. Subsequently, a composition of matter for electrolyte containing an electrolytic solution, a monomer as a raw material for the polymer compound, a polymerization initiator, and if necessary other material such as a polymerization inhibitor is prepared, which is injected into the pouch-like package member 40. After that, the package member 40 is hermetically sealed by using thermal fusion bonding method or the like. Subsequently, the monomer is thermally polymerized. Thereby, a polymer compound is formed, and therefore the gel electrolyte layer 36 is formed. 37 [0124] In the third procedure, the spirally wound body is formed and contained in the pouch-like package member 40 in the same manner as that of the foregoing second procedure, except that the separator 35 with both faces coated with a polymer compound is used. Examples of the polymer compound with which the separator 35 is coated include a polymer containing vinylidene fluoride as a component (a homopolymer, a copolymer, a multicomponent copolymer or the like). Specific examples thereof include polyvinylidene fluoride, a binary copolymer containing vinylidene fluoride and hexafluoropropylene as a component, and a ternary copolymer containing vinylidene fluoride, hexafluoropropylene, and chlorotrifluoroethylene as a component. In addition to the polymer containing vinylidene fluoride as a component, other one or more polymer compounds may be used. Subsequently, an electrolytic solution is prepared and injected into the package member 40. After that, the opening of the package member 40 as sealed by thermal fusion bonding method or the like. Subsequently, the resultant is heated while a weight is applied to the package member 40, and the separator 35 is in contact with the cathode 33 and the anode 34 with the polymer compound in between. Thereby, the polymer compound is impregnated with the electrolytic solution, and accordingly the polymer compound is gelated to form the electrolyte layer 36. [0125] In the third procedure, the swolleimess of the secondary battery is suppressed compared to the first procedure. Further, in the third procedure, the monomer, the solvent and the like as a raw material of the polymer compound are hardly left in the electrolyte layer 36 compared to in the second procedure. Thus, the formation step of the polymer compound is favorably controlled. Therefore, sufficient contact characteristics are obtained between the cathode 33/the anode 34/the separator 38 35 and the electrolyte layer 36. [Action and Effect of Secondary Battery] [0126] According to the laminated film type secondary battery, the anode 34 contains the titanium-containing lithium composite oxide as an anode active material, and the electrolytic solution contains the cyclic disulfonic acid anhydride. Therefore, for the reason similar to that of the foregoing cylindrical type secondary battery, even after repeated charge and discharge, resistance rise of the secondary battery is able to be suppressed. In particular, though battery swollenness is easily generated by being affected by gas generated resulting from decomposition reaction of the electrolytic solution in the laminated film type secondary battery, such battery swollenness is able to be suppressed. The other actions and the other effects are similar to those of the cylindrical type secondary battery. <2. Applications of Secondary Battery> [0127] Next, a description will be given of application examples of the foregoing secondary battery. [0128] Applications of the secondary battery are not particularly limited as long as the secondary battery is used for a machine, a device, apparatus, equipment, a system (collective entity of a plurality of devices and the like) or the like that is able to use the secondary battery as a drive power source, an electric power storage source for electric power storage or the like. In the case where the secondary battery is used as a power source, the secondary battery may be used as a main power source (power source used preferentially), or an auxiliary power source (power source used instead of a main power source or used being switched from the main power source). In the latter case, 39 the main power source is not limited to the secondary battery. [0129] Examples of appHcations of the secondary battery include electronic devices such as a video camera, a digital still camera, a mobile phone, a notebook personal computer, a cordless phone, a headphone stereo, a portable radio, a portable television, and a Personal Digital Assistant (PDA). Examples of the electronic devices include a lifestyle electric appliance such as an electric shaver; a memory device such as a backup power source and a memory card; and a medical electronic device such as a pacemaker and a hearing aid. Examples of applications of the secondary battery further include an electric power tool such as an electric drill and an electric saw; an electrical vehicle such as an electric automobile (including a hybrid car); and an electric power storage system such as a home battery system for storing electric power for emergency or the like. '[0130] Specially, the secondary battery is effectively applicable to the electronic device, the electric power tool, the electrical vehicle, the electric power storage system or the like. In these applications, since superior characteristics of the secondary battery are demanded, the characteristics are able to be effectively improved by using the secondary battery of the present technology. The electronic device executes various functions (music replay or the like) by using a secondary battery as a working electric power source. The electric power tool is a tool in which a moving part (for example, a drill or the like) is moved by using a secondary battery as a driving power source. The electrical vehicle is a vehicle that acts (runs) by using a secondary battery as a driving power source. As described above, an automobile including a drive source other than a secondary battery (hybrid vehicle or the like) may be adopted. The electric power storage system is a system using a secondary battery as an electric power 40 storage source. For example, in a home electric power storage system, electric power is stored in the secondary battery as an electric power storage source, and the electric power stored in the secondary battery is consumed according to needs. In the result, various devices such as home electric products become operational. [Examples] [0131] Specific examples of the present technology will be described in detail. (Examples 1-1 to 1-23) [0132] The laminated film type secondary batteries illustrated in FIG. 4 and FIG 5 were fabricated by the following procedure. After that, resistance characteristics of the secondary batteries were examined, and the results illustrated in Table 1 and Table 2 were obtained. [0133] In forming the cathode 33, 94 parts by mass of a cathode active material (lithium-containing compound), 3 parts by mass of a cathode binder (polyvinylidene fluoride: PVDF), and 3 parts by mass of a cathode electrical conductor (amorphous carbon) were mixed to obtain a cathode mixtvire. As the lithium-containing compound, the materials illustrated in Table 1 and Table 2 were used. Subsequently, the cathode mixture was dispersed in an organic solvent (!Sf-methyl-2-pyrrolidone (NMP)) to obtain cathode mixture slurry. Subsequently, both faces of the cathode current collector 33 A (Al foil, thickness: 15 pm) were coated with the cathode mixture slurry, which was dried to form the cathode active material layer 33B (thickness of a single side: 75 )im). After that, the cathode current collector 33 A on which the cathode active material layer 33B was formed was cut in the shape of a strip (60 mm wide, 80 mm long). [0134] In forming the anode 34, 96 parts by mass of an anode active material 41 (titanium-containing lithium composite oxide), 3 parts by mass of an anode binder (PVDF), and 1 part by mass of an anode electrical conductor (amorphous carbon) were mixed to obtain an anode mixture, hi addition, 97 parts by mass of an anode active material (carbon material) and 3 parts by mass of an anode binder (PVDF) were mixed to obtain an anode mixture. Types of the titanium-containing lithium composite oxide are as illustrated in Table 1 and Table 2. As the carbon material (C), amorphous carbon was used. "Li4Ti50i2+C coating" means that the surface of titanium-containing lithium composite oxide particles (Li4Ti50i2) are coated with carbon by using CVD method. Subsequently, the anode mixture was dispersed in an organic solvent (NMP) to obtain anode mixture slurry. Subsequently, both surfaces of the anode current collector 34A were coated with the anode mixture slurry, which was dried to form the anode active material layer 34B (thickness of a single side: 100 |xm). As the anode current collector 34A, an Al foil (thickness: 15 ^m) was used in the case where the titanium-containing lithium composite oxide was used, and a Cu foil (thickness: 15 [xm) was used in the case where the carbon material was used. After that, the anode current collector 34A on which the anode active material layer 34B was formed was cut in the shape of a strip (60 mm vdde, 80 mm long). [0135] In preparing an electrolytic solution, a disulfonic acid anhydride and a carboxylate ester were mixed as needed together with a solvent and an electrolyte salt (LiPFe). As a solvent, together with ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC), vinylene carbonate (VC) or 4-fluoro-l,3-dioxolane-2-one (FEC) was used according to needs. As composition of the electrolytic solution, based on EC/PC:DMC:EMC:LiPF6=34:25:25:16 (weight ratio), part of EC or PC was substituted 42 with VC or FEC, and part of EMC was substituted with disulfonic acid anhydride or carboxylate ester. As the disulfonic acid anhydride, 1,3-propane disulfonic acid anhydride (PSAH) or 1,2-ethane disulfonic acid anhydride (ESAH) as a cyclic disulfonic acid anhydride or methane sulfonic acid anhydride (MSHA) as a chain disulfonic acid anhydride was used. As the carboxylate ester, ethyl acetate (EA) or methyl propionate (MP) was used. Contents of the disulfonic acid anhydride were as illustrated in Table 1 and Table 2. [0136] In assembling the secondary battery, the cathode lead 31 made of Al was welded to one end of the cathode current collector 3 3 A, and the anode lead 32 made of Ni was welded to one end of the anode current collector 34A. Subsequently, the cathode 33, the separator 35 (microporous polyethylene film as a porous film, thickness: 16 ^m), the anode 34, and the separator 35 were layered in this order (the number of laminated layers of the cathode 33 was 5, and the number of laminated layers of the anode 34 was 6). Subsequently, the laminated body was spirally wound in the longitudinal direction to form a spirally wound body as a precursor of the spirally wound electrode body 30. After that, the winding end thereof was fixed by the protective tape 37 (adhesive tape). Subsequently, after the spirally wound body was sandwiched between the package members 40, the outermost peripheries except for one side were bonded by thermal fusion bonding to obtain a pouched state, and the spirally wound body was contained in the pouch-like package member 40. As the package member 40, an aluminum laminated film in which a nylon film (thickness: 30 p,m), an aluminum foil (thickness: 40 ^m), and a cast polypropylene film (thickness: 30 )im) were layered fi-om outside was used. Subsequently, 4 g of the electrolytic solution was injected into an opening of the package member 40, the separator 35 was impregnated 43 with the electrolytic solution, and thereby the spirally woimd electrode body 30 was formed. Finally, the opening of the package member 40 was sealed by thermal fusion bonding in the vacuum atmosphere. Thereby, the secondary battery was completed. [0137] In examining resistance characteristics, after resistance of the secondary battery was measured, the secondary battery was charged and discharged (500 cycles) in the atmosphere at 23 deg C, and resistance of the secondary battery was measured again. Based on the measurement results, resistance rise ratio (%)=[(resistance after charge and discharge - resistance before charge and discharge)/resistance before charge and discharge]* 100 was calculated. As charge and discharge conditions, after charge was performed for 2 hours at a current of 1400 mA with the upper limit voltage of 2.7 V, discharge was performed at a current of 1400 mA with the lower limit voltage of 1.8 V. 44 Table 1 Separator: Porous film Table 1 Cathode active Anode active Electrolytic solution Resistance material material Solvent Disulfonic acid Other solvent rise ratio anhydride (%) Type Content Type Content (wt%) (wt%) Example 1-1 LiNip 5C00 ;Mno 3O2 Li4Ti50i2 EC+DMC+EMC PSAH 1 - - 92 Example 1-2 LiNiosCoo^MnoaOz Li4Ti50i2 PC+DMC+EMC PSAH 1 - - 89 Example 1-3 LiNiosCoo.^MnojOz Li4Ti50i2 PC+DMC+EMC ESAH 1 - - 100 Example 1-4 LiNip sCopiMnojO; Li4Ti50i2 PC+DMC+EMC PSAH 0.1 VC 1 100 Example 1-5 LiNip 5Coo,2Mno.302 Li4Ti50i2 PC+DMC+EMC PSAH 1 VC 1 84 Example 1-6 LiNip 5Coo,;Mno,302 Li4Ti50i2 PC+DMC+EMC PSAH 5 VC 1 82 Example 1-7 LiNip 5Cop.;Mno.302 Li4Ti50i; PC+DMC+EMC PSAH 1 VC 0.1 91 Example 1-8 LiNip 5Cop,2Mnp302 Li4Ti50i2 PC+DMC+EMC PSAH 1 VC 5 83 Example 1-9 LiNip 77Coo2Mnoo302 Li4Ti50i2 PC+DMC+EMC PSAH 1 VC 1 87 Example 1-10 LiMn204 Li4Ti50i; PC+DMC+EMC PSAH 1 VC 1 83 Example 1-11 LiNip 5Coo2Mno,302 Li4Ti4 gsNbp 05O12 PC+DMC+EMC PSAH 1 VC 1 84 Example 1-12 LiNip 5Coo2Mno.302 UyyjTuiisMgo^ijsOn PC+DMC+EMC PSAH 1 VC 1 83 Example 1-13 | LiNip,5Cop,2Mnp,302 | Li4Ti50i2+C coating | PC+DMC+EMC | PSAH | 1 [ VC | 1 | 82 45 Table 2 Separator: Porous film Table 2 Cathode active Anode active Electrolytic solution Resistance material material rise ratio (%) Solvent Disulfonic acid Other solvent anhydride Type Content Type Content (wt%) (wt%) Example LiNio.5C002Mno.3O2 Li^TijO^ PC+DMC+ PSAH 1 VC 1 97 1-14 EA Example LiNio.5C002Mno.3O2 Li4Ti50i2 PC+DMC+ PSAH 1 VC 1 95 1-15 Kff Example LiNio 5Coo.2Mno 3O2 Li4Ti50i2 PC+DMC+ PSAH 1 FEC 1 86 1-16 EMC Example LiNio 5Coo.2Mno.3O2 C PC+DMC+ - - . . 217 1-17 EMC Example LiNio.5Coo.2Mno.3O2 Li4Ti50i2 PC+DMC+ .... 147 1-18 EMC Example LiNio.5Coo.2Mno.3O2 C PC+DMC+ PSAH 1 - - 159 1-19 EMC Example LiNio.5Coo.2Mno.3O2 Li4Ti50i2 PC+DMC+ MSAH 1 - - 141 1-20 EMC Example LiNio 77Coo.2Mno.03O2 Li4Ti50i2 PC+DMC+ PSAH 1 - - 153 1-21 EMC Example LiMn204 Li4Ti50i2 PC+DMC+ PSAH l . . 145 1-22 EMC Example LiNio.sCoo.2Mno.3O2 Li4Ti4 95NboosOi2 PC+DMC+ .... 146 1-23 I I I EMC I I I I I [0138] In the case where the anode active material was a carbon material (amorphous carbon), the resistance rise ratio was high without relation to whether or not the electrolytic solution contained the cyclic disulfonic acid anhydride (PSAH or the like). Meanwhile, in the case where the anode active material was a titanium-containing lithium composite oxide (Li4Ti50i2 or the like), if the electrolytic solution contained the cyclic disulfonic acid anhydride, the resistance rise ratio was remarkably low. [0139] In the case where the titanium-containing lithium composite oxide was used, 46 if the chain disulfonic acid anhydride (MS AH) was used as a disulfonic acid anhydride contained in the electrolytic solution, the resistance rise ratio was high. Meanwhile, in the case where the cyclic disulfonic acid anhydride (PSAH or the like) was used, the resistance rise ratio was remarkably low. [0140] In particular, in the case where the electrolytic solution contained the cyclic ester carbonate (PC), the unsaturated carbon bond cyclic ester carbonate (VC), or the halogenated cyclic ester carbonate (FEC), resistance rise ratio became lower. (Examples 2-1 to 2-23) [0141] Secondary batteries were fabricated by a procedure similar to that of Examples 1-1 to 1-23, except that the configuration of the separator 35 was changed, and resistance characteristics were examined. Accordingly, the results illustrated in Table 3 and Table 4 were obtained. [0142] As the separator 35, a separator in which polymer compoimd layers (PVDF: thickness of a single side: 2 ^m) were formed on both faces of a base material layer (microporous polyethylene film as a porous film, thickness: 12 |j,m) was used. In forming the polymer compound layer, a solution in which PVDF was dissolved in NMP was prepared, and both faces of the base material layer were coated with the solution, which was dried. 47 Table 3 Separator: Polymer compound layer/base material layer (porous film)/polymer compound layer Table 3 Cathode active Anode active Electrolytic solution Resistance material material Solvent Disulfonic acid Other solvent rise ratio anhydride (%) Type Content Type Content (wt%) (wt%) Example 2-1 LiNio.5Coo.2Mno 3O2 Li4Ti50i; EC+DMC+EMC PSAH 1 - - 88 Example 2-2 LiNip sCop.zMno 3O; Li^TijOi; PC+PMC+EMC PSAH 1 - - 85 Example 2-3 LiNio.5Coo.2Mno.3O2 Li4Ti50i2 PC+DMC+EMC ESAH 1 - - 95 Example 2-4 LiNip sCooaMnp 3O2 Li4Ti50i; PC+DMC+EMC PSAH 0.1 VC 1 95 Example 2-5 LiNio.5Cop.2Mnp 3O2 Li4Ti50i; PC+DMC+EMC PSAH 1 VC 1 80 Example 2-6 LiNip.5Coo.2Mno 3O; Li4Ti50i2 PC+DMC+EMC PSAH 5 VC 1 78 Example 2-7 LiNip.sCop.sMnp 3O2 Li4Ti50i2 PC+DMC+EMC PSAH 1 VC 0.1 87 Example 2-8 LiNip,5Coo ;Mno 3O; Li4Ti50i; PC+DMC+EMC PSAH 1 VC 5 79 Example 2-9 LiNip 77Coo.2Mnp 03O2 Li4Ti50i; PC+DMC+EMC PSAH 1 VC 1 83 Example 2-10 LiMn204 Li4Ti50i2 PC+DMC+EMC PSAH 1 VC 1 79 Example 2-11 LiNip 5Cop.2Mnp302 Li4Ti4 95Nboo50i2 PC+DMC+EMC PSAH 1 VC 1 80 Example 2-12 LiNio.5Cop 2Mno 3O2 Lij 75Ti4.875Mgo 375O12 PC+DMC+EMC PSAH 1 VC 1 79 Example 2-13 | LiNip 5Coo.2Mnp30; | Li4Ti50i2+C coating | PC+DMC+EMC | PSAH | 1 [ VC 1 | 78 48 Table 4 Separator: Polymer compound layer/base material layer (porous film)/polymer compound layer Table 4 Cathode active Anode active Electrolytic solution Resistance material material Solvent Disulfonic acid Other solvent rise ratio anhydride (%) Type Content Type Content (wt%) (wt%) Example LiNio 5C00 2Mno 3O2 Li^TijOiz PC+DMC+EA PSAH 1 VC 1 92 2-14 Example LiNio 5Coo2Mno.302 Li4Ti50i2 PC+DMC+MP PSAH 1 VC 1 90 2-15 Example LiNio 5Coo.2Mno302 Li4Ti50i2 PC+DMC-^EMC PSAH 1 PEC 1 82 2-16 Example LiNio.5Coo.2Mno 3O2 C PC-i-DMC+EMC - . . . 206 2-17 Example LiNio.5Coo.2Mno.3O2 Li4Ti50i2 PC+DMC+EMC .... 140 2-18 Example LiNio 5Coo.2Mno,302 C PC-^DMC+EMC PSAH 1 - - 151 2-19 Example LiNio 5Coo2Mno302 Li4Ti50i2 PC+DMC+EMC MSAH 1 - - 134 2-20 Example LiNio.TyCoo 2Mno 03O2 Li^TisO^ PC+DMC+EMC PSAH 1 - - 146 2-21 Example LiMn204 Li4Ti50,2 PC+DMC+EMC PSAH 1 - - 138 2-22 Example LiNiojCoo 2Mno 3O2 Li4Ti4 ^Nbo 05O12 PC+DMC+EMC .... 139 2-23 I I I I I I I I [0143] Even if the structure of the separator 35 was changed, the results similar to those of Table 1 and Table 2 were obtained. That is, in the case where the anode active material was the titanium-containing lithium composite oxide, if the electrolytic solution contained the cyclic disulfonic acid anhydride, the resistance rise ratio was remarkably low. In particular, in the case where the separator 35 had the polymer compound layer, the resistance rise ratio became lower compared to the case that the separator 35 did not have the polymer compound layer (Table 1 and Table 2). [0144] From the results of Table 1 to Table 4, it was found that in the case where 49 the anode contained the titanium-containing lithium composite oxide as an anode active material and the electrolytic solution contained the cyclic disulfonic acid anhydride, resistance rise was able to be suppressed even if charge and discharge were repeated. [0145] The present technology has been described with reference to the embodiment and the examples. However, the present technology is not limited to the described embodiment and the examples, and various modifications may be made. For example, the cathode active material of the present technology is similarly applicable to a lithium ion secondary battery in which the anode capacity includes the capacity by inserting and extracting lithium ions and the capacity associated with precipitation and dissolution of lithium metal, and the anode capacity is expressed by the sum of these capacities. In this case, the chargeable capacity of the anode material is set to a smaller value than that of the discharge capacity of the cathode. [0146] Further, in the embodiment and the examples, the description has been given with the specific examples of the case in which the battery structure is the cylindrical type or the laminated film type, and with the specific example in which the battery element has the spirally wound structure. However, applicable structures are not limited thereto. The lithium ion secondary battery of the present technology is similarly applicable to a battery having other battery structure such as a coin type battery, a square type battery, and a button type battery or a battery in which the battery element has other structure such as a laminated structure. [0147] Further, in the embodiment and the examples, for the compositions of the titanium-containing lithium composite oxide (values of x to z, m, n and the like), the description has been given of the appropriate ranges derived fi-om the results of the examples. However, the description does not totally deny a possibility that the 50 compositions are out of the foregoing ranges. That is, the foregoing appropriate ranges are only the ranges particularly preferable for obtaining the effects of the present technology. Therefore, as long as effect of the present technology is obtained, the compositions may be out of the foregoing ranges in some degrees. [0148] It is possible to achieve at least the following configurations from the above-described example embodiment of the disclosure. (1) A secondary battery including: a cathode; an anode; and an electrolytic solution, wherein the anode contains one or more of titanium-containing lithium composite oxides expressed by the following Formula 1 to Formula 3 as an anode active material, and the electrolytic solution contains cyclic disulfonic acid anhydride expressed by the following Formula 4 or cyclic disulfonic acid anhydride expressed by the following Formula 5 or both. Formula 1 Li [LixM 1 (1.3x)/2Ti(3+x)/2] O4 where Ml is one or more of Mg, Ca, Cu, Zn, and Sr, and x satisfies 0

Documents

Application Documents

# Name Date
1 762-del-2012-Form-3-(16-07-2012).pdf 2012-07-16
2 762-del-2012-Correspondence-Others-(16-07-2012).pdf 2012-07-16
3 762-del-2012-GPA.pdf 2012-10-29
4 762-del-2012-Form-5.pdf 2012-10-29
5 762-del-2012-Form-3.pdf 2012-10-29
6 762-del-2012-Form-2.pdf 2012-10-29
7 762-del-2012-Form-1.pdf 2012-10-29
8 762-del-2012-Drawings.pdf 2012-10-29
9 762-del-2012-Description (Complete).pdf 2012-10-29
10 762-del-2012-Correspondence-others.pdf 2012-10-29
11 762-del-2012-Claims.pdf 2012-10-29
12 762-del-2012-Abstract.pdf 2012-10-29
13 762-DEL-2012-PA [14-02-2018(online)]_154.pdf 2018-02-14
14 762-DEL-2012-PA [14-02-2018(online)].pdf 2018-02-14
15 762-DEL-2012-ASSIGNMENT DOCUMENTS [14-02-2018(online)]_174.pdf 2018-02-14
16 762-DEL-2012-ASSIGNMENT DOCUMENTS [14-02-2018(online)].pdf 2018-02-14
17 762-DEL-2012-8(i)-Substitution-Change Of Applicant - Form 6 [14-02-2018(online)]_80.pdf 2018-02-14
18 762-DEL-2012-8(i)-Substitution-Change Of Applicant - Form 6 [14-02-2018(online)]_181.pdf 2018-02-14
19 762-DEL-2012-8(i)-Substitution-Change Of Applicant - Form 6 [14-02-2018(online)].pdf 2018-02-14
20 762-DEL-2012-Power of Attorney-200218.pdf 2018-02-23
21 762-DEL-2012-OTHERS-200218.pdf 2018-02-23
22 762-DEL-2012-Correspondence-200218.pdf 2018-02-23
23 762-DEL-2012-FER.pdf 2019-02-11
24 762-DEL-2012-OTHERS [09-08-2019(online)].pdf 2019-08-09
25 762-DEL-2012-FER_SER_REPLY [09-08-2019(online)].pdf 2019-08-09
26 762-DEL-2012-CORRESPONDENCE [09-08-2019(online)].pdf 2019-08-09
27 762-DEL-2012-COMPLETE SPECIFICATION [09-08-2019(online)].pdf 2019-08-09
28 762-DEL-2012-CLAIMS [09-08-2019(online)].pdf 2019-08-09
29 762-DEL-2012-Power of Attorney-130819.pdf 2019-08-19
30 762-DEL-2012-Correspondence-130819.pdf 2019-08-19
31 762-DEL-2012-US(14)-HearingNotice-(HearingDate-09-02-2023).pdf 2023-01-18
32 762-DEL-2012-Proof of Right [27-01-2023(online)].pdf 2023-01-27
33 762-DEL-2012-PETITION UNDER RULE 137 [30-01-2023(online)].pdf 2023-01-30
34 762-DEL-2012-Correspondence to notify the Controller [01-02-2023(online)].pdf 2023-02-01

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