Nonaqueous electrolyte battery and production method therefor

专利摘要:
A flat exterior member made of a metal sheet and having two major flat portions facing each other, two first polarity active materials layers supported on the inner surface of the flat portions, a second polar electrode plate disposed at a position opposite the active material layer, and A nonaqueous electrolyte battery having a separator layer interposed between the active material layer and the pole plate of the second polarity, wherein the exterior material also serves as a current collector of the active material layer.
公开号:KR20020077488A
申请号:KR1020027010840
申请日:2001-12-25
公开日:2002-10-11
发明作者:이시다스미히토；다나카게이스케；가이야히데오；와타나베쇼이치로
申请人:마쯔시다덴기산교 가부시키가이샤；
IPC主号:

专利说明:

Non-aqueous electrolyte battery and its manufacturing method {NONAQUEOUS ELECTROLYTE BATTERY AND PRODUCTION METHOD THEREFOR}
[2] In recent years, wireless and portable electronic devices, such as AV equipment and personal computers, have advanced. Accordingly, a large number of high energy density nonaqueous electrolyte batteries containing nonaqueous electrolytes are employed. Among the nonaqueous electrolyte batteries, lithium secondary batteries are most commonly used.
[3] As a negative electrode of a lithium secondary battery, a negative electrode material which can occlude and release lithium and has a low electric potential close to lithium, like graphite or amorphous carbon, is used. On the other hand, like LiCoO ₂ and LiMn ₂ O ₄ , lithium can occlude and release lithium, and a lithium-containing transition metal compound having a high electric potential is used for the positive electrode material.
[4] The electrode plate of the nonaqueous electrolyte battery is manufactured as follows, for example.
[5] First, a slurry-like electrode mixture containing a positive electrode material or a negative electrode material, a binder, and a dispersion medium is prepared. The electrode mixture is applied to a current collector or a core material such as a metal sheet, a metal mesh, a metal lath plate, a punched metal, tacked, dried, cut into a desired shape, and becomes a pole plate.
[6] The nonaqueous electrolyte is prepared by dissolving a lithium salt such as LiPF ₆ or LiBF ₄ in a nonaqueous solvent. As the non-aqueous solvent, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, diethyl carbonate and the like are used. In recent years, mixed solvents composed of a chain compound and a cyclic compound have been frequently used.
[7] The conventional nonaqueous electrolyte battery is composed of, for example, a pole plate group in which a positive electrode and a negative electrode are spirally wound through a separator, and a cylindrical or horn-shaped container accommodating the pole plate group simultaneously with the nonaqueous electrolyte. The opening of the container is sealed by a sealing plate serving as an external terminal. The battery of such a structure is difficult to thin in design. However, with the recent miniaturization of electronic devices, there is a strong demand for a small-sized and light-weight battery that has sufficient energy density and can be accommodated in a limited space. In many cases, a battery less than a few mm thick is required.
[8] Thus, in recent years, polymer electrolytes have been employed in batteries. As the polymer electrolyte, a gel electrolyte composed of a liquid nonaqueous electrolyte and a polymer holding the same is used. Polymer electrolytes have the function of transferring ions and isolating between the plates. A high-energy-density thin polymer battery is developed by stacking a positive electrode and a negative electrode through a separator layer containing a polymer electrolyte and encapsulating it as a packaging material.
[9] The separator layer containing the polymer electrolyte is formed by absorbing a liquid nonaqueous electrolyte into a microporous membrane or a nonwoven fabric containing a gel former, for example, and sandwiching it between the electrode plates. As the gel former, a polymer which absorbs a liquid nonaqueous electrolyte to form a gel electrolyte is used.
[10] The separator layer which consists only of a polymer electrolyte can also be formed. For example, a method is prepared by mixing a gel-forming agent and a solvent to prepare a paste, laminating the electrode plates, drying, and then absorbing the liquid nonaqueous electrolyte into the gel-forming agent. In addition, a method of preparing a paste by mixing a gel-forming agent with a liquid nonaqueous electrolyte and then laminating electrode plates is known.
[11] Japanese Patent Application Laid-Open No. 2000-67850 discloses a technique for integrating an electrode plate through a separator layer made of a polymer electrolyte.
[12] Japanese Patent Application Laid-Open No. 2000-12084, Japanese Patent Application Laid-Open No. 2000-156209 and Japanese Patent Application Laid-Open No. 2000-223108 disclose a pair of electrode plates comprising a pair of current collectors and an active material layer formed on one surface thereof. Disclosed is a group of pole plates in which layers are opposed to each other and a pair of pole plates are sandwiched and supported by a pair of pole plates through a separator layer made of a polymer electrolyte. Moreover, the battery which accommodated the electrode plate group in the exterior material of the laminated sheet which consists of a resin layer and metal foil is disclosed.
[13] Japanese Unexamined Patent Application Publication No. 11-265699 discloses a battery in which a pole plate group having a separator layer made of a polymer electrolyte is contained in a bag-shaped film envelope having a gas removal safety mechanism.
[14] Japanese Laid-Open Patent Publication No. 9-506208 discloses a battery in which a group of electrode plates wound in a flat spiral shape having a separator layer made of a polymer electrolyte is housed in an envelope-shaped exterior material having external terminals.
[15] In the above-described conventional thin battery, any one of the conventional thin batteries is housed in a packaging material in which the electrode plate group is further prepared. Further, as long as the idea of using a separately prepared exterior material is used, there is a limit to the simplification of the exterior structure of the battery, the thinning of the battery and the improvement of energy density, and the simplification of the battery manufacturing process.
[16] [Initiation of invention]
[17] An object of the present invention is to provide a light weight and high energy density thin nonaqueous electrolyte battery having a large degree of freedom in capacity design and a simplified exterior structure. In particular, an object of the present invention is to provide a thin nonaqueous electrolyte battery having a novel structure in which a reduction in battery thickness and battery area is achieved.
[18] It is another object of the present invention to provide a method for producing an efficient nonaqueous electrolyte battery which can continuously perform a series of steps and does not require an exterior step.
[19] That is, the present invention comprises a flat exterior member made of a metal sheet and having two main flat portions facing each other, an active material layer having two first polarities supported on the inner surface of the flat portion, and a second polarity disposed at a position facing the active material layer. The non-aqueous electrolyte battery which has an electrode plate and a separator layer interposed between the said active material layer and a said pole plate of a said 2nd polarity, and whose said exterior material also serves as an electrical power collector of the said active material layer.
[20] The present invention also has an additional first polar pole plate adjacent to the second pole plate via a separator layer and an additional second polar pole plate adjacent to the further first pole plate via a separator layer. It relates to a non-aqueous electrolyte battery of two stacks.
[21] The present invention also has a non-aqueous electrolyte battery having a lead electrically connected to the pole plate of the second polarity, one end of the lead protruding from the exterior material to the outside, and the lead and the exterior material are insulated with a resin. It is about.
[22] It is preferable that an overcurrent blocking element sealed with a resin is set at a portion sandwiched between the peripheral edge portions of the lid of the lid.
[23] At least one of the separator layer and the active material layer preferably includes a polymer electrolyte.
[24] It is preferable that the said polymer electrolyte is a gel electrolyte which consists of a liquid nonaqueous electrolyte and the polymer holding it.
[25] The present invention also comprises a pair of metal sheets having a flat portion facing each other or a sheet of metal sheet bent to have two flat portions facing each other, wherein the peripheral edge portions of the pair of metal sheets face each other. The present invention relates to a nonaqueous electrolyte battery bonded between or between opposite peripheral edge portions of the sheet of metal.
[26] Preferably, the opposing peripheral edges are joined by laser welding or ultrasonic welding.
[27] It is preferable that the thickness of the said metal sheet is 10-100 micrometers.
[28] The present invention also provides a step of obtaining an outer electrode plate by (1a) forming an active material layer of a first polarity on a flat portion other than the periphery of one side of the metal sheet, and (2a) obtaining a pole plate of a second polarity. (3a) A pair of the outer electrode plates are prepared, and one outer electrode plate and the other outer electrode plate are disposed so as to face the active material layer inward to face each other, so that the pair of outer electrode plates face each other. The manufacturing method of the nonaqueous electrolyte battery which has the process of clamping the pole plate of a through a separator layer, and (4a) bonding between the peripheral edge parts of the said pair of outer electrode plates which oppose.
[29] In the step (1a), the present invention further provides a plurality of outer electrode plate units which are continuously formed by intermittently forming a plurality of first polarity active material layers on a flat portion other than the periphery of one side of the strip-shaped metal sheet. In the step (3a), a pair of said outer electrode plate assemblies are prepared, and each outer electrode plate of each outer electrode plate unit of one outer electrode plate assembly and the other outer electrode plate assembly is sequentially made. The manufacturing method of the nonaqueous electrolyte battery which arrange | positions the said active material layer inside, and opposes, and supports the said pole plate of a 2nd polarity sequentially through a separator layer by a pair of opposing outer pole plate units.
[30] In step (3a), the electrode plate of the first polarity is adjacent to the electrode plate of the second polarity through the separator layer, and the electrode plate of the second electrode polarity is further connected to the electrode plate of the additional first polarity through the separator layer. It can be adjacent.
[31] In the step (3a), the separator layer can be formed by applying a paste from the raw material of the separator layer onto the active material layer of the first polarity or the pole plate of the second polarity.
[32] It is preferable that the raw material of the said separator layer contains a gel forming agent.
[33] As the gel former, a polymer which absorbs a liquid nonaqueous electrolyte to form a gel electrolyte is used.
[34] The present invention also provides a process for preparing a metal sheet having a fold or virtual fold to bend to have two flat portions facing each other (lb), (2b) the above edges other than the perimeter of one side of the metal sheet; A step of obtaining an outer electrode plate by forming a pair of active material layers of the first polarity in a flat portion symmetrical with respect to the fold or virtual fold, (3b) obtaining a pole plate of the second polarity, (4b) the outer side Bending the electrode plate to the fold mark or the imaginary fold mark, and holding the second electrode plate of the second polarity through the separator layer with the pair of active material layers, and (5b) a circumferential edge of the opposing outer electrode plate. The manufacturing method of the nonaqueous electrolyte battery which has the process of bonding together.
[35] Here, the virtual fold means a line dividing the metal sheet, which is assumed as a target or reference for bending to have two flat portions facing the metal sheet.
[36] The present invention also provides, in step (1b), a strip metal sheet having a fold mark or a virtual fold mark parallel to the longitudinal direction, and in step (2b), one side of the strip metal sheet is formed. By forming intermittent plural pairs of first polarity active material layers in the flat portions symmetrical to the fold marks or virtual fold marks other than the circumferential edge portion, an outer electrode plate assembly composed of a plurality of continuous outer electrode plate units is produced. In the step (4b), a method of manufacturing a nonaqueous electrolyte battery is provided in which a pair of active material layers of each outer electrode plate unit are sequentially sandwiched with a second polar electrode plate through a separator layer.
[37] In the step (4b), the electrode plate of the first polarity is adjacent to the electrode plate of the second polarity through the separator layer, and the electrode plate of the second electrode polarity is further connected to the electrode plate of the additional first polarity through the separator layer. It can be adjacent.
[38] In the step (4b), the separator layer can be formed by applying a paste from the raw material of the separator layer onto the active material layer of the first polarity or the pole plate of the second polarity.
[39] It is preferable that the raw material of the said separator layer contains a gel forming agent.
[40] As the gel former, a polymer which absorbs a liquid nonaqueous electrolyte to form a gel electrolyte is used.
[1] The present invention relates to a nonaqueous electrolyte battery and a manufacturing method thereof.
[41] 1 is a longitudinal sectional view of an example of a nonaqueous electrolyte battery of one stack of the present invention.
[42] 2 is a perspective view of an example of an outer electrode plate composed of a metal sheet serving as a current collector and an active material layer formed on one surface thereof.
[43] 3 is a perspective view of an example of an outer electrode plate in which a region to which an adhesive is applied is indicated by broken lines.
[44] It is a longitudinal cross-sectional view of an example of a group of pole plates of one stack.
[45] Fig. 5 is a sectional view of a main part of an example of a nonaqueous electrolyte battery of one stack of the present invention having a PTC element.
[46] 6 is a cross-sectional view of an example of the outer electrode plate assembly before cutting.
[47] 7 is a cross-sectional view of an example of an outer electrode plate assembly having a separator layer before cutting.
[48] 8 is a perspective view showing an example of an internal configuration of the electrode plate group assembly before cutting.
[49] 9 is a longitudinal cross-sectional view of an example of the electrode plate group assembly before cutting.
[50] 10 is a longitudinal sectional view of an example of a battery assembly before cutting.
[51] It is a longitudinal cross-sectional view of an example of another electrode plate group assembly before cutting.
[52] 12 is a longitudinal sectional view of an example of a two-stack nonaqueous electrolyte battery of the present invention.
[53] It is a longitudinal cross-sectional view of an example of two stack plates.
[54] 14 is a plan view of an example of a nonaqueous electrolyte battery of the present invention.
[55] FIG. 15 is an example of the sectional view taken along the line I-I of FIG.
[56] FIG. 16 is an example of the II-II cross-sectional view of FIG. 14.
[57] 17 is an example of the sectional view taken along the line III-III of FIG.
[58] 18 is a perspective view of an unfinished nonaqueous electrolyte battery in which the outer electrode plate is bent to the middle thereof.
[59] 19 is a view showing the progress of the manufacturing method of the nonaqueous electrolyte battery of the present invention using the outer electrode plate assembly.
[60] 20 is another example of the I-I cross-sectional view of FIG. 14.
[61] 21 is another example of the II-II cross-sectional view of FIG. 14.
[62] FIG. 22 is another example of the III-III cross-sectional view of FIG. 14. FIG.
[63] Best Mode for Carrying Out the Invention
[64] Embodiment 1
[65] The longitudinal cross-sectional view of the nonaqueous electrolyte battery of this invention which concerns on Embodiment 1 is shown in FIG.
[66] The battery consists of a metal sheet 102 and has a flat exterior material having two major flat portions facing each other, an active material layer 103 having two first polarities supported on the inner surface of the flat portion, and a position facing the active material layer 103. And a separator layer 107 interposed between the second electrode plate 104 having the second polarity and the active material layer 103 and the second electrode plate 104 having the second polarity. It also serves as a collector. The metal sheet 102 and the active material layer 103 supported by the flat portion constitute the outer electrode plate 101.
[67] The separator layer 107 contains a polymer electrolyte. It is preferable to include the polymer electrolyte in the active material layer 106 and the active material layer 106 of the electrode plate 104 of the second polarity in order to improve the charge and discharge characteristics of the battery. In order to provide a polymer electrolyte in the active material layer, the polymer electrolyte is mixed with the raw material of the active material layer to prepare an electrode mixture, and the active material layer is formed using the electrode mixture. Or an active material layer containing the gel formation agent which consists of a crosslinkable polymer is formed, and after crosslinking a crosslinkable polymer, a liquid nonaqueous electrolyte is absorbed in an active material layer.
[68] A lead 109 is connected to an extension of the current collector 105 constituting the pole plate 104 of the second polarity. The periphery of the lead 109 sandwiched between the peripheral edges of the metal sheet 102 is covered with the insulating resin 110b. Although it is not necessary to necessarily provide a lead in the outer electrode plate 101, in FIG. 1, the lead 111 is sandwiched between the peripheral edge parts of the metal sheet 102, and it welds.
[69] The pair of outer electrode plates 101 are joined at opposing surfaces of the peripheral edge portions of the respective metal sheets 102. Thus, in this battery, the pair of metal sheets 102 can be joined to each other by welding in order to have the same polarity. According to laser welding or ultrasonic welding, firm bonding is possible. Even when joining between the peripheral edges of the metal sheet 102 with the adhesive 110a, since sufficient pressurization is possible, the reliability of a junction part becomes high. The adhesive 110a used at this time does not need to be insulating.
[70] In this battery, the other surface of the metal sheet 102 having the active material layer 103 on one surface becomes an outer surface of the packaging material. According to this structure, it is not necessary to separately prepare an exterior material for surrounding the power generation element. Therefore, a thin and compact battery of high energy density can be obtained.
[71] The outer surface of the outer electrode plate 101 may be covered with a resin layer for reinforcement. For example, except for the part used as an external terminal, it is effective to form a resin layer on the outer surface of the outer electrode plate 101. In addition, a resin film may be attached to the outer surface of the outer electrode plate 101. Preferably, the easily brittle parts such as corners of the battery are reinforced with resin.
[72] Next, the manufacturing method of the nonaqueous electrolyte battery concerning Embodiment 1 of this invention is demonstrated in detail.
[73] (i) step (1a)
[74] Step (1a) is a step of obtaining an outer electrode plate by forming a first polar active material layer on a flat portion other than the peripheral edge of one side of the metal sheet. 2 is a perspective view of the outer electrode plate 101 composed of the metal sheet 102 obtained in step (1a) and the active material layer 103 formed on one surface thereof.
[75] In the peripheral portion 108 of the metal sheet 102, the metal is exposed. When bonding between the opposing peripheral edge parts 108 with an adhesive agent, as shown in FIG. 3, the peripheral edge part 108 is made into the metal exposed part 108a of a broken line inside, and the metal exposed part 108b of a broken line outside. ), It is preferable to apply an adhesive to one of the metal exposure portion 108a and the metal exposure portion 108b, and to join the other metal exposure portion by ultrasonic welding or laser welding. By using an adhesive agent and welding together, joining strength can be raised significantly.
[76] The method for forming the active material layer 103 by applying the electrode mixture of the first polarity to a flat portion other than the peripheral portion 108 of one side of the metal sheet 102 is not particularly limited. For example, it can be conventionally used using a general factory value. It is preferable that the thickness of the active material layer 103 is 30-300 micrometers. The width of the peripheral portion 108 is, for example, 1 to 10 mm.
[77] The metal sheet 102 is used without a hole to serve as the current collector of the outer electrode plate 101 and the outer surface of the packaging material. Since the active material layer 103 formed inside the outer electrode plate 101 has an effect of improving the strength of the packaging material, the active material layer 103 can be used in an extremely thin metal sheet having a thickness of about 10 μm. The thin metal sheet is in close contact with the active material layer, and is suitable for forming a flexible outer electrode plate. As for the thickness of the metal sheet 102, 10-100 micrometers is suitable. If the metal sheet 102 is too thick, the thickness of the battery may increase or the energy density of the battery may decrease.
[78] In the case of using a thin metal sheet, it is necessary to consider the corrosion of the metal sheet. In view of corrosion resistance, when the outer electrode plate 101 is an anode, the metal sheet 102 is preferably made of aluminum or an aluminum alloy. On the other hand, when the outer electrode plate 101 is a cathode, the metal sheet 102 is preferably made of copper, iron, copper alloy or iron alloy. In the case where the metal sheet 102 is made of iron or iron alloy, nickel is preferably plated on the surface thereof.
[79] The positive electrode mixture is prepared by mixing, for example, a positive electrode active material, a conductive agent, a binder, a dispersion medium, and the like. The negative electrode mixture is prepared by mixing, for example, a negative electrode material, a binder, a dispersion medium and the like. As described above, the electrode mixture may further contain a polymer electrolyte or a gel forming agent.
[80] As the positive electrode active material, a positive electrode active material generally used as a nonaqueous electrolyte battery can be used without particular limitation. The positive electrode active material has, LiCoO _2, LiNiO, lithium-containing transition metal oxide, such as _2, LiMn ₂ O ₄ are preferred. It is preferable that the average particle diameter of a positive electrode active material is 1-100 micrometers.
[81] As the negative electrode material, a negative electrode material generally used in nonaqueous electrolyte batteries can be used without particular limitation. As the negative electrode material, natural graphite or artificial graphite is preferable. The average particle diameter of the negative electrode material is preferably 1 to 100 µm.
[82] As the conductive agent, carbon powder such as graphite powder, carbon black, or carbon fiber is preferably used.
[83] As the binder, a fluororesin that is resistant to nonaqueous electrolytes is preferable. For example, polytetrafluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene, a polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, etc. are preferable. These polymers can also be used as a gel forming agent.
[84] It is preferable to use N-methyl-2-pyrrolidone as a dispersion medium.
[85] (ii) step (2a)
[86] The step (2a) is a step of obtaining the pole plate 104 of the second polarity which is the counter electrode of the outer pole plate 101. The pole plate 104 of the second polarity can be obtained by providing the electrode mixture of the second polarity on both surfaces of the sheet-shaped current collector 105 to form the active material layer 106. The method of forming the active material layer 106 by providing the electrode mixture of the second polarity on both surfaces of the sheet-shaped current collector 105 is not particularly limited. For example, it can use a conventional general ceramics value. For example, the electrode mixture of a 2nd polarity is coated continuously on both surfaces of a strip | belt-shaped metal sheet using a general ceramic mill, and this is cut out. It is preferable that the thickness of the active material layer 106 is 30-300 micrometers, for example.
[87] As the sheet current collector 105, a metal sheet, a metal mesh, a punching metal, a metal lath plate, or the like can be used. The surface of the sheet-like current collector 105 may be roughened by etching, or may be provided with a conductive agent. When the pole plate 104 of the second polarity is the negative electrode, the sheet-shaped current collector 105 is preferably made of copper, iron, copper alloy or iron alloy. When the sheet current collector 105 is made of iron or iron alloy, it is preferable to plate nickel on the surface thereof. When the pole plate of the second polarity is a positive electrode, the sheet current collector 105 is preferably made of aluminum or an aluminum alloy. The thickness of the sheet current collector 105 is preferably 10 to 100 µm.
[88] The lead 109 is connected to the pole plate 104 of the second polarity. The lead 109 can be formed using a part of the current collector 105. The portion of the lead 109 sandwiched between the circumferential edge portions 108 of the metal sheet 102 serving as the current collector of the outer electrode plate 101 is covered with the insulating resin 110b.
[89] (iii) step (3a)
[90] The step (3a) is a step of sandwiching the pole plate 104 of the second polarity through the separator layer 107 in the pair of outer pole plates 101 having the active material layer 103 disposed therein. The separator layer 107 arrange | positions the separator layer 107 previously shape | molded in the film form between pole plates, or apply | coats the paste on one pole electrode from the raw material of the separator layer 107, and has a different polarity on it. It can form by stacking the pole plates of.
[91] The separator layer 107 may be formed only of a polymer electrolyte, or may be a composite of a microporous membrane or a nonwoven fabric with a polymer electrolyte. As the polymer electrolyte, conventionally known ones can be used without particular limitation. Especially, the gel electrolyte which consists of a liquid nonaqueous electrolyte and the polymer which hold | maintains it is preferable. The separator layer may contain powder such as alumina or silica. These powders are laminated and play a role of ensuring the isolation between the electrode plates in the pressurized electrode plate group.
[92] For example, as shown in FIG. 2 or 3, it is preferable to completely cover the active material layer 103 of the outer electrode plate 101 with the separator layer 107. By using the two separator layers 107, the pair of outer pole plates 101 are held by a pair of outer pole plates 101 and pressurized while heating to integrate all the pole plates and the separator layers. The electrode plate group as shown in FIG. 4 can be obtained. It is preferable that the heating temperature at this time is 80-160 degreeC. If the thermoplastic resin is applied to the circumferential edge portion 108 of the metal sheet 102 of the outer electrode plate 101 as an adhesive before pressing the pole plate group, the bonding between the circumferential edge portions 108 can be performed simultaneously with the pressing.
[93] As a liquid nonaqueous electrolyte, the nonaqueous solvent which melt | dissolved the solute is preferable. As the solute, various lithium salts such as LiPF ₆ and LiBF ₄ are suitable. As the non-aqueous solvent, ethylene carbonate, dimethyl carbonate ethyl methyl carbonate, propylene carbonate, diethyl carbonate and the like are used. These are used alone or in combination.
[94] As the polymer or gel-forming agent for holding a liquid nonaqueous electrolyte, a polymer crosslinked by UV irradiation or heating is preferably used. In the case of crosslinking the polymer or the gel-forming agent after forming the electrode plate group, a polymer that crosslinks by heating is particularly preferable. When the separator layer 107 is formed on the active material as shown in FIG. 3, a polymer crosslinked by UV irradiation may be used.
[95] Suitable gel forming agents include, for example, fluorine resins resistant to nonaqueous electrolytes. Among the fluorocarbon resins, polyvinylidene fluoride, copolymers of vinylidene fluoride and hexafluoropropylene are particularly preferable. Since a mixture of these polymers and solvents such as N-methyl-2-pyrrolidone can be arbitrarily adjusted, it is suitable as a paste from the raw material of the separator layer.
[96] Oil components, such as dibutyl phthalate, can be mixed with the paste which consists of raw materials of a separator layer. In this case, after forming a separator layer, an oil component is extracted and removed with solvents, such as ethyl, hexane, and acetone. As a result, many fine holes are formed in the separator layer. Since such a separator layer absorbs a liquid nonaqueous electrolyte promptly in a thin electrode plate group, gelation advances effectively.
[97] (Iv) step (4a)
[98] The step 4a is a step of joining the peripheral portions 108 of the metal sheet 102 of the opposing outer electrode plate 101 to each other. Bonding is performed by laser welding, ultrasonic welding, or an adhesive agent, for example.
[99] Ultrasonic welding and laser welding can directly join the circumferential edges of the metal sheet, so that the space around the circumferential edge required for bonding can be reduced as compared with the case of using an adhesive.
[100] In addition, as described above, the peripheral portion 108 is distinguished from the metal exposed portion 108a inside the broken line and the metal exposed portion 108b outside the broken line, as shown in FIG. And one of the metal exposed portions 108b, and the other metal exposed portion can be joined by ultrasonic welding or laser welding.
[101] As the adhesive, thermosetting resins such as epoxy resins and thermoplastic resins such as polyolefins can be used. The workability is excellent in the latter. Among the thermoplastic resins, polyethylene and polypropylene are suitable since the melting point is high.
[102] When the liquid nonaqueous electrolyte is injected into the battery after the bonding, the unbonded portion is provided without completely bonding the opposing peripheral edge portions 108. After the step 4a, a nonaqueous electrolyte is injected from the unbonded portion.
[103] Embodiment 2
[104] Polymer electrolytes generally contain flammable nonaqueous solvents. If the battery is short-circuited or the charging circuit breaks down, the battery may be overcharged after a long time with a large current value. In this case, the temperature of the battery is very high, the nonaqueous electrolyte is decomposed to generate flammable gas, and the battery may swell or the battery function may be degraded. In order to avoid this, an overcurrent blocking element is connected to the circuit of the apparatus in which the battery is mounted. As the overcurrent blocking device, for example, a device having a temperature fuse or a positive temperature resistance coefficient (hereinafter referred to as a PTC device) is preferably used. The PTC element has a function of interrupting or reducing the current at the time of temperature rise because the resistance increases due to the temperature rise.
[105] 5 is a main sectional view of the nonaqueous electrolyte battery according to the second embodiment of the present invention including the PTC element 112. Components having the same structure or composition as those in the first embodiment are assigned the same numbers as those in the first embodiment.
[106] The PTC element 112 is installed on the lead 109 sandwiched between the edge portions of the outer electrode plate 101 in a state of being sealed and fixed by the insulating resin 110b. The insulating resin 110b preferably has resistance to nonaqueous electrolyte.
[107] In the above configuration, since the PTC element 112 and the battery are integrated, the temperature change of the battery is sensitively transmitted to the PTC element 112, and an abnormal temperature rise can be effectively prevented.
[108] Embodiment 3
[109] In the step (1a), as shown in Fig. 6, by intermittently forming a plurality of first polarity active material layer 103 in a flat portion other than the peripheral portion of one side of the band-shaped metal sheet 202, It is effective to produce an outer electrode plate assembly composed of a plurality of continuous outer electrode plate units 201. By intermittently forming the plurality of first active material layers 103, a metal exposed portion (circumferential edge portion) 208 is left around each active material layer 103.
[110] The outer electrode plate assembly may be used separately from each of the outer electrode plate units 201, but the one used as the outer electrode plate assembly can perform a series of processes continuously and can manufacture a battery efficiently. That is, in step 3a, a pair of outer electrode plate assemblies are prepared, and a separator layer 107 is formed on each active material layer 103 of each outer electrode plate assembly as shown in FIG.
[111] Subsequently, as shown in FIG. 8, each outer electrode plate unit of one outer electrode plate assembly and each outer electrode plate unit of the other outer electrode plate assembly are disposed to face each other with their active material layers 103 disposed inward. The second polarity plate 104 is sequentially held through the separator layer 107 in a pair of opposing outer electrode plates.
[112] The second polar electrode plate 104 is formed by providing the active material layer 106 of the second polarity on both sides of the sheet-shaped current collector 105, and the sheet-shaped current collector 105 is formed of an insulating resin 110b. The coated lid 109 is connected. As a result, the electrode group assembly as shown in FIG. 9 can be obtained.
[113] In the step 1a, if the adhesive 110a is applied to the peripheral edge portion 208 of the outer electrode plate unit 201 in advance, the battery assembly can be obtained as shown in FIG. 10 in the step 3a. have. The battery assembly may be used as it is, or may be used separately.
[114] It is also possible to use only one outer electrode plate as an assembly, and to separate and use the other. In this case, the electrode plate group assembly as shown in FIG. 11 can be obtained by step (3a).
[115] Each component of the nonaqueous electrolyte battery according to the third embodiment has the same structure or composition as that of the first embodiment except that the metal sheet 202 of the outer electrode plate has a band shape. 6-12, the same code | symbol as Embodiment 1 is attached | subjected to the component which has the same structure or composition as Embodiment 1. In FIG.
[116] Embodiment 4
[117] 12 is a longitudinal sectional view of the nonaqueous electrolyte battery according to the fourth embodiment of the present invention. This battery is connected to the first polarized plate 101a adjacent to the second electrode plate 104 of the second polarity via the separator layer 107 and to the additional polar plate 10la of the first polarity. It is a 2 stack nonaqueous electrolyte battery which further has the pole plate 104 of an adjoining 2nd polarity.
[118] Although two stacked batteries are shown here, the number of the second pole plates 104 of the second polarity held by the outer pole plate 101 of the first polarity is arbitrary.
[119] Thus, when it has two or more pole plates 104 of a 2nd polarity, the pole plate of a further 1st polarity is interposed between the pole plates of a 2nd polarity. According to such a structure, by selecting an appropriate number of pole plates and the thickness of the active material layer, the capacity of the battery can be increased without damaging the high rate discharge characteristics. Therefore, in order to increase the battery capacity, the battery area does not become too large, the active material layer becomes thick, and the active material utilization rate and high rate discharge characteristics do not decrease.
[120] In the case of FIG. 12, the current collector 105 of the two pole plates 104 of the second polarity is connected to one lead 109 and is led out of the battery to the outside through the insulating resin 110b. On the other hand, the current collector 102a of the outer pole plate 101 and the pole plate 101a of the additional polarity having the same polarity is connected to the outer pole plate 101 in a state of being sandwiched between the peripheral edge portions of the metal sheet 102. In addition, the lead 111 is led to the outside of the battery.
[121] As the current collector 102a of the pole plate 101a of the first polarity, a metal sheet, a metal mesh, a punching metal, a metal lath plate, or the like can be used. The surface of the current collector 102a may be roughened by etching or may be provided with a conductive agent. When the additional polar plate 101a of the first polarity is the negative electrode, the current collector 102a is preferably made of copper, iron, copper alloy or iron alloy. When the current collector 102a is made of iron or iron alloy, it is preferable to plate nickel on the surface thereof. If the additional polar plate 101a of the first polarity is a positive electrode, the current collector 102a is preferably made of aluminum or an aluminum alloy. As for the thickness of the collector 102a, 10-100 micrometers is suitable.
[122] In the battery according to the fourth embodiment, in the step (3a), a pair of second pole plates, in which an additional first pole plate is sandwiched through the separator layer, is used instead of one second pole plate. This can be obtained in the same manner as the batteries of the first to third embodiments except for obtaining the electrode plate group as shown in FIG. 13.
[123] In addition, the nonaqueous electrolyte battery according to the fourth embodiment has the same structure or composition as that of the first embodiment except having two second polarity plates and an additional first polarity plate. 12 to 13, the same reference numerals as those in the first embodiment are assigned to the components having the same structure or composition as the first embodiment.
[124] Embodiment 5
[125] 14 is a plan view of the nonaqueous electrolyte battery according to the fifth embodiment of the present invention. 15, 16, and 17 show examples of the I-I front cross-sectional view, the II-II front cross-sectional view, and the III-III front cross-sectional view of FIG. 14, respectively.
[126] This battery has the same configuration as that of the battery according to Embodiment 1, except that the exterior material serving as the current collector of the outer electrode plate 301 is composed of one sheet of metal sheet bent to have two flat portions facing each other. 14 to 17, the same components as those in the first embodiment are assigned to the components having the same structure or composition as the first embodiment.
[127] Inside the outer electrode plate 301 composed of the metal sheet 302 and the active material layer 103 having the first polarity formed on one surface thereof, the current collector 105 and the both surfaces thereof are formed through the separator layer 107. The second polar electrode plate 104 composed of the bipolar active material layer 106 is housed. An adhesive 110a is joined between the peripheral portions of the metal sheet 302 serving as the current collector of the outer electrode plate 301. A lead 109 is connected to the current collector 105 of the pole plate 104 of the second polarity, and a portion to be sandwiched between the peripheral edge portions 308 of the metal sheet 302 of the lead 109 is an insulating resin. Covered at 110b.
[128] As shown in FIG. 16, the lead 111 is directly connected to the metal sheet 302 serving as the current collector of the outer electrode plate 301. The lead 111 can be connected to any portion of the metal sheet 302, but is sandwiched between the peripheral edge portions 308 of the metal sheet 302 in FIG. 16.
[129] As the battery according to the fifth embodiment, the metal sheet 302 serving as the packaging material is bent so as to have two flat portions facing each other, so that the crease 113 is formed as shown in FIG. 17.
[130] According to such a structure, since the space for joining is not needed in the site | part corresponding to the crease 113, only that part reduces a battery area. The joining process between the periphery of the metal sheet 302 can also be simplified.
[131] Next, the manufacturing method of the nonaqueous electrolyte battery concerning Embodiment 5 of this invention is demonstrated in detail.
[132] (i) step (1b)
[133] Step 1b is a step of preparing a metal sheet having a fold mark or a virtual fold mark to bend to have two flat portions facing each other. As this metal sheet, the same thing as the metal sheet used for the outer electrode plate which concerns on Embodiment 1 can be used. That is, the metal sheet of the shape which connects two metal sheets used for the outer electrode plate which concerns on Embodiment 1 is prepared, and the center is made into the fold mark or an imaginary fold mark. The metal sheet is preferably pasted with a fold mark.
[134] (ii) step (2b)
[135] Step (2b) is a step of obtaining an outer electrode plate by forming a pair of active material layers of a first polarity on a flat surface symmetrical with respect to the folds or virtual folds other than the periphery of one side of the metal sheet. to be.
[136] The method of applying the electrode mixture to the metal sheet is not particularly limited and can be used using a conventional general ceramic mill. It is preferable that the thickness of an active material layer is 30-300 micrometers, for example. It is preferable that the width of the circumferential edge of the metal sheet left for bonding is 1 to 10 mm.
[137] (iii) step (3b)
[138] Step (3b) is a step of obtaining a pole plate of a second polarity. The pole plate of the second polarity can be obtained like the pole plate of the second polarity according to the first embodiment.
[139] (Iv) step (4b)
[140] The step (4b) is a step of bending the outer electrode plate into a folded mark or a virtual folded mark to sandwich the pole plate of the second polarity through the separator layer with the pair of active material layers of the first polarity.
[141] 18 shows an unfinished nonaqueous electrolyte battery in a state where the outer electrode plate is bent from step (4b) to the middle. In Fig. 18, the outer electrode plate 301 has two active material layers 103 of the first polarity at positions symmetrical with respect to the folds 113 on the inner surface thereof. In the circumference | surroundings of the active material layer 103, the peripheral edge part 308 which is a metal exposure part is left as a joining site | part. Although not shown here, in the case of joining between the peripheral edge portions 308 with an adhesive, four sides of the peripheral edge portion 308 except for the vicinity corresponding to the fold 113 are attached. It is preferable to give. In the case where the peripheral edge portion 308 is joined by welding, the provision of the adhesive is not necessarily required.
[142] The separator layer 107 is arrange | positioned on the active material layer 103 of 1st polarity, and the pole plate 104 of the 2nd polarity provided with the lead 109 is mounted on one separator layer 107. As shown in FIG. . The portion of the lead 109 sandwiched between the circumferential edge portions 308 of the metal sheet 302 is covered with the insulating resin 110b. In addition, one end portion of the lead 111 of the outer electrode plate is placed on the circumferential edge portion 308 of the metal sheet 302.
[143] The electrode plate group is formed by completely bending the outer electrode plate 301 with the folds 113 as described above. In order to improve work accuracy and improve workability, it is preferable not to bend the metal sheet 302 according to the virtual fold marks, but to provide the fold marks 113 in advance on the metal sheet 302.
[144] The electrode plate group is pressurized after lamination so that each element is brought into close contact with each other to be integrated. In the case where the separator layer or the active material layer contains a thermal crosslinkable polymer as a raw material of the polymer electrolyte as the gel forming agent, pressurizing the electrode plate group at a temperature at which the gel forming agent crosslinks allows the formation of the polymer electrolyte and integration of the electrode plate group at the same time. It is preferable to make it. As such temperature, 80-130 degreeC is a suitable temperature.
[145] (v) process (5b)
[146] Step 5b is a step of joining the peripheral portions of opposing outer electrode plates. This process can be performed similarly to the process 4a of Embodiment 1.
[147] Embodiment 6
[148] In order to manufacture the battery efficiently, in step (1b), as shown in FIG. 19, the band-shaped metal sheet 402 having a crease (or virtual crease) 113 parallel to the longitudinal direction is provided. In step (2b), a plurality of pairs of first polarities are intermittently formed on a flat surface symmetrical with respect to the fold 113 except for the peripheral edge portion 408 of one side of the strip-shaped metal sheet 402. By forming the active material layer 103, it is effective to produce an outer electrode plate assembly composed of a plurality of continuous outer electrode plate units 401. In the step (4b), it is effective to sequentially sandwich the pole plates 104 of the second polarity through the separator layer 107 with the pair of active material layers 103 of each outer pole plate unit.
[149] In order to manufacture the battery efficiently, in the step 4b, the separator layer 107 is formed by coating the paste from the raw material of the separator layer on the active material layer 103 of the first polarity or the pole plate of the second polarity. It is effective to form It is preferable to make a paste from the raw material of a separator layer contain a gel former and a solvent or a liquid nonaqueous electrolyte.
[150] In FIG. 19, the manufacturing process of the nonaqueous electrolyte battery proceeds in the direction of the arrow.
[151] First, the active material layer 103 of the first polarity is sequentially formed at a position symmetrical with respect to the folds 113 of the strip-shaped metal sheet. At this time, if necessary, an adhesive for bonding or a lead for pole plate 111 of the first polarity is disposed around the active material layer 103, that is, around the edge portion 408 of the pole plate of the first polarity.
[152] Next, the separator layer 107 is provided so that the surface of the active material layer 103 may be covered. Although it is also possible to arrange the separator previously formed into a sheet shape on the active material layer, it is more efficient to apply the paste onto the active material layer sequentially from the raw material of the separator layer in a continuous manufacturing process.
[153] Next, on the separator layer 107, the pole plate 104 of the second polarity is placed. The lead 109 coated with the insulating resin 110b is connected to the pole plate 104 of the second polarity in advance.
[154] Subsequently, the folding mark 113 in the cut position 114 of the strip | belt-shaped metal sheet is isolate | separated from the edge part of one metal sheet. The outer electrode plate is bent by the folds 113, and one active material layer 103 is superimposed on the electrode plate 104 of the second polarity. Although it is also possible to bend the outer electrode plate without removing a part of the scheduled cutting position 114, it is preferable to remove a part from the viewpoint of workability and reliability. Next, the electrode plate group is pressed in the vertical direction.
[155] The joining between the peripheral edge portions of the opposing outer electrode plates may be performed after the electrode plate group is removed, but it is preferable that the battery assembly is obtained without being removed. And after completion of a battery assembly, it is preferable to remove each battery.
[156] Embodiment 7
[157] The nonaqueous electrolyte battery according to the seventh embodiment of the present invention is the same as the battery according to the fourth embodiment except that the exterior material serving as the current collector of the outer electrode plate is composed of one sheet of metal sheet bent to have two flat portions facing each other. Has a configuration. The plan view of the nonaqueous electrolyte battery according to the seventh embodiment is the same as that of the nonaqueous electrolyte battery of the present invention according to the fifth embodiment, and can be shown in FIG.
[158] 20, 21 and 22 show an example of the I-I sectional view, the II-II sectional view and the III-III sectional view of the battery according to the seventh embodiment having the surface appearance shown in FIG. 14, respectively. 20-22, the same code | symbol as Embodiment 4 or 5 is attached | subjected to the component similar to Embodiment 4 or Embodiment 5. In FIG.
[159] In other words, the battery has a separator layer 107 of the additional polar plate 101a of the first polarity and the additional polar plate 101a of the additional polarity adjacent to the second electrode plate 104 of the second polarity. It further has a pole plate 104 of the second polarity adjacent thereto. Although two stacks of batteries are shown here, the number of pole plates 104 of the second polarity held by the outer pole plate 301 of the first polarity is arbitrary.
[160] Hereinafter, the present invention will be described in detail with reference to Examples. All the batteries described herein are flat 10 cm long by 10 cm wide.
[161] Example 1
[162] In this embodiment, one stack of batteries as shown in Fig. 1 is manufactured in which the positive electrode is the outer electrode plate.
[163] (i) Manufacture of outer electrode plates
[164] LiCoO ₂ as a positive electrode active material, carbon powder as a conductive agent, a gel former which also functions as a binder, and N-methyl-2-pyrrolidone were mixed to prepare a positive electrode mixture. As the gel forming agent, a copolymer (hereinafter referred to as P (VDF-HFP)) consisting of 90% by weight of vinylidene fluoride units and 10% by weight of hexafluoropropylene units was used. N-methyl-2-pyrrolidone was used in an amount of 70 parts by weight based on 100 parts by weight of P (VDF-HFP). The weight ratio of active material: conductive agent: P (VDF-HFP) was 100: 5: 8.
[165] An aluminum film-shaped current collector having a thickness of 150 탆 and having a thickness of 150 mm was used as the metal sheet. As shown in FIG. 6, a positive electrode mixture having a thickness of 120 μm was intermittently applied to the center of one surface thereof, and a plurality of 86 × 86 mm square positive electrode active material layers were continuously formed to obtain an outer electrode plate assembly. An interval of about 17 mm was provided between each cathode active material layer.
[166] (ii) Preparation of Cathode
[167] Graphite powder as a negative electrode material, carbon black as a conductive agent, P (VDF-HFP) and N-methyl-2-pyrrolidone were mixed to prepare a negative electrode mixture. The weight ratio of active material: conductive agent: P (VDF-HFP) was 100: 8: 14. N-methyl-2-pyrrolidone was used in an amount of 70 parts by weight based on 100 parts by weight of P (VDF-HFP).
[168] A copper film current collector having a thickness of 10 µm was used in a strip shape having a width of 150 mm. The negative electrode mixture of 125 micrometers in thickness was apply | coated on both surfaces, and the negative electrode active material layer was formed, and the strip | belt-shaped negative electrode plate was obtained. From this negative electrode plate, a plurality of 88 x 88 mm square negative electrodes were cut out. Nickel lead was connected to the negative electrode current collector. The part sandwiched between the peripheral edges of the outer electrode plate of the lid was covered with an insulating resin.
[169] (iii) production of plate groups
[170] As shown in FIG. 7, the separator layer 7 which consists of P (VDF-HFP) was formed on each positive electrode active material layer of an outer electrode plate assembly. Specifically, the positive electrode active material layer was completely covered with a paste from P (VDF-HFP) mixed with N-methyl-2-pyrrolidone and dried to form a square separator layer having a thickness of 89 × 89 mm at a thickness of about 25 μm. Formed.
[171] Next, the end portion was removed from the outer electrode plate assembly having a width of 150 mm by leaving a circumferential edge portion formed of a metal exposed portion having a width of 7 mm. The peripheral portion of each outer electrode plate unit was distinguished from the inner metal exposed portion and the outer metal exposed portion, and inside, a polypropylene film having a thickness of 40 µm was disposed as an adhesive.
[172] As shown in FIG. 8, a pair of outer electrode plate units were sequentially arranged so that their anode active material layers faced each other, and one cathode was held in a pair of outer electrode plate units. The laminated electrode plate groups were sequentially heated under a pressure of 60 gf / cm 2 until the surface temperature reached 120 ° C, and were integrated flat to obtain an electrode plate group assembly shown in FIG. 9.
[173] (Iii) the junction between the perimeter edges
[174] The circumferential edge of the electrode plate assembly was pressed at 220 ± 5 ° C. for 10 seconds at 10 kgf / cm 2, and the polypropylene film disposed between the edges was melted and bonded. Only the unbonded site was left for pouring the nonaqueous electrolyte. The nonaqueous electrolyte was injected from the unbonded portion under reduced pressure, and heated to 60 ° C or higher to gelate P (VDF-HFP) in the electrode plate and separator layer.
[175] The nonaqueous electrolyte was prepared by dissolving LiPF ₆ at a concentration of 1 mol / liter in a mixed solvent having a volume ratio of 1: 1 of ethylene carbonate and diethyl carbonate.
[176] Thereafter, the inside of the battery was reduced in pressure, and the unbonded site was sealed. As a result, the aggregate of the battery B of a completely sealed structure as shown in FIG. 10 was obtained. The assembly of battery B was finally removed.
[177] Comparative Example 1
[178] Each electrode plate group was removed from the electrode plate group assembly obtained in Example 1, and surrounded by an exterior material having a thickness of 150 µm made of aluminum foil having a polypropylene layer on both sides. Subsequently, the nonaqueous electrolyte was injected into the packaging material and warmed to 60 ° C. or more to gel P (VDF-HFP) in the electrode plate and the separator layer, and then the packaging material was sealed. By this step, since the outer electrode plate is also enclosed in the outer packaging material, the anode lead is also connected to the outer electrode plate, and the positive electrode lead and the negative electrode lead are drawn out from the outer packaging material. In this way, the battery A of the airtight structure corresponding to the existing goods conventionally was obtained.
[179] Example 2
[180] A battery C having a sealed structure was obtained in the same manner as the battery B of Example 1, except that a resin layer having a thickness of 50 μm was formed on the outer surface of the current collector of the outer electrode plate.
[181] Example 3
[182] In this embodiment, two stacks of batteries, as shown in Fig. 12, having the positive electrode as the outer electrode plate were manufactured.
[183] (i) Preparation of Additional Anodes
[184] A positive electrode mixture similar to that used for the outer electrode plate was applied to both surfaces of an aluminum film-shaped current collector having a thickness of 150 μm in a band shape having a width of 150 mm, and an active material layer having a thickness of 120 μm was formed on both surfaces of the current collector. From the obtained strip | belt-shaped pole plate, the 86-86 mm square additional anode with a lead was penetrated.
[185] (ii) production of plate groups
[186] On both sides of the additional positive electrode, a paste was applied from P (VDF-HFP) mixed with N-methyl-2-pyrrolidone so that the positive electrode mixture was completely covered and dried to form a separator layer having a thickness of about 25 μm. It was. An additional positive electrode having a separator layer on both sides was sandwiched by two negative electrodes produced in Example 1.
[187] On the other hand, two outer electrode plate assemblies prepared in Example 1 were prepared, and the outer electrode plate units of one outer electrode plate assembly and the outer electrode plate units of the other outer electrode plate assembly were sequentially arranged so that their positive electrode active material layers faced each other. And an additional positive electrode held by the two negative electrodes was fitted in a pair of outer electrode plates. Then, the stacked electrode plate groups were heated under a pressure of 60 gf / cm 2 until the surface temperature reached 120 ° C, and were integrated flat to obtain an electrode plate group assembly.
[188] (iii) the junction between the peripheral edges
[189] The lead of the additional positive electrode was sandwiched between the peripheral edges of the outer electrode plate and conducted to the outer electrode plate.
[190] Example 4
[191] In the manufacturing process of the outer electrode plate, a gap of about 9 mm was provided between each of the cathode active material layers, and the end portion was removed from the outer electrode plate assembly having a width of 150 mm, leaving a circumferential edge portion consisting of a metal exposed portion having a width of 3 mm. Then, bonding was performed between the peripheral edge portions of the outer electrode plate by ultrasonic welding without bonding the peripheral edge portions by the adhesive. Other than the above point, it carried out similarly to the battery B of Example 1, and obtained the battery E of a sealed structure. The width of the circumferential edge portion to be the joint is reduced to 3 mm because the strength by the ultrasonic welding is high.
[192] Example 5
[193] In the manufacturing process of the outer electrode plate, a gap of about 7 mm is provided between the layers of each of the cathode active material layers, and a circumferential edge formed of a metal exposed portion of width 2 mm is cut off from the aggregate of the outer electrode plate having a width of 150 mm. Excluded. And the bonding between the opposing peripheral edge parts of an outer electrode plate was performed by laser welding, without bonding with an adhesive agent. Others were carried out in the same manner as the battery B of Example 1 to obtain a battery F having a sealed structure. The width of the circumferential edge portion to be the bonded portion is reduced to 2 mm because the bonding by laser welding has a higher strength than the bonding by ultrasonic welding.
[194] Example 6
[195] In the battery B, the metal exposed part of the outer side in which the polypropylene film was not arrange | positioned in the periphery of the outer electrode plate was bonded by laser welding, and the battery G was obtained. In the battery G, since the metal exposed portion inside the circumferential edge portion is joined by the adhesive and the metal exposed portion outside the circumferential edge portion by laser welding, the reliability of the bonding is improved than the battery B.
[196] Example 7
[197] In the battery B, the outer metal exposed portion in which the polypropylene film was not disposed in the peripheral edge portion of the outer electrode plate was bonded by ultrasonic welding to obtain the battery H. In battery H, since the metal exposed portion inside the circumferential edge is joined by an adhesive and the metal exposed portion outside the circumferential edge by ultrasonic welding, the reliability of the bonding is improved than that in the battery B.
[198] Example 8
[199] On the lead of the negative electrode drawn out from the inside of the battery, a PTC element with a current interruption temperature of 150 ° C was connected. The PTC element was encapsulated and fixed with an insulating resin having resistance to nonaqueous electrolyte, and sandwiched between the peripheral edge portions of the outer electrode plate. In the same manner as the battery B of the other Example 1, a battery I of a closed structure was obtained.
[200] Table 1 shows the outline, the thickness, and the energy density of the batteries A to I.
[201] Table 1
[202] battery Resin layer on the outer side of outer plate Stacks Battery thickness (mm) Energy density (Wh / l) A has exist One 0.9 267 B none One 0.6 400 C has exist One 0.7 343 D none 2 1.2 400 E none One 0.6 430 F none One 0.6 440 G none One 0.6 400 H none One 0.6 400 I none One 0.6 390
[203] The weight loss rate of batteries A to I, the capacity retention rate after storage, and the capacity retention rate after cycle were measured as follows.
[204] (Weight loss rate)
[205] The battery was charged at a current value of 1C at 20 ° C, and charging was continued until the current value became 0.05C at constant voltage after the battery voltage reached 4.2V. Subsequently, the charged battery was stored at 60 ° C. for 1000 hours. Then, the ratio of the weight loss after storage to the weight before storage was obtained as a percentage. The results are shown in Table 2.
[206] (Capacity retention rate after preservation)
[207] The battery after measuring the weight loss rate was discharged at a current value of 0.2 C at 20 ° C. The ratio of the discharge capacity of the battery after storage to the discharge capacity of the battery before storage was determined as a percentage. The results are shown in Table 2.
[208] (Capacity retention rate after the cycle)
[209] The battery was charged at a current value of 1C at 20 ° C, and charging was continued until the current value became 0.05C at constant voltage after the battery voltage reached 4.2V. Subsequently, the charged battery was discharged at 20 ° C. with a current value of 1 C until the battery voltage became 3 V. This operation was repeated 500 times. The ratio of the 500th discharge capacity to the first discharge capacity was obtained as a percentage. The results are shown in Table 2.
[210] TABLE 2
[211] battery Weight loss rate (%) Capacity maintenance rate after maintenance (%) Capacity retention rate after cycle (%) A 0.2 85 85 B 0.2 85 85 C 0.2 85 85 D 0.2 85 85 E 0.1 90 87 F 0.1 90 87 G 0.1 90 88 H 0.1 90 87 I 0.2 85 85
[212] In Tables 1 and 2, all of the batteries according to the present invention had high energy density, and moreover, the capacity retention rate after storage and the cycle retention capacity after storage equal to or higher than those of current products. In addition, it turns out that all the batteries which performed the welding between the peripheral edge parts by welding have low weight loss rate, and the sealing property of a battery is high. This means that the reliability of the nonaqueous electrolyte battery of the present invention is significantly improved as compared with the prior art.
[213] Example 9
[214] A battery J having a sealed structure was obtained in the same manner as the battery B of Example 1 except that the peripheral edge portion of the outer electrode plate was pressurized at 220 ± 5 ° C. and 5 kgf / cm 2 for 3 seconds.
[215] Example 10
[216] A battery K having a sealed structure was obtained in the same manner as the battery B of Example 1 except that the peripheral edge portion of the outer electrode plate was pressed at 220 ± 5 ° C. and 15 kgf / cm 2 for 3 seconds.
[217] Example 11
[218] A battery L having a sealed structure was obtained in the same manner as the battery B of Example 1 except that the peripheral portion of the outer electrode plate was pressurized at 220 ± 5 ° C. and 20 kgf / cm 2 for 3 seconds.
[219] The weight loss rate of the batteries J to L, the capacity retention rate after storage, and the capacity retention rate after the cycle were measured as described above. The results are shown in Table 3.
[220] TABLE 3
[221] battery Pressure (Kgf / ㎡) Weight loss rate (%) Capacity retention rate after storage (%) Capacity retention rate after cycle (%) B 10 0.2 85 85 J 5 0.5 50 30 K 15 0.2 85 85 L 20 0.35 70 65
[222] In Table 3, the battery J having a pressure of 5 kgf / cm 2 and a low pressure at the circumferential edge of the outer electrode plate has a high weight loss rate, and a capacity retention rate after storage and a capacity retention rate after a cycle are remarkably low. On the other hand, when such pressure is sufficient as 10-15 kgf / cm <2> in the peripheral part of an outer electrode plate, the performance of a battery improves remarkably. This shows the superiority of the battery structure of the present invention that outer electrodes having the same polarity can be joined to each other. That is, in the battery of the present invention in which the problem of the micro shorts due to the bonding between the peripheral edge portions of the outer electrode plate does not occur, sufficient pressure can be applied to the bonding portion, so that the reliability of the battery is significantly improved.
[223] In addition, the battery L having such a pressure of 20 kgf / cm 2 at the circumferential edge has low battery performance. This is considered to be because the pressure is too high, the melt of the polypropylene film protrudes to the outside, and the reliability of the joint is lowered.
[224] Example 12
[225] A battery M having a sealed structure was obtained in the same manner as the battery B of Example 1 except that the thickness of the positive electrode active material layer was 60 μm and the thickness of the negative electrode active material layer was 65 μm.
[226] Example 13
[227] A battery N having a sealed structure was obtained in the same manner as the battery B of Example 1 except that the thickness of the cathode active material layer was 270 µm and the thickness of the anode active material layer was 255 µm.
[228] Discharge characteristics of the batteries B, M and N were measured as follows.
[229] (2C / 0.2 ratio)
[230] The battery was charged at a current value of 1C at 20 ° C, and charging was continued until the current value became 0.05C at constant voltage after the battery voltage reached 4.2V. Subsequently, the charged battery was discharged at 20 ° C. with a current value of 2C until the battery voltage became 3V.
[231] Then, the battery was again charged at a current value of 1 C at 20 ° C., and after the battery voltage reached 4.2 V, charging was continued until the current value became 0.05 C at a constant voltage. Subsequently, the charged battery was discharged at 20 ° C. with a current value of 0.2 C until the battery voltage became 3 V.
[232] The ratio of the discharge capacity obtained by the discharge at the current value of 2C to the discharge capacity obtained by the discharge at the current value of 0.2C was calculated as a percentage. The results are shown in Table 4.
[233] (1C / 0.2 ratio)
[234] The battery was charged at a current value of 1C at 20 ° C, and charging was continued until the current value became 0.05C at constant voltage after the battery voltage reached 4.2V. Subsequently, the charged battery was discharged at 20 ° C. until the battery voltage became 3V at a current value of 1C.
[235] Then, the battery was again charged at a current value of 1 C at 20 ° C., and after the battery voltage reached 4.2 V, charging was continued until the current value became 0.05 C at a constant voltage. Subsequently, the charged battery was discharged at 20 ° C. with a current value of 0.2 C until the battery voltage became 3 V.
[236] The ratio of the discharge capacity obtained by the discharge at the current value of 1C to the discharge capacity obtained by the discharge at the current value of 0.2C was calculated as a percentage. The results are shown in Table 4.
[237] Table 4
[238] battery Thickness of Anode Active Material Layer (㎛) Thickness of anode active material layer (㎛) 2C / 0.2C Ratio (%) 1C / 0.2C Ratio (%) Capacity retention rate after cycle (%) B 120 125 90 98 85 M 60 65 96 99 90 N 270 255 40 70 20
[239] Table 4 shows that as the thickness of the active material layer increases, discharge characteristics, particularly high rate discharge characteristics, decrease. Conventionally, as a means of increasing the capacity of a thin battery, a method of forming an active material layer thickly is employed. However, when the active material layer becomes thick so that the results shown in Table 4 appear, high-rate discharge characteristics are impaired. On the other hand, in the battery of the present invention, the active material layer is divided into a pair of outer electrode plates. Therefore, it is not necessary to form a thick active material layer in order to raise battery capacity.
[240] Example 14
[241] (i) Manufacture of outer electrode plates
[242] LiCoO ₂ as a positive electrode active material, carbon powder as a conductive agent, P (VDF-HFP) and N-methyl-2-pyrrolidone were mixed to obtain a positive electrode mixture. The weight ratio of active material: conductive agent: P (VDF-HFP) was 100: 5: 8.
[243] An aluminum film-shaped current collector having a thickness of 200 mm and having a thickness of 200 mm was used as the metal sheet. In the center of the strip-shaped metal sheet, a crease parallel to the longitudinal direction was formed. On one side of the metal sheet, a resin layer made of polypropylene having a thickness of 50 µm was laminated except for the connection position of the external terminal.
[244] Subsequently, the positive electrode mixture is intermittently applied to each other at a position symmetrical with respect to the folds of the other surface of the metal sheet as shown in FIG. 19, and the positive electrode active material layer is continuously formed in two rows, thereby forming the outer electrode plate assembly. Got it. The formed positive electrode active material layers each had a square shape of 86 mm x 86 mm at a thickness of 120 µm.
[245] The spacing between the positive electrode active material layers provided in the column direction is 18 mm, and the spacing including the creases between the positive electrode active material layers provided in the width direction is 7 mm.
[246] (ii) Preparation of Cathode
[247] A negative electrode was prepared as in Example 1.
[248] (iii) production of plate groups
[249] As shown in Fig. 19, pastes were sequentially applied from P (VDF-HFP) mixed with N-methyl-2-pyrrolidone, so that each cathode active material layer was completely covered, dried, and dried at a thickness of about 25 mu m. A square separator layer of 89 × 89 mm was formed.
[250] Next, a polypropylene film having a width of 5 mm and a thickness of 50 µm was sequentially arranged as an adhesive so as to surround two cathode active material layers of each outer electrode plate unit.
[251] Next, the cathodes were sequentially placed on the separator layers in one row of the outer electrode plate assembly.
[252] Next, among the scheduled cut-out positions of the outer electrode plate assembly, the central fold marks were sequentially removed from one end of the current collector, and each outer electrode unit was bent with the fold marks. As a result, one positive electrode active material layer was stacked on the negative electrode through the separator layer, and the polypropylene films disposed on the peripheral edge of the outer electrode plate faced each other. Thereafter, the stacked electrode plate groups were sequentially heated under a pressure of 60 gf / cm 2 until their surface temperature became 120 ° C., and were integrated flatly.
[253] (iv) the junction between the peripheral edges
[254] The periphery of the outer edge corresponding to the fold of each outer electrode plate was pressed at 220 ± 5 ° C. and 10 kgf / cm 2 for 3 seconds to melt the polypropylene film to bond the edges. Only the unbonded site was left for pouring the nonaqueous electrolyte. The nonaqueous electrolyte was poured from the unbonded portion under reduced pressure, and heated to 60 ° C or higher to gel P (VDF-HFP) in the electrode plate and the separator layer. The same thing as Example 1 was used for the nonaqueous electrolyte. Thereafter, the inside of the battery was reduced in pressure, and the unbonded site was sealed. As a result, an aggregate of batteries P having a completely sealed structure as shown in FIG. 14 was obtained. The aggregate of batteries P was finally removed.
[255] Thus, a battery P having a thickness of 0.6 mm was obtained in a square shape of 100 mm x 96 mm.
[256] Example 15
[257] In the outer electrode plate assembly, the distance between the positive electrode active material layers provided in the column direction is 12 mm, and the space including the folds between the positive electrode active material layers provided in the width direction is 7 mm, and between the peripheral edge portions of the outer electrode plate. The battery Q having a thickness of 0.6 mm was obtained in a square shape of 95 mm × 93 mm in the same manner as in Example 14 except that the bonding was performed by ultrasonic welding without using a polypropylene film.
[258] Example 16
[259] In the outer electrode plate assembly, the gap between the positive electrode active material layers provided in the column direction is 10 mm, and the gap including the fold marks between the positive electrode active material layers provided in the width direction is 7 mm, between the peripheral edge portions of the outer electrode plate. Was carried out in the same manner as in Example 14 except that the bonding was performed by laser welding without using a polypropylene film, and a battery R having a thickness of 0.6 mm was obtained in a square shape of 94 mm x 92 mm.
[260] Comparative Example 2
[261] Each plate group was separated from the plate group assembly obtained in Example 1. FIG. And the electrode plate group was enclosed by the exterior material of thickness 150micrometer which consists of aluminum foil which has a polypropylene layer on both surfaces. Subsequently, the nonaqueous electrolyte was injected into the packaging material and heated to 60 ° C. or more to gel P (VDF-HFP) in the electrode plate and the separator layer, and then the packaging material was sealed. By this step, since the outer electrode plate is also enclosed in the outer packaging material, the anode lead is also connected to the outer electrode plate, and the positive electrode lead and the negative electrode lead are drawn out from the outer packaging material. Thus, a battery S having a thickness of 0.9 mm was obtained in a square shape of 100 mm x 96 mm.
[262] The weight loss rate of batteries P-S, capacity retention rate after storage, and capacity retention rate after cycle were measured as in the case of batteries A-L.
[263] Table 5 shows the results of the weight loss ratios of the batteries P to S, the capacity retention ratio after storage, and the capacity retention ratio after the cycle, together with the energy density and thickness of the batteries P to S.
[264] Table 5
[265] battery Weight loss rate (%) Capacity retention rate after storage (%) Capacity retention rate after cycle (%) Energy density (Wh / l) Battery thickness (mm) P 0.2 85 85 360 0.6 Q 0.2 90 87 390 0.6 R 0.2 90 87 400 0.6 S 0.2 85 85 278 0.9
[266] In Table 5, all of the batteries according to the present invention are thin and have high energy density, and further show a capacity retention ratio equivalent to or higher than that of the comparative example. In addition, it turns out that the battery which carried out the joining of the peripheral edge part by welding is low in weight loss rate, and the sealing property of a battery is high. This means that the reliability of the battery of the present invention is significantly improved as compared with the prior art.
[267] Further, by adopting the curved structure as in the present invention, it is possible to reduce the width of the circumferential edge portion of the outer electrode plate required for bonding, and as a result, it is understood that the battery area can be reduced.
[268] As described above, the present invention is to provide a non-aqueous electrolyte battery having a high energy density in a thin shape with a reduced thickness and area compared to the conventional one, and a simplified exterior structure. In particular, the battery of the present invention is improved in the problem of reliability and micro short-circuit in the sealed junction. In addition, according to the present invention, a non-aqueous electrolyte battery of high energy density and thinness having a simplified exterior structure can be manufactured by a continuous process with few steps.

权利要求:
Claims (19)
[1" claim-type="Currently amended] A flat exterior member made of a metal sheet and having two main flat portions facing each other, two first polarity active materials layers supported on the inner surface of the flat portion, a second polar electrode plate disposed at a position facing the active material layer, and the A nonaqueous electrolyte battery having a separator layer interposed between an active material layer and the second polar plate, and wherein the exterior material serves as a current collector of the active material layer.
[2" claim-type="Currently amended] The electrode plate according to claim 1, further comprising a pole plate of a further first polarity adjacent to the second pole plate through a separator layer and a further pole plate of a second pole adjacent to the further first pole electrode through a separator layer. A nonaqueous electrolyte cell that has two stacks.
[3" claim-type="Currently amended] The nonaqueous electrolyte of Claim 1, wherein the lead is electrically connected to the pole plate of the second polarity, one end of the lead is protruded from the exterior member to the outside, and the lead and the exterior member are insulated with resin. battery.
[4" claim-type="Currently amended] 4. The nonaqueous electrolyte battery according to claim 3, wherein an overcurrent blocking element sealed with resin is provided at a portion sandwiched between peripheral portions of the lid of the lid.
[5" claim-type="Currently amended] The nonaqueous electrolyte battery according to claim 1, wherein at least one of the separator layer and the active material layer comprises a polymer electrolyte.
[6" claim-type="Currently amended] The nonaqueous electrolyte battery according to claim 5, wherein the polymer electrolyte is a gel electrolyte composed of a liquid nonaqueous electrolyte and a polymer holding the same.
[7" claim-type="Currently amended] 2. A pair of metal sheets having a flat portion opposing each other or a sheet of metal sheet bent to have two flat portions opposing each other, wherein the peripheral edges of the pair of metal sheets are opposite. A nonaqueous electrolyte battery in which a portion is joined or between opposing peripheral edge portions of the sheet of metal.
[8" claim-type="Currently amended] 8. The nonaqueous electrolyte battery according to claim 7, wherein the opposing peripheral edge portions are joined by laser welding or ultrasonic welding.
[9" claim-type="Currently amended] The nonaqueous electrolyte battery according to claim 1, wherein the metal sheet has a thickness of 10 to 100 µm.
[10" claim-type="Currently amended] (1a) a step of obtaining an outer electrode plate by forming an active material layer of a first polarity on a flat portion other than the peripheral portion of one side of the metal sheet,
(2a) obtaining a pole plate of a second polarity,
(3a) A pair of outer electrode plates are prepared, and one outer electrode plate and the other outer electrode plate are disposed to face each other by disposing the active material layer inside, and in the pair of outer electrode plates that face each other, the pole plates of the second polarity are provided. The process of clamping through a separator layer, And
(4a) A method for manufacturing a nonaqueous electrolyte battery, comprising the step of joining the peripheral portions of the pair of opposing outer electrode plates.
[11" claim-type="Currently amended] The plurality of outer electrode plates according to claim 10, wherein in the step (1a), the plurality of outer electrode plates are continuously formed by intermittently forming a plurality of first polarity active material layers on flat portions other than the peripheral edges of one side of the strip-shaped metal sheet. In the step (3a), a pair of said outer electrode plate assemblies are prepared, and each outer electrode plate unit of one outer electrode plate assembly and each outer side of the other outer electrode plate assembly are sequentially prepared in step (3a). A method for producing a nonaqueous electrolyte battery, wherein the electrode plates are arranged with their active material layers facing each other to face each other, and the electrode plates of the second polarity are sequentially inserted through the separator layer in opposing pairs of outer electrode plates.
[12" claim-type="Currently amended] The electrode plate according to claim 10, wherein in the step (3a), the pole plate of the first polarity is adjacent to the pole plate of the second polarity through the separator layer, and the separator plate is further connected to the pole plate of the additional first polarity through the separator layer. The manufacturing method of the nonaqueous electrolyte battery which adjoins the pole plate of a 2nd polarity.
[13" claim-type="Currently amended] The nonaqueous electrolyte battery according to claim 10, wherein in the step (3a), the separator is formed by coating a paste from the raw material of the separator layer on the active material layer of the first polarity or the electrode plate of the second polarity. Recipe.
[14" claim-type="Currently amended] The manufacturing method of the nonaqueous electrolyte battery of Claim 13 in which the raw material of a said separator layer contains a gel former.
[15" claim-type="Currently amended] (1b) preparing a metal sheet having a crease or virtual crease to bend to have two flat portions facing each other,
(2b) a step of obtaining an outer electrode plate by forming a pair of active material layers of a first polarity in a flat portion that is a target for the fold marks or virtual fold marks other than the peripheral edge portion of one surface of the metal sheet;
(3b) obtaining a pole plate of a second polarity,
(4b) bending the outer electrode plate to the fold mark or imaginary fold mark, and sandwiching the pole plate of the second polarity through the separator layer in the pair of active material layers; and
(5b) A method for producing a nonaqueous electrolyte battery, comprising the step of joining the peripheral edge portions of opposing outer electrode plates.
[16" claim-type="Currently amended] 16. The strip-shaped metal sheet according to claim 15, wherein a strip-shaped metal sheet having fold marks or virtual fold marks parallel to the longitudinal direction is prepared, and in step (2b), one of the strip-shaped metal sheets is prepared. The outer electrode plate assembly composed of a plurality of outer electrode plate units which are continuous by forming a plurality of pairs of active material layers of the first polarity intermittently in the flat portions symmetrical to the fold marks or virtual fold marks other than the peripheral edges of the face. In the step (4b), a method of manufacturing a nonaqueous electrolyte battery in which a pair of active material layers of each outer electrode plate unit are sequentially sandwiched through the separator layer via the separator layer.
[17" claim-type="Currently amended] The electrode plate of claim 15, wherein in the step (4b), the electrode plate of the first polarity is adjacent to the electrode plate of the second polarity through the separator layer, and the separator plate is further connected to the electrode plate of the additional first polarity through the separator layer. The manufacturing method of the nonaqueous electrolyte battery which adjoins the pole plate of a 2nd polarity.
[18" claim-type="Currently amended] The nonaqueous electrolyte battery according to claim 15, wherein in the step (4b), the separator layer is formed by coating a paste from the raw material of the separator layer on the active material layer of the first polarity or the electrode plate of the second polarity. Recipe.
[19" claim-type="Currently amended] The method for producing a nonaqueous electrolyte battery according to claim 18, wherein the raw material of the separator layer contains a gel former.

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同族专利:

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公开号 | 公开日

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WO2002054525A1|2002-07-11|

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US20030134190A1|2003-07-17|

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KR100430123B1|2004-05-03|

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CN1406403A|2003-03-26|

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CN1198356C|2005-04-20|

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US7201997B2|2007-04-10|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-12-28|Priority to JPJP-P-2000-00403111

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2000-12-28|Priority to JP2000403111A

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2001-01-29|Priority to JPJP-P-2001-00019656

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2001-01-29|Priority to JP2001019656A

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2001-03-05|Priority to JP2001060873A

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2001-03-05|Priority to JPJP-P-2001-00060873

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2001-12-25|Application filed by 마쯔시다덴기산교 가부시키가이샤

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2002-10-11|Publication of KR20020077488A

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2004-05-03|Application granted

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2004-05-03|Publication of KR100430123B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2000-00403111|2000-12-28|

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JP2000403111A|JP3576102B2|2000-12-28|2000-12-28|Non-aqueous electrolyte battery|

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JPJP-P-2001-00019656|2001-01-29|

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JP2001019656A|JP3439743B2|2001-01-29|2001-01-29|Nonaqueous electrolyte battery and method for producing the same|

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JP2001060873A|JP2002260740A|2001-03-05|2001-03-05|Nonaqueous electrolyte battery and manufacturing method|

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JPJP-P-2001-00060873|2001-03-05|