TW200845458A - Lithium rechargeable battery by using laminated exterior package - Google Patents

Abstract

A lithium rechargeable battery is provided. A power generation element including a layer is enclosed in an exterior package body formed by a laminated exterior package material comprising a metal layer and a synthetic resin layer, wherein the power generation element is including a positive electrode layer, a negative electrode layer and a layer having lithium salt electrolyte. The lithium rechargeable battery is characterized that the power generation element and an absorption sheet are enclosed simultaneously in the exterior package body. The absorption sheet is formed by an absorption layer composed of at least one resin layer. The resin layer is including acid-absorbing inorganic particles and water-absorbing inorganic particles. According to 100 parts by weight of resin, the absorption layer has an amount of at least 5 parts by weight of the acid-absorbing inorganic particle and the water-absorbing inorganic particles.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 More specifically, the present invention relates to a clock filling which is excellent in durability, safety, and workability of the outer packaging material. [Prior Art] The material of the (four) material of the whole type = the past is the material of the pound steel.疋, metal sheets such as steel sheets are not recorded because of their rigidity, so they are uncomfortable = flattened in phase, and depending on their specificity, when the battery is used, the energy density per unit weight of the battery decreases. — = In this way, in recent years, a thin battery has been fabricated by laminating a metal smear with a resin film. The laminated outer material and the unrecorded steel plate are made of 2*soft', so it is suitable for processing the flat shape of the ridge, and can be pressed;;, so it has the feature that the battery can be easily sealed. However, it has a problem of high moisture permeability. ..., the mouth knife battery = transparent =, then the moisture present in the air will slowly invade the eight parts or the metal film is degraded. Since the heat sealing of the deteriorated material entangles also enters the inside of the battery, the above deterioration is promoted, and + leakage causes the battery life to be exhausted. The end of the money's end 6 200845458 25893pif In order to prolong the battery life, it is necessary to prevent water from invading as much as possible. It is known that the battery element and the hygroscopic material are simultaneously known in the outer casing of the synthetic resin, and then the outer casing is completely sealed. In order to prevent intrusion, and even if there is moisture intrusion, it will be used as a secondary battery. (For example, the patent document υ. In this battery, the substance that can be used is limited to moisture and does not remove hydrogen fluoride. If the compound is present, the hydrogen fluoride is reacted with the lithium salt electrolyte to cause deterioration of the material of the outer covering a. Further, the moisture absorbing material is in the form of a sheet in which the powder is adhered by Le 2, so that moisture is present. The inside of the powder pool is detached from the surface or end surface of the moisture absorbing material to cause defects on the electrode film and the electrical component. In addition, since the moisture absorbing material has extremely high performance, it is also present in the moisture absorbing material or the rechargeable battery. System = The operation of the hygroscopic material is very difficult. In addition, it is known that there is an electrolytic material, and the electrolyte __ layer of the outer bag containing the gold and plastic layers has a water permeability. Function and anti-money through the Wei riding charge 1€ pool (for example, special = 2). In this case, 'If the outer bag is formed by processing, = can produce a part that prevents the penetration ability. In addition, in order to make A and There are = water permeation function and acid permeation prevention function, and the particles of the material are absorbed. Therefore, it is possible to produce two batteries in the outer bag. The method should be applied to the battery with the above-mentioned molding processing. In the layered wrapper formed by the metal film and the heat-sealable resin film, the (4) (4) phase is attached with a wetting agent; the lithium rechargeable battery c c which seals the periphery of the moisture absorbent by heat sealing 200845458 25893ρι士 (for example, Patent Document 3). In this case, it is difficult to process the moisture-absorbing agent encapsulation portion, and the subsequent strength of the sealing portion is changed to S. The sealing portion is kept at the fourth degree, and must be enlarged. (4) The area of the second part is such that the amount of use of the laminated outer packaging material is increased or the size of the battery is increased, and the battery does not have an acid absorption capacity, so that the deterioration of the outer package caused by the other generation cannot be suppressed. Rat [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-243357 [Patent Document 2] Japanese Patent No. 3137〇61 A specification [Patent Document 3] Japanese Patent Laid-Open No. 2-3-187762 [Invention] k This invention In order to solve the above problems, it is an object of the invention to provide a clock-charged battery which is capable of preventing moisture from invading a battery or causing deterioration of an outer packaging material which can be caused by hydrogen generation inside a battery, and which is excellent in twisting property. It has been found that the bell-charged battery towel in which the discharge element is sealed in the laminated outer package has the suction (four) and the discharge element simultaneously sealed in the package, and the "well" has a layer of 丨 phase ± _ The above-mentioned object can be attained by the absorbent layer which comprises the unretained acid having the acid absorption Wei and the inorganic particles having the water absorption function. That is, the present invention relates to a lithium secondary battery in which an outer packaging body comprising a laminated outer covering material comprising a metal layer and a synthetic resin layer is filled with a layer containing a positive electrode layer and a negative electrode layer and a layer having a hetero electrolyte The discharge element is characterized in that: the discharge element and the absorption sheet are simultaneously enclosed in a package having an absorption layer composed of a resin layer or more of a layer of 200845458 25893ριί, the resin layer containing acid absorption The functional inorganic particles and the inorganic particles having a water absorbing function contain, in total, at least 5 parts by weight of the above-mentioned inorganic particles having an acid absorption function and inorganic particles having a water absorbing function with respect to 1 part by weight of the resin. Ο

In the present invention, since the absorbent sheet has an acid absorbing function and a water absorbing function, by accommodating the inside of the lithium rechargeable battery, it is possible to effectively absorb the water mixed in the production of the rechargeable battery and the hydrogen fluoride generated by the mixed water. And moisture which intrudes from the sealing portion of the outer package, hydrogen fluoride generated by the intrusion of moisture, and the influence of moisture and hydrogen fluoride on the discharge element, and the adhesion in the sealing portion of the outer package are lowered. Therefore, deterioration of the outer casing or heat generation and fire of the battery can be suppressed, and a lithium rechargeable battery excellent in durability and safety can be provided. Further, since the outer packaging material does not contain particles having an acid absorbing function and particles having a water absorbing function, it can be appropriately molded by press working. Therefore, the process charge of the clock-charged battery of the invention is also excellent. The above and other objects, features, and advantages of the present invention will become more apparent from the embodiments of the invention. The present invention will be described in detail with respect to the present invention. The rechargeable battery packs the discharge element in addition to the package. The second outer package is composed of a laminated surface comprising a metal layer and a synthetic resin layer. An example of the clock-charged battery of the present invention is shown in Figs. Figures 3 and 4, 9 are laminated outer packaging materials which are joined at the sealing portion 10 around 9 200845458 to form an outer envelope. The mounting material 9 comprises a metal layer and a synthetic resin layer. For example, the layer 9 may have a nylon film, an inscription and a polyolefin film in two layers, and the polyolefin film is welded to the inner side of the outer package. Or Li Zheng:, ','. 'The lines are sealed to form an outer package. As the polyolefin film, for example, an acryl film, a polyethylene film, a modified polyethylene film or the like can be used. The polysilicones 12 and 13 are respectively led out to the outside of the positive terminal and the negative package. The positive terminal and the metal _# such as Ming, copper, nickel or stainless steel, etc., are in the shape of a plate or a mesh. The knife can be attached to the laminated film η and the positive terminal for preventing the intrusion of outside air. The second pluggable terminal and the negative terminal have an adhesive material. The positive electrode is made of polyethylene or modified polypropylene. The shape of the outer body can be appropriately shaped, for example, a bag shape. The four sides of the rose voltage outer packaging material are knitted; the two layers (four) of the packaging material are placed along the center line to the soil 'the rectangular laminated outer two sides are heat-sealed or = coincident' only with the center The line is folded into a bag shape, and then the method of sealing is performed by opening: inserting the side and the center line; and the discharge element is further heat-transferred to the opening portion. Folding and (4) heat sealing, heat-sealing the two of the two openings in such a manner that the heat-sealed portion faces the center line of the outer packaging material 10 200845458 25893ριί, 2:= in the folding, inserting the mouth The discharge element is in the form of a garment, and then the mold is formed by heat-sealing the following portions. In addition, the __ side of the outer packaging material and the puller house the layer waste component in the recess, and the fifth (杈 reverse processing) will discharge it. The above other layers === the packaging material is superposed on the concave portion. In addition, there is also a recessed portion formed by λ °, and a packaging material is formed, and a concave portion is formed on both sides of the outer center line of the rectangular center line from the center line 2, or use. After the 邛/σ center line is folded in half, the discharge element in the present invention is a county electric component, and: a: contains the slagging solution used in s zhongtong 7: material layer, anode material layer, and lithium niobium electrolysis The layer of shell. The positive electrode material layer and the negative electrode material layer, for example, are formed on the current collectors 3 and 4, respectively. The positive electrode plate 5 and the negative electrode plate 6 are, for example, as shown in FIG. 2, and the layer 7 of the shell is laminated to form a discharge element 8 to be widely electrolyzed. The raw material and the negative electrode material may simultaneously contain respective electrode active materials. Resin, etc. Examples of the conductive auxiliary agent include graphite, =, rabbit fiber, and metals such as nickel, indium, copper, and silver. Further, for example, a resin such as a fluororesin or a fluororubber can be mentioned. ', the positive electrode active material can be used, such as Laizhong (Lic〇〇2), lock JJLlNl〇2), and M (UMnC)2). Further, in order to improve the conductivity of these positive electrode active materials, it is preferable to further mix the acetylene black negative electrode active material with the above-mentioned 12 200845458 25893 pif, and it is possible to use a soft or terminal carbon powder. The positive electrode material is coated on the current collector 4 of the amorphous carbon material positive electrode plate 5 and the negative electrode plate 6 as the material or the natural graphite or the like, and the positive electrode current collector 3 and the negative electrode are suitably used. The material of each current collector is: 2 and formed into a thin plate shape. Here, as the negative electrode current collector, steel I is used as the positive electrode current collector. The positive electrode plate and the negative electrode plate are not in direct contact with each other. The layer 7 is a layer 7 that contains the electrolyte electrolyte in the vicinity of the discharge element, usually using .7 or a laminate. The separator is a separator which consists of a liquid film or a gel-like film which is impregnated with a film, or a laminated structure separator which is made of a porous polypropylene and a polyethylene. When the electrode material or the electrode plate is separated from the film, it softens and loses porosity. Therefore, it has a safety mechanism for the movement of the plasma, that is, the battery reaction. The liquid electrolyte (electrolyte) is obtained by dissolving the clock salt electrolyte in a non-aqueous solvent. The gel-like electrolyte 'is obtained by holding the above liquid electrolyte in a polymer compound. As the nonaqueous solvent, for example, ethylene carbonate, carbonate, butylene carbonate, dinonyl carbonate, ethylene carbonate, ethyl decyl carbonate can be used. Carbonic acid vinegar; tetrahydrofuran, 2-mercaptotetrahydrofuran and the like ether; 1,3-dioxolane, 4-methyldioxolan and other cyclic ether; γ_丁内= 12 200845458 25893ριί Esterol; cyclobutyrate and the like. It is also possible to use: 3-methylcyclobutane, dimethoxyethoxyethane, diethoxyethane, ethoxymethoxyethane, ethyl diglyme, and the like. As the electrolyte, if it is an electrolyte which is dissolved in a non-aqueous solvent and generates a clock, the electrolyte may be used singly or in combination of two or more kinds. For example: lithium hexafluorophosphate (LipF6), lithium tetrafluoroborate (L1BF4), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiC104), tri-failed methanesulfonic acid clock (LiCF3s〇3), double (trifluoromethane)醯, f, lithium imide (LiWSOWF3) 2), tris(trifluoromethanesulfonyl)methyllithium (LiCXSOfF3) 3), lithium tetrachloroaluminate (LiAlcl4) or lithium hexafluoroantimonate (LiSiF6) . As a polymer compound which can be used for a gel electrolyte, for example, it can be listed. a gas-based compound such as a copolymer of vinyl fluoride or vinylidene fluoride and hexafluoropropylene, an ether-based polymer compound such as polyethylene oxide or a crosslinked body containing polyethylene oxide; or a poly Acrylonitrile and the like. In the lithium secondary battery of the present invention, the discharge element and the absorbent sheet are simultaneously sealed into the outer package. The absorbent sheet has an absorbing layer composed of one or more resin layers, and the resin layer contains inorganic particles having an acid absorbing function and inorganic particles having a water absorbing function. The above-mentioned absorbing layer may be composed of a single tree 曰f containing an organic particle having an acid absorption function and an inorganic particle having a water absorbing function, or may be composed of a resin layer containing an inorganic particle having an acid absorbing function and containing water. It is composed of a laminate formed of a resin layer of an inorganic particle that absorbs the function. Further, the above-mentioned absorbing layer contains a total of at least 5 parts by weight of the above-mentioned acid absorbing function with respect to the resin 100.

As the inorganic particles having the water absorption function, any material may be used as the material having the moisture absorption property, and it is preferably a material which is less in volume and shape due to moisture absorption; for example, : metal oxides, zeolites, strontium hydrotalcite, hydrotalcite oxides, magnesium sulfate (〇3 hydrate), phosphorus pentoxide, calcium chloride, and the like. Preferred are metal oxides, zeolites, strontium hydrotalcite, hydrotalcite oxides and magnesium sulfate (〇3 to 3 hydrate), more preferably zeolites, strontium hydrotalcites, hydrotalcite oxides and magnesium sulfate (〇~3 hydrate) . The inorganic particles having water absorbing ability may be used singly or in combination of plural kinds. 200845458 25893ριί and no water absorption function. The amount of the inorganic particles described above is preferably less than or equal to weight =, more preferably Π) to 100 parts by weight of the resin. 50 parts by weight. When the σ of the inorganic particles is at the lower limit, a sufficient absorption function cannot be obtained. If the total amount of the inorganic particles is too large, the surface of the inorganic particles may be reduced. Further, the above-mentioned nucleus-free granules and inorganic particles having water absorbing ability may be in the case of not-inorganic particles and the same inorganic particles having two kinds of absorbing functions, as described below. In the former case, the respective amounts of the unretained nucleus having a nuclear absorption and the inorganic particles having the water absorbing power b are preferably 2.5 parts by weight or more, more preferably more than 1 part by weight based on 1 part by weight of the resin. Equal to 5 parts by weight. The material having hygroscopic property as described above is preferably used in a state of being dehydrated and dried at a temperature lower than the decomposition temperature of each substance. In addition, hydrotalcite has a low hygroscopicity, but it is 3 (10). c. The calcined hydrotalcite which has been calcined below 30, and the hydrotalcite oxide which is calcined at 30 (TC or higher) is dehydrated in the form of 14 200845458 25893pif, and the hygroscopicity is increased, so it is suitable as a desiccant. Acidic absorption of inorganic particulate matter, zeolite, hydrotalcite, smoldering hydrotalcite, hydrotalcite oxidation = > Fushi, hydrotalcite, smoldering hydrotalcite, hydrotalcite oxide. Inorganic particles with acid absorption capacity, It can be used alone or in combination. As the resin used in the absorbent layer, any resin can be used as the resin which is easily invaded by the electrolyte, but it is preferably polyethylene, polypropylene, and methyl a copolymer of an olefin, ethylene and butene, an ethylene and a hexaionic polymer, a modified polyethylene, a modified polypropylene, an acetonitrile-acetic acid copolymer, and an ethylene-vinyl alcohol copolymer. J resin may be used alone, or a plurality of resins may be used in combination. In the film, it is preferred that the absorbent layer has a resin layer containing no inorganic particles on both sides thereof. Further, in the production of the resin, it is usually A small amount of inorganic particles is an additive such as a neutralizing agent, a stabilizer, an anti-caking agent, or a nucleating agent, and the inorganic particles in the resin layer containing no inorganic particles are inevitably contained as k. The amount of the inorganic particles used as the additive is usually about 0. 01 to 0.5 parts by weight with respect to 10 parts by weight of the resin. However, in the preferred embodiment of the present invention, The resin containing no inorganic particles described above is a resin which does not contain or contains almost no inorganic particles. By having a resin layer containing no such inorganic particles, it is possible to suppress inorganic particles having an acid absorption function in the absorption layer and having water. The detachment of the inorganic particles of the absorption function causes the internal contamination of the lithium rechargeable battery or the appearance of the electric power of the battery. The force of the acid and the water is broken from the electrocardiographic component.

As shown, the absorbent layer μ can also be coated with a resin 5 containing inorganic particles. By coating, the contamination of the above-mentioned clock-rechargeable battery 2 can be further suppressed, and the operation of the absorbent sheet can be made easier. As the resin in the resin layer containing no such inorganic particles, any resin can be used as the resin which is hard to be invaded by the electrolytic solution, but a thermoplastic resin is preferable, and polyethylene, polypropylene, polymethylpentene, and B are particularly preferable. Copolymer of women and butene, copolymer of ethylene and propylene, ionic polymer, modified polyethylene, modified polypropylene, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer. As the above resin, a single resin may be used alone, or a plurality of resins may be used in combination. The thickness of the absorbent sheet is appropriately determined depending on the amount of the inorganic particles having an acid absorption function and the amount of the inorganic particles having a water absorbing function, and the time at which the function of the absorbent sheet is desired to be maintained. If the thickness of the resin layer containing no inorganic particles is too thick, the absorption speed of the absorption layer becomes extremely slow, and if the thickness is too thin, the absorption speed of the absorption layer becomes too fast, making the operation of the absorbent sheet difficult. In addition, the influence of the thickness of the absorbing layer on the thickness of the lithium rechargeable battery must also be considered. The thickness of the absorbing layer is preferably 10 to 1000) Llm, and the thickness of the resin layer containing no inorganic particles is preferably 1 to 1 〇Qpm. The thickness of the absorbing layer is more preferably 20 to ΙΟΟμηη, and the thickness of the resin layer containing no inorganic particles is more preferably 2 to 20 μm 〇16 200845458 25893pif The particle size of the inorganic particles having an acid absorption function and the inorganic particles having a water absorbing function, If it is a particle diameter which can achieve a desired film thickness, arbitrary particle diameter can be used, It is preferable that it is G. G1~, More preferably, it is G i~3*. The arrangement position of the absorbent sheet in the rechargeable battery of the present invention is not particularly limited as long as it is inside the outer package. For example, as shown in Fig. 7, it is preferable to arrange the two sheets of absorbent sheets 14' so that the suction elements 8 are sandwiched by the suction U14, but only the sheets 14 may be disposed and received on either side. Further, as shown in Fig. 8, the absorbent sheet 14 can also be reinforced into a cylindrical shape and used in the form of an inner discharge member 8. Figs. 9 to 11 are cross-sectional views showing an example of the arrangement position of the absorption > 1 when the absorbent sheet 14 is sealed inside the outer package. FIG. 9 is an example of a configuration in which the discharge element 8 is sandwiched. As shown in Fig. 1(), the absorbent sheet 14 may be disposed in the vicinity of a portion where the positive electrode terminal 12 or the negative electrode terminal 13 is led out of the laminated outer casing. Further, as shown, the combination of the configuration in Fig. 9 and the configuration in Fig. 10 can also be employed. While the absorbent sheet 14 is disposed inside the outer casing, it is preferable to arrange the absorbent sheet 14 in the sealing portion 1 of the laminated outer casing. In this case, the absorbent sheet is disposed in at least the sealing portion. - Partially, it is better to arrange it on the whole of the π part. Examples thereof are shown in Figs. As shown in Fig. 12, a haptic absorbent sheet can be used on the sealing portion, as shown in Fig. η, or a second absorbent sheet can be used on one sealing portion. By arranging the absorbent sheet in the sealing portion of the outer package, the amount of moisture invaded from the sealing portion can be efficiently reduced, and the influence of hydrogen fluoride on the discharge element and the decrease in the adhesion of the sealing portion can be avoided for a long period of time. In the absorbent sheet of the present invention, an absorbent sheet formed by f-joining the tree 17 Ο c 200845458 25893pif f of the absorbing layer by radiation may be used. As the radiation, it is preferable to use the electron charging electric temperature to also have high heat resistance, and even when the absorption sheet of the clock (4) can be added to both sides or any surface, the table _ can be increased. Speed up the absorption of hydrogen and water. In addition, when the absorbing two-package material is aged, it exhibits the discharge of heat=;=, etc., so that the absorbent sheet of the present invention can also have a layer of adhesive on both sides or on either side thereof. Or a layer of an adhesive layer. By having a layer of a binder or an adhesive layer, a lithium rechargeable battery can be manufactured by attaching an absorbent sheet to a laminated outer covering material by using a dot agent, so that the arrangement position of the absorbent sheet can be fixed, and therefore, It is possible to prevent the deviation of the position of the absorbing sheet in the manufacturing step of the lithium secondary battery. The absorbent sheet of the present invention can be manufactured by the following method: using an extruder of a single shaft, a two-axis, a four-axis or the like, or a pressure kneader, a shift A well-known mixer such as a Banbury Mixer, which melts and kneads inorganic particles having an acid absorption function, inorganic particles having a water absorbing function, and a resin, and supplies the particles to a τ-die or The expansion forming device (4) is placed in the shape of the wire. The material is not connected to the film forming device by directly connecting the extruder used in the particle f匕 to the film forming device. In the case of granulation, an absorbent sheet is formed. 18 200845458 25893pif In the case where the absorbent layer of the absorbent sheet has no layer on both sides, the obtained particles are simultaneously supplied to the resin for the no-substrate layer. In a multilayer film forming apparatus such as a multilayer τ-die extrusion molding apparatus, a laminate film is not contained on both surfaces of the absorbing layer, whereby an absorbing sheet can be produced. The extrusion field or the straight shaft of the mixer is more than = the device is connected or connected by a gear pump, and the absorption sheet is formed in the case of e, /. In addition, if the sheet is cut to a desired size and then heated and compressed, then = The whole of the second absorbing layer is coated with the resin layer containing no inorganic particles, and the absorbing sheet and the discharge member which are to be obtained in this manner are further packaged, and the absorbing sheet is also sandwiched in the outer package = layer ^ as needed. The battery can be manufactured by heat sealing so that the positive electrode terminal and the negative electrode terminal are sealed from the outer casing. The dog can be used as a double absorption sheet, and can be used in addition to the rechargeable battery. EXAMPLES Hereinafter, the present invention is specifically and not limited to the following examples by way of examples. 彳-Production of the sub-(1) absorbent sheet of the present invention is carried out by two-pump extrusion of PCM_46 equipped with a two-axis extrusion company equipped with a quantitative dosing feeder. The machine "= household = stock limited fat and inorganic particles - melt-kneaded, and then used two ΐ ίίΐϊ 19 200845458 2t> manufactured by W0pit Co., Ltd.) to obtain a film thickness shown in Table 〗. The obtained film was stored in a drying chamber having a dew point of -5 ° C or less. Side = sheet production 1 (A sheet in which the absorbent sheet was placed only inside the test piece = a test piece having the configuration shown in Fig. 14 was produced as follows.

The operation of C: is carried out in a drying chamber having a dew point of _5 Gt: or less. The first use of the concave size is 3 〇mm, the length of 5 〇, the deep Μ 的 及 及 and the press (Laminating film forming test machine, Baoquan Co., Ltd. is made of sealant layer side (poly_film side) ) A method of forming a recessed portion, under the condition of a pressure of 5 MPa and a pressurization speed of ls/1 〇〇 mm, for laminating the outer covering material (aluminum laminated foil for lithium ion battery, manufactured by Showa Denko Packaging Co., Ltd., in nylon) A laminate having an aluminum foil between the film and the polyolefin film is subjected to a molding process. The recessed portion of the molded laminated outer covering material (9a) contains a separator which is folded into a width of 28 mm and a length of 48 mm (CELGARD shares are limited) (manufactured by the company) (17) formed by sandwiching between two sheets of absorbent sheets having a width of 28 sides and long servant legs. The unmolded laminated outer packaging material (9) which is cut into a width of 4 inches and a length of 60 mm and The laminated outer packaging material (9a) subjected to the above-mentioned molding is superposed in such a manner that the respective sealant layers are opposed to each other, and any three sides are heated at 5 mm under conditions of 2 Torr, iMPa, and 5 seconds. Sealed and processed into a bag shape. Ethylene carbonate, carbonic acid The oxime ester and the diethyl carbonate were mixed at a volume ratio of 1··1:1, and lithium hexafluorophosphate was dissolved therein in a manner of 1 mol/L to prepare an electrolytic solution (manufactured by Kishida Chemical Co., Ltd.), and 3 ml of the above electrolysis was carried out. The liquid is injected from the opening to impregnate the electrolyte in the separator, and then in 20 200845458 25893pif, a test of 5 mm sealing part 乍) 2 (the film and the film are placed inside the test piece and a = such as: A test piece having the configuration shown in Fig. 15 was produced. The operation shown below was carried out in a drying chamber having a road point temperature of _% 〇 C or less. First, the size of the concave portion was 3 mm in width, 50 mm in length, and 3.5 r in depth. In the case of the laminated film forming tester, the sealant layer side (polyolefin film side) is a recessed portion, and the pressure is 5 MPa and the pressurizing speed is ls/100 mm. Next, the lamination is outsourced (the use of the hetero-cell battery _ layer box 'Showa Electric 1 Packing Co., Ltd.' s two made t' between the nylon film and the polyolefin film) 2 mold 5 processing. The laminated outer packaging material (9a) has a concave Folded into a 28mm wide, 48mm long diaphragm ^ 2 Co., Ltd.) clipped in a wide 28, long 48 bribe

(17) formed by two pieces of L 6 . The laminated outer packaging material (9) which is cut into a width of 4 〇 coffee, long pressure and nm pressure processing and the above-mentioned mold mode; 2: ί外!! 装料料 (5), with the respective sealant layer opposite the clip 1 ;; along any of the three sides, between the overlapping laminated outer packaging materials _a, 5 seconds under the material and the film (14), in. c. Forming as follows: The above 3 sides are heat-sealed at a width of 5 mm, and the volume ratio of the second ":: mountain s two sa 1.1 is mixed with ethylene carbonate and fluorocarbon to form 1 qing / L In the way of the six external diseases, an electrolyte solution was prepared (Kishida Chemical Co., Ltd., manufactured by Kishida Chemical Co., Ltd.). 3 ml of the above electrolyte was injected from the opening to impregnate the electrolyte in a separator, and then the width was 5 mm. The absorbent sheet having a length of 55 mm was sandwiched between the openings (14), and the opening was heat-sealed at a width of 5 mm under conditions of rc, 1 MPa, and 5 seconds to prepare a test piece. Example 1 Using a 15-fold wound Hydrotalcite (dht-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) as an inorganic particle having an acid absorption function, using 15 parts by weight of an electromagnetic plate provided with a pore size of 2〇μηη stainless steel (manufactured by AS 〇NE Co., Ltd.) Magnesium sulphate hydrate (MG_0K-100, manufactured by Ako Chemical Co., Ltd.) classified by a vibrating screen (AS200DIGIT, manufactured by AS ONE Co., Ltd.) as an inorganic particle having a water absorbing function, using 1 part by weight of poly Propylene (p p,prime

Polypro F-744NP 'manufactured by Prime Polymer Co., Ltd.) As a resin, an absorbent sheet having a thickness of 5 μm was obtained in accordance with the method for producing an absorbent sheet described above. Using the obtained absorbent sheet, a test piece was produced in accordance with the method of producing a test piece. Example 2 A test piece was produced in the same manner as in Example 1 except that the amounts of hydrotalcite and magnesium sulfate were changed to parts by weight, respectively. Example 3 A test piece was produced in the same manner as in Example 1 except that a sapphire (Molecular Sieves 4A powder, manufactured by Ba Industrial Co., Ltd.) was used as the inorganic particles having a water absorbing function. Example 4 22 200845458 25893pif In addition to the use of strontium hydrotalcite (DTH-4C, manufactured by Kyowa Chemical Industry Co., Ltd.), it is also used as an inorganic particle having an acid absorption function and an inorganic particle having a water absorption function, and the amount thereof is adjusted to Test pieces were prepared in the same manner as in Example 1 except for 3 parts by weight. Example 5 In addition to the use of hydrotalcite oxide (KW-2200, manufactured by Kyowa Chemical Industry Co., Ltd.), it also serves as an inorganic particle having an acid absorption function and an inorganic particle having a water absorption function, and the amount thereof is adjusted to 3〇. A test piece was produced in the same manner as in Example 1 except that the weight was C. Example 6 A test piece was produced in the same manner as in Example 1 except that a modified polypropylene (ADMER QF551, manufactured by Mitsui Chemicals Co., Ltd.) was used as the resin. Example 7 A test piece was produced in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer (EVAFLEX P1007, manufactured by Mitsui/DuPont Chemical Co., Ltd.) was used as the resin. [Example 8] A test piece was produced in the same manner as in Example 1 except that an ethylene-vinyl alcohol copolymer (EVALF101B, manufactured by Kuraray Co., Ltd.) was used as the resin. Example 9 A test piece was produced in the same manner as in Example 1 except that low density polyethylene (LDPE, NEO-ZEX 0234CL, manufactured by Prime Polymer Co., Ltd.) was used as the resin. Paste Example 10 A test piece was produced in the same manner as in Example 1 except that polymethylpentene (TPXDX845, manufactured by Mitsui Chemicals, Inc.) was used as the resin. Example 11 30 parts by weight of hydrotalcite (dht-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) was used as inorganic particles having an acid absorption function, and 100 parts by weight of polypropylene (PP, Prime p〇lypr〇F-744NP) As a resin, a hydrotalcite-dispersed polypropylene sheet having a film thickness of 25 μm was produced as a resin in accordance with the method for producing an absorbent sheet. In addition, a sulphuric acid classified by an electromagnetic vibrating screen (AS2〇〇digi, manufactured by AS ONE Co., Ltd.) having a pore size of 2 〇gm, which is manufactured by As ONE Co., Ltd., was used. An anthraquinone hydrate (MG-0K-100, manufactured by Ako Chemical Co., Ltd.) is used as an inorganic particle having a water absorbing function, and 100 parts by weight of the above polypropylene is used as a resin, and a film thickness is produced according to the method for producing the above-mentioned absorbent sheet. 25_ Stone: Acid town disperse polypropylene sheet. Using two (four) machines (manufactured by Dacheng Laminator Co., Ltd., FL750), the two magnesium sulfate dispersion poly(four) sheets obtained were heated and laminated at 0.5 MPa and 18 (rc, lm/min). The film thickness was increased by sucking w, and the test piece was prepared according to the method of the test = 1. The second embodiment was made using the same absorbent sheet as in Example 1, and was produced according to the method of producing the test piece 2 24 200845458 25893pif. Test piece. Example 13 A test piece was produced in the same manner as in the production of the test piece 2 using the same absorbent sheet as in Example 2. Example 14 Using the same absorbent sheet as in Example 3, the method of producing the test piece 2 was carried out. A test piece was produced. Example 15 " Using the same absorbent sheet as in Example 4, a test piece was produced in accordance with the method of Production of Test Piece 2. Example 16 The same absorbent sheet as in Example 5 was used, and the test piece was produced 2 A test piece was produced by the method. Comparative Example 1 A test piece was produced in the same manner as in Example 1 except that inorganic particles having an acid absorption function and inorganic particles having a water absorption function were not used. A test piece was produced in the same manner as in Example 1 except that 30 parts by weight of sulfuric acid was used as the inorganic particles having a water absorbing function, and Comparative Example 3 was used. The inorganic particles having a water absorbing function were mixed, and 30 parts by weight of hydrotalcite was used as the inorganic particles having an acid absorbing function. 25 200845458 25893pif A test piece was produced in the same manner as in Example 1. Comparative Example 4 No absorption was used. A test piece was produced in accordance with the method of Production 1 of the test piece. / I... Comparative Example 5

The hydrotalcite was dispersed on the side of the polypropylene sheet of the absorbent sheet produced in Example 11 under the conditions of MPa.5 MPa, 180 ° C, and lm/min by a laminating machine (manufactured by Daisei Laminator Co., Ltd., FL760). The ceramic ion battery in the production of the test piece 1 was heated on the side of the sealant layer of the laminate foil to obtain an aluminum laminate foil having an acid/water absorption function. In addition to the use of the obtained aluminum laminate foil as the laminate outer packaging material, the test piece was produced in the same manner as in the production of the test piece 1 except for the use of the film. Comparative Example 6 Using a laminator (Dacheng Laminator Co., Ltd.: a type of hydrotalcite-dispersed polypropylene sheet side, and heating and laminating the lithium ion battery in the production of the test piece, the aluminum ion battery 6 was obtained, and the acid was obtained. /Last absorbing function of the water-absorbing function. In addition to the ^================================================================================== MM7 ° The polypropylene sheet of Example π Magnesium Sulfate was used as the water dispersion material produced in the absorbent sheet, and was dispersed without being thermally laminated, and was produced in accordance with the method 1 of the sample preparation. Test 26 200845458 25893pif sheet. Comparative Example 8 A test piece was produced in the same manner as in Example 1 except that the amounts of hydrotalcite and magnesium sulfate of Example 1 were changed to 0.5 parts by weight, respectively. Comparative Example 9 Use and Example In the same absorbent sheet, a test piece was produced in accordance with the method 2 of the test piece. However, the absorbent sheet was not disposed inside the test piece, and the test piece was placed only in the sealing portion. 27 200845458 25893pif [Formula] Absorbent sheet The structure and arrangement position

Arrangement position of absorbent sheet Absorbent sheet Mixing amount (parts by weight) Film thickness [μπι] Test piece sealing part Example 1 Polypropylene 100 50 Configuration - Hydrotalcite 15 Sulfuric acid town 15 Example 2 Polypropylene 100 50 Configuration - Hydrotalcite 30 Sulfuric acid town 30 Example 3 Polypropylene 100 50 configuration - hydrotalcite 15 Fossil 15 Example 4 Polypropylene 100 50 Disposal of a calcined hydrotalcite 30 Example 5 Polypropylene 100 50 Disposition of a hydrotalcite oxide 30 Example 6 Modified Polypropylene 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 7 Ethylene Vinyl Acetate Copolymer 100 50 Configuration of Hydrotalcite 15 Magnesium Sulfate 15 Example 8 Ethylene-Vinyl Alcohol Copolymer 100 50 Configuration of a Hydrotalcite 15 Sulfuric Acid Town 15 Example 9 Low Density Polyethylene 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 10 Polydecylpentene 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 11 Polypropylene 100 25 50 Configuration - Water Talc 30 polypropylene 100 25 magnesium sulfate 30 28 200845458 25893pif [Table 1-2] Example 12 Polypropylene roast 100 50 Disposed Hydrotalcite 15 Sulfuric Acid Apparatus 15 Example 13 Polypropylene 100 50 Configuration Configuration Hydrotalcite 30 Sulfuric Acid Town 30 Example 14 Polypropylene 100 50 Configuration Configuration Hydrotalcite 15 Zeolite 15 Example 15 Polypropylene 100 50 Configuration Configuration Crucible Hydrotalcite 30 Example 16 Polypropylene 100 50 Configuration Configuration Hydrotalcite Oxide 30 Comparative Example 1 Polypropylene 100 50 Configuration - Comparative Example 2 Polypropylene 100 50 Configuration - Sulfuric Acid Lock 30 Comparative Example 3 Polypropylene 100 50 Configuration - Hydrotalcite 30 Comparative Example 4 一—一—Comparative Example 5 Polypropylene 100 25 50 Heat-laminate the absorbent sheet on the laminated outer packaging material and attach the hydrotalcite 30 Polypropylene 100 25 Sulfuric acid town 30 Comparative Example 6 Polypropylene 100 50 Absorbent sheet Heat lamination on laminated outer packaging material and laminating hydrotalcite 15 magnesium sulfate 15 Comparative Example 7 Polypropylene 100 25 Configuration - hydrotalcite 30 Polypropylene 100 25 Sulfuric acid town 30 Comparative Example 8 Polypropylene 100 50 Configure a hydrotalcite 0.5 Sulfuric acid town 0.5 Comparative example 9 Polypropylene 100 50 _ Configure hydrotalcite 15 Sulfuric acid town 15 1 Reliability test will be the above The test piece was placed in a constant temperature and humidity chamber at 60 ° C and 95% RH for 30 days, and the appearance was visually observed, and the hydrogen fluoride concentration of the electrolyte 29 200845458 25893pif solution in the test piece was measured and taken together; / Long time 3 hard. Further, as shown below, the amount was measured by Karl Fischer Meth〇d, and the gasification air content was measured by ion chromatography. The test results are shown in 2 ^ 4· 〇 , moisture content of tears argon gas replacement dew point temperature is below _ thief gas replacement type glove phase (AS ONE Co., Ltd., S (M 〇〇〇) f

The Karl Fischer volumetric titration device (manufactured by Pingke Industry Co., Ltd., AQV-300) was used for the measurement. ° Hydrogen fluoride containing bismuth & if the hexa-acid clock (TipF6) used as the electrolyte is in the state of salt, the stability to moisture is weak, and it will react with water to form a fluorinated gas, but the dissociated hexa-W acid anion (PF〇 does not react with water. Therefore; 'The characteristics of ruthenium in the aqueous solution using LiPF6 are used to remove impurities from a pure water manufacturing apparatus (Japan) V [Ellix-UV3 manufactured by illipore Co., Ltd.). In pure water, the lmi electrolyte is diluted into a solution of (10), and an anion organic acid analysis column (super IC- manufactured by Dongwon Co., Ltd.) is used by an ion chromatograph (manufactured by Tosoh Corporation, 'IC-2001). AZ), an aqueous solution obtained by mixing 2.0 mm 〇 1 /L with 3.0 mmol / L of NazCOs was used as an eluent, and 3 was measured at a flow rate of 1.5 ml / min. 彳 ' 30 Examples of exemplified examples of implementing and applying the appraisal project exemplified Example 1 2 3 4 5 6 7 8 9 Nothing, no, no, no, no, no, no, no, no change, no change, no change Ϊ change and change Initialization of hydrogen fluoride concentration 30 30 30 30 30 30 30 30 30 [ppm] After the test 20 20 20 20 20 20 20 20 20 Initial moisture content 40 40 40 40 40 40 40 40 40 [ppm] 20 20 30 20 after the test 20 20 20 20 20 Evaluation item Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 No change in appearance No change, leakage, liquid leakage, leakage Leakage leakage without change Leakage hydrogen fluoride concentration [ppm] Initial 30 30 30 30 30 30 30 30 30 30 After test 20 20 250 80 150 270 270 260 40 240 Moisture content [ppm] Initial 40 40 40 40 40 40 40 40 40 40 After the test 20 20 500 60 450 480 500 490 40 470 200845458 25893pif [Table 2] Reliability test results [Table 3] Reliability test results 31 200845458 25893pif [Table 4] Reliable completion test evaluation project Lean application 13 Implementation Example 13 Example 14 Example 15 Example 16 Comparative Example 〇 No appearance ί No Ϊ No change No change No change y Expanded hydrogen fluoride concentration [ppm] Initial test After|30~ 10 30 1 〇30 30 1 f\ 30 30 Water content [ppm] #*7λΛ IPW After initial test ^~40~ ΓΤ〇~ I \J 40 10 ZU 40 20 1U 40 10 10 40 10 60 40 60 As shown in Tables 2 and 3, in the test pieces of Examples 1 to η in which the film was placed in the test piece, there was no change in appearance, and the concentration and content of hydrogen fluoride were low, and the period value was low. As a result, it has been found that when the absorbent sheet of the present invention is laminated inside the outer casing composed of the outer packaging material, the characteristics of the battery can be effectively and high, and thus a rechargeable battery excellent in durability and safety can be provided. On the other hand, in Comparative Example 1 and 4 in which the absorbent sheet was not disposed in the test piece, the ls_ship of the material and the enthalpy of the sealing portion were formed, thereby causing liquid leakage. Comparative Example of Inorganic Particles Not Mixed with Acid Absorption Function The swelling/funding inhibits an increase in water content, but is obtained when the appearance is observed. It is presumed that the reason is that the ratio of the water in the human body from the outside of the test piece to the inorganic particles of the hydrogenated/external 'unmixed person's water-repellent function produced by the action of the electrolyte, ie, lithium hexafluorophosphate, before being absorbed by the test piece, In comparison with Comparative Examples 1 and 4, it was found that there was a thirst-inhibiting effect of suppressing the concentration of hydrogen fluoride, but corrosion of the aluminum foil and peeling of the sealing portion occurred, thereby generating 32 f

200845458 25893pif placed on the ;; : 2:: T f laminated outer packaging material sealant side without matching = material: ί: List: in the mold house processing, laminated outsourcing ^ material section & wx and shot The interface of the upper _resin layer is damaged by the sulfur particles attached to the absorbing sheet on the layer μ overwrap material, and defects are generated. In Comparative Example 7 in which the water, the Moonstone knife-polished polypropylene sheet and the magnesium sulfate-dispersed polypropylene wafer were bonded together, no liquid leakage or expansion was observed, but the vaporized hydrogen concentration and water content were observed. The result is equal to or higher than the initial value. When the absorbent sheet in which the hydrotalcite-dispersed polypropylene sheet of Example 11 was dispersed with a magnesium sulfate-dispersed acrylic sheet was used, the hydrogen fluoride concentration and the water content were lower than the initial values. It is presumed that the reason is that the diffusion efficiency of hydrogen fluoride and water vapor into the absorption sheet is improved by making the same absorption sheet have an absorption function of acid and water. According to these results, it is judged that the absorption sheet having both the acid and water absorption functions in the same absorbent sheet is used, and the acid and water absorption efficiency is improved, and the battery characteristics are effectively improved. Comparative Example 8 is a case where the amount of the inorganic particles having an acid absorption function and the inorganic particles having a water absorbing function in the absorption layer is smaller than the range of the present invention. Its absorption capacity is insufficient' and liquid leakage occurs. Examples 12 to 16 are test pieces in which an absorbent sheet is also disposed in the sealing portion of the laminated outer package. As shown in Table 4, in Examples 12 to 16, it was confirmed that the hydrogen fluoride concentration and the water content reduction effect were better than those of Examples 1 to 11 in which the absorbent sheet was placed only in the test piece. On the other hand, in the case of arranging the absorbent sheet only in the sealing portion of the outer package, in the case of Example 9, 200845458, 25893pif, it was found that there was a partial inhibitory effect, but in the case of the appearance observation, the increase in the degree and the water content was found in the sealing portion. The general reason is that:

The coffee absorbs the fruit, but it will be affected; the hydrogen fluoride produced by the raw I, etc. = the second machine produced by the company (the absorption layer shown in Table 5 is limited by Chibei Co., Ltd.; the drying chamber of the degree below 1C is formed. The granules are stored on a dew point temperature machine, manufactured by: Ltd.: ^ = _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The multi-manifold square τ uses the above three extruders to create a phantom, and obtains the drying chamber from the tree without the inorganic particles by the east ^^ / absorbing layer/excluding tree riding without the inorganic particles. Preparation of two (2) absorbent sheets containing no inorganic particles on the coextruded film cut surface: 2 using a two-axis extruder equipped with a quantitative feeder (Chibei shares limited 34 200845458 25893pif company The manufactured PCM_46 two-axis extruder was melt-kneaded with the compounding agent shown in Table 5 in the amount shown in Table 5, and then formed into pellets by a cold-cut granulator. The formed particles are stored in a drying chamber having a dew point of 40 C or less. The formed particles are placed in a single axis. In the FS4 (manufactured by KK), as shown in Table 5, the resin containing the inorganic (four) resin layer was thrown into two single-axis extruders (pool PF: 制造 manufactured by FS3 〇) The coextrusion consisting of a resin layer containing no inorganic particles of inorganic particles is used in the above-mentioned three extruders. Out of the film. The coextruded film of the obtained babies was kept in the room. In the dry room where the dew point temperature is below the ship and the width is 60mm and the length is 11〇, the coextruded film is heated and compressed for 1 minute, as shown in the figure, then at 120°c, the ostrich is lowered. In the shaft containing inorganic particles, the production of the test piece containing the (3) test piece in the absorption layer was obtained. (The dry sheet C of the absorption sheet disposed only inside the test piece has the structure shown in FIG. The test piece. The following is not done at the dew point temperature of / Γ π, the dry line under the miscellaneous battery (four). The first division is made, should be with the polyene showa electrician packaging shares limited by the public 7W, length 250^ The layered body with the Ming pig is cut in the inner side to be folded in half, and the layer of the layer (the layer of the dense hydrocarbon film) is shown, and the short side is repeated. As shown in Fig. 16 (b), the other two sides (the portion shown by 1〇35 200845458 25893pif) were heat-sealed at a width of 5 mm, and two sheets of absorbent sheets having an opening on the short side were formed. 14) Clamp the folded film into a width of 11Qmm and a length of 6 (). • Remove the film (manufactured by CELGARD Co., Ltd.) to: 丨: 丨的体 = . Ratio of ethylene carbonate, dimethyl carbonate and carbonic acid The ethyl ester was mixed, and lithium hexafluorophosphate was dissolved therein to form electricity (manufactured by Kishida Chemical Co., Ltd.), 25 ml of the above electrolyte solution was injected from the opening, and the electrolytic solution was impregnated into the separator under reduced pressure. Then, the opening was heat-sealed at a width of 10 mm under conditions of °200 ° C for 5 seconds to prepare a test piece. ..., clothing (4) Preparation of test piece 2 (production of test piece in which the absorption piece is placed inside the test piece and the sealing part)

A test piece having the configuration shown in Fig. 17 was produced in the following manner. The following operations were performed in a drying chamber where the dew point temperature was -50 ° C or lower. First, the lithium-ion battery is cut with an aluminum laminate foil (Showa Electric Packaging Co., Ltd. 'ie, a laminated body with a foil between the niobium film and the poly thin film) (I 75 mm, length 250 mm, with a sealant) The layer (the layer of the polyolefin film) is folded inwardly, and the two short sides are overlapped. The absorbent sheet (14) having a width of 5 mm and a length of 120 mm is sandwiched between the other two sides (short >) The foil was heat-sealed between the foils under the condition of 20 (TC, 5 seconds, with the width of 5 sides being the one shown by the one side U0), and the shape of the bag having the opening on the short side was obtained. The sheet (14) was sandwiched between a separator (CELGARD Co., Ltd.) folded into a width of 110 mm and a length of 6 mm, and inserted from the opening of the bag to be produced. The alcohol ester, dimethyl carbonate and diethyl carbonate are mixed, and the hexafluoro coffee is transferred to the towel to form a liquid transfer (κ, in the manner of lm〇1/L 36 200845458 25893pif, and the above electrolyte is prepared from The opening part is injected to make the electric H salt pressure impregnated in the separator. Next, as shown in Fig. Η, the absorbing sheet of 10 mm and length 60 mm is used. ⑷ interposed in an opening portion, at 200C, 5 sec, 1〇mm wide opening to a test piece. ..., a f

The preparation of the absorbent sheet was carried out in accordance with the method of producing i of the absorbent sheet. In order to manufacture an absorbing layer, 15 parts by weight of hydrotalcite (DHT_4A, manufactured by Kyowa Chemical Industry Co., Ltd.) was used as the inorganic particles having an acid Wei function, and 15 parts by weight of a stainless steel sieve (As ONE) having a pore diameter (a) was used. Electromagnetic vibrating screen (manufactured by ASTM (8), manufactured by AS ONE Senses Co., Ltd.) is classified as magnesium sulfate (MG_0K-100, anhydrous sulphuric acid, alighted into a panicle) as an inorganic particle having water absorbing this force. 100 parts by weight of polypropylene (pp, prime Polypro F_744NP 'Primary Polymer Co., Ltd.) was used as the resin. As the resin for the resin layer containing no inorganic particles, low density polyethylene (LDPE, ΝΕΟ-ZEX 0234CX, manufactured by Prime Polymer Co., Ltd.) was used. The film was formed so as to form a film by a resin layer ΙΟμϊη/absorbent layer 50μηι/ inorganic resin-free resin layer 1〇μηη containing no inorganic particles, and the test piece was produced in accordance with the method 1 of the test piece. Sheet 0 Example 18 A test piece was produced in the same manner as in Example 17 except that the amounts of hydrotalcite and magnesium sulfate were changed to 30 parts by weight to 37 200845458 25893 pif, respectively. Example 19 A test piece was produced in the same manner as in Example 17 except that Fossil (Molecular Sieves 4A powder, manufactured by Ba Industrial Co., Ltd.) was used as the inorganic particles having a water absorbing function. Example 20

In addition to using smoldering hydrotalcite (DTH-4C, manufactured by Kyowa Chemical Industry Co., Ltd.) as both inorganic particles having acid absorption function and inorganic particles having water absorbing function, and adjusting the amount of mixing into weight ^, the rest A test piece was produced in the same manner as in Example 17. In the case of using the hydrotalcite oxide (KW-2200, manufactured by Kyowa Chemical Industry Co., Ltd.), it is also used as an inorganic particle having an acid absorption function, and an inorganic particle having a water absorption function, and the amount thereof is adjusted to A test piece was produced in the same manner as in Example 17 except for the case of the heavy portion. Example 22 ” ° A test piece was produced in the same manner as in Example 17 except that the resin of the absorbent layer was changed to a modified polypropylene (admer QF551, manufactured by Mitsui Chemicals, Inc.). A test piece was produced in the same manner as in Example 17 except that the resin of the absorbent layer was changed to ethylene-vinyl acetate-based copolymer (EVAFLEX® 1007, manufactured by Mitsui & DuPont Chemical Co., Ltd.).衣 38 200845458 25893pif Example 24 A test piece was produced in the same manner as in Example 17 except that the resin of the absorbent layer was changed to an ethylene-vinyl alcohol copolymer (EVALF101B, manufactured by Kuraray Co., Ltd.). [Example 25] A test piece was produced in the same manner as in Example 17 except that the resin of the absorbent layer was changed to low density polyethylene (LDPE, NEO-ZEX 0234CL, manufactured by Prime Polymer Co., Ltd.). r 4 Example 26 A test piece was produced in the same manner as in Example 17 except that the resin of the absorbent layer was changed to polydecylpentene (TPX DX845, manufactured by Mitsui Chemicals, Inc.). (Example 27) A test piece was produced in the same manner as in Example 17 except that the resin for the inorganic particle-free resin layer was changed to modified polypropylene (ADMER QF551, manufactured by Mitsui Chemicals, Inc.). Example 28: The same procedure as in Example Π except that the resin for the inorganic particle-free resin was changed to the ethylene-acetate copolymer (EVAFLEX P1007, manufactured by Mitsui & DuPont Chemical Co., Ltd.) The method was to make a test piece. Example 29 A test piece was produced in the same manner as in Example 17 except that the resin for the inorganic particle-free resin layer was changed to an ethylene-vinyl alcohol copolymer (EVAL F101B, manufactured by Kuraray Co., Ltd.) 39 200845458 25893pif. . Example 30 A test piece was produced in the same manner as in Example except that the resin for the inorganic particle-free resin layer was changed to polypropylene (PP, Prime Polypro F-744NP, manufactured by Prime Polymer Co., Ltd.). fExample 31

A test piece was produced in the same manner as in Example 以外 except that the resin for the inorganic particle-free resin layer was changed to polydecylpentene (TPXDX845, manufactured by Mitsui Chemicals, Inc.).

Example 32 A test piece was produced by the same method as that of Example 17. Example 33 A test piece was produced by the same method as the absorbent sheet of Example 18. Example 34 A test piece was produced by the same method as the absorbent sheet of Example 19. Example 35 A test piece was produced by the same method as the absorbent sheet of Example 20. Example 36 A test piece was produced by the same method as the absorbent sheet of Example 21. According to the production of the test piece 2, according to the production of the test piece 2, according to the production of the test piece 2, according to the production of the test piece 2, according to the production of the test piece 2 40 200845458 25893pif ΆΜ 37 using the same material as in the case of '17 In the method of producing the absorbent sheet 2, the absorbent sheet was produced, and a test piece was produced in accordance with the method 2 of the test piece. i. Application 38 The absorbent sheet prepared in Example 17 was allowed to stand in an environment of 25 ° C and 60% RH for one week, and then a test piece was produced in accordance with the method 2 of the test piece. Comparative Example 10 A test piece was produced in the same manner as in Example 17 except that the inorganic particles having an acid absorption function and the inorganic particles having a water absorbing function were not used. Comparative Example η A test piece was produced in the same manner as in Example 17 except that the inorganic particles having an acid absorption function were not used, and 3 parts by weight of magnesium sulfate was used as the inorganic particles having a water absorbing function. Comparative Example 12 A test piece was produced in the same manner as in Example 17 except that the inorganic particles having a water absorbing function were not mixed, and 30 parts by weight of hydrotalcite was used as the inorganic particles having an acid absorbing function. Comparative Example 13 A test piece was produced according to the method of Production 1 of the test piece without using an absorbent sheet. Comparative Example 14 The same procedure as in Example 17 was carried out except that the absorbent sheet did not have a resin layer containing no inorganic particles, and the other 41 200845458 25893pif was produced. Test piece. Comparative Example 15 Using the same absorbent sheet as in Example 17, the test piece was produced in accordance with the method of the test piece 2 ", and the absorbent sheet was not disposed inside the test piece, 'The absorbent sheet was placed only in the sealing portion, and the test was made. sheet. Comparative Example The absorbent sheet prepared in Comparative Example 14 was allowed to stand in an environment of 25 ° C and 60% RH for one week, and then a test piece was produced in accordance with the method 2 of the test piece. 42 200845458 25893pif [Table 5-1] Composition and arrangement position of the absorbent sheet: Resin layer containing no inorganic particles Absorbing layer of the absorbent sheet Position of the resin film thickness [μηι] Mixing amount of the mixing agent [Parts by weight 1 Film thickness [μιη] Test In-Chip Sealing Example 17 LDPE 10 ΡΡ 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 18 LDPE 10 ΡΡ 100 50 Configuration - Hydrotalcite 30 Magnesium Sulfate 30 Example 19 LDPE 10 ΡΡ 100 50 Configuration - Hydrotalcite 15 &gt Fushi 15 Example 20 LDPE 10 ΡΡ 100 50 Configuration - Hydrazine Hydrotalcite 30 Example 21 LDPE 10 ΡΡ 100 50 Configuration - Hydrotalcite Oxide 30 Example 22 LDPE 10 Modified Polypropylene 100 50 Configuration - Hydrotalcite 15 Sulfuric acid town 15 Example 23 LDPE 10 ethylene-vinyl acetate copolymer 100 50 configuration - hydrotalcite 15 sulfuric acid town 15 Example 24 LDPE 10 ethylene-vinyl alcohol copolymer 100 50 configuration - hydrotalcite 15 sulfuric acid town 15 Example 25 LDPE 10 LDPE 100 50 configuration of a hydrotalcite 15 sulphuric acid town 15 Example 26 LDPE 10 polymethylpentene 100 50 configuration - hydrotalcite 15 Sulfuric Acid Town 15 Example 27 Modified Polypropylene 10 PP 100 50 Configuration - Hydrotalcite 15 Magnesium Sulfate 15 Example 28 Ethylene Vinyl Acetate Copolymer 10 PP 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Apparatus 15 43 200845458 厶jpu丄[ Table 5-2] Example 29 Ethylene-Ethylene Alcohol Copolymer 10 PP 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 30 PP 10 PP 100 50 Configuration of a Hydrotalcite 15 Sulfuric Acid Town 15 Example 31 Polymethyl Pentene 10 PP 100 50 Configuration - Hydrotalcite 15 Sulfuric Acid Town 15 Example 32 LDPE 10 PP 100 50 Configuration Configuration Hydrotalcite 15 Sulfuric Acid Town 15 Example 33 LDPE 10 PP 100 50 Configuration Configuration Hydrotalcite 30 Sulfuric Acid Town 30 Example 34 LDPE 10 PP 100 50 Configuration configuration Hydrotalcite 15 Fossil 15 Example 35 LDPE 10 PP 100 50 Configuration configuration Neodymium hydrotalcite 30 Example 36 LDPE 10 PP 100 50 Configuration configuration hydrotalcite oxide 30 Example 37 LDPE 10 PP 100 50 Configuration Configuration Hydrotalcite 15 Sulfur Magnesium 15 Comparative Example 10 LDPE 10 PP 100 50 Configuration A Comparative Example LDP LDPE 10 PP 100 50 Configuration of Barium Sulfate 30 Comparative Example 12 LDP E 10 PP 100 50 Configuration - Hydrotalcite 30 Comparative Example 13 No No No No No - No. 14 - PP 100 50 Configuration of a hydrotalcite 15 Magnesium Sulfate 15 Comparative Example 15 LDPE 10 PP 100 50 - Configuration of hydrotalcite 15 Sulfuric acid Town 15 (1) Reliability Test 1 The test piece prepared above was placed in a constant temperature and humidity chamber 44 200845458 at 60 ° C and 95% RH for 30 days, and the appearance was visually observed, and the concentration of hydrogen sulfide in the liquid was measured. The amount of water. In addition, as shown below: J solution: Seoul, Hugh method for determination, hydrogen fluoride content is the root: from ΐ 曰 5 曰 method into the 仃 just set. The test results are shown in Tables 6 to 8. The color and the argon gas replacement dew point temperature is _5 〇 ° C or less (AS, SG.l 〇〇〇 " ^ ^ measured as electrolyte used lithium hexafluorophosphate (TiPF) state' for moisture stability Sexually weak, it will react with water to dissociate the hexa-acid anion yang.) but it will not collide with water. 2) Using a six-acid clock (LiPF6) in a dilute aqueous solution, the mosquito used to remove impurities from the manufacturing device (1 E 1X-UV3 manufactured by JEOL Ltd.), and diluting 1 ml of the electrolyte into (10) (5) The solution, the suppression mode of the ion chromatograph (manufactured by Dong # Co., Ltd. 'IC-2001), using an anion organic acid analysis column (super IC_AZ manufactured by Tosoh Corporation), using 2 〇Inm〇1/L An aqueous solution mixed with 3. (hnm〇l/L of ΝΜΟ3 was used as an eluent, and 3 was measured at a flow rate of 1.5 ml/min. 45 200845458 25893ριί

[Table 6] Results of Reliability Test 1 Evaluation Item Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 No change in appearance No change No change No Change No change No change No change No change No change No change Hydrogen fluoride concentration [ppm] Initial 30 30 30 30 30 30 30 30 30 30 After the test 20 20 20 20 20 20 20 20 20 20 Water content [ppm] Initial 40 40 40 40 40 40 40 40 40 40 After the test 20 20 20 20 20 20 20 20 20 20 Evaluation item Example 27 Example 28 Example 29 Example 30 Example 31 Comparison Example 10 Comparative Example 11 Comparative Example 12 Comparison Example 13 Comparative Example 14 No change in appearance No change No change No change No change Liquid leakage Expansion liquid Leakage No change Fluoride concentration [ppm] Initial 30 30 30 30 30 30 30 30 30 30 After test 20 20 20 20 20 250 60 150 270 20 Moisture content [ppm] Initial 40 40 40 40 40彳40 40 40 40 40 After the test 20 20 20 20 20 500 30 450 480 20 [Table 7] Results of reliability test 1 46 200845458 [Table 8]

On the other hand, in Comparative Example 1〇 and Comparative Example 13 in which the absorbent sheet was not disposed during the test month, the occurrence of the (4) rot-like closure portion of the outer packaging material occurred. In the case where the inorganic particles having the acid (four) function were not mixed, the effect of suppressing the increase in the water content was found in Example 11, but the swelling was observed at the appearance of the observation. It is presumed that the reason is that hydrogen is immersed in the outside of the test piece, and the hydrogen fluoride is generated by the action of the electrolyte, that is, lithium hexafluorophosphate, before being absorbed by the absorbent sheet. Further, in Comparative Example 12 in which inorganic particles having a water absorbing function were not mixed, compared with Comparative Example 10 and Comparative Example 13, it was found that 47 200845458 25893ριί ==: π: but the ratio of occurrence of _corrosion-disposing absorption sheet == Two-part:: There is an increase ratio that can effectively suppress the concentration of hydrogen and water content.

The effect is obtained, but it is affected by the absorption of moisture by the vaporization of nitrogen, etc. Than ^,, =^ immersed in the micro-cause ^ temperature is _5G °G "" single (four) ^ compared to the 11 concentration and water content is transferred to the embodiment 17 _ιιΐ ί ^ 疋 'If you will compare The absorption sheet expands at 25 ° C, production and on the disc, and the silk is hydrogenated. (2) Reliability test 2

In order to evaluate the operability of the absorbent sheet, as in Example 38 and Comparative Example 16, the prepared absorbent sheet was placed in an environment of 25 ° and 60% RH, and then "made" to be the same as the reliability test. Evaluation of the style. The test results are shown in Table 9. [Table 9] Results of the reliability test 2 Evaluation item Example 38 μΖ52~ No change in appearance Fluoride argon concentration [ppm] Initial 30 After the test 10^~~1 Initial in the water 40 40 [ppm] 10 tin 48 after the test 200845458—According to Table 9, it is shown that 'the absorption sheet has a resin layer containing no inorganic particles=38, even if it is placed in a hygroscopic environment, the hydrogen fluoride concentration and water content are reduced from the initial value, and the reliability test 1 is obtained. As a result of the same, in Comparative Example 16 in which the absorbent sheet did not have a resin layer containing no inorganic particles, the appearance was swollen, and the concentration of cesium fluoride and the water content were confirmed to increase. As a result of the above, the absorbent sheet of the present invention has an effect of lowering the influence of humidity in the production of the absorbent sheet and the production environment of the battery, and therefore it is possible to provide a rechargeable battery which is excellent in productivity. (3) SEM observation * In order to investigate whether or not the inorganic particles were detached from the absorbent sheet, the end faces of the absorbent sheets produced in Examples Π and J7 and Comparative Example 14 were observed by (scanning electron microscope).

In Comparative Example 14 in which the film did not have a resin layer containing no inorganic particles, η ' was broken on the end surface after the absorption was broken, and the particles flanked by the end surface were formed. However, in fact, J ^ found such a care. The knot shows that the absorbent sheet of the present invention having a resin layer of the organic particles, and the detachment, can provide safety and durability. 2] Although the present invention has been disclosed by way of example, It is not used: Ming: Anyone who is familiar with this skill 'can not change from the spirit of the invention II' can make some changes and run Han, so this = the attached towel should be full-time _ defined. n 蔓干围 49 200845458 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a positive (negative) electrode plate of a lithium secondary battery of the present invention. Fig. 2 is a cross-sectional view showing an example of a discharge element of a lithium secondary battery of the present invention. Fig. 3 is a plan view showing an example of a lithium secondary battery of the present invention. Fig. 4 is a plan view showing an example of a rechargeable battery of the present invention. Fig. 5 is a cross-sectional view showing an example of an absorbent sheet of the present invention. Fig. 6 is a perspective view showing an example of an absorbent sheet of the present invention. Fig. 7 is a perspective view showing an example of application of the absorbent sheet of the present invention. Fig. 8 is a perspective view showing an example of application of the absorbent sheet of the present invention. Fig. 9 is a cross-sectional view showing an example of a lithium secondary battery of the present invention. Fig. 10 is a cross-sectional view showing an example of a lithium secondary battery of the present invention. Fig. 11 is a cross-sectional view showing an example of a lithium secondary battery of the present invention. Fig. 12 is a cross-sectional view showing an example of a lithium secondary battery of the present invention. Fig. 13 is a cross-sectional view showing an example of a lithium secondary battery of the present invention. Fig. 14 is a perspective view showing a test piece produced by producing a test piece without a resin layer containing no inorganic particles. Fig. 15 is a perspective view showing a test piece produced by producing 2 a test piece which does not have a resin layer containing no inorganic particles. Fig. 16 is a perspective view showing a test piece produced by producing a test piece having a resin layer containing no inorganic particles. Fig. 17 is a perspective view showing a test piece produced by producing 2 a test piece having a resin layer containing no inorganic particles. 50 200845458 [Explanation of main component symbols] 1 · Cathode material 2 : Anode material 3 · Positive electrode collector * 4: Negative electrode collector 5 : Positive plate 6 : Negative plate 7 : Electrolyte-containing layer 8 : Discharge element 9: Laminated outer packaging material 9a: Molded laminated outer covering material 10: sealing portion 11: adhesive film 12: positive electrode terminal 13: negative electrode terminal 14: absorbent sheet I 15 : resin layer 16 containing no inorganic particles: absorbent layer 17: Laminate 51 of the absorbent sheet and the separator

Claims (1)

200845458 X. Patent application scope: A bell charging battery in which an outer packaging body composed of a laminated outer covering material comprising a metal layer and a synthetic resin layer is enclosed with a positive electrode material layer and a negative electrode material layer and has lithium a discharge element of a layer of a salt electrolyte, characterized in that: the discharge element and the absorption sheet are simultaneously sealed in the outer package; the absorption sheet has an absorption layer composed of one or more resin layers, and the resin layer is An inorganic particle having an acid absorption function and an inorganic particle having water and a work force, wherein the absorption layer contains at least 5 parts by weight of the above-mentioned inorganic particles having an acid absorption function and the above-mentioned water with respect to the resin 100 Absorbing inorganic particles. The lithium rechargeable battery according to claim 1, wherein the absorbent sheet is laminated on both surfaces of the absorbent layer, and further has a resin layer containing no inorganic particles. The rechargeable battery according to claim 1 or 2, wherein the outer casing has a sealing portion, and at least a part of the sealing portion is sealed by the t-absorbing sheet. 4. The lithium rechargeable battery according to claim 1 or 2, wherein the layer having the lithium salt electrolyte is impregnated with an electrolyte for dissolving the M salt electrolyte in a nonaqueous solvent or A porous resin film of a gel electrolyte. 5. The lithium charging battery according to claim 1 or 2, wherein the absorption layer is a single sheet containing the inorganic particles having the acid absorption function and the inorganic particles having the water absorption function. 52 200845458 The resin layer is composed of a resin layer comprising a resin layer containing the above-described inorganic particles having an acid absorption function and a resin layer containing the inorganic particles having the water absorption function. 6. The lithium rechargeable battery according to claim 1 or 2, wherein the inorganic particles having an acid absorption function are selected from the group consisting of One or more of the group consisting of zeolite, hydrotalcite, smoldering hydrotalcite and hydrotalcite oxide, the inorganic particles having water absorption function are selected from the group consisting of 'fuss, smoldering hydrotalcite, hydrotalcite One or more of the group consisting of cerium and magnesium sulfate. 7. The lithium-ion rechargeable battery according to claim 1 or 2, wherein the resin in the absorption layer contains a copolymer selected from the group consisting of polyethylene, polypropylene, and butene, and ethylene. Copolymer with propylene, copolymer of polymethane pentaerythritol and ethyl acetate, 2 kinds of acetamethylene and ethylene glycol, ionic polymer, modified polyethylene and modified poly- 1 or more. R8 Gan t application patent range No. 1 or 2 of the clock charging electricity / eight, in the above-mentioned absorption layer radiation cross-linking treatment. 9. The electric battery according to item 4 of claim 2, which is characterized in that the resin in the tree layer of the inorganic particles is not selected from the group consisting of: material, polydi::I ethylene and butene. Copolymer, copolymer of propylene and ethylene: alcohol::, copolymer of ethylene and vinyl acetate, ethylene and constituents = polymer, modified red olefinic polypropylene, and There is no one or more of the group. A lithium rechargeable battery according to claim 2 of the patent scope, characterized in that it has a function of 53 200845458 ---λ g. ·Responsible for the whole layer of the resin layer that is loaded with the money particles π·γ Please patent scope! Item or the bell filling treatment described in item 2 is magnetic. The double-sided or arbitrary-surface of the above-mentioned absorbent sheet is subjected to a fortune, and the clock of the first or second item is charged. Forming 54 on either or both sides of the sheet