JP7229854B2 - NONAQUEOUS ELECTROLYTE BATTERY AND MANUFACTURING METHOD THEREOF - Google Patents

Description

TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte battery having high productivity and excellent sealability at high temperatures, and a method for producing the same.

2. Description of the Related Art Non-aqueous electrolyte batteries having a flat battery container, which are called coin-shaped batteries and button-shaped batteries, are used in various applications by taking advantage of their characteristics such as high capacity and high voltage. Along with the expansion of the field of application, flat-type non-aqueous electrolyte batteries are required to improve various characteristics.

For example, in view of the fact that there are cases where a tire punctures while a vehicle is running and leads to a serious accident, a tire pressure monitoring system (Tire Pressure Monitoring System) is being developed to ensure safety while the vehicle is running. ) is becoming popular. A flat non-aqueous electrolyte battery is used as the power supply for the system, but since the system is installed inside the tire, which is in a hot and humid environment, the battery that serves as the power supply also has long-term characteristics. Sealing performance that can be maintained is required.

In order to satisfy the above requirements, gaskets for flat batteries, which are particularly used for heat-resistant applications, use fluororesins such as tetrafluoroethylene-perfluoroalkoxyethylene copolymers, polyphenylene ethers, polysulfones, polyarylates, and polyethersulfones. , polyphenylene sulfide, polyetheretherketone, and other heat-resistant resins having a melting point exceeding 240° C. have been proposed (Patent Document 1).

By forming a gasket using the above resin, it is possible to obtain a gasket whose strength is suppressed from being lowered even in a high temperature atmosphere of 100° C. or higher. It is necessary to suppress moisture intrusion, and a resin composition with a low moisture permeation rate is desired as a gasket material (Patent Document 2).

Polyphenylene sulfide is an example of a resin that is excellent in strength, heat resistance, and moisture resistance and can meet the above requirements. (Patent Documents 3 and 4).

JP 2005-216867 A JP 2001-126684 A JP-A-10-97852 JP 2008-177196 A

By the way, linear polyphenylene sulfide has a high value of lightness L ^* in the L ^* a ^* b ^* color space and generally has a whitish color. , it is difficult to distinguish only by color. For this reason, in the process of arranging the separator in the outer can or sealing plate to which the gasket is attached, even if an attempt is made to detect misalignment of the separator by visual inspection or image inspection, it cannot be determined correctly whether it will take time or not. A problem arises in that it becomes difficult to remove defective products in which the separator is displaced from the predetermined position.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a non-aqueous electrolyte battery with high productivity and excellent sealing performance at high temperatures, and a method for producing the same.

In a first aspect of the non-aqueous electrolyte battery of the present invention, a positive electrode, a negative electrode, a separator are placed in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. and a non-aqueous electrolyte, the gasket is composed of a crosslinked polyphenylene sulfide resin composition, and the value of lightness L ^* in the L ^* a ^* b ^* color space of the resin composition is 74 or less. It is characterized by being

In a second aspect of the non-aqueous electrolyte battery of the present invention, a positive electrode and a negative electrode are placed in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. , a separator and a nonaqueous electrolyte are accommodated, the gasket is composed of a crosslinked polyphenylene sulfide resin composition, and the value of lightness L ^* in the L ^* a ^* b ^* color space of the resin composition is It is characterized by being a value that is 12 or more lower than the value of lightness L ^* in the L ^* a ^* b ^* color space of the separator.

That is, a non-aqueous electrolyte in which a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte are accommodated in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. When manufacturing a battery, by forming the gasket from a crosslinked polyphenylene sulfide resin composition, the brightness L in the L ^* a ^* b ^* color space is higher than that of a gasket formed from a linear polyphenylene sulfide resin composition. ^* can be easily adjusted to a low value, and a gasket with a lightness L ^* of 74 or less can be obtained without containing a pigment or the like.

Therefore, the relative difference in lightness L ^* between the gasket and the separator can be increased to, for example, 12 or more, and misalignment of the separator can be easily detected by visual inspection or image inspection.

ADVANTAGE OF THE INVENTION According to this invention, the non-aqueous electrolyte battery with high productivity and excellent sealing property at high temperature, and its manufacturing method can be provided.

1 is a longitudinal sectional view schematically showing an example of a non-aqueous electrolyte battery of the present invention; FIG.

FIG. 1 shows a longitudinal sectional view schematically showing one example of the non-aqueous electrolyte battery of the present invention. The non-aqueous electrolyte battery shown in FIG. The open end of the outer can 5 is tightened inward, and the gasket 7 abuts against the sealing plate 6, thereby sealing the opening of the outer can 5 and forming a sealed structure inside the battery. It's becoming That is, the non-aqueous electrolyte battery 1 shown in FIG. A power generating element including a positive electrode 2, a negative electrode 3 and a separator 4 is loaded, and a non-aqueous electrolyte (not shown) is further accommodated. The outer can 5 and the sealing plate 6 are made of metal such as stainless steel, the outer can 5 also serves as a positive electrode terminal, and the sealing plate 6 also serves as a negative electrode terminal.

In the first aspect of the non-aqueous electrolyte battery of the present invention, the gasket interposed between the outer can and the sealing plate has a lightness L ^* value in the L ^* a ^* b ^* color space of 74 or less, preferably It is composed of a crosslinked polyphenylene sulfide resin composition of 70 or less.

Polyolefin, for example, is generally used as a material for separators in non-aqueous electrolyte batteries. Such separators have a lightness L ^* value of, for example, 86 or more in the L ^* a ^* b ^* color space. Therefore, if the gasket is composed of the crosslinked polyphenylene sulfide resin composition having the above brightness, the gasket and the separator can be easily distinguished by visual inspection or image inspection. Therefore, if such a gasket is used, misalignment of the separator can be easily detected by visual inspection or image inspection when the general-purpose separator is placed in the outer can or sealing plate to which the gasket is attached. Non-defective products can be easily eliminated, and the productivity of non-aqueous electrolyte batteries can be improved.

Further, in the second aspect of the non-aqueous electrolyte battery of the present invention, the value of the brightness L ^* in the L ^* a ^* b ^* color space of the gasket interposed between the outer can and the sealing plate is equal to the L It is composed of a crosslinked polyphenylene sulfide resin composition that is 12 or more, more preferably 16 or more, and particularly preferably 20 or more lower than the value of lightness L ^* in the ^* a ^* b ^* color space.

If the gasket is composed of a crosslinked polyphenylene sulfide resin composition that satisfies the above value in lightness L ^* with respect to the separator, the gasket and the separator can be easily distinguished by visual inspection or image inspection. When placing the separator in the outer can or sealing plate, misalignment of the separator can be accurately detected by visual inspection or image inspection, so defective products can be easily eliminated, and highly reliable non-aqueous electrolyte batteries can be manufactured. be able to.

In addition, by lowering the lightness L ^* value of the crosslinked polyphenylene sulfide resin composition constituting the gasket, the separator has a lightness L ^* lower than that of a general-purpose polyolefin separator (a separator with a lightness L ^* value of less than 85). is used, a certain or more difference can be provided between the values of the brightness L ^* of the gasket and the separator, and misalignment of the separator can be easily detected by visual inspection or image inspection.

Therefore, also in the second aspect of the non-aqueous electrolyte battery of the present invention, the cross-linked polyphenylene sulfide resin composition constituting the gasket interposed between the outer can and the sealing plate has an L ^* a ^* b ^* color space The value of lightness L ^* is preferably 74 or less, more preferably 70 or less.

The L ^* a ^* b ^* color space referred to in this specification is a color system represented by three coordinates standardized by the Commission Internationale de l'Eclairage (CIE), and has lightness L ^* and chromaticity (a ^* b ^* ), and each value of L ^* a ^* b ^* can be measured by a spectrodensitometer or the like.

As described above, the non-aqueous electrolyte battery of the present invention achieves improved reliability by adopting a configuration that facilitates detection of defective products in the battery assembly process.

In addition, since the crosslinked polyphenylene sulfide resin has high strength and is excellent in heat resistance and moisture resistance, the non-aqueous electrolyte battery of the present invention includes a resin composition containing this in both the first aspect and the second aspect. By using a gasket made of material, it is possible to ensure good sealing performance (especially sealing performance at high temperatures).

A crosslinked polyphenylene sulfide resin is a polyphenylene sulfide having a two-dimensional or three-dimensional crosslinked structure. It is obtained by a method of forming a crosslinked structure by heat treatment with.

The crosslinked polyphenylene sulfide resin composition may contain only the crosslinked polyphenylene sulfide resin, but may contain other components together with the crosslinked polyphenylene sulfide resin within a range that does not impair the heat resistance and moisture resistance of the resin composition. , and may be contained within a range that does not significantly affect the value of lightness L ^* in the L ^* a ^* b ^* color space.

The content of the crosslinked polyphenylene sulfide resin in the crosslinked polyphenylene sulfide resin composition should be 90% by mass or more from the viewpoint of ensuring good gasket strength, heat resistance, and moisture resistance due to the use of the crosslinked polyphenylene sulfide resin. is preferred. Since the crosslinked polyphenylene sulfide resin composition may be composed of only the crosslinked polyphenylene sulfide resin, the upper limit of the content of the crosslinked polyphenylene sulfide resin in the crosslinked polyphenylene sulfide resin composition is 100% by mass. However, when other components are also added, the content of the crosslinked polyphenylene sulfide resin is preferably 99% by mass or less from the viewpoint of ensuring the effects of their use.

Examples of components other than the crosslinked polyphenylene sulfide resin that can be added to the crosslinked polyphenylene sulfide resin composition include polyolefin elastomers and filler materials (inorganic particles, etc.). When the crosslinked polyphenylene sulfide resin composition also contains a polyolefin elastomer, the flexibility of the resin composition is improved. can be higher.

When a polyolefin elastomer is contained in a crosslinked polyphenylene sulfide resin composition, a modified olefin copolymer having a functional group such as a carboxylic acid group, an amide group, or an epoxy group, or an α having 3 to 20 carbon atoms with ethylene. - A copolymer with an olefin is exemplified, and the content thereof is preferably 1% by mass or more from the viewpoint of satisfactorily ensuring the effect of using the polyolefin elastomer. However, if the amount of the polyolefin-based elastomer in the crosslinked polyphenylene sulfide resin composition is too large, the moisture permeability of the resin composition may increase, and the moisture resistance of the gasket may decrease. Therefore, the content of the polyolefin elastomer in the crosslinked polyphenylene sulfide resin composition is preferably 20% by mass or less, more preferably 10% by mass or less.

Crosslinkable polyphenylene sulfide resin compositions, including, for example, those containing polyolefin-based elastomers, are available on the market and can be obtained and used to manufacture gaskets.

The gasket can be formed by injection molding a crosslinked polyphenylene sulfide resin composition.

The gasket preferably has an average surface roughness Ra of 5 μm or less. In this case, the adhesion between the outer can and the sealing plate is further improved, so that the non-aqueous electrolyte battery can be more effectively sealed. .

The average surface roughness Ra of the gasket referred to in this specification is the arithmetic average roughness specified in JIS B 0601. -21D"), observe 3 fields of view of 90 μm × 90 μm at 50 times magnification, measure with 900 × 900 pixels for each field of view, and calculate by arithmetically averaging the absolute value from the average line of each point It is a value obtained by further arithmetically averaging the numerical values of each field of view obtained.

The non-aqueous electrolyte battery of the present invention can take the form of a primary battery (non-aqueous electrolyte primary battery), and can also take the form of a secondary battery (non-aqueous electrolyte secondary battery). .

The positive electrode of the non-aqueous electrolyte battery includes a positive electrode mixture molded body obtained by molding a positive electrode mixture containing a positive electrode active material, a conductive aid, and a binder into pellets, or a positive electrode formed from the positive electrode mixture. A structure in which a mixture layer is formed on the surface of a current collector can be used.

Examples of positive electrode active materials include manganese dioxide; vanadium oxide, niobium oxide, titanium oxide, sulfides such as iron disulfide; graphite fluoride; Li _x Mn ₃ O ₆ (0<x<2), Li _x MnO Lithium-containing manganese oxides such as ₂ (0<x<1 ₎ , _{LixTi5 / 3O4} (4/3≤x<7/3), _LiMn2O4 and some of these elements with other elements Composite oxide with substituted spinel structure, lithium-containing layered structure represented by Li _1+x M ¹ O ₂ (−0.1<x<0.1, M ¹ : Co, Ni, Mn, Al, Mg, etc.) various lithium-containing composite oxides such as composite oxides and olivine-type compounds represented by LiM ² PO ₄ (M ² : Co, Ni, Mn, Fe, etc.);

Examples of the layered lithium-containing composite oxide include lithium cobaltate such as LiCoO ₂ and LiNi _1-a Co _a-b Al _b O ₂ (0.1≦a≦0.3, 0.01≦b≦0 .2), etc., and oxides containing at least Co, Ni and Mn (LiMn _1/3 Ni _1/3 Co _1/3 O ₂ , LiMn _5/12 Ni _5/12 Co _1/6 O ₂ , LiNi _{3 /5Mn1 /} 5Co1 _{/ 5O2} , etc.).

Conductive agents related to the positive electrode mixture include, for example, acetylene black; ketjen black; carbon blacks such as channel black, furnace black, lamp black, and thermal black; carbon fibers; and other carbon materials such as metal fibers. carbon fluoride; metal powders such as copper and nickel; organic conductive materials such as polyphenylene derivatives;

Examples of the binder for the positive electrode mixture include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), and polyvinylpyrrolidone (PVP).

In the case of a positive electrode mixture molded body, the positive electrode can be produced by, for example, press-molding a positive electrode mixture prepared by mixing a positive electrode active material, a conductive aid, a binder, etc. into a predetermined shape. .

In the case of a positive electrode having a positive electrode material mixture layer and a current collector, for example, the positive electrode active material, conductive aid, binder, etc. are mixed with water or an organic solvent such as N-methyl-2-pyrrolidone (NMP). to prepare a positive electrode mixture-containing composition (slurry, paste, etc.) (the binder may be dissolved in a solvent), apply it on the current collector, dry it, and calender it if necessary. It can be manufactured through a step of applying a press treatment such as.

However, the positive electrode is not limited to those produced by each of the methods described above, and may be produced by other methods.

As for the composition of the positive electrode mixture related to the positive electrode, the amount of the positive electrode active material is preferably 80 to 98% by mass, and the content of the conductive aid is preferably 1.5 to 10% by mass. is preferably 0.5 to 10% by mass.

In the case of the positive electrode mixture molded body, the thickness is preferably 0.15 to 4 mm. On the other hand, in the case of a positive electrode having a positive electrode mixture layer and a current collector, the thickness of the positive electrode mixture layer (thickness per side of the current collector) is preferably 30 to 300 μm.

When a current collector is used for the positive electrode, examples of the current collector include those made of stainless steel such as SUS316, SUS430, and SUS444; aluminum and aluminum alloy; Wire mesh, expanded metal, lath mesh, punching metal, metal foam, foil (plate) and the like can be exemplified. The thickness of the current collector is preferably 0.05 to 0.2 mm, for example.

The negative electrode of the non-aqueous electrolyte battery has a structure in which a negative electrode mixture layer containing a negative electrode active material, a binder, etc. is formed on a current collector, a structure in which a metal foil as a negative electrode active material is used as it is, and a may have a structure in which a metal foil serving as a negative electrode active material and a current collector are laminated.

When the non-aqueous electrolyte battery is a primary battery, negative electrode active materials include metallic lithium and lithium alloys (lithium-aluminum alloys).

When the non-aqueous electrolyte battery is a secondary battery, negative electrode active materials include metallic lithium, lithium alloys (lithium-aluminum alloys), graphite, pyrolytic carbons, cokes, vitreous carbon, organic high carbon materials such as sintered molecular compounds, mesocarbon microbeads, carbon fibers and activated carbon; alloys containing elements such as Si and Sn that can be alloyed with lithium; oxides of Si and Sn;

For the binder in the case of the negative electrode having the negative electrode mixture layer, the same binders as those exemplified above as the binders related to the positive electrode mixture can be used. In addition, the negative electrode mixture layer may contain a conductive aid, and as the conductive aid in that case, the same various conductive aids exemplified above as the conductive aid related to the positive electrode mixture may be used. can be done.

In the case of a negative electrode having a negative electrode mixture layer and a current collector, for example, a negative electrode active material, a binder, and, if necessary, a conductive aid are dispersed in water or an organic solvent such as NMP to form a negative electrode mixture. A step of preparing a containing composition (slurry, paste, etc.) (the binder may be dissolved in a solvent), coating it on a current collector, drying it, and subjecting it to press treatment such as calendering, if necessary. can be manufactured via

However, the negative electrode is not limited to those manufactured by each of the above methods, and may be manufactured by other methods.

As for the composition of the negative electrode mixture layer, for example, the content of the negative electrode active material is preferably 70 to 99% by mass, and the content of the binder is preferably 1 to 30% by mass. Moreover, when a conductive aid is used, the content of the conductive aid in the negative electrode mixture layer is preferably 1 to 20% by mass. Furthermore, the thickness of the negative electrode mixture layer (thickness per side of the current collector) is preferably 1 to 100 μm.

For the current collector of the negative electrode, for example, foils, punched metals, expanded metals, nets, etc. made of copper, stainless steel, nickel, titanium or alloys thereof can be used. Foil is preferably used.

A resin-made microporous membrane (microporous film) or a non-woven fabric can be preferably used for the separator of the non-aqueous electrolyte battery.

The resin forming the separator is preferably polyolefin such as polyethylene (PE) or polypropylene (PP). If the separator is made of polyolefin, the value of lightness L ^* in the L ^* a ^* b ^* color space is, for example, 86 or more, so the lightness L ^* of the crosslinked polyphenylene sulfide resin composition constituting the gasket is relatively large. , making it easier to distinguish from the gasket by visual inspection or image inspection.

When the separator is a microporous membrane, the thickness is preferably 10 to 30 μm, and when it is a nonwoven fabric, the thickness is preferably 20 to 500 μm.

For the non-aqueous electrolyte of the non-aqueous electrolyte battery, for example, a solution (non-aqueous electrolyte) in which a lithium salt is dissolved in an organic solvent is used. Lithium salts in this case include _inorganic lithium salts such as _{LiClO4 , LiPF6} , _LiBF4 , _{LiAsF6 and LiSbF6 ; LiCF3SO3} , _LiCF3CO2 , _Li2C2F4 ( _SO3 ) ₂ , LiN(CF ₃ SO ₂ ) ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiC _n F _2n+1 SO ₃ (n≧2), LiN(R _f OSO ₂ ) ₂ [wherein R _f is a fluoroalkyl group], etc. organic lithium salt; and the like.

Examples of organic solvents for the non-aqueous electrolyte include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; chains such as methyl propionate; cyclic esters such as γ-butyrolactone; chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme, and tetraglyme; cyclic ethers such as dioxane, tetrahydrofuran, and 2-methyltetrahydrofuran; nitriles such as pionitrile and methoxypropionitrile; sulfites such as ethylene glycol sulfite; and the like. These may be used singly or in combination of two or more. In addition, in order to obtain a battery with better characteristics, it is desirable to use a combination of solvents such as a mixed solvent of ethylene carbonate and chain carbonate that can obtain high electrical conductivity.

In addition, vinylene carbonates, 1,3-propanesultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, and fluorobenzene are added to these non-aqueous electrolytes for the purpose of improving properties such as safety, charge-discharge cycle, and high-temperature storage. , t-butylbenzene and the like can be added as appropriate.

The concentration of the lithium salt in the nonaqueous electrolyte is preferably 0.5 to 1.5 mol/l, more preferably 0.9 to 1.25 mol/l.

Moreover, the non-aqueous electrolyte may be made into a gel (gel electrolyte) using a gelling agent such as a known polymer.

A polymer electrolyte or a solid electrolyte can also be used as the non-aqueous electrolyte instead of the non-aqueous electrolyte.

The shape of the non-aqueous electrolyte battery in a plan view may be circular or polygonal such as quadrangular (square or rectangular). Moreover, in the case of a polygon, the corners thereof may be curved.

The nonaqueous electrolyte battery of the present invention can be applied to the same uses as conventionally known nonaqueous electrolyte batteries (primary batteries or secondary batteries).

The present invention will be described in detail below based on examples. However, the following examples do not limit the present invention.

(Example 1)
A positive electrode mixture prepared by mixing manganese dioxide, which is a positive electrode active material, carbon black, which is a conductive agent, and PTFE, which is a binder, in a mass ratio of 93:3:4, is molded, and has a diameter of 16 mm. A positive electrode (positive electrode mixture compact) having a thickness of 1.8 mm was obtained.

In addition, as a precursor for constituting the negative electrode, an aluminum foil having a thickness of 10 μm was press-bonded to one side of a lithium foil having a thickness of 0.6 mm, and this was punched into a circle having a diameter of 16 mm to form a lithium layer and an aluminum layer. A laminate was obtained.

Next, LiClO ₄ was dissolved at a concentration of 0.5 mol/l in a mixed solvent in which propylene carbonate and 1,2-dimethoxyethane were mixed at a volume ratio of 1:1. % to prepare a non-aqueous electrolyte.

The positive electrode, the laminate of the lithium layer and the aluminum layer, and the nonaqueous electrolyte are used, and the gasket is composed of 100 parts by mass of a crosslinked polyphenylene sulfide resin and a copolymer of ethylene and glycidyl methacrylate (mass ratio: 88:12) and 7 parts by mass. A ring gasket (average surface roughness: 0.6 μm) made of a resin composition (polymer alloy) is used, and the separator is a PPS nonwoven fabric (thickness 400 μm) was used to assemble a coin-shaped non-aqueous electrolyte primary battery according to the following procedure.

First, after attaching a gasket to the sealing plate, the laminate for constituting the negative electrode is placed on the inner bottom surface of the sealing plate so that the lithium layer is in contact with the sealing plate. placed on the body. At this time, the image data of the entire sealing plate on which the separator is arranged is captured by a camera, the positions of the gasket and the separator are determined from the image data, and the position of the separator that is displaced from the gasket by a certain amount or more is detected. In this manner, the assembly apparatus is constructed so that the sealing plates with the separators not arranged at the predetermined positions are sorted out and the battery is assembled using only the sealing plates with the separators arranged correctly.

After placing the positive electrode (mixture molded body) on the separator of the selected sealing plate and further injecting the non-aqueous electrolyte, the outer can is covered from above and the opening is crimped to seal. A coin-shaped non-aqueous electrolyte primary battery having a diameter of 20 mm and a height of 3.2 mm was assembled with the structure shown in FIG.

In the assembly process, the laminate of the lithium layer and the aluminum layer is brought into contact with the non-aqueous electrolyte, so that the aluminum layer reacts with the lithium in the battery, and the lithium-aluminum alloy layer is formed on the surface of the negative electrode. was formed.

Also, three plates of the resin composition constituting the gasket were prepared, and the lightness L ^* of the resin composition was measured using a reflection spectrodensitometer manufactured by X-Rite (X-rite 939).

After calibration ^with a white reference plate and a black reference plate, the lightness L ^* was measured with a measurement spot size of 3.4 mm and the average value was calculated. It became 65.0.

The separator was also used as a measurement sample, and the brightness L ^* of three separators was measured in the same manner to obtain the average value. The average brightness L ^* of the separator was 89.0. The difference in lightness L ^* between the constituent resin composition and the separator was 24.0.

(Comparative example 1)
A circular gasket (average surface roughness: 0.6 μm) made of linear polyphenylene sulfide resin was used as the gasket. When the lightness L ^* of the resin composition constituting the gasket was measured in the same manner as in Example 1, it was 78.3, and the difference in lightness L ^* from the separator was 10.7. After that, when an attempt was made to assemble a coin-type non-aqueous electrolyte primary battery in the same manner as in Example 1, the difference in brightness between the gasket and the separator was so small that the position of the separator could not be detected correctly.

Therefore, the positions of the separators were visually determined using a magnifying glass, and the sealing plates in which the separators were correctly arranged were selected to assemble coin-type non-aqueous electrolyte primary batteries.

The batteries of Example 1 and Comparative Example 1 were held in a constant temperature bath at 100° C. for 75 days, taken out after storage and allowed to cool, and an alternating current of 1 kHz was applied to the batteries cooled to room temperature to measure the internal resistance of the batteries. bottom. The internal resistance of the battery before high-temperature storage was also measured in advance, and the degree of increase in internal resistance before and after high-temperature storage was used to evaluate the sealing performance of the gasket.

In addition, the batteries of Example 1 and Comparative Example 1 were held in a constant temperature bath at 100° C. for 75 days, taken out after storage, allowed to cool, and discharged by connecting a 400 Ω discharge resistor to the battery cooled to room temperature, The closed circuit voltage (CCV) of the battery was measured 1 second after the start of discharge. The sealing performance of the gasket was evaluated by the discharge voltage of the battery after high-temperature storage.

Table 1 shows the measurement results.

From the results shown in Table 1, the battery of Example 1 using the gasket composed of the crosslinked polyphenylene sulfide resin composition was composed of the conventional linear polyphenylene sulfide resin composition even after high-temperature storage. It exhibited excellent characteristics equivalent to those of the battery of Comparative Example 1 using a gasket, and was confirmed to have excellent sealing properties.

REFERENCE SIGNS LIST 1 non-aqueous electrolyte battery 2 positive electrode 3 negative electrode 4 separator 5 outer can 6 sealing plate 7 gasket

Claims (9)

A non-aqueous electrolyte battery in which a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte are accommodated in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. There is
The gasket is composed of a crosslinked polyphenylene sulfide resin composition,
A non-aqueous electrolyte battery, wherein the resin composition has a lightness L ^* value of 74 or less in an L ^* a ^* b ^* color space. 2. The non-aqueous electrolyte battery according to claim 1, wherein the resin composition has a lightness L ^* value of 70 or less in the L ^* a ^* b ^* color space. A non-aqueous electrolyte battery in which a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte are accommodated in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. There is
The gasket is composed of a crosslinked polyphenylene sulfide resin composition,
The value of lightness L ^* in the L ^* a ^* b ^* color space of the resin composition is lower than the value of lightness L ^* in the L ^* a ^* b ^* color space of the separator by 12 or more. non-aqueous electrolyte battery. The value of lightness L ^* in the L ^* a ^* b ^* color space of the resin composition is a value lower than the value of lightness L ^* in the L ^* a ^* b ^* color space of the separator by 20 or more. The non-aqueous electrolyte battery described. 5. The nonaqueous electrolyte battery according to claim 1, wherein the resin composition contains a polyolefin elastomer. The non-aqueous electrolyte battery according to any one of claims 1 to 5, wherein the separator is made of polyolefin. 7. The non-aqueous electrolyte battery according to claim 1, wherein said gasket has an average surface roughness Ra of 5 μm or less. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte housed in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. A method of manufacturing,
A method for producing a non-aqueous electrolyte battery, comprising using the above-described gasket made of a crosslinked polyphenylene sulfide resin composition having a lightness L ^* value of 74 or less in an L ^* a ^* b ^* color space. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte housed in a battery container having an outer can, a sealing plate, and a gasket disposed between the outer can and the sealing plate. A method of manufacturing,
The gasket made of a crosslinked polyphenylene sulfide resin composition having a lightness L ^* value in the ^{L *} a ^* b ^* color space that is 12 or more lower than the lightness L ^* value in the L*a ^* b ^* color space of the separator. A method for manufacturing a non-aqueous electrolyte battery, characterized by using

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