JP7240824B2 - Deep-drawn molded case for exterior of power storage device and power storage device - Google Patents

Deep-drawn molded case for exterior of power storage device and power storage device Download PDF

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JP7240824B2
JP7240824B2 JP2018109135A JP2018109135A JP7240824B2 JP 7240824 B2 JP7240824 B2 JP 7240824B2 JP 2018109135 A JP2018109135 A JP 2018109135A JP 2018109135 A JP2018109135 A JP 2018109135A JP 7240824 B2 JP7240824 B2 JP 7240824B2
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浩 畑
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株式会社レゾナック・パッケージング
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/16—Capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Description

本発明は、例えば、電動工具用、車載用、回生エネルギー回収用、デジタルカメラ用、ミニ四駆用等に用いられる蓄電池（リチウムイオン２次電池等）、コンデンサ（キャパシタ）、全固体電池等の蓄電デバイスの外装材として使用される深絞り成形ケースに関する。 For example, the present invention can be used for electric tools, vehicles, regenerative energy recovery, digital cameras, storage batteries (lithium ion secondary batteries, etc.), capacitors, all-solid batteries, etc. The present invention relates to a deep-drawn case used as an exterior material for an electric storage device.

本明細書および特許請求の範囲において、「深絞り成形」の語は、「プレス成形の絞り加工において、被加工材の外周にあるしわ抑え面の対応部位も、ダイスの穴内へ引き込ませながら加工する成形」を意味するものである。 In this specification and the scope of claims, the term "deep drawing" means "in the drawing of press forming, the corresponding part of the wrinkle suppressing surface on the outer periphery of the workpiece is also drawn into the hole of the die. It means "molding to".

近年、スマートフォン、タブレット端末等のモバイル電気機器の薄型化、軽量化に伴い、これらに搭載されるリチウムイオン二次電池、リチウムポリマー二次電池、リチウムイオンキャパシタ、電気２重層コンデンサ等の蓄電デバイスの外装材としては、従来の金属缶に代えて、耐熱性樹脂層（基材層）／外側接着剤層／金属箔層／内側接着剤層／熱融着性樹脂層（内側層）からなる積層体が用いられている（特許文献１参照）。また、電気自動車等の電源、蓄電用途の大型電源、キャパシタ等も上記構成の積層体（外装材）で外装されることも増えてきている。 In recent years, along with the thinning and weight reduction of mobile electric devices such as smartphones and tablet terminals, the demand for power storage devices such as lithium-ion secondary batteries, lithium-polymer secondary batteries, lithium-ion capacitors, and electric double layer capacitors mounted on these devices has increased. Instead of conventional metal cans, the exterior material is a laminate consisting of a heat-resistant resin layer (base layer) / outer adhesive layer / metal foil layer / inner adhesive layer / heat-fusible resin layer (inner layer). body is used (see Patent Document 1). In addition, power sources for electric vehicles, large power sources for power storage, capacitors, and the like are also increasingly being sheathed with the above-described laminated body (exterior material).

前記外装材に対して張り出し成形や深絞り成形が行われることによって、略直方体形状等の立体形状に成形される。このような立体形状に成形することにより、蓄電デバイス本体部を収容するための収容空間を確保することができる。そして、立体形状に成形された成形ケースの収容凹部内に蓄電デバイス本体部が収容され、平面状の外装材がその内側層側を前記成形ケースに向けて重ね合わされ、該平面状外装材の内側層の周縁部と、前記成形ケースの封止用周縁部（フランジ部）の内側層とがヒートシールによりシール接合されて封止されることによって、電池等の蓄電デバイスが構成される。 By subjecting the exterior material to stretch molding or deep drawing, the exterior material is molded into a three-dimensional shape such as a substantially rectangular parallelepiped shape. By molding into such a three-dimensional shape, it is possible to secure a housing space for housing the electricity storage device main body. Then, the power storage device main body is accommodated in the accommodation recess of the molding case molded into a three-dimensional shape, and the planar exterior material is overlaid with the inner layer side facing the molding case, and the inner side of the planar exterior material. A power storage device such as a battery is constructed by heat-sealing and sealing the peripheral edge portion of the layer and the inner layer of the sealing peripheral edge portion (flange portion) of the molding case.

特開２００３－２８８８６５号公報JP 2003-288865 A

しかしながら、上記層構成からなる外装材を深絞り成形してなる成形ケースで外装されてなる蓄電デバイスでは、時間の経過により電解液が漏出しやすい場合があった。このように電解液が漏出するのは、深絞り成形後の成形ケースにおいてピンホール等が発生していることが主な原因になっている。本発明者は、このような蓄電デバイス外装用深絞り成形ケースにおける前記問題を解決すべく鋭意研究した結果、本発明を完成するに至ったものである。 However, in an electric storage device that is covered with a molded case formed by deep-drawing the outer covering material having the above-described layer structure, the electrolyte may easily leak over time. The leakage of the electrolytic solution is mainly caused by the occurrence of pinholes or the like in the molded case after deep drawing. The present inventor has completed the present invention as a result of intensive research to solve the above-mentioned problems in such a deep-drawn case for exterior of an electric storage device.

本発明は、かかる技術的背景に鑑みてなされたものであって、時間が経過しても成形ケースにピンホール等が発生し難く、電解液の漏れ発生を防止できる、蓄電デバイス外装用深絞り成形ケースおよび蓄電デバイスを提供することを目的とする。 The present invention has been made in view of the above technical background, and is a deep drawing for the exterior of an electricity storage device that is less likely to cause pinholes or the like in the molded case even with the passage of time and can prevent the occurrence of electrolyte leakage. It is an object of the present invention to provide a molded case and an electricity storage device.

前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.

［１］外側層としての耐熱性樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層とを含んでなる外装材の深絞り成形ケースであって、
前記深絞り成形ケースは、蓄電デバイス本体部を収容し得る収容ケースと、該収容ケースの下面開放口の周縁から略水平方向の外方に向けて延ばされた封止用周縁部とを有する立体形状であり、前記収容ケースの天面形状は、四角以上の略多角形形状であり、
前記収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面で前記深絞り成形ケースを切断する断面図において、前記深絞り成形ケースの側面の厚さを「ｂ1」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部の厚さを「ａ1」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部の厚さを「ｃ1」（μｍ）としたとき、
ｂ1＞ｃ1＞ａ1 … 式（１）
ｃ1＞ｂ1＞ａ1 … 式（２）
ｂ1＝ｃ1＞ａ1 … 式（３）
上記の式（１）、式（２）および式（３）の３つの関係式のうちいずれか１つの関係式を満たすと共に、
前記収容ケースをその天面における互いに隣り合わない任意の２つの角部を通る鉛直面で切断した断面図において、前記天面を構成する金属箔層の厚さを「ｄ3」（μｍ）とし、前記封止用周縁部を構成する金属箔層の厚さを「ｅ3」（μｍ）としたとき、ｄ3／ｅ3の値が０．７０以上であることを特徴とする蓄電デバイス外装用深絞り成形ケース。 [1] A deep-drawn case for an exterior material comprising a heat-resistant resin layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between these layers, ,
The deep drawn case has a housing case capable of housing the electricity storage device main body, and a sealing peripheral edge portion extending outward in a substantially horizontal direction from the periphery of the opening on the lower surface of the housing case. It has a three-dimensional shape, and the top surface shape of the storage case is a substantially polygonal shape with a square or more,
In a cross-sectional view of the deep-drawn case cut along a vertical plane passing through any two non-adjacent corners of the top surface of the storage case, the thickness of the side surface of the deep-drawn case is "b 1 " ( μm), the thickness of the first corner portion connecting the top surface and the side surface is “a 1 ” (μm), and the thickness of the second corner portion connecting the sealing peripheral edge portion and the side surface is When "c 1 " (μm),
b 1 >c 1 >a 1 Formula (1)
c 1 >b 1 >a 1 Formula (2)
b1 = c1 > a1 ... Formula (3)
While satisfying any one of the three relational expressions of the above formulas (1), (2) and (3),
In a cross-sectional view of the storage case cut along a vertical plane passing through two non-adjacent corners of the top surface, the thickness of the metal foil layer forming the top surface is defined as "d 3 " (μm). , wherein the value of d3 / e3 is 0.70 or more, where " e3 " (μm) is the thickness of the metal foil layer forming the peripheral portion for sealing. Deep-drawn case for .

［２］外側層としての耐熱性樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層とを含んでなる外装材の深絞り成形ケースであって、
前記深絞り成形ケースは、蓄電デバイス本体部を収容し得る収容ケースと、該収容ケースの下面開放口の周縁から略水平方向の外方に向けて延ばされた封止用周縁部とを有する立体形状であり、前記収容ケースの天面形状は、四角以上の略多角形形状であり、
前記収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面で前記深絞り成形ケースを切断する断面図において、前記深絞り成形ケースの側面を構成する熱融着性樹脂層の厚さを「ｂ2」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部を構成する熱融着性樹脂層の厚さを「ａ2」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部を構成する熱融着性樹脂層の厚さを「ｃ2」（μｍ）としたとき、
ｂ2＞ｃ2＞ａ2 … 式（４）
ｃ2＞ｂ2＞ａ2 … 式（５）
ｂ2＝ｃ2＞ａ2 … 式（６）
上記の式（４）、式（５）および式（６）の３つの関係式のうちいずれか１つの関係式を満たすことを特徴とする蓄電デバイス外装用深絞り成形ケース。 [2] A deep-drawn case for an exterior material comprising a heat-resistant resin layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between these layers, ,
The deep drawn case has a housing case capable of housing the electricity storage device main body, and a sealing peripheral edge portion extending outward in a substantially horizontal direction from the periphery of the opening on the lower surface of the housing case. It has a three-dimensional shape, and the top surface shape of the storage case is a substantially polygonal shape with a square or more,
A heat-sealable resin layer forming a side surface of the deep-drawn case in a cross-sectional view of the deep-drawn case cut along a vertical plane passing through any two corners that are not adjacent to each other on the top surface of the storage case. The thickness of the heat-fusible resin layer constituting the first corner connecting the top surface and the side surface is "a 2 " (μm), and the sealing When the thickness of the heat-fusible resin layer constituting the second corner portion connecting the fixing peripheral edge portion and the side surface is defined as "c 2 " (μm),
b 2 >c 2 >a 2 (4)
c 2 >b 2 >a 2 (5)
b2 = c2 > a2 ... Formula (6)
A deep-drawn case for an exterior of an electric storage device, characterized by satisfying any one of the three relational expressions of the above formulas (4), (5) and (6).

［３］外側層としての耐熱性樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層とを含んでなる外装材の深絞り成形ケースであって、
前記深絞り成形ケースは、蓄電デバイス本体部を収容し得る収容ケースと、該収容ケースの下面開放口の周縁から略水平方向の外方に向けて延ばされた封止用周縁部とを有する立体形状であり、前記収容ケースの天面形状は、四角以上の略多角形形状であり、
前記収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面で前記深絞り成形ケースを切断する断面図において、前記深絞り成形ケースの側面を構成する金属箔層の厚さを「ｂ3」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部を構成する金属箔層の厚さを「ａ3」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部を構成する金属箔層の厚さを「ｃ3」（μｍ）としたとき、
ｂ3＞ｃ3＞ａ3 … 式（７）
ｃ3＞ｂ3＞ａ3 … 式（８）
ｂ3＝ｃ3＞ａ3 … 式（９）
上記の式（７）、式（８）および式（９）の３つの関係式のうちいずれか１つの関係式を満たすことを特徴とする蓄電デバイス外装用深絞り成形ケース。 [3] A deep-drawn case for an exterior material comprising a heat-resistant resin layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between these layers, ,
The deep drawn case has a housing case capable of housing the electricity storage device main body, and a sealing peripheral edge portion extending outward in a substantially horizontal direction from the periphery of the opening on the lower surface of the housing case. It has a three-dimensional shape, and the top surface shape of the storage case is a substantially polygonal shape with a square or more,
Thickness of the metal foil layer forming the side surface of the deep-drawn case in a cross-sectional view of the deep-drawn case cut along a vertical plane passing through any two non-adjacent corners on the top surface of the storage case is “b 3 ” (μm), the thickness of the metal foil layer constituting the first corner portion connecting the top surface and the side surface is “a 3 ” (μm), and the sealing peripheral edge portion and the When the thickness of the metal foil layer constituting the second corner connecting the side surface is "c 3 " (μm),
b 3 >c 3 >a 3 (7)
c 3 >b 3 >a 3 (8)
b3 = c3 > a3 ... Formula (9)
A deep-drawn case for the exterior of an electric storage device, characterized by satisfying any one of the three relational expressions of the above formulas (7), (8) and (9).

［４］前記内側層は、複数層の熱融着性樹脂層で形成されている前項１～３のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケース。 [4] The deep-drawn case for exterior of an electric storage device according to any one of the preceding items 1 to 3, wherein the inner layer is formed of a plurality of heat-fusible resin layers.

［５］前記金属箔層は、アルミニウム箔で形成されている前項１～４のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケース。 [5] The deep-drawn case for exterior of an electric storage device according to any one of the preceding items 1 to 4, wherein the metal foil layer is made of aluminum foil.

［６］前記金属箔層における少なくとも前記内側層側の面に化成皮膜層が形成されている前項１～５のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケース。 [6] The deep-drawn case for exterior of an electric storage device according to any one of the preceding items 1 to 5, wherein a chemical conversion film layer is formed on at least the inner layer side surface of the metal foil layer.

［７］蓄電デバイス本体部と、
前項１～６のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケースを含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。 [7] an electricity storage device main body;
An exterior member including the deep-drawn case for exterior of an electricity storage device according to any one of the preceding items 1 to 6,
An electricity storage device, wherein the electricity storage device main body is covered with the exterior member.

［１］～［３］の発明では、深絞り成形時に無理な歪みが加わっていないため、時間が経過しても成形ケースにピンホール等が発生し難く、電解液の漏れ発生を防止できる。 In the inventions [1] to [3], since no excessive strain is applied during deep drawing, pinholes and the like are less likely to occur in the molded case even after a lapse of time, and electrolyte leakage can be prevented.

［４］の発明では、内側層は、複数の熱融着性樹脂層で形成されているから、深絞り成形ケースが膨らんだ場合であっても熱融着性樹脂層（内側層）が破れにくい。また、内側層を構成する複数層の熱融着性樹脂層のうち最内層の熱融着性樹脂層として接着性の良い樹脂を用いることで、デラミネーションが発生し難いものとなり、電解液の漏れ発生を十分に防止できる。 In the invention [4], since the inner layer is formed of a plurality of heat-fusible resin layers, even if the deep-drawn case expands, the heat-fusible resin layer (inner layer) is torn. Hateful. In addition, by using a resin with good adhesiveness as the innermost heat-fusible resin layer of the plurality of heat-fusible resin layers constituting the inner layer, delamination is less likely to occur, and the electrolytic solution Leakage can be sufficiently prevented.

［５］の発明では、金属箔層はアルミニウム箔で形成されているから、深絞り成形ケースにおけるピンホール等の発生を十分に防止できる。 In the invention [5], since the metal foil layer is made of aluminum foil, the occurrence of pinholes and the like in the deep-drawn case can be sufficiently prevented.

［６］の発明では、金属箔層における少なくとも内側層側の面に化成皮膜層が形成されているから、腐食を原因とする金属箔層でのピンホール等の発生を十分に防止できる。 In the invention [6], since the chemical conversion coating layer is formed on at least the inner layer side surface of the metal foil layer, it is possible to sufficiently prevent the occurrence of pinholes and the like in the metal foil layer caused by corrosion.

［７］の発明では、深絞り成形ケースにピンホール等が発生し難いので、電解液の漏れ発生を十分に防止できる蓄電デバイスを提供できる。 In the invention [7], since pinholes and the like are less likely to occur in the deep-drawn case, it is possible to provide an electricity storage device that can sufficiently prevent leakage of the electrolytic solution.

本発明に係る蓄電デバイス用深絞り成形ケースの一実施形態を示す斜視図である。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing one embodiment of a deep-drawn case for an electricity storage device according to the present invention; 深絞り成形を行う前の外装材を示す断面図である。FIG. 4 is a cross-sectional view showing the exterior material before deep drawing. 図１の深絞り成形ケースを、収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面（四角形の天面における隣り合わない２つの角部を通る鉛直面）で切断した断面図である。The deep-drawn case of FIG. 1 was cut along a vertical plane passing through any two non-adjacent corners on the top surface of the storage case (a vertical plane passing through two non-adjacent corners on the rectangular top surface). It is a sectional view. 本発明に係る蓄電デバイスの一実施形態を示す断面図である。1 is a cross-sectional view showing an embodiment of an electricity storage device according to the present invention; FIG.

本発明について以下詳述する。本発明に係る蓄電デバイス用深絞り成形ケース１０は、外側層としての耐熱性樹脂層２と、内側層としての熱融着性樹脂層３と、これら両層間に配置された金属箔層４とを含んでなる外装材の深絞り成形ケース（深絞り成形体）である。前記深絞り成形ケース１０は、蓄電デバイス本体部３１を収容し得る収容ケース２８と、該収容ケース２８の下面開放口２８ａの周縁から略水平方向の外方に向けて延ばされた封止用周縁部５３とを有する立体形状であり、前記収容ケース２８の天面５１の形状は、四角以上の略多角形形状である（図１参照）。 The present invention will be described in detail below. A deep-drawn case 10 for an electricity storage device according to the present invention includes a heat-resistant resin layer 2 as an outer layer, a heat-fusible resin layer 3 as an inner layer, and a metal foil layer 4 disposed between these layers. It is a deep-drawn case (deep-drawn molded body) of an exterior material comprising: The deep drawn case 10 includes a housing case 28 capable of housing the electricity storage device main body 31 and a sealing opening extending outward in a substantially horizontal direction from the peripheral edge of the lower surface opening 28a of the housing case 28. The top surface 51 of the storage case 28 has a three-dimensional shape having a peripheral edge portion 53, and the shape of the top surface 51 of the storage case 28 is a substantially polygonal shape with a square or more (see FIG. 1).

図１に示す実施形態では、前記収容ケース２８は、略直方体形状であり、その下面が開放されていて下面開放口２８ａが設けられている（図３参照）。しかして、前記深絞り成形ケース１０は、略水平方向に延ばされた天面５１、該天面５１の周縁から第１コーナー部５５を介して下方に向けて延ばされた側面５２と、該側面５２の下端から第２コーナー部５６を介して略水平方向の外方に向けて延ばされた封止用周縁部５３と、を備えている（図１、図３参照）。 In the embodiment shown in FIG. 1, the storage case 28 has a substantially rectangular parallelepiped shape, and has an open bottom surface to provide a bottom opening 28a (see FIG. 3). Thus, the deep drawn case 10 includes a top surface 51 extending in a substantially horizontal direction, a side surface 52 extending downward from the periphery of the top surface 51 via a first corner portion 55, and a sealing edge portion 53 extending outward in a substantially horizontal direction from the lower end of the side surface 52 via a second corner portion 56 (see FIGS. 1 and 3).

第１発明は、前記収容ケース２８の天面５１における互いに隣り合わない任意の２つの角部４１、４２を通る鉛直面で前記深絞り成形ケース１０を切断する断面図（図３参照）において、前記天面５１と前記封止用周縁部５３とを繋ぐ側面５２の厚さを「ｂ1」（μｍ）とし、前記天面５１と前記側面５２とを繋ぐ第１コーナー部５５の厚さを「ａ1」（μｍ）とし、前記封止用周縁部５３と前記側面５２とを繋ぐ第２コーナー部５６の厚さを「ｃ1」（μｍ）としたとき、
ｂ1＞ｃ1＞ａ1 … 式（１）
ｃ1＞ｂ1＞ａ1 … 式（２）
ｂ1＝ｃ1＞ａ1 … 式（３）
上記の式（１）、式（２）および式（３）の３つの関係式のうちいずれか１つの関係式を満たすと共に、前記収容ケース２８の天面５１における互いに隣り合わない任意の２つの角部４１、４２を通る鉛直面で前記深絞り成形ケース１０を切断する断面図（図３参照）において、前記天面５１を構成する金属箔層の厚さを「ｄ3」（μｍ）とし、前記封止用周縁部５３を構成する金属箔層の厚さを「ｅ3」（μｍ）としたとき、ｄ3／ｅ3の値が０．７０以上であることを特徴とする。 The first invention is a cross-sectional view (see FIG. 3) taken by cutting the deep drawn case 10 along a vertical plane passing through two arbitrary corners 41 and 42 that are not adjacent to each other on the top surface 51 of the housing case 28, Let the thickness of the side surface 52 connecting the top surface 51 and the sealing peripheral edge portion 53 be "b 1 " (μm), and the thickness of the first corner portion 55 connecting the top surface 51 and the side surface 52 be When "a 1 " (μm) and the thickness of the second corner portion 56 connecting the sealing edge portion 53 and the side surface 52 is "c 1 " (μm),
b 1 >c 1 >a 1 Formula (1)
c 1 >b 1 >a 1 Formula (2)
b1 = c1 > a1 ... Formula (3)
Any two of the three relational expressions of the above expressions (1), (2) and (3) are satisfied, and any two not adjacent to each other on the top surface 51 of the storage case 28 are satisfied. In the cross-sectional view (see FIG. 3) of the deep drawn case 10 cut along the vertical plane passing through the corners 41 and 42, the thickness of the metal foil layer forming the top surface 51 is assumed to be "d 3 " (μm). A value of d 3 /e 3 is 0.70 or more, where "e 3 " (μm) is the thickness of the metal foil layer forming the sealing edge portion 53 .

第２発明は、前記収容ケース２８の天面５１における互いに隣り合わない任意の２つの角部４１、４２を通る鉛直面で前記深絞り成形ケース１０を切断する断面図（図３参照）において、前記天面５１と前記封止用周縁部５３とを繋ぐ側面５２を構成する熱融着性樹脂層の厚さを「ｂ2」（μｍ）とし、前記天面５１と前記側面５２とを繋ぐ第１コーナー部５５を構成する熱融着性樹脂層の厚さを「ａ2」（μｍ）とし、前記封止用周縁部５３と前記側面５２とを繋ぐ第２コーナー部５６を構成する熱融着性樹脂層の厚さを「ｃ2」（μｍ）としたとき、
ｂ2＞ｃ2＞ａ2 … 式（４）
ｃ2＞ｂ2＞ａ2 … 式（５）
ｂ2＝ｃ2＞ａ2 … 式（６）
上記の式（４）、式（５）および式（６）の３つの関係式のうちいずれか１つの関係式を満たすことを特徴とする。 The second invention is a cross-sectional view (see FIG. 3) taken by cutting the deep drawn case 10 along a vertical plane passing through arbitrary two corners 41 and 42 that are not adjacent to each other on the top surface 51 of the housing case 28, The thickness of the heat-fusible resin layer constituting the side surface 52 that connects the top surface 51 and the sealing peripheral edge portion 53 is set to "b 2 " (μm), and the top surface 51 and the side surface 52 are connected. The thickness of the heat-fusible resin layer forming the first corner portion 55 is set to “a 2 ” (μm), and the thermal When the thickness of the fusible resin layer is “c 2 ” (μm),
b 2 >c 2 >a 2 (4)
c 2 >b 2 >a 2 (5)
b2 = c2 > a2 ... Formula (6)
It is characterized by satisfying any one of the above three relational expressions of formulas (4), (5) and (6).

第３発明は、前記収容ケース２８の天面５１における互いに隣り合わない任意の２つの角部４１、４２を通る鉛直面で前記深絞り成形ケース１０を切断する断面図（図３参照）において、前記天面５１と前記封止用周縁部５３とを繋ぐ側面５２を構成する金属箔層の厚さを「ｂ3」（μｍ）とし、前記天面５１と前記側面５２とを繋ぐ第１コーナー部５５を構成する金属箔層の厚さを「ａ3」（μｍ）とし、前記封止用周縁部５３と前記側面５２とを繋ぐ第２コーナー部５６を構成する金属箔層の厚さを「ｃ3」（μｍ）としたとき、
ｂ3＞ｃ3＞ａ3 … 式（７）
ｃ3＞ｂ3＞ａ3 … 式（８）
ｂ3＝ｃ3＞ａ3 … 式（９）
上記の式（７）、式（８）および式（９）の３つの関係式のうちいずれか１つの関係式を満たすことを特徴とする。 The third invention is a cross-sectional view (see FIG. 3) taken by cutting the deep drawn case 10 along a vertical plane passing through arbitrary two corners 41 and 42 that are not adjacent to each other on the top surface 51 of the housing case 28, The thickness of the metal foil layer forming the side surface 52 that connects the top surface 51 and the sealing peripheral edge portion 53 is set to "b 3 " (μm), and the first corner that connects the top surface 51 and the side surface 52 Let the thickness of the metal foil layer forming the portion 55 be "a 3 " (μm), and the thickness of the metal foil layer forming the second corner portion 56 connecting the sealing peripheral edge portion 53 and the side surface 52 be When "c 3 " (μm),
b 3 >c 3 >a 3 (7)
c 3 >b 3 >a 3 (8)
b3 = c3 > a3 ... Formula (9)
It is characterized by satisfying any one of the above three relational expressions of formulas (7), (8) and (9).

上記第１発明、第２発明および第３発明では、深絞り成形時に無理な歪みが加わっていないため、時間が経過しても成形ケースにピンホール等が発生し難く、蓄電デバイスにおいて電解液の漏れ発生を防止できる。上記第１発明、第２発明および第３発明は、成形深さが２．０ｍｍ以上の深絞り成形がなされた深絞り成形ケースにおいて特に電解液の漏れ防止効果が顕著なものとなる。 In the above-mentioned first, second and third inventions, since no excessive strain is applied during deep drawing, pinholes and the like are less likely to occur in the molded case even with the passage of time. Leakage can be prevented. According to the first, second and third inventions, the leakage prevention effect of the electrolytic solution is particularly remarkable in a deep-drawn case which is deep-drawn to a depth of 2.0 mm or more.

上記第１発明において、前記封止用周縁部５３の厚さを「ｅ1」とし、前記成形ケース１０の側面５２の高さ（成形深さと略同等）を「Ｌ」としたとき、Ｌが３．５ｍｍ以上である場合には、
ｃ1＞ｅ1＞ｂ1＞ａ1 … 式（１０）
ｃ1＞ｅ1＞ｄ1＞ａ1 … 式（１１）
上記の式（１０）および式（１１）の関係式を満たす構成であるのが好ましく、この場合には、成形ケースにおけるピンホール等の発生を十分に防止できて、蓄電デバイスにおいて電解液の漏れ発生を十分に防止できる。 In the first invention, when the thickness of the sealing peripheral portion 53 is "e 1 " and the height of the side surface 52 of the molding case 10 (substantially equivalent to the molding depth) is "L", L is If it is 3.5 mm or more,
c 1 >e 1 >b 1 >a 1 Formula (10)
c 1 >e 1 >d 1 >a 1 Formula (11)
It is preferable that the structure satisfies the relational expressions of the above formulas (10) and (11). The occurrence can be sufficiently prevented.

また、上記第３発明において、前記封止用周縁部５３を構成する金属箔層の厚さを「ｅ3」（μｍ）としたとき、ｂ3≧ｃ3である場合にはｂ3≧ｅ3の関係式を満たす構成であるのが好ましく、ｂ3＜ｃ3である場合にはｂ3＜ｅ3の関係式を満たす構成になっているのが好ましい。 In the third invention, when the thickness of the metal foil layer forming the sealing edge portion 53 is " e3 " (μm), when b3 ≧ c3 , then b3 ≧e 3 , and when b 3 <c 3 , it is preferable that the configuration satisfies the relational expression b 3 <e 3 .

本発明において、前記収容ケース２８の天面５１の形状は、四角以上の略多角形形状である。前記略多角形形状としては、特に限定されるものではないが、例えば、略四角形形状（図１参照）、略六角形形状、略八角形形状等が挙げられる。 In the present invention, the shape of the top surface 51 of the housing case 28 is a substantially polygonal shape with a square or more. The substantially polygonal shape is not particularly limited, but includes, for example, a substantially quadrangular shape (see FIG. 1), a substantially hexagonal shape, a substantially octagonal shape, and the like.

前記深絞り成形ケース１０は、（成形前の）外装材１を深絞り成形して得られる成形体であるが、前記外装材１は、外側層としての耐熱性樹脂層２と、内側層としての熱融着性樹脂層３と、これら両層間に配置された金属箔層４とを含んでなる外装材である（図２参照）。 The deep-drawn case 10 is a molded body obtained by deep-drawing the exterior material 1 (before molding). The exterior material 1 includes a heat-resistant resin layer 2 as an outer layer and a and a metal foil layer 4 disposed between the two layers (see FIG. 2).

前記耐熱性樹脂層（外側層）２は、外装材として良好な成形性を確保する役割を主に担う部材である、即ち成形時の金属箔のネッキングによる破断を防止する役割を担うものである。 The heat-resistant resin layer (outer layer) 2 is a member that mainly plays the role of ensuring good moldability as an exterior material, that is, plays the role of preventing breakage due to necking of the metal foil during molding. .

前記耐熱性樹脂層（外側層）２を構成する耐熱性樹脂としては、外装材（深絞り成形ケース）をヒートシールする際のヒートシール温度で溶融しない耐熱性樹脂を用いる。前記耐熱性樹脂としては、熱融着性樹脂層３を構成する樹脂の融点より１０℃以上高い融点を有する耐熱性樹脂を用いるのが好ましく、熱融着性樹脂層３を構成する樹脂の融点より２０℃以上高い融点を有する耐熱性樹脂を用いるのが特に好ましい。 As the heat-resistant resin forming the heat-resistant resin layer (outer layer) 2, a heat-resistant resin that does not melt at the heat-sealing temperature at which the exterior material (deep-drawn case) is heat-sealed is used. As the heat-resistant resin, it is preferable to use a heat-resistant resin having a melting point higher than the melting point of the resin forming the heat-fusible resin layer 3 by 10° C. or more. It is particularly preferable to use a heat-resistant resin having a melting point higher by 20° C. or more than the above.

前記耐熱性樹脂層（外側層）２としては、特に限定されるものではないが、例えば、延伸ナイロンフィルム等の延伸ポリアミドフィルム、延伸ポリエステルフィルム等が挙げられる。中でも、前記耐熱性樹脂延伸フィルム層２としては、二軸延伸ナイロンフィルム等の二軸延伸ポリアミドフィルム、二軸延伸ポリブチレンテレフタレート（ＰＢＴ）フィルム、二軸延伸ポリエチレンテレフタレート（ＰＥＴ）フィルム又は二軸延伸ポリエチレンナフタレート（ＰＥＮ）フィルムを用いるのが特に好ましい。また、前記耐熱性樹脂延伸フィルム層２としては、同時２軸延伸法により延伸された耐熱性樹脂二軸延伸フィルムを用いるのが好ましい。前記ナイロンとしては、特に限定されるものではないが、例えば、６ナイロン、６，６ナイロン、ＭＸＤナイロン等が挙げられる。なお、前記耐熱性樹脂層２は、単層（単一の延伸フィルム）で形成されていても良いし、或いは、例えば延伸ポリエステルフィルム／延伸ポリアミドフィルムからなる複層（延伸ＰＥＴフィルム／延伸ナイロンフィルムからなる複層等）で形成されていても良い。 Examples of the heat-resistant resin layer (outer layer) 2 include, but are not limited to, a stretched polyamide film such as a stretched nylon film, and a stretched polyester film. Among them, as the heat-resistant resin stretched film layer 2, a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched It is particularly preferred to use polyethylene naphthalate (PEN) films. As the heat-resistant resin stretched film layer 2, it is preferable to use a heat-resistant resin biaxially stretched film stretched by a simultaneous biaxial stretching method. Examples of the nylon include, but are not particularly limited to, 6 nylon, 6,6 nylon, MXD nylon, and the like. In addition, the heat-resistant resin layer 2 may be formed of a single layer (single stretched film), or may be a multilayer made of, for example, a stretched polyester film/stretched polyamide film (stretched PET film/stretched nylon film). It may be formed with a multilayer etc.).

なお、前記耐熱性樹脂層（外側層）２は、耐熱性樹脂が塗布されることにより形成された樹脂層であってもよい。 The heat-resistant resin layer (outer layer) 2 may be a resin layer formed by applying a heat-resistant resin.

前記耐熱性樹脂層２の厚さは、９μｍ～５０μｍであるのが好ましい。上記好適下限値以上に設定することで外装材１として十分な強度を確保できると共に、上記好適上限値以下に設定することで深絞り成形時の応力を小さくできて成形性を向上させることができる。 The thickness of the heat-resistant resin layer 2 is preferably 9 μm to 50 μm. By setting it to the preferred lower limit or more, sufficient strength can be secured as the exterior material 1, and by setting it to the preferred upper limit or less, the stress during deep drawing can be reduced, and formability can be improved. .

前記熱融着性樹脂層（内側層）３は、リチウムイオン二次電池等で用いられる腐食性の強い電解液などに対しても優れた耐薬品性を具備させると共に、外装材（深絞り成形ケース）にヒートシール性を付与する役割を担うものである。 The heat-fusible resin layer (inner layer) 3 has excellent chemical resistance against highly corrosive electrolytic solutions used in lithium ion secondary batteries and the like, and is used as an exterior material (deep drawing It plays the role of imparting heat sealability to the case).

前記熱融着性樹脂としては、特に限定されるものではないが、例えば、ポリエチレン、ポリプロピレン、エチレンアクリル酸エチル（ＥＥＡ）、エチレンアクリル酸メチル（ＥＡＡ）、エチレンメタクリル酸メチル樹脂（ＥＭＭＡ）、エチレン－酢酸ビニル共重合体樹脂（ＥＶＡ）、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリエチレン、オレフィン系樹脂アイオノマー等が挙げられる。 The heat-sealable resin is not particularly limited, but examples include polyethylene, polypropylene, ethylene ethyl acrylate (EEA), ethylene methyl acrylate (EAA), ethylene methyl methacrylate resin (EMMA), ethylene -Vinyl acetate copolymer resin (EVA), maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, olefin resin ionomer, and the like.

前記熱融着性樹脂層３としては、特に限定されるものではないが、熱可塑性樹脂未延伸フィルム層であるのが好ましい。前記熱可塑性樹脂未延伸フィルム層３は、特に限定されるものではないが、ポリエチレン、ポリプロピレン、オレフィン系共重合体、これらの酸変性物およびアイオノマーからなる群より選ばれた少なくとも１種の熱可塑性樹脂からなる未延伸フィルムにより構成されるのが好ましい。 Although the heat-fusible resin layer 3 is not particularly limited, it is preferably an unstretched thermoplastic resin film layer. The thermoplastic resin unstretched film layer 3 is not particularly limited, but at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefinic copolymers, acid-modified products thereof, and ionomers. It is preferably composed of an unstretched film made of resin.

前記熱融着性樹脂層３の厚さは、２０μｍ～１５０μｍに設定されるのが好ましい。２０μｍ以上とすることでピンホールの発生を十分に防止できると共に、１５０μｍ以下に設定することで樹脂使用量を低減できてコスト低減を図り得る。中でも、前記熱融着性樹脂層３の厚さは３０μｍ～１００μｍに設定されるのが特に好ましい。なお、前記熱融着性樹脂層３は、単層であってもよいし、複層であってもよい。 The thickness of the heat-fusible resin layer 3 is preferably set to 20 μm to 150 μm. By setting the thickness to 20 μm or more, it is possible to sufficiently prevent the occurrence of pinholes, and by setting the thickness to 150 μm or less, it is possible to reduce the amount of resin used, thereby reducing costs. Above all, it is particularly preferable to set the thickness of the heat-fusible resin layer 3 to 30 μm to 100 μm. The heat-fusible resin layer 3 may be a single layer or multiple layers.

前記熱融着性樹脂層３には、通常、滑剤が添加される。前記滑剤が添加されていることで成形時の成形性を向上させることができる。前記熱融着性樹脂層３における滑剤の含有率は、２００ｐｐｍ～５０００ｐｐｍの範囲に設定されるのが好ましい。 A lubricant is usually added to the heat-fusible resin layer 3 . Addition of the lubricant can improve moldability during molding. The content of the lubricant in the heat-fusible resin layer 3 is preferably set within the range of 200 ppm to 5000 ppm.

前記滑剤としては、特に限定されるものではないが、例えば、飽和脂肪酸アミド、不飽和脂肪酸アミド、置換アミド、メチロールアミド、飽和脂肪酸ビスアミド、不飽和脂肪酸ビスアミド、脂肪酸エステルアミド、芳香族系ビスアミド等が挙げられる。 Examples of the lubricant include, but are not limited to, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. mentioned.

前記金属箔層４は、外装材（深絞り成形ケース）に酸素や水分の侵入を阻止するガスバリア性を付与する役割を担うものである。前記金属箔層４としては、特に限定されるものではないが、例えば、アルミニウム箔、銅箔、ＳＵＳ箔、ニッケル箔等が挙げられ、アルミニウム箔が一般的に用いられる。前記金属箔層４の厚さは、１５μｍ～１５０μｍであるのが好ましい。１５μｍ以上であることで金属箔を製造する際の圧延時のピンホール発生を防止できると共に、１５０μｍ以下であることで深絞り成形時の応力を小さくできて成形性を向上させることができる。中でも、前記金属箔層４の厚さは、２０μｍ～１００μｍであるのがより好ましい。 The metal foil layer 4 plays a role of imparting a gas barrier property to the exterior material (deep-drawn case) to prevent permeation of oxygen and moisture. Examples of the metal foil layer 4 include, but are not limited to, aluminum foil, copper foil, SUS foil, nickel foil, etc. Aluminum foil is generally used. The thickness of the metal foil layer 4 is preferably 15 μm to 150 μm. When the thickness is 15 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing the metal foil, and when it is 150 μm or less, the stress during deep drawing can be reduced and formability can be improved. Above all, the thickness of the metal foil layer 4 is more preferably 20 μm to 100 μm.

前記金属箔層４は、少なくとも内側の面４ａ（第２接着剤層６側の面）に、化成処理が施されているのが好ましい。このような化成処理が施されていることによって内容物（電池の電解液、食品、医薬品等）による金属箔表面の腐食を十分に防止できる。例えば次のような処理をすることによって金属箔に化成処理を施す。即ち、例えば、脱脂処理を行った金属箔の表面に、
１）リン酸、クロム酸及びフッ化物の金属塩の混合物からなる水溶液
２）リン酸、クロム酸、フッ化物金属塩及び非金属塩の混合物からなる水溶液
３）アクリル系樹脂又は／及びフェノール系樹脂と、リン酸と、クロム酸と、フッ化物金属塩との混合物からなる水溶液
のいずれかを塗工した後、乾燥することにより化成処理を施し、化成皮膜を形成する。 Preferably, at least the inner surface 4a (the surface on the second adhesive layer 6 side) of the metal foil layer 4 is subjected to a chemical conversion treatment. Such chemical conversion treatment can sufficiently prevent corrosion of the metal foil surface due to contents (eg, battery electrolyte, food, pharmaceuticals, etc.). For example, the metal foil is chemically treated by the following treatment. That is, for example, on the surface of a metal foil that has been degreased,
1) Aqueous solution consisting of a mixture of metal salts of phosphoric acid, chromic acid and fluoride 2) Aqueous solution consisting of a mixture of phosphoric acid, chromic acid, fluoride metal salts and non-metal salts 3) Acrylic resin and/or phenolic resin or an aqueous solution consisting of a mixture of phosphoric acid, chromic acid, and a metal fluoride salt, and then dried to perform a chemical conversion treatment to form a chemical conversion film.

前記第１接着剤層（外側接着剤層）５としては、特に限定されるものではないが、例えば、２液反応型接着剤により形成された接着剤層等が挙げられる。前記２液反応型接着剤としては、例えば、ポリウレタン系ポリオール、ポリエステル系ポリオール及びポリエーテル系ポリオールからなる群より選ばれるポリオールの１種または２種以上からなる第１液と、ポリイソシアネートからなる第２液（硬化剤）とで構成される２液反応型接着剤などが挙げられる。前記第１接着剤層５は、例えば、前記２液反応型接着剤等の接着剤が、前記「金属箔層４の上面」に、又は／及び、「前記耐熱性樹脂層２の下面」に、グラビアコート法等の手法により塗布されることによって形成される。 The first adhesive layer (outer adhesive layer) 5 is not particularly limited, but may be, for example, an adhesive layer formed of a two-liquid reactive adhesive. As the two-liquid reactive adhesive, for example, a first liquid consisting of one or more polyols selected from the group consisting of polyurethane-based polyols, polyester-based polyols and polyether-based polyols, and a first liquid consisting of polyisocyanate A two-liquid reactive adhesive composed of two liquids (curing agent) and the like can be mentioned. In the first adhesive layer 5, for example, an adhesive such as the two-liquid reactive adhesive is applied to the "upper surface of the metal foil layer 4" and/or to the "lower surface of the heat-resistant resin layer 2". , and is formed by coating with a method such as a gravure coating method.

前記第２接着剤層（内側接着剤層）６としては、特に限定されるものではないが、例えば、ポリウレタン系接着剤、アクリル系接着剤、エポキシ系接着剤、ポリオレフィン系接着剤、エラストマー系接着剤、フッ素系接着剤等により形成された接着剤層が挙げられる。中でも、酸変性オレフィン系樹脂（無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリエチレン等）からなる第１液と、ポリイソシアネートからなる第２液（硬化剤）とで構成される２液反応型接着剤を用いるのが好ましく、この場合には、外装材の耐電解液性及び水蒸気バリア性をさらに向上させることができる。 The second adhesive layer (inner adhesive layer) 6 is not particularly limited, but examples include polyurethane adhesives, acrylic adhesives, epoxy adhesives, polyolefin adhesives, and elastomer adhesives. Adhesive layers formed of adhesives, fluorine-based adhesives, and the like can be used. Among them, a two-liquid reactive adhesive composed of a first liquid made of an acid-modified olefin resin (maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, etc.) and a second liquid (curing agent) made of polyisocyanate. is preferably used, and in this case, the electrolytic solution resistance and water vapor barrier properties of the exterior material can be further improved.

なお、上記実施形態では、第１接着剤層５と第２接着剤層６を設けた構成を採用しているが、これら両層５、６は、いずれも必須の構成層ではなく、これらを設けない構成を採用することもできる。 In the above-described embodiment, the configuration in which the first adhesive layer 5 and the second adhesive layer 6 are provided is adopted. It is also possible to employ a configuration that does not provide.

しかして、上記構成の外装材（図２参照）１を深絞り成形することにより、図１に示すような蓄電デバイス外装用深絞り成形ケース１０を得ることができる。前記蓄電デバイス外装用深絞り成形ケース１０の形状としては、特に限定されないが、例えば、図１に示すような１つの面（下面；底面）が開放された略直方体形状等が挙げられる。 Thus, by deep-drawing the exterior material (see FIG. 2) 1 having the above configuration, a deep-drawn case 10 for exterior of an electric storage device as shown in FIG. 1 can be obtained. The shape of the deep-drawn case 10 for the exterior of the electric storage device is not particularly limited, but includes, for example, a substantially rectangular parallelepiped shape with one open surface (lower surface; bottom surface) as shown in FIG.

次に、本発明に係る蓄電デバイス３０の一実施形態を図４に示す。図４に示すように、本発明に係る蓄電デバイス外装用深絞り成形ケース１０の収容凹部（収容ケース）内に、略直方体形状の蓄電デバイス本体部３１が収容され、該蓄電デバイス本体部３１の下に、上記（成形前の）平面状外装材１がその内側層３側を内方（上側）にして配置され、該平面状外装材１の内側層３の周縁部と、前記深絞り成形ケース１０の封止用周縁部（フランジ部）５３の内側層３とがヒートシールによりシール接合されて封止されることによって、本発明の蓄電デバイス３０が構成されている。図４において、３９は、前記外装材１の周縁部と、前記深絞り成形ケース１０の封止用周縁部（フランジ部）５３とが接合（溶着）されたヒートシール部である。 Next, FIG. 4 shows an embodiment of the electricity storage device 30 according to the present invention. As shown in FIG. 4 , an electricity storage device main body 31 having a substantially rectangular parallelepiped shape is accommodated in an accommodation recess (accommodation case) of the deep-drawn case 10 for exterior of an electricity storage device according to the present invention. Below, the planar exterior material 1 (before molding) is arranged with the inner layer 3 side facing inward (upper side), and the peripheral edge portion of the inner layer 3 of the planar exterior material 1 and the deep draw molding The power storage device 30 of the present invention is configured by heat-sealing and sealing the inner layer 3 of the sealing edge portion (flange portion) 53 of the case 10 . In FIG. 4, reference numeral 39 denotes a heat-sealed portion where the peripheral portion of the exterior material 1 and the sealing peripheral portion (flange portion) 53 of the deep drawn case 10 are joined (welded).

前記蓄電デバイス本体部３１としては、特に限定されるものではないが、例えば、電池本体部、キャパシタ本体部、コンデンサ本体部等が挙げられる。 The electricity storage device main body 31 is not particularly limited, but examples thereof include a battery main body, a capacitor main body, and a capacitor main body.

次に、本発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

＜実施例１＞
厚さ３０μｍのアルミニウム箔（ＪＩＳ Ｈ４１６０で規定されるＡ８０２１Ｈ材）（金属箔）４の両面に、リン酸、ポリアクリル酸（アクリル系樹脂）、クロム(III)塩化合物、水、アルコールからなる化成処理液を塗布した後、１８０℃で乾燥を行って、化成皮膜を形成した。この化成皮膜のクロム付着量は片面当たり２ｍｇ／ｍ2であった。 <Example 1>
On both sides of a 30 μm thick aluminum foil (A8021H material specified in JIS H4160) (metal foil) 4, a chemical compound consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol After applying the treatment liquid, drying was performed at 180° C. to form a chemical conversion film. The amount of chromium deposited on this chemical conversion film was 2 mg/m 2 per side.

次に、前記化成処理済みアルミニウム箔４の一方の面に、２液硬化型のポリエステル－ウレタン系接着剤（外側接着剤）５を介して厚さ１５μｍの二軸延伸ナイロンフィルム（外側層用フィルム）２をドライラミネートして（貼り合わせて）積層体を得た。 Next, a 15 μm thick biaxially oriented nylon film (outer layer film ) 2 was dry-laminated (bonded together) to obtain a laminate.

次いで、得られた積層体のアルミニウム箔４の他方の面に、２液硬化型のマレイン酸変性ポリプロピレン系接着剤（内側接着剤）６を介して、厚さ２５μｍの無延伸ポリプロピレンフィルム（内側層）３をドライラミネートした（貼り合わせた）後、４０℃で８日間エージングする（加熱する）ことによって、図２に示す構成の外装材１を得た。前記無延伸ポリプロピレンフィルムは、ランダムポリプロピレン、ブロックポリプロピレン、ランダムポリプロピレンの順に共押出で積層させた３層の積層フィルムであり、最表層（最外側層）となるランダムポリプロピレンには滑剤としてエルカ酸アミドが１０００ｐｐｍ配合されている。 Next, on the other surface of the aluminum foil 4 of the obtained laminate, a 25 μm thick unstretched polypropylene film (inner layer ) 3 was dry-laminated (bonded) and then aged (heated) at 40° C. for 8 days to obtain the exterior material 1 having the structure shown in FIG. The unstretched polypropylene film is a three-layer laminated film in which random polypropylene, block polypropylene, and random polypropylene are laminated in this order by coextrusion, and the random polypropylene serving as the outermost layer (outermost layer) contains erucamide as a lubricant. Contains 1000ppm.

次に、株式会社アマダ製の深絞り成形具を用いて前記外装材（１５０ｍｍ×２００ｍｍの大きさに切り出した外装材）に対して、縦５０ｍｍ×横３０ｍｍ×深さ２．３ｍｍの略直方体形状（１つの面が開放された略直方体形状）に深絞り成形（プレス速度：２０ｓｐｍ、しわ抑え圧力１．６０ＭＰａ）を行って、図１、３に示す蓄電デバイス外装用深絞り成形ケース１０を得た。得られた成形ケースは、平面視において、縦１２０ｍｍ×横１００ｍｍの大きさであり、封止用周縁部の幅はそれぞれ３５ｍｍであった。 Next, using a deep drawing tool manufactured by Amada Co., Ltd., the exterior material (exterior material cut into a size of 150 mm × 200 mm) is formed into a substantially rectangular parallelepiped shape of 50 mm long × 30 mm wide × 2.3 mm deep Deep drawing (press speed: 20 spm, wrinkle suppression pressure: 1.60 MPa) is performed on the (substantially rectangular parallelepiped shape with one side open) to obtain the deep drawn case 10 for the exterior of the electric storage device shown in FIGS. rice field. The obtained molded case had a size of 120 mm long×100 mm wide in plan view, and the width of each of the peripheral edge portions for sealing was 35 mm.

＜実施例２＞
深絞り成形条件として、成形高さを４．４ｍｍ、しわ抑え圧力を１．２０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。 <Example 2>
As the deep drawing conditions, the deep drawing case for the exterior of the electric storage device shown in FIGS. Obtained.

＜参考例４＞
深絞り成形条件として、成形高さを５．７ｍｍ、しわ抑え圧力を０．４０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 4 >
As the deep drawing conditions, the deep drawing case for the exterior of the electric storage device shown in FIGS. Obtained.

＜参考例５＞
厚さ３０μｍのアルミニウム箔に代えて、厚さ４０μｍのアルミニウム箔を使用し、成形高さを４．４ｍｍ、しわ抑え圧力を０．８０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 5 >
In the same manner as in Example 1, except that an aluminum foil with a thickness of 40 μm was used instead of the aluminum foil with a thickness of 30 μm, the molding height was set to 4.4 mm, and the wrinkle suppression pressure was set to 0.80 MPa. 1 and 3 were obtained.

＜参考例６＞
厚さ２５μｍの無延伸ポリプロピレンフィルムに代えて、厚さ４０μｍの無延伸ポリプロピレンフィルムを使用し、成形高さを４．４ｍｍ、しわ抑え圧力を０．４０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 6 >
The same as in Example 1 except that an unstretched polypropylene film with a thickness of 40 μm was used instead of the unstretched polypropylene film with a thickness of 25 μm, the molding height was set to 4.4 mm, and the wrinkle suppression pressure was set to 0.40 MPa. As a result, the deep-drawn case for exterior of the electric storage device shown in FIGS. 1 and 3 was obtained.

＜参考例１＞
厚さ１５μｍの二軸延伸ナイロンフィルムに代えて、厚さ１５μｍの二軸延伸ポリエチレンテレフタレート（ＰＥＴ）フィルムを使用し、成形高さを３．５ｍｍ、しわ抑え圧力を０．４０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 1 >
A biaxially oriented polyethylene terephthalate (PET) film with a thickness of 15 μm was used instead of the biaxially oriented nylon film with a thickness of 15 μm. , in the same manner as in Example 1, a deep-drawn molded case for exterior of an electric storage device shown in FIGS. 1 and 3 was obtained.

＜参考例２＞
厚さ１５μｍの二軸延伸ナイロンフィルムに代えて、厚さ１５μｍの二軸延伸ポリブチレンテレフタレート（ＰＢＴ）フィルムを使用し、成形高さを３．５ｍｍ、しわ抑え圧力を０．４０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 2 >
Except that a biaxially oriented polybutylene terephthalate (PBT) film with a thickness of 15 μm was used instead of the biaxially oriented nylon film with a thickness of 15 μm, and the forming height was set to 3.5 mm, and the wrinkle suppression pressure was set to 0.40 MPa. In the same manner as in Example 1, a deep-drawn molded case for exterior of an electric storage device shown in FIGS. 1 and 3 was obtained.

＜参考例３＞
厚さ１５μｍの二軸延伸ナイロンフィルムに代えて、厚さ１５μｍの二軸延伸ナイロンフィルムと厚さ９μｍの二軸延伸ポリエチレンテレフタレート（ＰＥＴ）フィルムとが積層された積層フィルム（ナイロンフィルムを最外側に配置する）を使用し、成形高さを３．５ｍｍ、しわ抑え圧力を０．４０ＭＰａに設定した以外は、実施例１と同様にして、図１、３に示す蓄電デバイス外装用深絞り成形ケースを得た。
< Reference example 3 >
Instead of the 15 μm-thick biaxially oriented nylon film, a laminated film (the nylon film is the outermost 1 and 3 in the same manner as in Example 1, except that the molding height was set to 3.5 mm and the wrinkle suppression pressure was set to 0.40 MPa. got

＜比較例１＞
深絞り成形条件として、成形高さを５．７ｍｍ、しわ抑え圧力を１．２０ＭＰａに設定した以外は、実施例１と同様にして、蓄電デバイス外装用深絞り成形ケースを得た。 <Comparative Example 1>
A deep drawn case for exterior of an electric storage device was obtained in the same manner as in Example 1, except that the forming height was set to 5.7 mm and the wrinkle suppressing pressure was set to 1.20 MPa as the deep drawing forming conditions.

＜比較例２＞
深絞り成形条件として、成形高さを６．５ｍｍ、しわ抑え圧力を１．２０ＭＰａに設定した以外は、実施例１と同様にして、蓄電デバイス外装用深絞り成形ケースを得た。 <Comparative Example 2>
A deep drawn case for exterior of an electric storage device was obtained in the same manner as in Example 1, except that the forming height was set to 6.5 mm and the wrinkle suppressing pressure was set to 1.20 MPa as the deep drawing forming conditions.

＜比較例３＞
厚さ１５μｍの二軸延伸ナイロンフィルムに代えて、厚さ１５μｍの二軸延伸ポリエチレンテレフタレート（ＰＥＴ）フィルムを使用し、成形高さを３．５ｍｍに設定した以外は、実施例１と同様にして、蓄電デバイス外装用深絞り成形ケースを得た。 <Comparative Example 3>
In the same manner as in Example 1, except that a 15 μm thick biaxially oriented polyethylene terephthalate (PET) film was used instead of the 15 μm thick biaxially oriented nylon film, and the molding height was set to 3.5 mm. , a deep-drawn molded case for exterior of an electric storage device was obtained.

＜比較例４＞
成形高さを３．５ｍｍに設定した以外は、実施例１と同様にして、蓄電デバイス外装用深絞り成形ケースを得た。 <Comparative Example 4>
A deep-drawn molded case for exterior of an electric storage device was obtained in the same manner as in Example 1, except that the molding height was set to 3.5 mm.

Figure 0007240824000001
Figure 0007240824000001

Figure 0007240824000002
Figure 0007240824000002

Figure 0007240824000003
Figure 0007240824000003

上記のようにして得られた各蓄電デバイス外装用深絞り成形ケースについて、該成形ケースの下記各部での厚さを次のようにして測定した。具体的には、成形ケースをアクリル系樹脂で固めた後、成形ケースの収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面で成形ケースを切断し、その切断面の走査電子顕微鏡（ＳＥＭ）による断面観察を行い、スケールバーとの比較により、成形ケース１０の下記各部での厚さｂ1、ａ1、ｃ1、ｄ1、ｅ1を測定した。即ち、
「ｂ1」…成形ケースの側面の厚さ（側面における上下方向の高さの二等分中間位置での厚さ；図３参照）
「ａ1」…天面と側面とを繋ぐ第１コーナー部の厚さ（上記切断面における第１コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での第１コーナー部の厚さ；図３参照）
「ｃ1」…封止用周縁部と側面とを繋ぐ第２コーナー部の厚さ（上記切断面における第２コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での第２コーナー部の厚さ；図３参照）
「ｄ1」…成形ケースの天面の厚さ（天面における２つの対角線の交点位置での天面の厚さ）
「ｅ1」…封止用周縁部の厚さ（封止用周縁部における幅方向の二等分中間位置での厚さ）をそれぞれ測定した。これら各部の厚さの測定結果を表１に示す。 With respect to each of the deep-drawn cases for the exterior of an electric storage device obtained as described above, the thickness of each of the following portions of the formed case was measured as follows. Specifically, after solidifying the molded case with an acrylic resin, the molded case is cut along a vertical plane passing through two arbitrary corners that are not adjacent to each other on the top surface of the storage case of the molded case, and the cut surface is Cross-sectional observation was performed using a scanning electron microscope (SEM), and thicknesses b 1 , a 1 , c 1 , d 1 , and e 1 at the following portions of the molded case 10 were measured by comparison with scale bars. Namely
“b 1 ” … Thickness of the side surface of the molded case (thickness at the halfway point of the vertical height of the side surface; see FIG. 3)
"a 1 " ... the thickness of the first corner connecting the top surface and the side surface (the first corner thickness; see Fig. 3)
“c 1 ” … Thickness of the second corner portion connecting the sealing peripheral edge portion and the side surface (at the halfway position from one end to the other end of the curved portion of the second corner portion on the cut surface The thickness of the second corner of the; see Figure 3)
"d 1 " ... thickness of the top surface of the molded case (thickness of the top surface at the intersection of two diagonal lines on the top surface)
“e 1 ”: The thickness of the sealing peripheral portion (thickness at the midpoint of the bisected portion in the width direction of the sealing peripheral portion) was measured. Table 1 shows the measurement results of the thickness of each part.

また、得られた各蓄電デバイス用深絞り成形ケースについて、内側層３の下記各部での厚さを上記と同様に切断面の走査電子顕微鏡（ＳＥＭ）による断面観察により測定した。即ち、
「ｂ2」…成形ケースの側面を構成する内側層の厚さ（側面における上下方向の高さの二等分中間位置での内側層の厚さ）
「ａ2」…天面と側面とを繋ぐ第１コーナー部を構成する内側層の厚さ（上記切断面における第１コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での内側層の厚さ）
「ｃ2」…封止用周縁部と側面とを繋ぐ第２コーナー部を構成する内側層の厚さ（上記切断面における第２コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での内側層の厚さ）
「ｄ2」…成形ケースの天面を構成する内側層の厚さ（天面における２つの対角線の交点位置での内側層の厚さ）
「ｅ2」…封止用周縁部を構成する内側層の厚さ（封止用周縁部における幅方向の二等分中間位置での内側層の厚さ）
をそれぞれ測定した。これら各部の厚さの測定結果を表２に示す。 In addition, the thickness of each of the following parts of the inner layer 3 of each of the obtained deep-drawn cases for electric storage devices was measured by cross-sectional observation of the cut surface with a scanning electron microscope (SEM) in the same manner as described above. Namely
“b 2 ”: Thickness of the inner layer forming the side surface of the molded case (thickness of the inner layer at the midpoint of the vertical height on the side surface)
“a 2 ” … Thickness of the inner layer that forms the first corner connecting the top surface and the side surface (the halfway point from one end to the other end of the curved portion of the first corner on the cut surface inner layer thickness at position)
“c 2 ” … the thickness of the inner layer forming the second corner connecting the sealing peripheral portion and the side surface (the thickness of the inner layer from one end to the other end of the curved portion of the second corner on the cut surface) thickness of the inner layer at the intermediate position of the equal division)
“d 2 ”: Thickness of the inner layer forming the top surface of the molded case (thickness of the inner layer at the intersection of two diagonal lines on the top surface)
“e 2 ”: Thickness of the inner layer constituting the sealing peripheral edge (thickness of the inner layer at the midpoint of the widthwise bisector of the sealing peripheral edge)
were measured respectively. Table 2 shows the measurement results of the thickness of each part.

また、得られた各蓄電デバイス用深絞り成形ケースについて、金属箔層４の下記各部での厚さを上記と同様に切断面の走査電子顕微鏡（ＳＥＭ）による断面観察により測定した。即ち、
「ｂ3」…成形ケースの側面を構成する金属箔層の厚さ（側面における上下方向の高さの二等分中間位置での金属箔層の厚さ）
「ａ3」…天面と側面とを繋ぐ第１コーナー部を構成する金属箔層の厚さ（上記切断面における第１コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での金属箔層の厚さ）
「ｃ3」…封止用周縁部と側面とを繋ぐ第２コーナー部を構成する金属箔層の厚さ（上記切断面における第２コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での金属箔層の厚さ）
「ｄ3」…成形ケースの天面を構成する金属箔層の厚さ（天面における２つの対角線の交点位置での金属箔層の厚さ）
「ｅ3」…封止用周縁部を構成する金属箔層の厚さ（封止用周縁部における幅方向の二等分中間位置での金属箔層の厚さ）
をそれぞれ測定した。これら各部の厚さの測定結果を表２に示す。 In addition, the thicknesses of the metal foil layer 4 at the following portions of each of the obtained deep-drawn cases for electric storage devices were measured by cross-sectional observation with a scanning electron microscope (SEM) in the same manner as described above. Namely
“b 3 ”: Thickness of the metal foil layer forming the side surface of the molded case (thickness of the metal foil layer at the midpoint of the vertical height on the side surface)
“a 3 ” … Thickness of the metal foil layer forming the first corner connecting the top surface and the side surface (bisected from one end to the other end of the curved part of the first corner on the cut surface thickness of the metal foil layer at the intermediate position)
“c 3 ”: Thickness of the metal foil layer forming the second corner connecting the sealing peripheral portion and the side surface (the thickness from one end to the other end of the curved portion of the second corner on the cut surface thickness of the metal foil layer at the midpoint of the bisection)
“d 3 ”: thickness of the metal foil layer forming the top surface of the molded case (thickness of the metal foil layer at the intersection of two diagonal lines on the top surface)
“e 3 ”: Thickness of the metal foil layer forming the peripheral portion for sealing (thickness of the metal foil layer at the midpoint of the bisected portion in the width direction of the peripheral portion for sealing)
were measured respectively. Table 2 shows the measurement results of the thickness of each part.

また、得られた各蓄電デバイス用深絞り成形ケースについて、外側層２の下記各部での厚さを上記と同様に切断面の走査電子顕微鏡（ＳＥＭ）による断面観察により測定した。即ち、
「ｂ4」…成形ケースの側面を構成する外側層の厚さ（側面における上下方向の高さの二等分中間位置での外側層の厚さ）
「ａ4」…天面と側面とを繋ぐ第１コーナー部を構成する外側層の厚さ（上記切断面における第１コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での外側層の厚さ）
「ｃ4」…封止用周縁部と側面とを繋ぐ第２コーナー部を構成する外側層の厚さ（上記切断面における第２コーナー部の湾曲箇所の一方の端から他方の端までの二等分中間位置での外側層の厚さ）
「ｄ4」…成形ケースの天面を構成する外側層の厚さ（天面における２つの対角線の交点位置での外側層の厚さ）
「ｅ4」…封止用周縁部を構成する外側層の厚さ（封止用周縁部における幅方向の二等分中間位置での外側層の厚さ）
をそれぞれ測定した。これら各部の厚さの測定結果を表３に示す。 In addition, the thickness of each of the following portions of the outer layer 2 of each obtained deep-drawn case for an electric storage device was measured by cross-sectional observation of the cut surface with a scanning electron microscope (SEM) in the same manner as described above. Namely
“b 4 ”: Thickness of the outer layer forming the side surface of the molded case (thickness of the outer layer at the midpoint of the vertical height of the side surface)
“a 4 ” … Thickness of the outer layer forming the first corner connecting the top surface and the side surface (halfway between one end and the other end of the curved portion of the first corner on the cut surface outer layer thickness at position)
“c 4 ”: Thickness of the outer layer forming the second corner connecting the sealing peripheral edge and the side surface (the thickness of the outer layer from one end to the other end of the curved portion of the second corner on the cut surface) thickness of the outer layer at the intermediate position of the equal division)
“d 4 ”: Thickness of the outer layer forming the top surface of the molded case (thickness of the outer layer at the intersection of two diagonal lines on the top surface)
“e 4 ”: Thickness of the outer layer forming the peripheral portion for sealing (thickness of the outer layer at the midpoint of the bisected portion in the width direction of the peripheral portion for sealing)
were measured respectively. Table 3 shows the measurement results of the thickness of each part.

更に、得られた各蓄電デバイス用深絞り成形ケースについて下記評価法に基づいて評価を行った。その結果を表３に示す。 Furthermore, each of the obtained deep-drawn cases for electric storage devices was evaluated based on the following evaluation methods. Table 3 shows the results.

＜成形後の外観評価法＞
得られた蓄電デバイス外装用深絞り成形ケースにおけるピンホールの有無および各層間のデラミネーション（剥離）の有無を調べ、下記判定基準に基づいて外観を評価した。
（判定基準）
「○」…第１、第２コーナー部および他の部位にピンホールがなく、各層間のデラミネーション（剥離）も認められなかった
「×」…第１コーナー部又は／及び第２コーナー部にピンホールが発生していた。
「××」…層間にデラミネーション（剥離）が認められた。 <Appearance evaluation method after molding>
The presence of pinholes and the presence of delamination (peeling) between layers in the obtained deep-drawn case for exterior of an electric storage device was examined, and the appearance was evaluated based on the following criteria.
(criterion)
"◯": No pinholes in the first and second corners and other parts, and no delamination (peeling) between layers was observed. "X": At the first corner and/or the second corner. A pinhole had occurred.
"XX": Delamination (peeling) was observed between the layers.

＜電解液の漏れ防止性評価法＞
得られた蓄電デバイス外装用深絞り成形ケース１０の中に電解液を１５ｍＬ入れた後、成形ケース１０の内側層３側に、実施例１に記載の平面状の外装材１と同一の外装材（縦１２０ｍｍ×横１００ｍｍ）の内側層３を重ね合わせた後、封止用周縁部の領域をシール幅５ｍｍで１７０℃で６秒間ヒートシールすることにより、模擬的蓄電デバイスを得た。前記模擬的蓄電デバイスを１００℃の条件下で３０日間保管した後、該模擬的蓄電デバイスにおける電解液漏れの有無および深絞り成形ケースの外観を調べ、下記判定基準に基づいて液漏れ防止性および外観を評価した。
（液漏れ防止性の判定基準）
「○」…模擬的蓄電デバイスにおいて電解液漏れが認められなかった
「×」…模擬的蓄電デバイスにおいて電解液漏れが認められた
（外観の判定基準）
「○」…模擬的蓄電デバイスの外装ケースの外観は電解液注入前と変化がなく良好な外観を呈していた
「×」…模擬的蓄電デバイスの外装ケースは、電解液による剥離や変色が認められた。 <Method for evaluating leakage prevention of electrolyte solution>
After putting 15 mL of the electrolytic solution into the obtained deep-drawn case 10 for exterior of the electric storage device, the same exterior material as the planar exterior material 1 described in Example 1 is placed on the inner layer 3 side of the molded case 10. After superimposing the inner layer 3 (120 mm long×100 mm wide), a simulated electricity storage device was obtained by heat-sealing the area of the peripheral edge portion for sealing with a sealing width of 5 mm at 170° C. for 6 seconds. After storing the simulated electricity storage device for 30 days under conditions of 100 ° C., the presence or absence of electrolyte leakage in the simulated electricity storage device and the appearance of the deep drawn case were examined. Appearance was evaluated.
(Judgment criteria for liquid leakage prevention)
“◯”: No electrolyte leakage was observed in the simulated electricity storage device “×”: Electrolyte leakage was observed in the simulated electricity storage device (appearance criteria)
"○": The exterior case of the simulated electricity storage device had a good appearance without any change from before the electrolyte was injected. was taken.

表から明らかなように、本発明に係る実施例１～２及び参考例１～６の蓄電デバイス外装用深絞り成形ケースは、成形ケースにピンホール等が発生し難く、蓄電デバイスにおける電解液の漏れ発生を防止できる。
これに対し、本発明の規定範囲を逸脱する比較例１～４の成形ケースでは、蓄電デバイスにおける電解液の漏れ発生を防止できなかった。なお、比較例２の成形ケースでは、成形後の外観評価を行った時点で既にピンホールが発生していたため、電解液の漏れ防止性評価は行わなかった。 As is clear from the table, the deep-drawn cases for the exterior of the electric storage device of Examples 1 to 2 and Reference Examples 1 to 6 according to the present invention are less likely to have pinholes, etc., and the electrolytic solution in the electric storage device is less likely to form. Leakage can be prevented.
On the other hand, in the molded cases of Comparative Examples 1 to 4, which deviate from the specified range of the present invention, it was not possible to prevent the electrolyte from leaking from the electricity storage device. In addition, in the molded case of Comparative Example 2, pinholes had already occurred when the external appearance was evaluated after molding, so the leakage prevention property of the electrolytic solution was not evaluated.

本発明に係る蓄電デバイス外装用深絞り成形ケースは、具体例として、例えば、
・リチウム２次電池（リチウムイオン電池、リチウムポリマー電池等）などの蓄電デバイス
・リチウムイオンキャパシタ
・電気２重層コンデンサ
・全固体電池
等の各種蓄電デバイスの外装ケースとして用いられる。 Specific examples of the deep-drawn case for exterior of an electric storage device according to the present invention include, for example,
・Used as an exterior case for various storage devices such as storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.), lithium ion capacitors, electric double layer capacitors, and all-solid-state batteries.

１…外装材
２…耐熱性樹脂層（外側層）
３…熱融着性樹脂層（内側層）
４…金属箔層
１０…蓄電デバイス外装用深絞り成形ケース
１５…外装部材
２８…収容ケース
２８ａ…下面開放口
３０…蓄電デバイス
３１…蓄電デバイス本体部
４１…天面の角部（コーナー部）
４２…天面の角部（コーナー部）
５１…天面
５２…側面
５３…封止用周縁部
５５…第１コーナー部
５６…第２コーナー部 1 ... exterior material 2 ... heat-resistant resin layer (outer layer)
3... Heat-fusible resin layer (inner layer)
4... Metal foil layer 10... Deep drawn case 15... Exterior member 28... Housing case 28a... Lower surface opening 30... Electricity storage device 31... Electricity storage device main body 41... Top surface corner (corner part)
42 ... Corner part (corner part) of the top surface
51... Top surface 52... Side surface 53... Peripheral portion for sealing 55... First corner portion 56... Second corner portion

Claims (5)

外側層としての耐熱性樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層とを含んでなる外装材の深絞り成形ケースであって、
前記耐熱性樹脂層は延伸ポリアミドフィルム単層で形成されており、
前記深絞り成形ケースは、蓄電デバイス本体部を収容し得る収容ケースと、該収容ケースの下面開放口の周縁から略水平方向の外方に向けて延ばされた封止用周縁部とを有する立体形状であり、前記収容ケースの天面形状は、四角以上の略多角形形状であり、
前記収容ケースの天面における互いに隣り合わない任意の２つの角部を通る鉛直面で前記深絞り成形ケースを切断する断面図において、前記深絞り成形ケースの側面の厚さを「ｂ1」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部の厚さを「ａ1」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部の厚さを「ｃ1」（μｍ）としたとき、
ｂ1＞ｃ1＞ａ1 … 式（１）
ｃ1＞ｂ1＞ａ1 … 式（２）
ｂ1＝ｃ1＞ａ1 … 式（３）
上記の式（１）、式（２）および式（３）の３つの関係式のうちいずれか１つの関係式を満たすと共に、
前記収容ケースをその天面における互いに隣り合わない任意の２つの角部を通る鉛直面で切断した断面図において、前記天面を構成する金属箔層の厚さを「ｄ3」（μｍ）とし、前記封止用周縁部を構成する金属箔層の厚さを「ｅ3」（μｍ）としたとき、ｄ3／ｅ3の値が０．８７以上であり、
さらに、前記鉛直面で前記深絞り成形ケースを切断する前記断面図において、前記深絞り成形ケースの側面を構成する熱融着性樹脂層の厚さを「ｂ2」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部を構成する熱融着性樹脂層の厚さを「ａ2」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部を構成する熱融着性樹脂層の厚さを「ｃ2」（μｍ）としたとき、
ｂ2＞ｃ2＞ａ2 … 式（４）
ｃ2＞ｂ2＞ａ2 … 式（５）
ｂ2＝ｃ2＞ａ2 … 式（６）
上記の式（４）、式（５）および式（６）の３つの関係式のうちいずれか１つの関係式を満たし、
さらに、前記鉛直面で前記深絞り成形ケースを切断する前記断面図において、前記深絞り成形ケースの側面を構成する金属箔層の厚さを「ｂ3」（μｍ）とし、前記天面と前記側面とを繋ぐ第１コーナー部を構成する金属箔層の厚さを「ａ3」（μｍ）とし、前記封止用周縁部と前記側面とを繋ぐ第２コーナー部を構成する金属箔層の厚さを「ｃ3」（μｍ）としたとき、
ｂ3＞ｃ3＞ａ3 … 式（７）
ｃ3＞ｂ3＞ａ3 … 式（８）
ｂ3＝ｃ3＞ａ3 … 式（９）
上記の式（７）、式（８）および式（９）の３つの関係式のうちいずれか１つの関係式を満たすことを特徴とする蓄電デバイス外装用深絞り成形ケース。 A deep-drawn case for an exterior material comprising a heat-resistant resin layer as an outer layer, a heat-sealable resin layer as an inner layer, and a metal foil layer disposed between these layers,
The heat-resistant resin layer is formed of a stretched polyamide film single layer,
The deep drawn case has a housing case capable of housing the electricity storage device main body, and a sealing peripheral edge portion extending outward in a substantially horizontal direction from the periphery of the opening on the lower surface of the housing case. It has a three-dimensional shape, and the top surface shape of the storage case is a substantially polygonal shape with a square or more,
In a cross-sectional view of the deep-drawn case cut along a vertical plane passing through any two non-adjacent corners of the top surface of the storage case, the thickness of the side surface of the deep-drawn case is "b 1 " ( μm), the thickness of the first corner portion connecting the top surface and the side surface is “a 1 ” (μm), and the thickness of the second corner portion connecting the sealing peripheral edge portion and the side surface is When "c 1 " (μm),
b 1 >c 1 >a 1 Formula (1)
c 1 >b 1 >a 1 Formula (2)
b1 = c1 > a1 ... Formula (3)
While satisfying any one of the three relational expressions of the above formulas (1), (2) and (3),
In a cross-sectional view of the storage case cut along a vertical plane passing through two non-adjacent corners of the top surface, the thickness of the metal foil layer forming the top surface is defined as "d 3 " (μm). , and the value of d 3 /e 3 is 0.00, where the thickness of the metal foil layer forming the sealing edge portion is "e 3 " (μm). is 87 or more,
Furthermore, in the cross-sectional view of the deep-drawn case cut along the vertical plane, the thickness of the heat-fusible resin layer constituting the side surface of the deep-drawn case is defined as "b 2 " (μm), The thickness of the heat-fusible resin layer constituting the first corner portion connecting the surface and the side surface is set to "a 2 " (μm), and the second corner portion connecting the sealing peripheral portion and the side surface is When the thickness of the constituent heat-fusible resin layer is “c 2 ” (μm),
b 2 >c 2 >a 2 (4)
c 2 >b 2 >a 2 (5)
b2 = c2 > a2 ... Formula (6)
satisfies any one of the three relational expressions of the above formulas (4), (5) and (6),
Furthermore, in the cross-sectional view of the deep-drawn case cut along the vertical plane, the thickness of the metal foil layer forming the side surface of the deep-drawn case is defined as "b 3 " (μm), and the top surface and the The thickness of the metal foil layer forming the first corner connecting the side surface is set to "a 3 " (μm), and the thickness of the metal foil layer forming the second corner connecting the sealing peripheral portion and the side surface. When the thickness is “c 3 ” (μm),
b 3 >c 3 >a 3 (7)
c 3 >b 3 >a 3 (8)
b3 = c3 > a3 ... Formula (9)
A deep-drawn case for the exterior of an electric storage device, characterized by satisfying any one of the three relational expressions of the above formulas (7), (8) and (9). 前記内側層は、複数層の熱融着性樹脂層で形成されている請求項１に記載の蓄電デバイス外装用深絞り成形ケース。 2. The deep-drawn case for exterior of an electric storage device according to claim 1, wherein said inner layer is formed of a plurality of heat-sealable resin layers. 前記金属箔層は、アルミニウム箔で形成されている請求項１または２に記載の蓄電デバイス外装用深絞り成形ケース。 3. The deep-drawn case according to claim 1, wherein the metal foil layer is made of aluminum foil. 前記金属箔層における少なくとも前記内側層側の面に化成皮膜層が形成されている請求項１～３のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケース。 4. The deep-drawn case for exterior of an electric storage device according to claim 1, wherein a chemical conversion film layer is formed on at least the inner layer side surface of the metal foil layer. 蓄電デバイス本体部と、
請求項１～４のいずれか１項に記載の蓄電デバイス外装用深絞り成形ケースを含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。
an electricity storage device main body;
An exterior member including the deep-drawn case for exterior of an electricity storage device according to any one of claims 1 to 4,
An electricity storage device, wherein the electricity storage device main body is covered with the exterior member.
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CN112563629B (en) * 2020-11-20 2023-06-09 曙鹏科技（深圳）有限公司 Method for manufacturing soft package battery and first soft package half-shell
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014139945A (en) 2010-10-14 2014-07-31 Toppan Printing Co Ltd Exterior material for lithium ion battery
JP2016225301A (en) 2014-09-26 2016-12-28 大日本印刷株式会社 Battery packaging material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012033394A (en) * 2010-07-30 2012-02-16 Fujimori Kogyo Co Ltd Laminate for battery exterior package
CN104112827A (en) * 2013-04-19 2014-10-22 藤森工业株式会社 Sealing member, manufacturing method for sealing member and container for electric storage device
JP6717190B2 (en) * 2014-04-09 2020-07-01 凸版印刷株式会社 Power storage device exterior material, power storage device, and method for manufacturing embossed type exterior material
TWI691113B (en) * 2015-07-01 2020-04-11 日商昭和電工包裝股份有限公司 Exterior materials for power storage device and power storage device
JP6738189B2 (en) * 2016-04-21 2020-08-12 昭和電工パッケージング株式会社 Exterior material for power storage device and power storage device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014139945A (en) 2010-10-14 2014-07-31 Toppan Printing Co Ltd Exterior material for lithium ion battery
JP2016225301A (en) 2014-09-26 2016-12-28 大日本印刷株式会社 Battery packaging material

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