JP5387062B2 - Secondary battery - Google Patents

Secondary battery Download PDF

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JP5387062B2
JP5387062B2 JP2009053379A JP2009053379A JP5387062B2 JP 5387062 B2 JP5387062 B2 JP 5387062B2 JP 2009053379 A JP2009053379 A JP 2009053379A JP 2009053379 A JP2009053379 A JP 2009053379A JP 5387062 B2 JP5387062 B2 JP 5387062B2
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gas
opening
secondary battery
seal
opening portion
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JP2010211927A (en
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博基 田口
雄児 丹上
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Nissan Motor Co Ltd
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Description

本発明は、外装部材により電池要素を内部に封止する二次電池に関するものである。   The present invention relates to a secondary battery in which a battery element is sealed inside by an exterior member.

電池内部で発生したガスを外部に排出するために、外装部材を貼り合わせた接合領域の一部に他の領域よりも接合強度を弱めた架橋構造部と、ガスを外部に開放するためのガス開放室と、を備えた二次電池が知られている（たとえば特許文献１参照。）。   In order to discharge the gas generated inside the battery to the outside, a bridging structure part in which the bonding strength is weaker than in other areas in a part of the bonding area where the exterior member is bonded, and a gas for releasing the gas to the outside A secondary battery including an open chamber is known (see, for example, Patent Document 1).

国際公開２００６−０９８２４２号International Publication No. 2006-098242

上記の架橋構造部において剥離が始まると、二次電池は短時間で性能が大きく低下するおそれがある。   If peeling starts in the above-mentioned crosslinked structure part, the performance of the secondary battery may be greatly reduced in a short time.

本発明が解決しようとする課題は、性能を長く維持することができる二次電池を提供することである。   The problem to be solved by the present invention is to provide a secondary battery capable of maintaining the performance for a long time.

本発明は、外装部材を貼り合わせたシール部に、シール部内に密閉され、ガスを吸着するガス吸着部と、シール部の内周縁からガス吸着部までの全域に亘って設けられ、シール部の他の部分よりも開封強度が相対的に弱い第１の開封部と、シール部の他の部分よりも開封強度が相対的に弱く、且つ、第１の開封部よりも開封強度が相対的に強い第２の開封部を有するガス排出部と、を設けることで上記課題を解決する。 The present invention relates to a seal portion bonded to the outer member, is sealed in the sealing portion, and a gas suction portion for sucking the gas, provided to extend from the inner circumference of the seal portion in the entire region up to the gas suction part, of the seal portion The first opening portion having relatively lower opening strength than other portions, the opening strength being relatively weaker than other portions of the seal portion, and the opening strength being relatively lower than that of the first opening portion. The above-mentioned problem is solved by providing a gas discharge part having a strong second opening part.

本発明によれば、シール部において他の部分よりも開封強度が相対的に弱い第１の開封部によって、電池内部で発生したガスを先ずガス吸着部に導くことができる。そして、第２の開封部の開封強度をシール部の他の部分よりも相対的に弱く、且つ、第１の開封部よりも相対的に強くしたので、ガス吸着部がガスを十分に吸着した後に第２の開封部が開封してガスを排出することができる。このため、ガスを外部に排出するまでの時間を長くすることができ、二次電池の性能を長く維持することができる。   According to the present invention, the gas generated in the battery can be first guided to the gas adsorbing portion by the first opening portion whose opening strength is relatively weaker than other portions in the sealing portion. And, since the opening strength of the second opening part is relatively weaker than other parts of the seal part and relatively stronger than the first opening part, the gas adsorbing part sufficiently adsorbs the gas. Later, the second opening can be opened and the gas discharged. For this reason, the time until the gas is discharged to the outside can be extended, and the performance of the secondary battery can be maintained long.

図１は、本発明の第１実施形態におけるラミネート電池を示す平面図である。FIG. 1 is a plan view showing a laminated battery according to a first embodiment of the present invention. 図２は、図１のII−II線に沿った断面図である。FIG. 2 is a cross-sectional view taken along line II-II in FIG. 図３は、図１のIII−III線に沿った断面図である。FIG. 3 is a cross-sectional view taken along line III-III in FIG. 図４は、図３のIＶ部を示す拡大平面図であるFIG. 4 is an enlarged plan view showing the IV portion of FIG. 図５は、図４のＶ−Ｖ線に沿った断面図である。FIG. 5 is a cross-sectional view taken along line VV in FIG. 図６は、本発明の第２実施形態におけるラミネート電池のガス排出部を示す平面図である。FIG. 6 is a plan view showing a gas discharge part of the laminated battery in the second embodiment of the present invention. 図７は、本発明の第３実施形態におけるラミネート電池のガス排出部を示す平面図である。FIG. 7 is a plan view showing a gas discharge part of the laminated battery in the third embodiment of the present invention. 図８Ａは、本発明の第１実施形態におけるラミネート電池がガスを排出する様子を示す図である（その１）。FIG. 8A is a diagram showing a state in which the laminated battery in the first embodiment of the present invention discharges gas (part 1). 図８Ｂは、本発明の第１実施形態におけるラミネート電池がガスを排出する様子を示す図である（その２）。FIG. 8B is a diagram showing a state in which the laminated battery in the first embodiment of the present invention discharges gas (part 2). 図８Ｃは、本発明の第１実施形態におけるラミネート電池がガスを排出する様子を示す図である（その３）。FIG. 8C is a diagram showing a state in which the laminated battery in the first embodiment of the present invention discharges gas (part 3). 図８Ｄは、本発明の第１実施形態におけるラミネート電池がガスを排出する様子を示す図である（その４）。FIG. 8D is a diagram showing a state in which the laminated battery in the first embodiment of the present invention discharges gas (part 4).

以下、本発明の実施形態を図面に基づいて説明する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings.

《第１実施形態》
図１は本発明の第１実施形態におけるラミネート電池を示す平面図、図２は図１のII−II線に沿った断面図、図３は図１のIII−III線に沿った断面図である。 << First Embodiment >>
1 is a plan view showing a laminated battery according to a first embodiment of the present invention, FIG. 2 is a cross-sectional view taken along line II-II in FIG. 1, and FIG. 3 is a cross-sectional view taken along line III-III in FIG. is there.

先ず、本発明の実施形態に係るラミネート電池１０は、積層可能な平板状（薄型）のリチウムイオン二次電池である。このラミネート電池１０は、図１〜図３に示すように、３枚の正極板１０１と、５枚のセパレータ１０２と、３枚の負極板１０３と、正極端子１０４と、負極端子１０５と、上部外装部材１０６と、下部外装部材１０７と、特に図示しない電解質と、から構成されており、例えば１０ｍｍ以下の総厚を有している。本実施形態では、このうちの正極板１０１、セパレータ１０２、負極板１０３及び電解質を特に発電要素１０８と称する。   First, a laminated battery 10 according to an embodiment of the present invention is a flat (thin) lithium ion secondary battery that can be stacked. As shown in FIGS. 1 to 3, the laminate battery 10 includes three positive plates 101, five separators 102, three negative plates 103, a positive terminal 104, a negative terminal 105, and an upper portion. It is comprised from the exterior member 106, the lower exterior member 107, and the electrolyte which is not specifically illustrated, for example, has a total thickness of 10 mm or less. In the present embodiment, the positive electrode plate 101, the separator 102, the negative electrode plate 103, and the electrolyte are particularly referred to as a power generation element 108.

発電要素１０８の正極板１０１は、図２及び図３に示すように、正極端子１０４まで延びている正極側集電体１０１ａと、この正極側集電体１０１ａの一部の両主面にそれぞれ形成された正極層１０１ｂ，１０１ｃと、を有している。   As shown in FIGS. 2 and 3, the positive electrode plate 101 of the power generation element 108 is respectively provided on the positive electrode side current collector 101a extending to the positive electrode terminal 104 and both main surfaces of a part of the positive electrode side current collector 101a. And formed positive electrode layers 101b and 101c.

正極側集電体１０１ａは、例えば、アルミニウム箔、アルミニウム合金箔、銅箔、又は、ニッケル箔等の電気化学的に安定した金属箔で構成されている。   The positive electrode side current collector 101a is made of an electrochemically stable metal foil such as an aluminum foil, an aluminum alloy foil, a copper foil, or a nickel foil.

正極層１０１ｂ，１０１ｃは、正極活物質と、カーボンブラック等の導電剤と、ポリ四フッ化エチレンの水性ディスパージョン等の接着剤と、を混合したものを、正極側集電体１０１ａの一部の両主面に塗布し、乾燥及び圧延することにより形成されている。正極活物質としては、例えば、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）、又は、コバルト酸リチウム（ＬｉＣｏＯ２）等のリチウム複合酸化物や、カルコゲン（Ｓ、Ｓｅ、Ｔｅ）化物等を挙げることができる。 The positive electrode layers 101b and 101c are formed by mixing a positive electrode active material, a conductive agent such as carbon black, and an adhesive such as an aqueous dispersion of polytetrafluoroethylene with a part of the positive electrode side current collector 101a. It is formed by applying to both main surfaces, drying and rolling. Examples of the positive electrode active material include lithium composite oxides such as lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), and lithium cobaltate (LiCoO 2 ), and chalcogen (S, Se, Te) compounds. Etc.

発電要素１０８の負極板１０３は、負極端子１０５まで延びている負極側集電体１０３ａと、この負極側集電体１０３ａの一部の両主面にそれぞれ形成された負極層１０３ｂ，１０３ｃと、を有している。   The negative electrode plate 103 of the power generation element 108 includes a negative electrode side current collector 103a extending to the negative electrode terminal 105, and negative electrode layers 103b and 103c respectively formed on both main surfaces of a part of the negative electrode side current collector 103a. have.

負極側集電体１０３ａは、例えば、ニッケル箔、銅箔、ステンレス箔、又は、鉄箔等の電気化学的に安定した金属箔で構成されている。   The negative electrode side current collector 103a is made of an electrochemically stable metal foil such as a nickel foil, a copper foil, a stainless steel foil, or an iron foil.

負極層１０３ｂ，１０３ｃは、上記の正極活物質のリチウムイオンを吸蔵及び放出する負極活物質に、有機物焼成体の前駆体材料としてのスチレンブタジエンゴム樹脂粉末の水性ディスパージョンを混合し乾燥させた後に粉砕することで、炭素粒子表面に炭化したスチレンブタジエンゴムを担持させたものを主材料とし、これにアクリル樹脂エマルジョン等の結着剤をさらに混合し、この混合物を負極側集電体１０３ａの一部の両主面に塗布し、乾燥及び圧延することにより形成されている。負極活物質としては、例えば、非晶質炭素、難黒鉛化炭素、易黒鉛化炭素、又は、黒鉛等を挙げることが出来る。   The negative electrode layers 103b and 103c are prepared by mixing an aqueous dispersion of styrene butadiene rubber resin powder as a precursor material of an organic fired body with the negative electrode active material that absorbs and releases lithium ions of the positive electrode active material, and then drying the negative electrode active material. By pulverizing, the main material is carbonized styrene butadiene rubber supported on the surface of the carbon particles, and a binder such as an acrylic resin emulsion is further mixed therewith, and this mixture is mixed with one of the negative electrode side current collector 103a. It is formed by applying to both main surfaces of the part, drying and rolling. Examples of the negative electrode active material include amorphous carbon, non-graphitizable carbon, graphitizable carbon, and graphite.

特に、負極活物質として非晶質炭素や難黒鉛化炭素を用いると、充放電時における電位の平坦特性に乏しく放電量に伴って出力電圧も低下するので、通信機器や事務機器の電源には不向きであるが、電気自動車の電源として用いる急激な出力低下がないので有利である。   In particular, when amorphous carbon or non-graphitizable carbon is used as the negative electrode active material, the flatness of the potential during charge / discharge is poor and the output voltage decreases with the amount of discharge. Although unsuitable, it is advantageous because there is no sudden drop in output used as a power source for electric vehicles.

発電要素１０８のセパレータ１０２は、正極板１０１と負極板１０３との短絡を防止するもので、電解質を保持する機能を備えても良い。このセパレータ１０２は、例えば、ポリエチレン（ＰＥ）やポリプロピレン（ＰＰ）等のポリオレフィンから構成される微多孔性膜であり、過電流が流れると、その発熱によって層の空孔が閉塞され電流を遮断する機能をも有する。   The separator 102 of the power generation element 108 prevents a short circuit between the positive electrode plate 101 and the negative electrode plate 103 and may have a function of holding an electrolyte. The separator 102 is a microporous film made of a polyolefin such as polyethylene (PE) or polypropylene (PP), for example. When an overcurrent flows, the pores of the layer are blocked by the heat generation, thereby blocking the current. It also has a function.

なお、本発明におけるセパレータは、ポリオレフィン等の単層膜のみに限定されず、ポリプロピレン膜をポリエチレン膜でサンドイッチした三層構造や、ポリオレフィン微多孔性膜と有機不織布等を積層したものを用いることもできる。このように、セパレータを複層化することで、過電流の防止機能、電解質保持機能及びセパレータの形状維持（剛性向上）機能等の諸機能を付与することができる。   The separator in the present invention is not limited to a single-layer film such as polyolefin, but may be a three-layer structure in which a polypropylene film is sandwiched with a polyethylene film, or a laminate of a polyolefin microporous film and an organic nonwoven fabric or the like. it can. Thus, by forming the separator in multiple layers, various functions such as an overcurrent prevention function, an electrolyte holding function, and a separator shape maintenance (stiffness improvement) function can be provided.

以上の発電要素１０８は、セパレータ１０２を介して正極板１０１と負極板１０３とが交互に積層されている。そして、３枚の正極板１０１は、正極側集電体１０１ａを介して、金属箔製の正極端子１０４にそれぞれ接続される一方で、３枚の負極板１０３は、負極側集電体１０３ａを介して、同様に金属箔製の負極端子１０５にそれぞれ接続されている。   In the power generation element 108 described above, the positive electrode plates 101 and the negative electrode plates 103 are alternately stacked via the separators 102. The three positive plates 101 are respectively connected to the positive terminal 104 made of metal foil via the positive current collector 101a, while the three negative plates 103 are connected to the negative current collector 103a. In the same manner, each is connected to a negative electrode terminal 105 made of metal foil.

なお、発電要素１０８の正極板１０１、セパレータ１０２、及び、負極板１０３は、本発明では上記の枚数に何ら限定されず、例えば、１枚の正極板、３枚のセパレータ、１枚の負極板でも発電要素を構成することができ、必要に応じて、正極板、セパレータ及び負極板の枚数を選択して構成することができる。   The positive electrode plate 101, the separator 102, and the negative electrode plate 103 of the power generation element 108 are not limited to the above number in the present invention. For example, one positive plate, three separators, one negative plate However, the power generation element can be configured, and the number of positive plates, separators, and negative plates can be selected and configured as necessary.

正極端子１０４も負極端子１０５も電気化学的に安定した金属材料であれば、特に限定されないが、正極端子１０４としては、上述の正極側集電体１０１ａと同様に、例えば、アルミニウム箔、アルミニウム合金箔、銅箔、又は、ニッケル箔等を挙げることができる。また、負極端子１０５としては、上述の負極側集電体１０３ａと同様に、例えば、ニッケル箔、銅箔、ステンレス箔、又は、鉄箔等を挙げることができる。また、本実施形態では、電極板１０１，１０３の集電体１０１ａ，１０３ａを構成する金属箔自体を電極端子１０４，１０５まで延長することにより、電極板１０１，１０３を電極端子１０４，１０５に直接接続しているが、電極板１０１，１０３の集電体１０１ａ，１０３ａと、電極端子１０４、１０５とを、集電体１０１ａ，１０３ａを構成する金属箔とは別の材料や部品により接続してもよい。   The positive electrode terminal 104 and the negative electrode terminal 105 are not particularly limited as long as they are electrochemically stable metal materials. Examples of the positive electrode terminal 104 include, for example, an aluminum foil and an aluminum alloy, similar to the positive electrode side current collector 101a described above. A foil, copper foil, nickel foil, etc. can be mentioned. Moreover, as the negative electrode terminal 105, nickel foil, copper foil, stainless steel foil, iron foil, etc. can be mentioned similarly to the above-mentioned negative electrode side collector 103a, for example. In the present embodiment, the metal foil itself constituting the current collectors 101 a and 103 a of the electrode plates 101 and 103 is extended to the electrode terminals 104 and 105, so that the electrode plates 101 and 103 are directly connected to the electrode terminals 104 and 105. Although connected, the current collectors 101a and 103a of the electrode plates 101 and 103 and the electrode terminals 104 and 105 are connected by materials and parts different from the metal foils constituting the current collectors 101a and 103a. Also good.

発電要素１０８は、図２及び図３に示すようなカップ状に成型された上部外装部材１０６と、平板状の下部外装部材１０７との間に収容されている。また、上部外装部材１０６と下部外装部材１０７は、それぞれ対向する外縁部分を貼り合わせたシール部２０により、封止している。本実施形態における上部外装部材１０６及び下部外装部材１０７は何れも、特に図示しないが、内側樹脂層、金属層、及び、外側樹脂層から成るラミネート材（ラミネートフィルム）で構成されている。   The power generation element 108 is accommodated between an upper exterior member 106 molded into a cup shape as shown in FIGS. 2 and 3 and a flat lower exterior member 107. Further, the upper exterior member 106 and the lower exterior member 107 are sealed by the seal portion 20 in which the opposing outer edge portions are bonded together. Both the upper exterior member 106 and the lower exterior member 107 in the present embodiment are made of a laminate material (laminate film) made of an inner resin layer, a metal layer, and an outer resin layer, although not particularly illustrated.

このラミネート材の内側樹脂層は、例えば、ポリエチレン、変性ポリエチレン、ポリプロピレン、変性ポリプロピレン、又は、アイオノマー等の耐電解液性及び熱融着性に優れた樹脂フィルムで構成されている。金属層は、例えばアルミニウム等の金属箔で構成されている。外側樹脂層は、例えば、ポリアミド系樹脂やポリエステル系樹脂等の電気絶縁性に優れた樹脂フィルムで構成されている。   The inner resin layer of the laminate material is made of a resin film excellent in electrolytic solution resistance and heat fusion properties such as polyethylene, modified polyethylene, polypropylene, modified polypropylene, or ionomer. The metal layer is made of a metal foil such as aluminum. The outer resin layer is made of, for example, a resin film excellent in electrical insulation, such as a polyamide resin or a polyester resin.

なお、ラミネート電池１０内部の封止性を維持するために、シール部２０に、例えば、ポリエチレンやポリプロピレン等から構成されたシールフィルムを介在させても良い。このシールフィルムは、正極端子１０４及び負極端子１０５の何れにおいても、外装部材１０６，１０７の内側樹脂層を構成する合成樹脂材料と同系統のもので構成することが熱融着性の観点から好ましい。   In order to maintain the sealing performance inside the laminated battery 10, a seal film made of, for example, polyethylene or polypropylene may be interposed in the seal portion 20. It is preferable from the viewpoint of heat-sealability that the sealing film is made of the same system as the synthetic resin material constituting the inner resin layer of the exterior members 106 and 107 in both the positive electrode terminal 104 and the negative electrode terminal 105. .

これらの外装部材１０６，１０７によって、上述した発電要素１０８、電極端子１０４，１０５の一部を包み込み、当該外装部材１０６，１０７により形成される空間に、有機液体溶媒に過塩素酸リチウムやホウフッ化リチウム、六フッ化リン酸リチウム等のリチウム塩を溶質とした液体電解質を注入しながら、当該空間を真空状態とした後に、外装部材１０６，１０７の外周部分を熱プレスにより熱融着してシール部２０を形成する。これにより、外装部材１０６，１０７の内部に発電要素１０８及び電極端子１０４，１０５の一部が収容されて封止される。   These exterior members 106 and 107 enclose part of the power generation element 108 and the electrode terminals 104 and 105 described above, and in the space formed by the exterior members 106 and 107, lithium perchlorate or borofluoride is added to the organic liquid solvent. While injecting a liquid electrolyte in which a lithium salt such as lithium or lithium hexafluorophosphate as a solute is injected, the space is evacuated, and the outer peripheral portions of the exterior members 106 and 107 are heat-sealed by a hot press and sealed. Part 20 is formed. Thereby, a part of the power generation element 108 and the electrode terminals 104 and 105 are accommodated in the exterior members 106 and 107 and sealed.

有機液体溶媒として、プロピレンカーボネート（ＰＣ）やエチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、メチルエチルカーボネート等のエステル系溶媒を挙げることができる。なお、本発明の有機液体溶媒はこれに限定されることなく、エステル系溶媒に、γ−ブチラクトン（γ−ＢＬ）やジエトシキエタン（ＤＥＥ）等のエーテル系溶媒その他を混合、調合した有機液体溶媒を用いることもできる。   Examples of the organic liquid solvent include ester solvents such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl ethyl carbonate. The organic liquid solvent of the present invention is not limited to this, and an organic liquid solvent prepared by mixing and preparing an ether solvent such as γ-butylactone (γ-BL) or dietoshietane (DEE) in an ester solvent. It can also be used.

図４は図３のIＶ部を示す拡大平面図、図５は図４のＶ−Ｖ線に沿った断面図である。   4 is an enlarged plan view showing an IV portion of FIG. 3, and FIG. 5 is a cross-sectional view taken along line VV of FIG.

図４及び図５に示すように、シール部２０における長辺の略中央部分には、電池要素１０８が発生するガスを吸着するガス吸着部２１と、ガスをガス吸着部２１に導く第１の開封部２２と、ガスを電池外部に排出するガス排出部２３と、が設けられている。なお、本実施形態では、ガス吸着部２１、第１の開封部２２、及びガス排出部２３をシール部２０の短辺部分に設けてもよい。   As shown in FIGS. 4 and 5, a gas adsorbing portion 21 that adsorbs the gas generated by the battery element 108 and a first gas that leads the gas to the gas adsorbing portion 21 are provided at a substantially central portion of the long side of the seal portion 20. An opening portion 22 and a gas discharge portion 23 for discharging gas to the outside of the battery are provided. In the present embodiment, the gas adsorption unit 21, the first opening unit 22, and the gas discharge unit 23 may be provided on the short side portion of the seal unit 20.

ガス吸着部２１は、電池の長時間の使用や高温地での使用等に起因して、電解質の分解等により電池要素１０８が発生したガスを吸着する部材である。ガス吸着部２１は、例えば、活性炭、カーボンナノチューブ、カーボンシート、シリカゲル、活性アルミナゼオライト等を用いて構成することができる。ガス吸着部２１は、シール部２０において、内周縁と外周縁との略中間に配置され、外装部材１０６，１０７を熱融着して形成されるシール部２０内に密封されている。   The gas adsorbing unit 21 is a member that adsorbs gas generated by the battery element 108 due to electrolyte decomposition due to long-time use of the battery or use in a high temperature area. The gas adsorption unit 21 can be configured using, for example, activated carbon, carbon nanotubes, carbon sheets, silica gel, activated alumina zeolite, or the like. The gas adsorbing portion 21 is disposed in the seal portion 20 approximately in the middle between the inner peripheral edge and the outer peripheral edge, and is sealed in the seal portion 20 formed by heat-sealing the exterior members 106 and 107.

第１の開封部２２は、シール部２０において開封強度（融着強度、剥離強度）が最も弱く設定されており、電池要素１０８が発生したガスの内圧上昇によってシール部２０の中でも最初に開封して、当該ガスをガス吸着部２１に積極的に導く。この第１の開封部２２は、たとえば、外装部材１０６，１０７を熱融着する際に、シール部２０の他の部分を熱融着する際の第１の温度Ｔ１よりも低い第２の温度Ｔ２で熱融着することで形成される（Ｔ１＞Ｔ２）。なお、外装部材１０６，１０７の間に、それらの内側樹脂層よりも融点の高いシートフィルムや架橋処理したメッシュ材を介在させたり、少なくとも一方の外装部材１０６，１０７の内側樹脂層を架橋処理することで、第１の開封部２２を形成してもよい。   The first opening portion 22 is set to have the weakest opening strength (fusion strength, peel strength) in the seal portion 20, and is opened first in the seal portion 20 due to the increase in the internal pressure of the gas generated by the battery element 108. Thus, the gas is positively guided to the gas adsorption unit 21. For example, when the exterior members 106 and 107 are heat-sealed, the first opening portion 22 has a second temperature lower than the first temperature T1 when heat-sealing other portions of the seal portion 20. It is formed by heat fusion at T2 (T1> T2). In addition, a sheet film having a higher melting point than those of the inner resin layers or a mesh material subjected to crosslinking treatment is interposed between the exterior members 106 and 107, or the inner resin layer of at least one of the exterior members 106 and 107 is crosslinked. Thus, the first opening portion 22 may be formed.

この第１の開封部２２は、シール部２０の内周縁とガス吸着部２１との間に配置されており、本実施形態では、シール部２０の内周縁からガス吸着部２１までの全域に亘って設けられている。一方、ラミネート電池１０の長手方向においては、本実施形態ではガス吸着部２１よりも幅が狭くなっているが、ガス吸着部２１と同じ程度の幅としてもよいし、或いは、ガス吸着部２１からシール部２０の内周縁に向かって広がるような形状としてもよい。   The first opening portion 22 is disposed between the inner peripheral edge of the seal portion 20 and the gas adsorption portion 21. In the present embodiment, the first opening portion 22 extends over the entire area from the inner peripheral edge of the seal portion 20 to the gas adsorption portion 21. Is provided. On the other hand, in the longitudinal direction of the laminated battery 10, the width is narrower than that of the gas adsorption unit 21 in the present embodiment, but the width may be the same as that of the gas adsorption unit 21, or from the gas adsorption unit 21. It is good also as a shape which spreads toward the inner periphery of the seal | sticker part 20. As shown in FIG.

ガス排出部２３は、第１の開封部２２に次いで開封する第２の開封部２３１と、各外装部材１０６，１０７を貫通する貫通孔２３２と、を有している。   The gas discharge part 23 has a second opening part 231 that is opened next to the first opening part 22, and a through hole 232 that penetrates the exterior members 106 and 107.

第２の開封部２３１は、シール部２０の中で第１の開封部２２に次いで開封強度が弱く設定されており、ガス吸着部２１がガスを十分に吸着した後にガスを排出する。この第２の開封部２３１は、たとえば、外装部材１０６，１０７を熱融着する際に、第１の温度Ｔ１よりも低く、且つ、第２の温度Ｔ２よりも高い第３の温度Ｔ３で熱融着することで形成されている（Ｔ１＞Ｔ３＞Ｔ２）。なお、外装部材１０６，１０７の間に、それらの内側樹脂層よりも融点の高いシートフィルムや架橋処理したメッシュ材を介在させたり、少なくとも一方の外装部材１０６，１０７の内側樹脂層を架橋処理することで、第２の開封部２３１を形成してもよい。   The second opening portion 231 is set to have a lower opening strength next to the first opening portion 22 in the seal portion 20 and discharges the gas after the gas adsorbing portion 21 has sufficiently adsorbed the gas. For example, when the exterior members 106 and 107 are heat-sealed, the second opening portion 231 is heated at a third temperature T3 that is lower than the first temperature T1 and higher than the second temperature T2. It is formed by fusing (T1> T3> T2). In addition, a sheet film having a higher melting point than those of the inner resin layers or a mesh material subjected to crosslinking treatment is interposed between the exterior members 106 and 107, or the inner resin layer of at least one of the exterior members 106 and 107 is crosslinked. Thus, the second opening portion 231 may be formed.

この第２の開封部２３１は、本実施形態では、ガス吸着部２１とシール部２０の外周縁との間に配置されている。また、ラミネート電池１０の長手方向においては、本実施形態ではガス吸着部２１よりも幅が狭くなっているが、ガス吸着部２１と同じ程度の幅としてもよいし、ガス吸着部２１からシール部２０の外周縁に向かって広がるような形状としてもよい。また、図６に示すように、第２の開封部２３１を、第１の開封部２２及びガス吸着部２１とはオフセットした位置に配置し、その一端をシール部２０の内周縁と接続させてもよい。   In the present embodiment, the second opening portion 231 is disposed between the gas adsorption portion 21 and the outer peripheral edge of the seal portion 20. In the present embodiment, the width of the laminated battery 10 is narrower than that of the gas adsorbing portion 21. However, the width may be the same as that of the gas adsorbing portion 21. It is good also as a shape which spreads toward 20 outer periphery. Further, as shown in FIG. 6, the second opening portion 231 is disposed at a position offset from the first opening portion 22 and the gas adsorption portion 21, and one end thereof is connected to the inner peripheral edge of the seal portion 20. Also good.

貫通孔２３２は、図４及び図５に示すように、第２の開封部２３１において外装部材１０６，１０７を貫通しており、第１の開封部２２及び第２の開封部２３１が開封すると、電池内部が貫通孔２３２を介して外部と連通する。なお、貫通孔２３２は、それぞれの外装部材１０６，１０７のいずれか一方のみを貫通してもよい。また、図７に示すように、ガス排出部２３に貫通孔２３２を設けず、第２の開封部２３１をシール部２０の外周縁に直接接続させて、この第２の開封部２３１がシール部２０の外側端面で開封することでガスを外部に排出してもよい。   As shown in FIGS. 4 and 5, the through-hole 232 penetrates the exterior members 106 and 107 in the second opening portion 231, and when the first opening portion 22 and the second opening portion 231 are opened, The inside of the battery communicates with the outside through the through hole 232. Note that the through hole 232 may penetrate only one of the exterior members 106 and 107. Further, as shown in FIG. 7, the gas discharge part 23 is not provided with the through hole 232, and the second opening part 231 is directly connected to the outer peripheral edge of the seal part 20, and the second opening part 231 is the seal part. The gas may be discharged to the outside by opening at the outer end face of 20.

以下に作用について説明する。   The operation will be described below.

図８Ａ〜図８Ｄは本発明の第１実施形態におけるラミネート電池がガスを排出する様子を示す図である。   8A to 8D are views showing how the laminated battery in the first embodiment of the present invention discharges gas.

図８Ａに示すように、電池要素１０８がガスを発生して内圧上昇が起こると、外装部材１０６，１０７は圧力を受けて、シール部２０の内周縁に、引き剥がされる方向の応力が印加される。ここで、シール部２０において、第１の開封部２２の開封強度が最も弱く設定されているので、シール部２０が受ける引き剥がされる方向の応力は、第１の開封部２２に集中し、シール部２０において最初に第１の開封部２２が剥離する。この第１の開封部２２の剥離は、シール部２０の内周縁からガス吸着部２１に向かって進展する。   As shown in FIG. 8A, when the battery element 108 generates gas and the internal pressure rises, the exterior members 106 and 107 receive pressure, and a stress in the peeling direction is applied to the inner peripheral edge of the seal portion 20. The Here, since the opening strength of the first opening portion 22 is set to be the weakest in the seal portion 20, the stress in the peeling direction received by the seal portion 20 is concentrated on the first opening portion 22, and the seal In the part 20, the 1st opening part 22 peels first. The peeling of the first opening portion 22 progresses from the inner peripheral edge of the seal portion 20 toward the gas adsorption portion 21.

図８Ｂに示すように、第１の開封部２２の剥離がガス吸着部２１まで到達して、第１の開封部２２が開封すると、電池内部で発生したガスがガス吸着部２１に至り、ガス吸着部２１がガスを吸着する。その結果、ガスによる電池の内圧上昇が抑制される。   As shown in FIG. 8B, when the peeling of the first opening portion 22 reaches the gas adsorbing portion 21 and the first opening portion 22 is opened, the gas generated inside the battery reaches the gas adsorbing portion 21, and the gas The adsorption part 21 adsorbs gas. As a result, an increase in the internal pressure of the battery due to the gas is suppressed.

図８Ｃに示すように、ガスの発生量がガス吸着部２１の吸着許容量を超えると、シール部２０は、引き剥がされる方向の応力を再び受ける。シール部２０において、第２の開封部２３１は、第１の開封部２２に次いで開封強度を弱く設定されているので、第１の開封部２２の開封後においては、引き剥がされる方向の応力が第２の開封部２３１に集中し、第２の開封部２３１が剥離する。この第２の開封部２３１の剥離は、シール部２０の外周縁に向かって進展する。また、ガス吸着に伴うガス吸着部２１の厚みや温度の増加によっても、第２の開封部２３１の剥離が促進される。   As shown in FIG. 8C, when the amount of gas generation exceeds the adsorption allowable amount of the gas adsorption unit 21, the seal unit 20 receives the stress in the peeling direction again. In the seal part 20, the second opening part 231 is set to have a weaker opening strength next to the first opening part 22, so that after the opening of the first opening part 22, the stress in the direction to be peeled off is applied. It concentrates on the 2nd opening part 231, and the 2nd opening part 231 peels. The peeling of the second opening portion 231 progresses toward the outer peripheral edge of the seal portion 20. Moreover, peeling of the 2nd opening part 231 is accelerated | stimulated also by the increase in the thickness and temperature of the gas adsorption part 21 accompanying gas adsorption.

図８Ｄに示すように、第２の開封部２３１の剥離が貫通孔２３２まで到達すると、第２の開封部２３１も開封し、第１の開封部２２及び第２の開封部２３１を介して電池内部と貫通孔２３２とが連通し、ガスが貫通孔２３２を介して電池外部に排出される。   As shown in FIG. 8D, when the peeling of the second opening portion 231 reaches the through hole 232, the second opening portion 231 is also opened, and the battery is opened via the first opening portion 22 and the second opening portion 231. The inside and the through hole 232 communicate with each other, and the gas is discharged to the outside of the battery through the through hole 232.

このように本実施形態では、シール部２０において他の部分よりも開封強度が相対的に弱い第１の開封部２２によって、電池内部で発生したガスを先ずガス吸着部２１に導くことができる。そして、第２の開封部２３１の開封強度をシール部２０において他の部分よりも相対的に弱く、且つ第１の開封部２２よりも相対的に強くしたので、ガス吸着部２１がガスを十分に吸着した後に第２の開封部２３１が開封してガスを排出することができる。このため、シール部２０の剥離が開始してからガスを外部に排出するまでの時間を長くすることができ、ラミネート電池１０の性能を長く維持することができる。   As described above, in the present embodiment, the gas generated inside the battery can be first guided to the gas adsorbing portion 21 by the first opening portion 22 having relatively lower opening strength than the other portions in the seal portion 20. Since the opening strength of the second opening portion 231 is relatively weaker than the other portions in the seal portion 20 and relatively stronger than the first opening portion 22, the gas adsorbing portion 21 has sufficient gas. The second unsealing part 231 can be unsealed and the gas can be discharged after adsorbing to the gas. For this reason, it is possible to lengthen the time from the start of peeling of the seal portion 20 until the gas is discharged to the outside, and the performance of the laminated battery 10 can be maintained long.

たとえば、５５℃の環境下において、２．５［Ｖ］から４．２［Ｖ］までの１［Ｃ］での充電と、４．２［Ｖ］から２．５［Ｖ］までの１［Ｃ］の放電とを繰り返した場合、単にガス排出部を設けただけの従来構造では１００日でガスを外部に排出したのに対し、本実施形態の構造では１２０日までガスを外部に排出しなかった。このことからも、本実施形態のラミネート電池１０では性能を長く維持できることが分かる。   For example, in an environment of 55 ° C., charging at 1 [C] from 2.5 [V] to 4.2 [V] and 1 [C] from 4.2 [V] to 2.5 [V] C] is repeated, the conventional structure in which the gas discharge unit is simply provided discharges the gas to the outside in 100 days, whereas in the structure of this embodiment, the gas is discharged to the outside until 120 days. There wasn't. This also shows that the performance of the laminate battery 10 of this embodiment can be maintained for a long time.

また、本実施形態では、第１の開封部２２を第２の開封部２３１に対して電池内側に配置することで、ガスの発生による内圧上昇の際に、最初に第１の開封部２２を開封させてガスをガス吸着部２１に積極的に導くことができる。   Further, in the present embodiment, the first opening portion 22 is disposed inside the battery with respect to the second opening portion 231, so that the first opening portion 22 is first formed when the internal pressure increases due to the generation of gas. The gas can be positively guided to the gas adsorbing portion 21 by being opened.

さらに、ガス吸着部２１を第１の開封部２２と第２の開封部２３１との間に配置することで、第１の開封部２２が確実にガスをガス吸着部２１に導いて、ガスをガス吸着部２１に吸着させることができる。   Furthermore, by disposing the gas adsorption part 21 between the first opening part 22 and the second opening part 231, the first opening part 22 reliably guides the gas to the gas adsorption part 21, It can be adsorbed by the gas adsorption part 21.

また、本実施形態では、第２の開封部２３１に貫通孔２３２を設け、又は第２の開封部２３１をシール部２０の外側端面で露出させることで、ガスを外部に排出させることができる。   In the present embodiment, the through hole 232 is provided in the second opening portion 231, or the second opening portion 231 is exposed at the outer end surface of the seal portion 20, whereby the gas can be discharged to the outside.

１０…ラミネート電池
１０１…正極板
１０１ａ…正極側集電体
１０１ｂ，１０１ｃ…正極層
１０２…セパレータ
１０３…負極板
１０３ａ…負極側集電体
１０３ｂ，１０３ｃ…負極層
１０４…正極端子
１０５…負極端子
１０６…上部外装部材
１０７…下部外装部材
１０８…発電要素
２０…シール部
２１…ガス吸着部
２２…第１の開封部
２３…ガス排出部
２３１…第２の開封部
２３２…貫通孔 DESCRIPTION OF SYMBOLS 10 ... Laminate battery 101 ... Positive electrode plate 101a ... Positive electrode side collector 101b, 101c ... Positive electrode layer 102 ... Separator 103 ... Negative electrode plate 103a ... Negative electrode side collector 103b, 103c ... Negative electrode layer 104 ... Positive electrode terminal 105 ... Negative electrode terminal 106 ... Upper exterior member 107 ... Lower exterior member 108 ... Power generation element 20 ... Sealing part 21 ... Gas adsorption part 22 ... First opening part 23 ... Gas discharge part 231 ... Second opening part 232 ... Through hole

Claims (5)

外装部材を貼り合わせたシール部により電池要素を内部に封止する二次電池であって、
前記シール部は、
前記電池要素が発生するガスを外部に排出するガス排出部と、
前記シール部内に密閉され、前記ガスを吸着するガス吸着部と、
前記シール部の内周縁から前記ガス吸着部までの全域に亘って設けられ、前記シール部の他の部分よりも開封強度が相対的に弱い第１の開封部と、を備え、
前記ガス排出部は、前記シール部の他の部分よりも開封強度が相対的に弱く、且つ、前記第１の開封部よりも開封強度が相対的に強い第２の開封部を有することを特徴とする二次電池。
It is a secondary battery that seals the battery element inside by a seal portion to which an exterior member is bonded,
The seal portion is
A gas discharge part for discharging the gas generated by the battery element to the outside;
A gas adsorbing part that is sealed in the seal part and adsorbs the gas;
A first opening part that is provided over the entire area from the inner peripheral edge of the seal part to the gas adsorbing part, and has a relatively lower opening strength than other parts of the seal part,
The gas discharge part has a second opening part whose opening strength is relatively weaker than other parts of the sealing part and whose opening strength is relatively stronger than that of the first opening part. Secondary battery.
請求項１記載の二次電池であって、
前記第１の開封部は、前記第２の開封部よりも電池内側に配置されることを特徴とする二次電池。 The secondary battery according to claim 1,
The secondary battery is characterized in that the first opening part is disposed inside the battery with respect to the second opening part. 請求項２記載の二次電池であって、
前記ガス吸着部は、前記第１の開封部と前記第２の開封部との間に配置されていることを特徴とする二次電池。 The secondary battery according to claim 2,
The secondary battery according to claim 1, wherein the gas adsorbing portion is disposed between the first opening portion and the second opening portion. 請求項１〜３の何れかに記載の二次電池であって、
前記ガス排出部は、前記外装部材を貫通する貫通孔を有し、
前記第２の開封部は、前記貫通孔に連通可能であることを特徴とする二次電池。 The secondary battery according to any one of claims 1 to 3,
The gas discharge part has a through-hole penetrating the exterior member,
The secondary battery is characterized in that the second opening portion can communicate with the through hole. 請求項１〜３の何れかに記載の二次電池であって、
前記第２の開封部は、前記シール部の外側端面で露出していること特徴とする二次電池。 The secondary battery according to any one of claims 1 to 3,
The secondary battery is characterized in that the second opening portion is exposed at an outer end face of the seal portion.
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