JP4059327B2 - Polymer electrolyte battery - Google Patents
Polymer electrolyte battery Download PDFInfo
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- JP4059327B2 JP4059327B2 JP07324298A JP7324298A JP4059327B2 JP 4059327 B2 JP4059327 B2 JP 4059327B2 JP 07324298 A JP07324298 A JP 07324298A JP 7324298 A JP7324298 A JP 7324298A JP 4059327 B2 JP4059327 B2 JP 4059327B2
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- polymer electrolyte
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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
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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
- 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
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Description
【0001】
【発明の属する技術分野】
本発明は、ポリマー電解質電池に関し、さらに詳しくは、特に携帯用機器、電気自動車、ロードレベリングなどに使用するのに適したポリマー電解質電池に関する。
【0002】
【従来の技術】
シート状の電解質を用いることにより、A4版、B5版などの大面積でしかも薄形の電池の作製が可能になり、各種薄形製品への適用が可能になって、電池の使用範囲が大きく広がっている。特にポリマー電解質を用いた電池は、耐漏液性を含めた安全性、貯蔵性が優れており、しかも薄く、フレキシブルなため、機器の形状に合わせた電池を設計できるという、今までの電池にない特徴を持っている。
【0003】
このポリマー電解質電池は、通常、アルミニウムフィルムを芯材にしたラミネートフィルムを外装体に用い、薄いシート状の電極とシート状のポリマー電解質層とを組み合わせて、薄形電池に仕上げられる。
【0004】
【発明が解決しようとする課題】
このポリマー電解質電池では、正負両電極やポリマー電解質層が本質的に遊離の液を含まない固体状であるため、正負両電極とポリマー電解質層とからなるユニットセルまたは該ユニットセルを複数個積層したユニットセル積層体を外装体で外装する際に、上記ユニットセルにおける電極の裏面側の金属箔の露出部分とラミネートフィルムなどからなる外装体の内面との密着性がないため、シール時に微量の気体が電池内に残存しやすく、その残存した気体が電池特性を低下させたり、外装体と電極などとの間にずれを生じさせ、折り曲げ時に皺が発生する原因になるという問題があった。
【0005】
従って、本発明は、上記のような従来技術の問題点を解決し、ユニットセルにおける電極の裏面側の金属箔の露出部分と外装体の内面との密着性を高め、フレキシブルで、折り曲げによる皺の発生が少なく、かつ貯蔵による電池ふくれが少なく、貯蔵性能の良好なポリマー電解質電池を提供することを目的とする。
【0006】
【課題を解決するための手段】
本発明は、ユニットセルにおける外装体の内面と対向する電極の金属箔の露出部分(以下、簡略化して「金属箔」で説明する)と外装体の内面(以下、簡略化して「外装体」で説明する)との対向面の全部または一部を、ポリマー電解質層または電極合剤層に含まれる電解質に含有されているものと同質のポリマーおよび電解質溶媒を含有する混合物により接着することによって、上記課題を解決したものである。
【0007】
本発明において、ユニットセルの金属箔と外装体との接着に用いるポリマーと電解液溶媒とを含有する混合物は、接着性を有するとともに粘性を有しているので、電池全体のフレキシブル性を好適に保ち、電池の折り曲げ時に皺が発生するのを防止する。
【0008】
また、上記金属箔と外装体との接着に用いるポリマーと電解液溶媒は、ポリマー電解質層または電極合剤層に含まれる電解質に含有されているポリマーや電解液溶媒などと実質的に同質のもの(つまり、同様の材質からなるもの)であるため、電池特性を低下させることがなく、また、上記のように電極の金属箔と外装体とを接着することによって、電池内部に電池特性の低下を引き起こす酸素や水分などを含む気体が混入するのを防止することができる。
【0009】
【発明の実施の形態】
接着は、ユニットセルの金属箔と外装体との対向面の全部または一部に行えばよいが、接着面積は広いほど好ましく、上記部分の全部またはほぼ全部について行うのが好ましい。
【0010】
本発明においていうポリマーと電解液溶媒とを含有する混合物は、ポリマー電解質層または電極の作製にあたって使用する電解液を含んだモノマー溶液であってもよい。つまり、電池内でポリマーとして存在するものと電解液溶媒とを含んでいればよく、それ以外に電池に使用できるものを含んでいてもよい。
【0011】
上記のような電解液を含むモノマー溶液の場合、ユニットセルを2個以上積層したユニットセル積層体の各ユニットセルを並列接続する場合にも有効に使用できるし、また、ユニットセル積層体のユニットセル間の金属面が対向する隙間に使用する接着剤にも適用できる。
【0012】
本発明において、一対の正極合剤層および負極合剤層を有する1個のユニットセルを外装体で外装して電池に仕上げる場合は、正極や負極は集電体となる金属箔の一方の面にのみ合剤層を形成する必要があるが、上記ユニットセル積層体の場合は、両端の電極、すなわち、外装体の内面と対向する電極のみ金属箔の一方の面にのみ合剤層を形成しておき、それらより内部側の正極や負極は金属箔の両面に合剤層を形成したものでもよい。
【0013】
【実施例】
つぎに、実施例を挙げて本発明をより具体的に説明する。ただし、本発明はそれらの実施例のみに限定されるものではない。なお、以下においては、(1)ユニットセルの金属箔と外装体との対向面のほぼ全部を後に詳細を示す特定の接着剤で接着した場合を実施例1、(2)上記対向面の周縁部のみ上記接着剤で接着した場合を実施例2、(3)上記対向面の中央部のみ上記接着剤で接着した場合を実施例3、(4)接着剤を用いず、上記対向面をまったく接着しなかった場合を比較例1として説明していくが、それらの説明に先立って正極、負極およびポリマー電解質層の作製について説明する。
【0014】
正極の作製:
正極活物質であるLiCoO2 50重量部、電導助剤であるアセチレンブラック10重量部、バインダであるポリフッ化ビニリデン10重量部を均一になるように混合し、さらに、電解液40重量部を加えて混合し、ペースト状の正極合剤を調製した。上記電解液はプロピレンカーボネートとエチレンカーボネートとの体積比1:1の混合溶媒にLiPF6 を1.22モル/リットル溶解させたものである。そして、上記のように調製したペースト状の正極合剤を集電体となるアルミニウム箔の一方の面に塗布し、加熱してゲル化させることによりアルミニウム箔上にゲル状の正極合剤層を形成して、シート状の正極を作製した。
【0015】
負極の作製:
負極活物質である黒鉛40重量部とポリフッ化ビニリデン5重量部と上記正極に用いたものと同様の電解液55重量部とを混合して、ペースト状の負極合剤を調製し、このペースト状の負極合剤を集電体となる銅箔の一方の面に塗布し、加熱してゲル化させることにより銅箔上にゲル状の負極合剤層を形成して、シート状の負極を作製した。
【0016】
ポリマー電解質層の作製:
厚さ70μmのポリオレフィン不織布に、2−エトキシエチルアクリレートとトリエチレングリコールジメタクリレートとエチレングリコールエチルカーボネートメタクリレートとの混合物(それら3成分のモノマーの混合比は重量比で50:13:33)15重量部とその重合開始剤である過酸化ベンゾイル0.75重量部と前記同様の電解液85重量部とを混合した溶液を含浸させ、加熱してモノマーを重合させるとともに全体をゲル化して、シート状のゲル状ポリマー電解質層を作製した。
【0017】
このポリマー電解質層を上記正極と負極との間に配置し、圧着してユニットセルを構成した。ただし、上記正極と負極との配置はそれぞれの合剤層がポリマー電解質層を介して対向するように配置した。つまり、正極の裏面側(ポリマー電解質層と対向しない側)ではアルミニウム箔が露出し、負極の裏面側では銅箔が露出している。そして、このユニットセルを外装する外装体としてポリエステルフィルム−アルミニウムフィルム−変性ポリオレフィンフィルムからなる三層構造のラミネートフィルムを準備した。なお、電極の裏面側とは集電体としての金属箔に合剤層を形成していない側をいい、表面側とは金属箔に合剤層を形成していて、ポリマー電解質層と対向する側をいう。
【0018】
実施例1
接着剤として、プロピレンカーボネートとエチレンカーボネートとの体積比1:1の混合溶媒80重量部に、前記ポリマー電解質層の作製にあたって使用したものと同様の3種類のアクリル系モノマー混合物20重量部と重合開始剤としての過酸化ベンゾイル0.8重量部を加え、加熱して上記モノマーを重合させるとともにゲル化して粘稠液を準備した。
【0019】
上記ユニットセルを外装体で外装するにあたり、ユニットセルの金属箔と外装体にはそれらの対向面(正極の裏面側のアルミニウム箔の露出部分と外装体の内面とが対向する面および負極の裏面側の銅箔の露出部分と外装体の内面とが対向する面)のほぼ全部に上記接着剤を塗布し、外装時に該接着剤塗布部分を押圧して接着剤で上記部分を接着し、ポリマー電解質電池を作製した。
【0020】
ここで、上記電池の概略構造を図1を参照しつつ説明すると、シート状の正極1とシート状の負極2との間にシート状のポリマー電解質層3が配置してユニットセルが構成され、そのユニットセルをラミネートフィルムからなる外装体4で外装し、正極1および負極2から正極端子5および負極端子6を外装体4の外部に引き出して電池が構成されている。
【0021】
図2は正極1の集電体であるアルミニウム箔1aと外装体4の内面とを接着剤7で接着した状態および負極2の集電体である銅箔2aと外装体4の内面とを接着剤7で接着した状態を模式的に示す要部拡大断面図である。正極1は集電体であるアルミニウム箔1aの一方の面にゲル状の正極合剤層1bを形成してなり、その正極合剤層1bをポリマー電解質層3と対向するように配置しているため、正極1の裏面側はアルミニウム箔1aで構成され、そのアルミニウム箔1aと外装体4との対向面が上記接着剤7で接着されている。また、負極2は集電体である銅箔2aの一方の面にゲル状の負極合剤層2bを形成してなり、その負極合剤層2bをポリマー電解質層3と対向するように配置しているため、負極2の裏面側は銅箔2aで構成され、その銅箔2aと外装体4との対向面が上記接着剤7で接着されている。なお、上記図1や図2は模式的に図示したものであって、各構成部材の寸法比は必ずしも正確ではない。
【0022】
実施例2
ユニットセルの金属箔と外装体との対向面の周縁部にのみ実施例1と同様の接着剤を塗布し、外装時に該接着剤塗布部分を押圧して接着剤で上記部分を接着した以外は、実施例1と同様にポリマー電解質電池を作製した。
【0023】
実施例3
ユニットセルの金属箔と外装体との対向面の中央部にのみ実施例1と同様の接着剤を塗布し、外装時に該接着剤塗布部分を押圧して接着剤で上記部分を接着した以外は、実施例1と同様にポリマー電解質電池を作製した。
【0024】
比較例1
ユニットセルの金属箔と外装体とを接着剤で接着しなかった以外は、実施例1と同様にポリマー電解質電池を作製した。
【0025】
上記実施例1〜3および比較例1の電池の電池容量、折り曲げ時の皺の発生状況、上記折り曲げによる短絡発生の有無および貯蔵による電池のふくれ(膨れ)を調べた。その結果を表1に示す。電池容量は、4.2V、0.2Cの定電流定電圧(CCCV法)で8時間充電した後、0.2Cで2.75Vまで放電したときの放電容量を測定し、表1には従来品に相当する比較例1の電池の容量を100とした指数で表示し、折り曲げ時の皺の発生状況は、電池を直径4mmの円柱に添わせて90°まで折り曲げ、その際の皺の発生状況を肉眼で観察することによって評価した。また、折り曲げによる短絡の発生の有無は、上記折り曲げテストによる皺の発生状況を肉眼で観察した後、その電池の開路電圧の変化を24時間後に測定し、開路電圧が折り曲げ前に比べて低下したものを短絡が発生しているものと判定した。なお、この折り曲げによる短絡発生の有無を調べるのは、折り曲げによる皺の発生が原因になって、電極に歪みが加わり、電極構成材料がゲル状ポリマー電解質層を突き破って、短絡発生を引き起こすか否かを調べるためである。また、電池のふくれは、電池を温度60℃、相対湿度90%の雰囲気中に20日間貯蔵した後、電池の厚さをシックネスゲージで5点測定し、そのうちの最大値を採用して、貯蔵後の厚さの最大値と貯蔵前の厚さの最大値との差を求めたものである。なお、上記実施例1〜3の電池、比較例1の電池のいずれも、作製時の設定総厚は1.0mmであった。
【0026】
【表1】
【0027】
表1に示す結果から明らかなように、実施例1〜3は、フレキシブルで、折り曲げ時の皺の発生がないかまたは少なく、かつ折り曲げによる皺の発生に基づく短絡の発生がなく、貯蔵による電池ふくれも小さく、貯蔵性能が優れていることを示していた。
【0028】
なお、上記実施例では、ポリマー電解質層中のポリマーと同質のポリマーとなるモノマーを含有する粘稠液を接着剤として用いたが、それに代えてポリフッ化ビニリデンとプロピレンカーボネートなどの電解液溶媒との混合物を接着剤として用いてもよい。また、電極の裏面側の金属箔の露出部分と外装体の内面との接着にあたては、実施例のように上記3成分系モノマーをあらかじめ重合することなく、モノマーと溶媒(電解液)と重合開始剤などを含む混合物を上記接着部分に塗布し、その後、加熱して接着効果を得てもよい。また、上記接着剤を構成するポリマーも、実施例で用いたもの以外に、上記のポリフッ化ビニリデンや後述する光硬化性樹脂などを用いてもよい。
【0029】
また、上記実施例では1個のユニットセルを外装して電池に仕上げた場合を示したが、それに代えて複数個のユニットセルを積層したユニットセル積層体を外装して電池に仕上げてもよい。
【0030】
なお、ポリマー電解質のゲル化に際しては、上記実施例で示した以外に、たとえば、ラジカル重合型の不飽和ポリエステル、または、ラジカル重合型のアクリル系エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート、アルキッドアクリレート、シリコンアクリレートなどの光硬化性樹脂を紫外線あるいは電子線を用いてゲル化させるものであってもよい。
【0031】
【発明の効果】
以上説明したように、本発明では、フレキシブルで、折り曲げた場合でも皺の発生が少なく、かつ貯蔵による電池ふくれが少ない、貯蔵性能が良好なポリマー電解質電池を提供することができた。
【図面の簡単な説明】
【図1】本発明に係るポリマー電解質電池の一例を模式的に示す断面図である。
【図2】正極の裏面側のアルミニウム箔の露出部分と外装体の内面とを接着剤で接着した状態および負極の裏面側の銅箔の露出部分と外装体の内面とを接着剤で接着した状態を模式的に示す要部拡大断面図である。
【符号の説明】
1 正極
1a アルミニウム箔
1b 正極合剤層
2 負極
2a 銅箔
2b 負極合剤層
3 ポリマー電解質層
4 外装体
7 接着剤[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer electrolyte battery, and more particularly to a polymer electrolyte battery particularly suitable for use in portable devices, electric vehicles, road leveling and the like.
[0002]
[Prior art]
By using a sheet-like electrolyte, it is possible to produce large-area and thin batteries such as A4 and B5 plates, which can be applied to various thin products, and the range of use of the battery is large. It has spread. Batteries using polymer electrolytes in particular have excellent safety and storage characteristics including leakage resistance, and are thin and flexible, so it is not possible to design batteries that match the shape of the device. Has characteristics.
[0003]
This polymer electrolyte battery is usually finished into a thin battery by using a laminate film having an aluminum film as a core material as an exterior body and combining a thin sheet electrode and a sheet polymer electrolyte layer.
[0004]
[Problems to be solved by the invention]
In this polymer electrolyte battery, since both the positive and negative electrodes and the polymer electrolyte layer are essentially solid containing no free liquid, a unit cell composed of both the positive and negative electrodes and the polymer electrolyte layer or a plurality of the unit cells are laminated. When the unit cell laminate is packaged with an exterior body, there is no adhesion between the exposed portion of the metal foil on the back side of the electrode in the unit cell and the inner surface of the exterior body composed of a laminate film, etc. However, the remaining gas deteriorates the battery characteristics or causes a shift between the outer package and the electrode, which causes wrinkles at the time of bending.
[0005]
Therefore, the present invention solves the problems of the prior art as described above, improves the adhesion between the exposed portion of the metal foil on the back surface side of the electrode in the unit cell and the inner surface of the exterior body, is flexible, and is free from bending. An object of the present invention is to provide a polymer electrolyte battery having a good storage performance with less generation of battery and less battery blistering due to storage.
[0006]
[Means for Solving the Problems]
The present invention relates to an exposed portion of a metal foil of an electrode facing the inner surface of an exterior body in a unit cell (hereinafter simply described as “metal foil”) and an inner surface of the exterior body (hereinafter simply referred to as “exterior body”). By adhering all or a part of the opposite surface to a polymer electrolyte layer or a mixture containing an electrolyte solvent containing the same polymer as that contained in the electrolyte contained in the electrode mixture layer, and It solves the above problems.
[0007]
In the present invention, since the mixture containing the polymer foil and the electrolyte solution solvent used for bonding the metal foil of the unit cell and the exterior body has adhesiveness and viscosity, the flexibility of the entire battery is preferably improved. To prevent wrinkling when the battery is bent.
[0008]
In addition, the polymer and electrolyte solution solvent used for bonding the metal foil and the outer package are substantially the same as the polymer and electrolyte solution contained in the electrolyte contained in the polymer electrolyte layer or electrode mixture layer. (That is, made of the same material), the battery characteristics are not deteriorated, and the battery characteristics are reduced inside the battery by bonding the metal foil of the electrode and the exterior body as described above. It is possible to prevent a gas containing oxygen, moisture, or the like causing contamination from being mixed.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Bonding may be performed on all or part of the facing surface between the metal foil of the unit cell and the exterior body, but the larger the bonding area is, the more preferable it is performed on all or almost all of the above part.
[0010]
The mixture containing the polymer and the electrolyte solution solvent in the present invention may be a monomer solution containing an electrolyte solution used for producing a polymer electrolyte layer or an electrode. That is, what is necessary is just to contain what exists as a polymer in a battery, and electrolyte solution solvent, and what may be used for a battery other than that may be included.
[0011]
In the case of the monomer solution containing the electrolytic solution as described above, it can be used effectively also when each unit cell of the unit cell laminate in which two or more unit cells are laminated is connected in parallel. It is applicable also to the adhesive agent used for the clearance gap where the metal surface between cells opposes.
[0012]
In the present invention, when a unit cell having a pair of a positive electrode mixture layer and a negative electrode mixture layer is packaged with an outer package to finish a battery, the positive electrode and the negative electrode are on one side of a metal foil serving as a current collector. However, in the case of the above unit cell laminate, the mixture layer is formed only on one surface of the metal foil only on the electrodes on both ends, that is, on the electrode facing the inner surface of the outer package. In addition, the positive electrode and the negative electrode on the inner side from these may have a mixture layer formed on both surfaces of the metal foil.
[0013]
【Example】
Next, the present invention will be described more specifically with reference to examples. However, this invention is not limited only to those Examples. In the following, (1) a case where almost all of the facing surfaces of the metal foil of the unit cell and the exterior body are bonded with a specific adhesive which will be described in detail later, Example 1, (2) Periphery of the facing surfaces Example 2 when only the part is bonded with the adhesive, and (3) Example 3 when only the central part of the facing surface is bonded with the adhesive. (4) Without using the adhesive, the facing surface is completely Although the case where it did not adhere | attach is demonstrated as the comparative example 1, preparation of a positive electrode, a negative electrode, and a polymer electrolyte layer is demonstrated prior to those description.
[0014]
Production of positive electrode:
50 parts by weight of LiCoO 2 as a positive electrode active material, 10 parts by weight of acetylene black as a conductive auxiliary agent, and 10 parts by weight of polyvinylidene fluoride as a binder are mixed uniformly, and 40 parts by weight of an electrolytic solution is further added. The mixture was mixed to prepare a paste-like positive electrode mixture. The electrolyte solution is obtained by dissolving LiPF 6 in a mixed solvent of propylene carbonate and ethylene carbonate in a volume ratio of 1: 1 at 1.22 mol / liter. Then, the paste-like positive electrode mixture prepared as described above is applied to one surface of an aluminum foil serving as a current collector, and heated to be gelled, whereby a gel-like positive electrode mixture layer is formed on the aluminum foil. It formed and produced the sheet-like positive electrode.
[0015]
Production of negative electrode:
A paste-like negative electrode mixture was prepared by mixing 40 parts by weight of graphite as a negative electrode active material, 5 parts by weight of polyvinylidene fluoride, and 55 parts by weight of an electrolytic solution similar to that used for the positive electrode. Is applied to one surface of a copper foil serving as a current collector, and is heated to gel, thereby forming a gel-like negative electrode mixture layer on the copper foil to produce a sheet-like negative electrode did.
[0016]
Preparation of polymer electrolyte layer:
15 parts by weight of a 70 μm-thick polyolefin non-woven fabric, a mixture of 2-ethoxyethyl acrylate, triethylene glycol dimethacrylate, and ethylene glycol ethyl carbonate methacrylate (the mixing ratio of these three components is 50:13:33 by weight) And 0.75 parts by weight of the polymerization initiator benzoyl peroxide and 85 parts by weight of the same electrolytic solution as described above are impregnated, heated to polymerize the monomer, and the whole is gelled to form a sheet-like material. A gel polymer electrolyte layer was prepared.
[0017]
This polymer electrolyte layer was disposed between the positive electrode and the negative electrode, and pressed to form a unit cell. However, the positive electrode and the negative electrode were arranged so that the respective mixture layers were opposed to each other through the polymer electrolyte layer. That is, the aluminum foil is exposed on the back side of the positive electrode (the side not facing the polymer electrolyte layer), and the copper foil is exposed on the back side of the negative electrode. And the laminated film of the three-layer structure which consists of a polyester film-aluminum film-modified polyolefin film was prepared as an exterior body which coat | covers this unit cell. The back side of the electrode refers to the side where the mixture layer is not formed on the metal foil as the current collector, and the front side is the side where the mixture layer is formed on the metal foil and faces the polymer electrolyte layer. Say the side.
[0018]
Example 1
As an adhesive, 80 parts by weight of a mixed solvent of propylene carbonate and ethylene carbonate in a volume ratio of 1: 1, 20 parts by weight of the same three types of acrylic monomer mixture used for the preparation of the polymer electrolyte layer, and polymerization start 0.8 parts by weight of benzoyl peroxide as an agent was added and heated to polymerize the monomer and gelled to prepare a viscous liquid.
[0019]
When the unit cell is packaged with an exterior body, the metal foil and the exterior body of the unit cell are arranged on the opposing surfaces (the surface where the exposed portion of the aluminum foil on the back surface side of the positive electrode faces the inner surface of the exterior body, and the back surface of the negative electrode) The adhesive is applied to almost the entire surface of the exposed copper foil on the side facing the inner surface of the exterior body, and the adhesive-applied portion is pressed at the exterior to adhere the portion with an adhesive. An electrolyte battery was produced.
[0020]
Here, the schematic structure of the battery will be described with reference to FIG. 1. A sheet cell
[0021]
FIG. 2 shows a state in which the
[0022]
Example 2
Except for applying the same adhesive as in Example 1 only to the peripheral edge of the facing surface between the metal foil of the unit cell and the exterior body, and pressing the adhesive application part at the exterior to adhere the part with an adhesive. A polymer electrolyte battery was produced in the same manner as in Example 1.
[0023]
Example 3
Except for applying the same adhesive as in Example 1 only to the central part of the opposing surface between the metal foil of the unit cell and the exterior body, and pressing the adhesive application part at the exterior to adhere the above part with an adhesive. A polymer electrolyte battery was produced in the same manner as in Example 1.
[0024]
Comparative Example 1
A polymer electrolyte battery was produced in the same manner as in Example 1 except that the metal foil of the unit cell and the outer package were not adhered with an adhesive.
[0025]
The battery capacities of the batteries of Examples 1 to 3 and Comparative Example 1, the state of occurrence of wrinkles at the time of bending, the presence or absence of occurrence of a short circuit due to the bending, and the swelling (swelling) of the battery due to storage were examined. The results are shown in Table 1. The battery capacity was 4.2 V, 0.2 C constant current and constant voltage (CCCV method), charged for 8 hours, then discharged at 0.2 C to 2.75 V, and the discharge capacity was measured. The capacity of the battery of Comparative Example 1 corresponding to the product is displayed with an index of 100, and the state of occurrence of wrinkles at the time of folding is that the battery is bent to 90 ° along with a 4 mm diameter cylinder, and wrinkles are generated at that time The situation was evaluated by observing with the naked eye. In addition, whether or not a short circuit occurred due to bending was observed with naked eyes after the occurrence of wrinkles in the bending test, and the change in the open circuit voltage of the battery was measured after 24 hours, and the open circuit voltage was lower than before bending. It was determined that the short circuit occurred. The reason for examining whether or not a short circuit occurs due to bending is whether or not the electrode is distorted due to the generation of wrinkles due to bending, and whether or not the electrode constituent material breaks through the gel polymer electrolyte layer and causes a short circuit. This is to find out. The battery bulges are stored for 20 days in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90%. The thickness of the battery is measured with a thickness gauge at five points, and the maximum value is used for storage. The difference between the maximum value of the later thickness and the maximum value of the thickness before storage is obtained. In addition, all the batteries of Examples 1 to 3 and the battery of Comparative Example 1 had a set total thickness at the time of production of 1.0 mm.
[0026]
[Table 1]
[0027]
As is apparent from the results shown in Table 1, Examples 1 to 3 are flexible, have little or no generation of wrinkles at the time of bending, and have no short circuit due to the generation of wrinkles due to bending, and batteries by storage The blisters were also small, indicating excellent storage performance.
[0028]
In the above examples, a viscous liquid containing a monomer that becomes a polymer of the same quality as the polymer in the polymer electrolyte layer was used as an adhesive, but instead of polyvinylidene fluoride and an electrolyte solvent such as propylene carbonate. The mixture may be used as an adhesive. In addition, for adhesion between the exposed portion of the metal foil on the back side of the electrode and the inner surface of the exterior body, the monomer and solvent (electrolytic solution) are not polymerized in advance as in the examples, without previously polymerizing the ternary monomer. A mixture containing a polymerization initiator and the like may be applied to the adhesive portion, and then heated to obtain an adhesive effect. In addition to the polymer used in the examples, the above-described polyvinylidene fluoride, a photocurable resin described later, and the like may be used as the polymer constituting the adhesive.
[0029]
Moreover, although the case where one unit cell was packaged and finished into a battery was shown in the above embodiment, a unit cell laminate in which a plurality of unit cells are laminated may be packaged and finished into a battery instead. .
[0030]
In addition, in the gelation of the polymer electrolyte, in addition to those shown in the above examples, for example, radical polymerization type unsaturated polyester, or radical polymerization type acrylic epoxy acrylate, urethane acrylate, polyester acrylate, alkyd acrylate, silicon A photocurable resin such as acrylate may be gelled using ultraviolet rays or an electron beam.
[0031]
【The invention's effect】
As described above, the present invention can provide a polymer electrolyte battery that is flexible, has little wrinkles even when bent, and has little battery blistering due to storage, and has good storage performance.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an example of a polymer electrolyte battery according to the present invention.
FIG. 2 shows a state in which the exposed portion of the aluminum foil on the back surface side of the positive electrode and the inner surface of the exterior body are adhered with an adhesive, and an exposed portion of the copper foil on the back surface side of the negative electrode and the inner surface of the exterior body are adhered with an adhesive. It is a principal part expanded sectional view which shows a state typically.
[Explanation of symbols]
DESCRIPTION OF
Claims (2)
少なくとも外装体の内面に対向する電極の、外装体側の金属箔は露出しており、
上記電極の金属箔の露出部分と外装体の内面との対向面の全部または一部を、ポリマー電解質層または電極合剤層に含まれる電解質に含有されているものと同質のポリマーおよび電解液溶媒を含有する混合物により接着したことを特徴とするポリマー電解質電池。A sheet-like positive electrode formed by forming a positive electrode mixture layer on at least one surface of a metal foil, a sheet-like negative electrode formed by forming a negative electrode mixture layer on at least one surface of the metal foil, and a sheet-like polymer electrolyte layer the a pair of a positive electrode of the positive electrode mixture layer and the negative electrode mixture layer of the negative electrode, the positive electrode mixture layer and the negative electrode mixture layer and configured the unit cell or the unit in the a polymer electrolyte layer disposed between In a polymer electrolyte battery in which a unit cell laminate in which a plurality of cells are laminated is packaged with an exterior body,
At least the metal foil on the exterior body side of the electrode facing the inner surface of the exterior body is exposed,
All or part of the surface facing the inner surface of the exposed portion and the exterior body of gold Shokuhaku of the electrode, a polymer of those same quality were or polymer electrolyte layer is contained in the electrolyte contained in the electrode mixture layer and polymer electrolyte battery characterized by being bonded by a mixture containing electrolyte solvent.
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JP07324298A JP4059327B2 (en) | 1998-03-06 | 1998-03-06 | Polymer electrolyte battery |
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JP07324298A JP4059327B2 (en) | 1998-03-06 | 1998-03-06 | Polymer electrolyte battery |
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JP4059327B2 true JP4059327B2 (en) | 2008-03-12 |
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