JP4514422B2 - Non-aqueous electrolyte battery - Google Patents

Non-aqueous electrolyte battery Download PDF

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JP4514422B2
JP4514422B2 JP2003312194A JP2003312194A JP4514422B2 JP 4514422 B2 JP4514422 B2 JP 4514422B2 JP 2003312194 A JP2003312194 A JP 2003312194A JP 2003312194 A JP2003312194 A JP 2003312194A JP 4514422 B2 JP4514422 B2 JP 4514422B2
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battery
aqueous electrolyte
lithium
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negative electrode
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JP2005079077A (en
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徹 雨堤
誠二 森田
信博 西口
悟 成瀬
将之 村木
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Sanyo Electric 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、非水系電解液電池に関し、特にリチウム金属を使用せず、組み立て工程を簡略化することができると共に、耐熱性が向上した非水系電解液電池に関する。   The present invention relates to a non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte battery that can simplify the assembly process without using lithium metal and has improved heat resistance.

最近の各種のエレクトロニクス機器の普及に伴い、これらの機器中に組み込まれるＩＣメモリーや時計回路などの停電時のバックアップ用電源として、コイン型の電池をプリント基板などに直接実装する方法が広く採用されている。   With the recent widespread use of various electronic devices, a method of directly mounting a coin-type battery on a printed circuit board is widely used as a backup power source in the event of a power failure, such as an IC memory or a clock circuit incorporated in these devices. ing.

ところで、電子部品を基板に安価に実装するために、電子部品を基板に装着した後、リフローハンダ付けにより電子部品を直接基板に実装することが行われている。このリフローハンダ付けは、基板にクリームハンダを塗布し、クリームハンダの塗布面に電子部品を載置した後、基板ごとリフロー炉を通過させて２２０〜２４０℃の温度で約１分間加熱してハンダを溶融させるようにしているため、リフローハンダ付けされる電子部品は２４０℃程度の耐熱性が要求される。   By the way, in order to mount an electronic component on a substrate at low cost, after mounting the electronic component on the substrate, the electronic component is directly mounted on the substrate by reflow soldering. In this reflow soldering, cream solder is applied to a substrate, electronic parts are placed on the surface of the cream solder, and then the substrate is passed through a reflow furnace and heated at a temperature of 220 to 240 ° C. for about 1 minute. Therefore, an electronic component to be reflow soldered is required to have a heat resistance of about 240 ° C.

最近、耐熱性を有する小型のコイン型の非水系電解液電池が開発され、リフローハンダ付けが可能な電池として広く使用されるようになっている（下記特許文献１参照）。このコイン型の非水系電解液電池の構造及びその実装形態を図面を用いて簡単に説明する。   Recently, a small coin-type non-aqueous electrolyte battery having heat resistance has been developed and widely used as a battery that can be reflow soldered (see Patent Document 1 below). The structure of the coin-type non-aqueous electrolyte battery and its mounting form will be briefly described with reference to the drawings.

図２は、コイン型の非水系電解液電池の内部構造の一例を示す断面図であり、図３は下記特許文献１に開示されているコイン型の非水系電解液電池をプリント配線基板にリフローハンダ付けにより取り付けた状態を示す側面図である。   FIG. 2 is a cross-sectional view showing an example of the internal structure of a coin-type non-aqueous electrolyte battery, and FIG. 3 shows the reflow of the coin-type non-aqueous electrolyte battery disclosed in Patent Document 1 below to a printed wiring board. It is a side view which shows the state attached by soldering.

コイン型の非水系電解液電池１０は、図２に示すように、ステンレススチール製の正極ケース１２内に、必要に応じてステンレススチール等の金属からなる正極集電体１４、リチウム含有二酸化マンガン等の正極活物質を含有する正極１６、非水系電解液が含浸されたポリエーテルエーテルケトンやガラス繊維不織布等の多孔性絶縁性薄膜からなるセパレータ１８、リチウム金属からなる負極２０が配置され、ステンレススチール鋼からなる封口板２２がガスケット２４により正極ケース１２と絶縁された状態で、正極ケース１２の端部をかしめることにより固定された構造を有している。   As shown in FIG. 2, a coin-type non-aqueous electrolyte battery 10 includes a positive electrode current collector 14 made of a metal such as stainless steel, a lithium-containing manganese dioxide, and the like in a positive electrode case 12 made of stainless steel. A positive electrode 16 containing a positive electrode active material, a separator 18 made of a porous insulating thin film such as polyetheretherketone or glass fiber nonwoven fabric impregnated with a non-aqueous electrolyte, and a negative electrode 20 made of lithium metal are disposed, and is made of stainless steel. The sealing plate 22 made of steel is fixed by caulking the end of the positive electrode case 12 with the gasket 24 being insulated from the positive electrode case 12 by the gasket 24.

このようなコイン形の非水系電解液電池１０をプリント配線基板２６上の導電性パターン２８及び３０に固着する際には、例えば図３に示したように、一方の導電性パターン２８上にクリームハンダ３２を介してコイン形の非水系電解液電池１０の封口板２２を下方に向けて載置し、他方の導電性パターン３０上には同じくクリームハンダ３４を介してコイン形の非水系電解液電池１０の正極ケース１２に当接した状態で導電性板３６を載置し、その後プリント配線基板２６ごとリフロー炉を通過させて２２０〜２４０℃の温度で約１分間加熱してハンダを溶融させてコイン形の非水系電解液電池１０を固定するようにしている。   When such a coin-shaped non-aqueous electrolyte battery 10 is fixed to the conductive patterns 28 and 30 on the printed wiring board 26, for example, as shown in FIG. The sealing plate 22 of the coin-shaped non-aqueous electrolyte battery 10 is placed downward via the solder 32, and the coin-shaped non-aqueous electrolyte is also placed on the other conductive pattern 30 via the cream solder 34. The conductive plate 36 is placed in contact with the positive electrode case 12 of the battery 10, and then the printed wiring board 26 is passed through a reflow furnace and heated at a temperature of 220 to 240 ° C. for about 1 minute to melt the solder. The coin-shaped non-aqueous electrolyte battery 10 is fixed.

このようなリフローハンダ付け可能なコイン形リチウム二次電池としては、正極活物質として主としてリチウム含有酸化マンガンを用い、負極活物質には即時放電可能なリチウム金属ないしはリチウム合金（例えば、リチウム−アルミニウム合金）が用いられている。しかしながら、リチウム金属及びリチウム合金は大気中の水分と反応するために安全性に劣るので、負極組み立て工程においてはドライエアー雰囲気内での組み立てが必要となり、高コストとなる。加えて、リチウム金属及びリチウム合金も、リフロー時には電解液と反応して表面に反応生成物の被膜を形成し、負極と電解液との界面のインピーダンスが大きくなるために、放電特性に悪影響を与えるという問題があった。   As such a reflow solderable coin-type lithium secondary battery, lithium-containing manganese oxide is mainly used as a positive electrode active material, and a lithium metal or lithium alloy (for example, lithium-aluminum alloy) that can be immediately discharged is used as the negative electrode active material. ) Is used. However, since lithium metal and lithium alloy react with moisture in the atmosphere and are inferior in safety, assembly in a dry air atmosphere is required in the negative electrode assembly process, resulting in high costs. In addition, lithium metal and lithium alloys also react with the electrolyte during reflow to form a reaction product film on the surface, which increases the impedance at the interface between the negative electrode and the electrolyte, adversely affecting the discharge characteristics. There was a problem.

このような問題点は、負極活物質としてリチウム金属ないしはリチウム合金を使用しなければ解決することができるものであるが、負極活物質としてリチウム金属ないしはリチウム合金を使用しない場合には、使用前に充電により正極活物質から負極にリチウムを移動させる必要が生じる。しかしながら、従来からコイン形の非水系電解液電池１０の正極活物質として使用されているリチウム含有酸化マンガンは、充電により負極に移動させることができる程度のリチウム分を含有する化合物とすると吸湿性がきわめて強くなるために、通常の室内で安定的に化学的に合成することが困難であった（下記特許文献２参照）。   Such problems can be solved if lithium metal or lithium alloy is not used as the negative electrode active material, but before using lithium metal or lithium alloy as the negative electrode active material, It is necessary to transfer lithium from the positive electrode active material to the negative electrode by charging. However, the lithium-containing manganese oxide conventionally used as the positive electrode active material of the coin-type non-aqueous electrolyte battery 10 has a hygroscopic property when it is a compound containing a lithium content that can be transferred to the negative electrode by charging. Since it became very strong, it was difficult to synthesize chemically stably in a normal room (see Patent Document 2 below).

特開２００２−２９８８０４号公報（段落［００１９］〜［００２０］、図３）JP 2002-298804 A (paragraphs [0019] to [0020], FIG. 3) 特開平２−２３４３６５号公報（２頁右下欄１７行〜３頁左上欄１１行）JP-A-2-234365 (page 2, lower right column, line 17 to page 3, upper left column, line 11)

そこで、本発明者等は、通常の室内で安定的に製造でき、充電により負極に移動させることができる程度のリチウム分を含有している化合物を種々検討した結果、リチウムを含有するモリブデン化合物が上述の問題点を解決することができることを見出し、加えて、このリチウムを含有するモリブデン化合物は、非水系電解液電池を組み立てた後にリフロー工程のような高温に加熱される工程を経ると、このような高温に加熱される工程が存在しない通常の場合と比すると、かえって電池の２サイクル目以降の放電特性が良好となることを見出し、本発明を完成するに至ったのである。   Therefore, as a result of various investigations on a compound containing lithium that can be stably manufactured in a normal room and transferred to the negative electrode by charging, the present inventors have found that a molybdenum compound containing lithium is In addition to finding out that the above-mentioned problems can be solved, the lithium-containing molybdenum compound is subjected to a process of being heated to a high temperature such as a reflow process after the non-aqueous electrolyte battery is assembled. Compared to the normal case where there is no process heated to such a high temperature, the present inventors have found that the discharge characteristics after the second cycle of the battery are better and have completed the present invention.

すなわち、本発明は、組み立て工程を簡略化することができると共に、耐熱性が向上した非水系電解液電池を提供することを目的とする。   That is, an object of the present invention is to provide a non-aqueous electrolyte battery that can simplify the assembly process and has improved heat resistance.

本願の上記目的は以下の構成により達成することができる。すなわち、本願の請求項１に係る非水系電解液電池は、正極活物質としてリチウムを含有するモリブデン酸化物ＬｉｘＭｏＯｙ（１≦ ｘ≦２、３≦ｙ≦５）、負極活物質としてアルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウムから選択される少なくとも１種の金属を用いたことを特徴とするリフローハンダ付け実装用の非水系電解液二次電池である。
The above object of the present application can be achieved by the following configuration. That is, the non-aqueous electrolyte battery according to claim 1 of the present application is a molybdenum oxide Li x MoO y (1 ≦ x ≦ 2, 3 ≦ y ≦ 5) containing lithium as a positive electrode active material, and aluminum as a negative electrode active material. A non-aqueous electrolyte secondary battery for reflow soldering mounting using at least one metal selected from tin, bismuth, strontium, silicon, zinc, cadmium, calcium, and barium.

リチウムを含有するモリブデン酸化物ＬｉｘＭｏＯｙ（１≦ｘ≦２、３≦ｙ≦５）は、電池を組み立てた後に充電によりリチウムの一部を負極に移動させるために、リチウム含有量が多いもの、すなわちＬｉ２ＭｏＯ３が好ましい。 Molybdenum oxide Li x MoO y (1 ≦ x ≦ 2, 3 ≦ y ≦ 5) containing lithium has a large lithium content because a part of lithium is transferred to the negative electrode by charging after the battery is assembled. Preferred is Li 2 MoO 3 .

アルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウム等の金属は、電池が組み立てられた後に最初の充電により正極活物質のリチウムを含有するモリブデン酸化物ＬｉｘＭｏＯｙ（１≦ｘ≦２、３≦ｙ≦５）から移動してきたリチウムを取り込んで、安定なリチウム合金を形成する。 Metals such as aluminum, tin, bismuth, strontium, silicon, zinc, cadmium, calcium, and barium are molybdenum oxides Li x MoO y (1 ≦≦ 1) containing lithium as a positive electrode active material by first charging after the battery is assembled. The lithium which has moved from x ≦ 2, 3 ≦ y ≦ 5) is taken in to form a stable lithium alloy.

なお、非水系電解液を構成する非水溶媒（有機溶媒）は、カーボネート類、ラクトン類、エーテル類、エステル類、芳香族炭化水素などが挙げられ、これらの中でカーボネート類、ラクトン類、エーテル類、ケトン類、エステル類などが好ましく、カーボネート類がさらに好適に用いられる。   The nonaqueous solvent (organic solvent) constituting the nonaqueous electrolytic solution includes carbonates, lactones, ethers, esters, aromatic hydrocarbons, etc. Among these, carbonates, lactones, ethers , Ketones, esters and the like are preferable, and carbonates are more preferably used.

カーボネート類の具体例としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、γ−ブチロラクトン、γ−バレロラクトン、γ−ジメトキシエタン、テトラヒドロフラン、アニソール、１，４−ジオキサン、ジエチルカーボネートなどを挙げることができ、これら溶媒の２種類以上を混合して用いることもできる。高温での安定性の点からはプロピレンカーボネートとジエチレングリコールジメチルエーテルとの混合物が好適に用いられる。   Specific examples of carbonates include propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, γ-dimethoxyethane, tetrahydrofuran, anisole, 1,4-dioxane, diethyl carbonate, and the like. Two or more of these solvents can be used in combination. From the viewpoint of stability at high temperature, a mixture of propylene carbonate and diethylene glycol dimethyl ether is preferably used.

非水系電解液を構成する電解質は、過塩素酸リチウム（ＬｉＣｌＯ４）、六フッ化リン酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）、六フッ化砒酸リチウム（ＬｉＡｓＦ６）、トリフルオロメチルスルホン酸リチウム（ＬｉＣＦ３ＳＯ３）、ビストリフルオロメチルスルホニルイミドリチウム［ＬｉＮ（ＣＦ３ＳＯ２）２］などのリチウム塩が挙げられる。中でもＬｉＰＦ６、ＬｉＢＦ４、ＬｉＮ（ＣＦ３ＳＯ２）２を用いるのが好ましく、前記非水溶媒に対する溶解量は、０．５〜２．０モル／ｌとするのが好ましい。 The electrolyte constituting the non-aqueous electrolyte is lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), trifluoro Examples thereof include lithium salts such as lithium methyl sulfonate (LiCF 3 SO 3 ) and lithium bistrifluoromethylsulfonylimide [LiN (CF 3 SO 2 ) 2 ]. Of these, LiPF 6 , LiBF 4 , and LiN (CF 3 SO 2 ) 2 are preferably used, and the amount dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / l.

また、本願の請求項２ に係る発明は、前記請求項１に記載の非水系電解液二次電池において、前記負極が、アルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウムから選択される少なくとも１種の金属とステンレススチールとのクラッド材から形成されていることを特徴とする。耐高温性及び充放電特性の点からはアルミニウムとステンレススチールとのクラッド材が好ましい。
The invention according to claim 2 of the present application is the nonaqueous electrolyte secondary battery according to claim 1, wherein the negative electrode is made of aluminum, tin, bismuth, strontium, silicon, zinc, cadmium, calcium, or barium. It is characterized by being formed from a clad material of at least one selected metal and stainless steel. From the viewpoint of high temperature resistance and charge / discharge characteristics, a clad material of aluminum and stainless steel is preferable.

また、本願の請求項３に係る発明は、前記請求項１又は２に記載の非水系電解液二次電池に
おいて、形状がコイン形であることを特徴とする。
The invention according to claim 3 of the present application is characterized in that, in the non-aqueous electrolyte secondary battery according to claim 1 or 2, the shape is a coin shape.

本発明は、上述の構成を備えることにより以下のような優れた効果を奏する。すなわち、本願の請求項１に係る非水系電解液二次電池の発明によれば、負極活物質として水分との反応性に富むリチウム金属及びリチウム合金を使用していないので、耐熱性に富む非水系二次電池が得られると共に、通常の室内で安定的に製造することができ、更に、別途リチウム源を設ける必要なしに電池組立後に単に充電することにより正常に作動する非水系電解液二次電池が得られる。
加えて、電池の組立後にリフローハンダ付け実装工程のような高温に加熱される工程を経ると、このような高温に加熱される工程が存在しない通常の場合と比すると、かえって電池の２サイクル目以降の放電特性が良好となる。
従来の非水系電解液二次電池では高温に加熱されるようなことは電池劣化の原因となるために避けるべきであるとされているのに対し、本発明の非水系電解液電池ではかえって２サイクル目以降の放電特性が良好となる。
The present invention has the following excellent effects by having the above-described configuration. That is, according to the invention of the non-aqueous electrolyte secondary battery according to claim 1 of the present application, lithium metal and lithium alloy that are highly reactive with moisture are not used as the negative electrode active material. An aqueous secondary battery can be obtained and can be stably manufactured in a normal room, and further, a non-aqueous electrolyte secondary that operates normally by simply charging after battery assembly without the need for a separate lithium source. A battery is obtained.
In addition, after the assembly of the battery, a process that is heated to a high temperature such as a reflow soldering mounting process, the second cycle of the battery is compared with a normal case where there is no process that is heated to such a high temperature. Subsequent discharge characteristics are improved.
In the conventional non-aqueous electrolyte secondary battery, it is said that heating to a high temperature should be avoided because it causes deterioration of the battery, whereas in the non-aqueous electrolyte battery of the present invention, 2 Discharge characteristics after the cycle are improved.

また、本願の請求項２に係る非水系電解液二次電池の発明によれば、アルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウム等の金属側はそのまま負極活物質として、ステンレススチール側はそのまま負極用端子として使用することができるので、負極及び負極端子を一度に形成することができるようになるから、製造工程が簡略化される。
Further, according to the invention of the non-aqueous electrolyte secondary battery according to claim 2 of the present application, the metal side of aluminum, tin, bismuth, strontium, silicon, zinc, cadmium, calcium, barium or the like is used as the negative electrode active material as it is. Since the stainless steel side can be used as a negative electrode terminal as it is, the negative electrode and the negative electrode terminal can be formed at a time, so that the manufacturing process is simplified.

また、本願の請求項３に係る非水系電解液二次電池によれば、容易に上述の請求項１又は２に記載の発明で奏される効果を奏することができるコイン形の非水系電解液二次電池が得られる。
Moreover, according to the non-aqueous electrolyte secondary battery according to claim 3 of the present application, a coin-shaped non-aqueous electrolyte that can easily achieve the effect of the invention according to claim 1 or 2 described above. A secondary battery is obtained.

以下、本発明を実施するための最良の形態を実施例により詳細に説明する。   Hereinafter, the best mode for carrying out the present invention will be described in detail by way of examples.

［正極の作成］
正極活物質としてリチウムモリブデン酸化物（Ｌｉ２ＭｏＯ３）の粉末９０質量％に対し導電剤としてカーボン１０質量％をよく混合し、この混合物に結着剤５質量％を添加してよく混練し、粉砕・整粒して正極合剤を作成した。そして、この正極合剤を５トン／ｃｍ２の圧力により加圧成形して、直径２ｍｍ、厚み１．０ｍｍの円筒状の正極を作成し、２５０℃で熱処理することにより正極に含まれる水分を除去して使用した。 [Creation of positive electrode]
10% by mass of carbon as a conductive agent is mixed well with 90% by mass of a powder of lithium molybdenum oxide (Li 2 MoO 3 ) as a positive electrode active material, and 5% by mass of a binder is added to this mixture and kneaded well. A positive electrode mixture was prepared by grinding and sizing. Then, this positive electrode mixture is subjected to pressure molding at a pressure of 5 ton / cm 2 to prepare a cylindrical positive electrode having a diameter of 2 mm and a thickness of 1.0 mm, and heat treatment at 250 ° C. to thereby remove moisture contained in the positive electrode. Removed and used.

［電池の作製］
負極にアルミニウム−ステンレススチールからなるクラッド材を使用し、このクラッド材のアルミニウム金属側の上にガラス繊維不織布からなるセパレータを設置し、そのセパレータに対して電解液を４ｍｇ注入した。この上に、上記のようにして作製した正極を置き、ガスケットを介してステンレス鋼製の正極缶を被せ、かしめることにより厚み１．４ｍｍ、外形４ｍｍの電池とした。このときの電解液は、プロピレンカーボネートとジエチレングリコールジメチルエーテルとを体積比が５０：５０で、ＬｉＮ（ＣＦ３ＳＯ２）２を１Ｍとなるように添加したものを用いた。このようにして作製した電池を以下「Ａ１」と称する。 [Production of battery]
A clad material made of aluminum-stainless steel was used for the negative electrode, a separator made of a glass fiber non-woven fabric was placed on the aluminum metal side of the clad material, and 4 mg of electrolyte was injected into the separator. On top of this, the positive electrode produced as described above was placed, covered with a positive electrode can made of stainless steel via a gasket, and caulked to obtain a battery having a thickness of 1.4 mm and an outer diameter of 4 mm. The electrolytic solution used here was propylene carbonate and diethylene glycol dimethyl ether added at a volume ratio of 50:50 and LiN (CF 3 SO 2 ) 2 of 1M. The battery thus produced is hereinafter referred to as “A1”.

実施例２としては、正極活物質にリチウムモリブデン酸化物（Ｌｉ２ＭｏＯ４）を用いた以外は実施例１と同様の方法で電池を作製した。このようにして作製した電池を以下「Ａ２」と称する。 As Example 2, a battery was fabricated in the same manner as in Example 1 except that lithium molybdenum oxide (Li 2 MoO 4 ) was used as the positive electrode active material. The battery thus produced is hereinafter referred to as “A2”.

実施例３としては、正極活物質にリチウムモリブデン酸化物（Ｌｉ２ＭｏＯ５）を用いた以外は実施例１と同様の方法で電池を作製した。このようにして作製した電池を以下「Ａ３」と称する。 As Example 3, a battery was fabricated in the same manner as in Example 1 except that lithium molybdenum oxide (Li 2 MoO 5 ) was used as the positive electrode active material. The battery thus produced is hereinafter referred to as “A3”.

（放電特性の測定）
上記の方法で作成したＡ１、Ａ２、Ａ３の電池に対して、２４０℃のリフローハンダ付け工程を行わなかった「リフローなし」電池と、２４０℃のリフローハンダ付け工程を２回行った「２４０℃リフロー」電池について以下の充放電条件でサイクル試験を行った。
充電条件：電池電圧３Ｖとなるまで２０μＡの定電流で充電。
その後、３Ｖの定電圧で３０時間充電。
放電条件：２０μＡの定電流で電池電圧が２Ｖとなるまで放電。 (Measurement of discharge characteristics)
For the batteries A1, A2, and A3 prepared by the above method, a “no reflow” battery that did not perform the reflow soldering process at 240 ° C. and a “240 ° C.” that performed the reflow soldering process at 240 ° C. twice. A cycle test was conducted on the “reflow” battery under the following charge / discharge conditions.
Charging conditions: Charging with a constant current of 20 μA until the battery voltage reaches 3V.
After that, it is charged for 30 hours at a constant voltage of 3V.
Discharge conditions: Discharge until the battery voltage reaches 2 V at a constant current of 20 μA.

３サイクルまでの放電容量の測定結果をまとめて表１に示し、また３０サイクルまでの放電容量の変化を図１に示す。この表１及び図１の結果によれば、１サイクル目では従来どおりどの活物質も「リフローなし」電池と比較すると「２４０℃リフロー」電池の放電容量の低下が確認できるが、「２４０℃リフロー」電池では２サイクル目以降に大幅な放電容量の増加が見られる。１サイクル目の放電容量の低下は、リフロー時に高温となったために電解液と正極に含まれるリチウムが反応し、正極のリチウムインターカーレーション・デインターカーレーション反応が抑制されたために放電容量低下につながったものと考えられる。   The measurement results of the discharge capacity up to 3 cycles are shown together in Table 1, and the change in the discharge capacity up to 30 cycles is shown in FIG. According to the results of Table 1 and FIG. 1, in the first cycle, any active material can be confirmed to have a reduced discharge capacity of the “240 ° C. reflow” battery as compared with the “no reflow” battery, but the “240 ° C. reflow” The battery has a significant increase in discharge capacity after the second cycle. The decrease in the discharge capacity in the first cycle is due to the fact that the electrolyte and lithium contained in the positive electrode react because of the high temperature during reflow, and the lithium intercalation / deintercalation reaction of the positive electrode is suppressed, resulting in a decrease in discharge capacity. It is thought that it was connected.

Figure 0004514422
Figure 0004514422

２サイクル目の放電容量の増加は、以下のような原因によるものと考える。すなわち、第１回目の充電を終えた本発明の「リフローなし」電池を分解してセパレータを確認したところ、針状結晶が見られ、デンドライト生成によるダメージが発生していた。これに対し、第１回目の充電を終えた「２４０℃リフロー」電池では、デンドライト生成の形跡は見受けられなかった。   The increase in the discharge capacity at the second cycle is considered to be due to the following causes. That is, when the “no reflow” battery of the present invention after the first charge was disassembled and the separator was confirmed, acicular crystals were seen and damage due to dendrite generation occurred. In contrast, in the “240 ° C. reflow” battery that completed the first charge, there was no evidence of dendrite formation.

これより、本発明の「リフローなし」電池では、充放電を繰り返すことで負極表面上にデンドライトが除々に成長し、電池の短絡を引き起こすために充放電サイクルの増大と共に放電容量の低下を強いられる、しかし、「２４０℃リフロー」電池では、リフローハンダ付け工程で２００℃以上の熱が加えられることにより、負極のアルミニウムが活性化されて合金化しやすくなり、１５サイクル程度までの初期の充放電特性は向上するが、その後は徐々に「リフローなし」電池と同様な傾向の変化を示し、実質的に同放電容量に推移するものと考えられる。   As a result, in the “non-reflow” battery of the present invention, dendrite grows gradually on the negative electrode surface by repeating charge and discharge, and the discharge capacity is forced to decrease along with an increase in charge / discharge cycle in order to cause a short circuit of the battery. However, in the “240 ° C. reflow” battery, heat of 200 ° C. or more is applied in the reflow soldering process, so that the aluminum of the negative electrode is activated and easily alloyed, and the initial charge / discharge characteristics up to about 15 cycles. However, after that, it is considered that the battery gradually changes in the same tendency as the “non-reflow” battery and substantially changes to the same discharge capacity.

なお、上記実施例においては、負極としてアルミニウム−ステンレススチールからなるクラッド材からなるものを用いた例のみを示したが、ステンレススチールは電気化学的には単にアルミニウム金属の支持体として作用しているものであるから、上に例示したその他の金属とステンレススチールからなるクラッド材を使用しても同様の作用・効果を奏することは当業者にとり自明であろう。   In the above embodiment, only an example using a clad material made of aluminum-stainless steel as a negative electrode has been shown, but stainless steel acts electrochemically as an aluminum metal support. Therefore, it will be apparent to those skilled in the art that the same action and effect can be obtained even when a clad material made of other metals and stainless steel exemplified above is used.

本発明の非水電解液電池の放電容量のサイクル特性を示す図である。It is a figure which shows the cycling characteristics of the discharge capacity of the nonaqueous electrolyte battery of this invention. 従来のコイン形非水系電解液電池の断面図である。It is sectional drawing of the conventional coin type non-aqueous electrolyte battery. 従来のコイン型の非水系電解液電池をプリント配線基板にリフローハンダ付けにより取り付けた状態を示す側面図である。It is a side view which shows the state which attached the conventional coin type non-aqueous electrolyte battery to the printed wiring board by reflow soldering.

符号の説明Explanation of symbols

１０ コイン形非水電解液電池
１２ 正極ケース
１４ 正極集電体
１６ 正極
１８ セパレータ
２０ 負極
２２ 封口板
２４ ガスケット
２６ プリント配線基板
２８，３０ 導電性パターン
３２，３４ クリームハンダ
３６ 導電性板 DESCRIPTION OF SYMBOLS 10 Coin type non-aqueous electrolyte battery 12 Positive electrode case 14 Positive electrode collector 16 Positive electrode 18 Separator 20 Negative electrode 22 Sealing plate 24 Gasket 26 Printed wiring boards 28 and 30 Conductive patterns 32 and 34 Cream solder 36 Conductive plate

Claims (3)

正極活物質としてリチウムを含有するモリブデン酸化物ＬｉｘＭｏＯｙ（１≦ｘ≦２、３≦ｙ≦５）、負極活物質としてアルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウムから選択される少なくとも１種の金属を用いたことを特徴とするリフローハンダ付け実装用の非水系電解液二次電池。 Molybdenum oxide Li x MoO y (1 ≦ x ≦ 2, 3 ≦ y ≦ 5) containing lithium as the positive electrode active material, aluminum, tin, bismuth, strontium, silicon, zinc, cadmium, calcium, barium as the negative electrode active material A non-aqueous electrolyte secondary battery for reflow soldering mounting, wherein at least one metal selected from the group consisting of: 前記負極活物質が、アルミニウム、錫、ビスマス、ストロンチウム、硅素、亜鉛、カドミウム、カルシウム、バリウムから選択される少なくとも１種の金属とステンレススチールとのクラッド材から形成されていることを特徴とする請求項１に記載の非水系電解液二次電池。   The negative electrode active material is formed of a clad material of at least one metal selected from aluminum, tin, bismuth, strontium, silicon, zinc, cadmium, calcium, and barium and stainless steel. Item 2. The nonaqueous electrolyte secondary battery according to Item 1. 前記非水系電解液二次電池の形状がコイン形であることを特徴とする請求項１又は２に記載の非水系電解液二次電池。
The non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the non-aqueous electrolyte secondary battery has a coin shape.
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