JP2001068162A - Nonaqueous electrolyte secondary battery and its charging discharging method - Google Patents
Nonaqueous electrolyte secondary battery and its charging discharging methodInfo
- Publication number
- JP2001068162A JP2001068162A JP23757899A JP23757899A JP2001068162A JP 2001068162 A JP2001068162 A JP 2001068162A JP 23757899 A JP23757899 A JP 23757899A JP 23757899 A JP23757899 A JP 23757899A JP 2001068162 A JP2001068162 A JP 2001068162A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- alkali metal
- secondary battery
- electrolyte secondary
- battery
- Prior art date
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Classifications
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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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解質二次電
池、特に、負極と電解質との界面で起こる反応の均一性
を改良した非水電解質二次電池およびその充放電方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having improved uniformity of a reaction occurring at an interface between a negative electrode and an electrolyte, and a method for charging and discharging the same.
【０００２】[0002]
【従来の技術】今日、負極活物質であるリチウム等のア
ルカリ金属と、プロピレンカーボネート、γ−ブチロラ
クトン、ジメトキシエタン、テトラヒドロフラン、ジオ
キソラン等の有機溶媒にＬｉＣｌＯ4，ＬｉＢＦ4，Ｌｉ
ＡｓＦ6，ＬｉＰＦ6，ＬｉＣＦ 3ＳＯ3等の溶質を溶解さ
せた電解質とを組み合わせた非水電解質電池は、高エネ
ルギー密度を有することから、電子時計、カメラを始め
とする小型電子機器に広く用いられている。2. Description of the Related Art Today, negative electrode active materials such as lithium are used.
Lucari metal, propylene carbonate, γ-butyrol
Cuton, dimethoxyethane, tetrahydrofuran, geo
LiClO for organic solvents such as xolanFour, LiBFFour, Li
AsF6, LiPF6, LiCF ThreeSOThreeDissolved solutes etc.
Non-aqueous electrolyte batteries combined with
Starting with electronic watches and cameras
Widely used in small electronic devices.
【０００３】この種の電池を充電すると、負極表面上
に、樹枝状、フィブリル状または針状形態のアルカリ金
属、いわゆるデンドライトが析出する。これは、アルカ
リ金属を活物質とする負極上に存在する不動態皮膜の化
学的組成や構造が局所的に異なり、負極での反応が不均
一に進行することに起因する。デンドライトが生成し、
これが成長すると、負極と正極との間で内部短絡が起こ
るという問題が生じる。また、次の放電過程では、デン
ドライトが局所的に溶解して寸断されやすく、充電中に
析出した全てのアルカリ金属を溶解させることができ
ず、充放電効率が著しく低下するという問題もある。When this type of battery is charged, dendrites, dendrites, fibrils or needle-like alkali metals are deposited on the surface of the negative electrode. This is due to the fact that the chemical composition and structure of the passive film existing on the negative electrode using an alkali metal as an active material are locally different, and the reaction at the negative electrode proceeds unevenly. Dendrite is generated,
When this grows, there arises a problem that an internal short circuit occurs between the negative electrode and the positive electrode. Further, in the next discharging process, there is a problem that the dendrite is locally melted and easily cut, so that all the alkali metals precipitated during charging cannot be dissolved, and the charging / discharging efficiency is significantly reduced.
【０００４】負極上に生成するデンドライトの問題を回
避するために、充電時にアルカリ金属イオンを吸蔵し、
放電時にアルカリ金属イオンを放出する材料、例えばグ
ラファイトを負極に用いた非水電解質二次電池が普及し
ている。しかし、近年の電池の高容量化に伴い、限界に
近い領域まで負極材料にアルカリ金属イオンを吸蔵させ
るようになってきており、電池の充放電サイクルの繰り
返しに伴い負極上にアルカリ金属が析出し、容量が劣化
する傾向が大きくなってきている。したがって、アルカ
リ金属イオンを吸蔵・放出する材料を負極に用いたとし
ても、依然としてデンドライトによる正極と負極との内
部短絡や充放電効率の低下の問題が残る。In order to avoid the problem of dendrite generated on the negative electrode, occlusion of alkali metal ions during charging,
A non-aqueous electrolyte secondary battery using a material that releases an alkali metal ion at the time of discharge, for example, graphite, as a negative electrode has become widespread. However, with the increase in capacity of batteries in recent years, it has become possible to occlude the alkali metal ions in the negative electrode material to a region near the limit, and the alkali metal precipitates on the negative electrode with repeated charge / discharge cycles of the battery. The capacity tends to deteriorate. Therefore, even if a material that occludes and releases alkali metal ions is used for the negative electrode, there still remains a problem of internal short circuit between the positive electrode and the negative electrode due to dendrites and a reduction in charge / discharge efficiency.
【０００５】デンドライトの析出を抑制するには、負極
表面上の不動態皮膜の均一性を向上させることが有効で
ある。このような方法として、例えばＪｏｕｒｎａｌ
ｏｆＥｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔ
ｙ、第１４１巻、第Ｌ１０８〜Ｌ１１０頁（１９９４
年）に記載されているような電解質に微量のフッ酸を添
加する方法や同第１４１巻、第２３７９〜２３８５頁
（１９９４年）に記載されているような負極と電解質と
を３日間接触させて静置しておく方法がある。しかし、
現実には、電池内部で電極やセパレータにたわみが生じ
るため、電池の充放電中に不動態皮膜の均一性、さらに
は負極と電解質との界面で起こる反応の均一性を保つこ
とは困難である。In order to suppress the precipitation of dendrite, it is effective to improve the uniformity of the passive film on the negative electrode surface. As such a method, for example, Journal
ofElectrochemical Society
y, volume 141, pages L108-L110 (1994)
And the negative electrode described in Vol. 141, pp. 2379-2385 (1994) is brought into contact with the electrolyte for 3 days. There is a way to keep it still. But,
In reality, since the electrodes and separators bend inside the battery, it is difficult to maintain the uniformity of the passive film during the charging and discharging of the battery, and the uniformity of the reaction occurring at the interface between the negative electrode and the electrolyte. .
【０００６】[0006]
【発明が解決しようとする課題】アルカリ金属を活物質
とする負極上での不動態皮膜の形成は、特に、負極との
反応によりフッ化リチウム（ＬｉＦ）を形成する塩、例
えば６フッ化リン酸リチウム（ＬｉＰＦ6）を用いた場
合に速やかである。このため、電池の充放電容量が極め
て小さい場合や充放電サイクルの初期では、デンドライ
トの生成が抑制される。しかし、時間の経過および電池
の充放電サイクルを繰り返すとともに皮膜の厚さや量は
増していくため、均一な皮膜の形成は困難となる。Ｌｉ
Ｆの皮膜は強度が大きいため、一旦不均一な皮膜が形成
されると、逆に、デンドライトの生成と成長が促進され
るという問題が生じる。The formation of a passivation film on a negative electrode containing an alkali metal as an active material is performed, in particular, by forming a salt forming lithium fluoride (LiF) by reaction with the negative electrode, for example, phosphorus hexafluoride. It is prompt when lithium oxide (LiPF 6 ) is used. For this reason, when the charge / discharge capacity of the battery is extremely small or at the beginning of the charge / discharge cycle, generation of dendrites is suppressed. However, as the passage of time and the charge / discharge cycle of the battery are repeated, the thickness and amount of the film increase, making it difficult to form a uniform film. Li
Since the film of F has high strength, once a non-uniform film is formed, the problem arises that the formation and growth of dendrites are promoted.
【０００７】本発明は、負極上でのデンドライトの生成
と成長の抑制が困難であることに鑑み、析出したデンド
ライトを効率的に溶解させることに着目してなされたも
のである。すなわち、本発明は、デンドライトを充放電
サイクルの放電過程で効率的に溶解させることが可能で
あり、充放電サイクルを繰り返しても巨大なデンドライ
トが成長することのない負極を用いることにより、充放
電サイクルの寿命が長く、信頼性の高い非水電解質二次
電池を提供することを目的とする。The present invention has been made in view of the fact that it is difficult to suppress generation and growth of dendrites on a negative electrode, and to dissolve deposited dendrites efficiently. That is, according to the present invention, the dendrite can be efficiently dissolved in the discharge process of the charge / discharge cycle, and the charge / discharge is performed by using the negative electrode in which the huge dendrite does not grow even when the charge / discharge cycle is repeated. An object of the present invention is to provide a non-aqueous electrolyte secondary battery having a long cycle life and high reliability.
【０００８】[0008]
【課題を解決するための手段】本発明は、正極と、アル
カリ金属イオン伝導性の電解質と、空孔率が４０％以上
のセパレータと、アルカリ金属を活物質とする負極とか
らなる非水電解質二次電池に関する。ここで、前記アル
カリ金属イオン伝導性の電解質としては、負極内または
負極上にＬｉＦを形成する塩を用いることができる。ま
た、前記非水電解質二次電池は、充電時に負極上にアル
カリ金属が析出し、放電時に負極上のアルカリ金属が溶
解する非水電解質二次電池であることが好ましい。ま
た、アルカリ金属を活物質とする負極としては、充電時
にアルカリ金属イオンを吸蔵し、放電時にアルカリ金属
イオンを放出する材料やアルカリ金属を貫通孔を有する
金属箔集電体に圧入したものを用いることが好ましい。The present invention provides a non-aqueous electrolyte comprising a positive electrode, an alkali metal ion-conductive electrolyte, a separator having a porosity of 40% or more, and a negative electrode containing an alkali metal as an active material. Related to secondary batteries. Here, as the alkali metal ion-conductive electrolyte, a salt that forms LiF in or on the negative electrode can be used. Further, it is preferable that the non-aqueous electrolyte secondary battery is a non-aqueous electrolyte secondary battery in which an alkali metal is deposited on a negative electrode during charging and an alkali metal on the negative electrode is dissolved during discharging. In addition, as the negative electrode using an alkali metal as an active material, a material that absorbs alkali metal ions during charging and releases alkali metal ions during discharging or a material obtained by press-fitting an alkali metal into a metal foil current collector having a through hole is used. Is preferred.
【０００９】また、本発明は、充電時に負極上にアルカ
リ金属を０.４ｍＡ／ｃｍ2以下の電流密度で析出させ、
放電時に負極上のアルカリ金属を０.２〜３.０ｍＡ／ｃ
ｍ2の電流密度で溶解させることを特徴とする前記非水
電解質二次電池の充放電方法に関する。Further, according to the present invention, an alkali metal is deposited on a negative electrode at a current density of 0.4 mA / cm 2 or less during charging,
0.2-3.0 mA / c of alkali metal on the negative electrode during discharge
The present invention relates to a method for charging and discharging the non-aqueous electrolyte secondary battery, wherein the method is performed by dissolving at a current density of m 2 .
【００１０】[0010]
【発明の実施の形態】セパレータが存在する電池が放電
すると、負極表面に対して垂直方向だけでなく、負極表
面に沿った方向にイオン電流が流れると考えられる。負
極表面に沿った方向のイオン電流は、成長したデンドラ
イトを放電過程で寸断し、負極上から遊離させる傾向が
あり、負極の充放電効率を低下させる原因となる。DESCRIPTION OF THE PREFERRED EMBODIMENTS When a battery having a separator is discharged, it is considered that an ionic current flows not only in a direction perpendicular to the surface of the negative electrode but also in a direction along the surface of the negative electrode. The ion current in the direction along the surface of the negative electrode tends to break the grown dendrite during the discharging process and release the dendrite from the negative electrode, which causes a reduction in the charge / discharge efficiency of the negative electrode.
【００１１】本発明の非水電解質二次電池に用いられる
セパレータは、空孔率が４０％以上である。空孔率が４
０％以上であるため、負極表面に対して垂直方向のイオ
ン電流の寄与が大きくなり、デンドライトの寸断や遊離
が抑制され、充放電効率も向上する。空孔率が４０％未
満になると、負極表面に沿った方向のイオン電流の寄与
が大きくなり、成長したデンドライトを放電過程で寸断
し、負極上から遊離させる傾向も大きくなり、負極の充
放電効率は低下する。一方、空孔率が大きくなりすぎる
と、一部のデンドライトがセパレータ内に食い込んで溶
解が困難になりやすいため、空孔率は４０〜５５％であ
ることが好ましい。The porosity of the separator used in the non-aqueous electrolyte secondary battery of the present invention is 40% or more. Porosity of 4
Since it is 0% or more, the contribution of the ionic current in the direction perpendicular to the negative electrode surface increases, so that dendrite breakage and separation are suppressed, and charge / discharge efficiency also improves. When the porosity is less than 40%, the contribution of the ionic current in the direction along the negative electrode surface increases, and the tendency of the grown dendrite to break during the discharging process and to be released from the negative electrode increases, and the charge and discharge efficiency of the negative electrode increases. Drops. On the other hand, if the porosity is too large, a portion of the dendrites may easily penetrate into the separator and become difficult to dissolve, so that the porosity is preferably 40 to 55%.
【００１２】セパレータの空孔率は、式： ｛１−ｗ／（ｄ×ｖ）｝×１００ （式中、ｄ、ｖおよびｗは、それぞれセパレータとして
用いる材料の真密度、見かけ体積および重量を示す。）
から算出される値（％）である。セパレータとして用い
るのに好ましい材料は、ポリオレフィンなどの多孔質フ
ィルムである。The porosity of the separator is represented by the formula: {1-w / (d × v)} × 100 (where d, v and w are the true density, apparent volume and weight of the material used as the separator, respectively) Shown.)
Is a value (%) calculated from. A preferred material for use as a separator is a porous film such as a polyolefin.
【００１３】本発明の非水電解質二次電池には、アルカ
リ金属イオン伝導性の電解質が用いられる。この電解質
はアルカリ金属の塩と溶媒とからなり、アルカリ金属の
塩としては、特に限定はないが、例えばＬｉＰＦ6、Ｌ
ｉＢＦ4、ＬｉＣＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＣＦ3Ｃ
Ｏ2、ＬｉＡｓＦ6などのＬｉ塩を用いることができる。
これらは単独で用いてもよく、２種以上を組み合わせて
用いてもよい。The nonaqueous electrolyte secondary battery of the present invention uses an alkali metal ion conductive electrolyte. This electrolyte is composed of an alkali metal salt and a solvent, and the alkali metal salt is not particularly limited. For example, LiPF 6 , LPF
iBF 4 , LiCO 4 , LiCF 3 SO 3 , LiCF 3 C
Li salts such as O 2 and LiAsF 6 can be used.
These may be used alone or in combination of two or more.
【００１４】ＬｉＰＦ6、ＬｉＢＦ4などの塩は、ＬｉＦ
の厚い表面皮膜を形成してデンドライトを成長させやす
いため、空孔率が４０％未満のセパレータを用いると、
電池の性能は不充分となる。しかし、空孔率が４０％以
上、さらには４０〜５５％のセパレータを用いることに
より、これらの塩を用いても優れた性能の電池を得るこ
とができるようになる。Salts such as LiPF 6 and LiBF 4 are LiF
When a separator having a porosity of less than 40% is used, it is easy to form a thick surface film and grow dendrite.
Battery performance will be inadequate. However, by using a separator having a porosity of 40% or more, and more preferably 40 to 55%, a battery with excellent performance can be obtained even when these salts are used.
【００１５】前記溶媒としては、例えばエチレンカーボ
ネート、プロピレンカーボネート、ブチレンカーボネー
ト、ジメチルカーボネート、ジエチルカーボネート、エ
チルメチルカーボネート、１，２−ジメトキシエタン、
γ−ブチロラクトン、テトラヒドロフラン、２−メチル
テトラヒドロフラン、１，３−ジオキソランなどがあげ
られる。これらは単独で用いてもよく、２種以上を組み
合わせて用いてもよい。中でもエチレンカーボネートと
ジエチルカーボネートとを組み合わせて使用することが
好ましい。Examples of the solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane,
γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan and the like. These may be used alone or in combination of two or more. Among them, it is preferable to use a combination of ethylene carbonate and diethyl carbonate.
【００１６】本発明の非水電解質二次電池には、アルカ
リ金属を活物質とする負極が用いられる。アルカリ金属
としては、Ｌｉ、Ｎａ、Ｋなどを単独で、または複数組
み合わせて用いることができる。これらのうちでは、特
にＬｉが好ましく用いられる。このような負極として
は、特に限定はないが、例えばグラファイトなどの充電
時にアルカリ金属イオンを吸蔵し、放電時にアルカリ金
属イオンを放出する材料にアルカリ金属イオンを吸蔵さ
せたもの、アルカリ金属を集電体に圧着させたものなど
が用いられる。特に、入手時から存在するアルカリ金属
の表面の皮膜を破壊して、負極上でのアルカリ金属の析
出点を増加させ、一析出点あたりのデンドライトの縦方
向への成長およびデンドライトの寸断ならびに負極から
の遊離を抑制することができるという点から、アルカリ
金属を貫通孔を有する金属箔集電体に圧入したものが好
ましい。圧入する方法としては、アルカリ金属の箔を集
電体に貼り合わせ、１５０〜２５０ｋｇｆ／ｃｍ2程度
の圧力で圧着する方法などが挙げられる。In the non-aqueous electrolyte secondary battery of the present invention, a negative electrode containing an alkali metal as an active material is used. As the alkali metal, Li, Na, K and the like can be used alone or in combination. Among these, Li is particularly preferably used. Such a negative electrode is not particularly limited. For example, a material in which alkali metal ions are occluded in a material that absorbs alkali metal ions at the time of charging such as graphite and discharges the alkali metal ions during discharging, and that collects alkali metal What is pressed on the body is used. In particular, it destroys the film on the surface of the alkali metal that is present at the time of acquisition, increases the precipitation point of the alkali metal on the negative electrode, grows dendrite in a vertical direction per one precipitation point, and cuts the dendrite and the negative electrode. It is preferable that an alkali metal is press-fitted into a metal foil current collector having a through hole from the viewpoint that release of the metal foil can be suppressed. As a method for press-fitting, a method in which an alkali metal foil is bonded to a current collector and pressure-bonded at a pressure of about 150 to 250 kgf / cm 2 may be used.
【００１７】貫通孔を有する金属箔集電体において、貫
通孔の穴径は０．２〜０．４ｍｍであることが好まし
く、金属箔集電体の空孔率（空孔率はセパレータの空孔
率と同様にして求められる。）は４０〜６０％であるこ
とが好ましい。また、金属箔集電体の厚さは１５〜２５
μｍであることが好ましい。金属箔としては、例えば銅
箔、ニッケル箔などが用いられる。In a metal foil current collector having a through hole, the hole diameter of the through hole is preferably 0.2 to 0.4 mm, and the porosity of the metal foil current collector (the porosity is the porosity of the separator). (Determined in the same manner as the porosity) is preferably 40 to 60%. The thickness of the metal foil current collector is 15 to 25.
μm is preferred. As the metal foil, for example, a copper foil, a nickel foil, or the like is used.
【００１８】本発明の非水電解質二次電池に用いられる
正極は、特に限定はなく、一般に非水電解質二次電池に
用いられるものでよい。The positive electrode used for the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and may be one generally used for a non-aqueous electrolyte secondary battery.
【００１９】本発明の一の非水電解質二次電池において
は、充電時に負極上にアルカリ金属が析出し、放電時に
負極上のアルカリ金属が溶解する。充電時の電流密度の
好ましい範囲は、電池の充放電効率が大きくなるという
点から、０.４ｍＡ／ｃｍ2以下、さらには０．１〜０．
２ｍＡ／ｃｍ2である。充電時の電流密度が大きくなり
すぎると、充放電効率が低下しやすい。これは、析出し
たアルカリ金属の形態が太いフィブリル状から細い針状
に変化するためと考えられる。一方、放電時の電流密度
の好ましい範囲は、０．２〜３．０ｍＡ／ｃｍ2、さら
には０．８〜２．０ｍＡ／ｃｍ2である。放電時の電流
密度が大きくなりすぎても、小さくなりすぎても、充放
電効率は低下する。これは、放電時の電流密度が大きく
なると、負極表面に沿った方向のイオン電流が支配的と
なり、析出したアルカリ金属が寸断され、負極から遊離
しやすいため、および放電時の電流密度が小さくなりす
ぎると、析出したアルカリ金属の表面に形成されるＬｉ
Ｆの皮膜が破壊されにくくなるなどのため、と考えられ
る。In one non-aqueous electrolyte secondary battery of the present invention, an alkali metal precipitates on the negative electrode during charging, and dissolves the alkali metal on the negative electrode during discharging. The preferable range of the current density at the time of charging is 0.4 mA / cm 2 or less, and more preferably 0.1 to 0.4, from the viewpoint that the charging and discharging efficiency of the battery is increased.
It is 2 mA / cm 2 . If the current density during charging is too high, the charge / discharge efficiency tends to decrease. This is considered because the form of the precipitated alkali metal changes from a thick fibril shape to a thin needle shape. On the other hand, the preferable range of the current density at the time of discharging is 0.2 to 3.0 mA / cm 2 , and more preferably 0.8 to 2.0 mA / cm 2 . If the current density at the time of discharging becomes too large or too small, the charging / discharging efficiency decreases. This is because, when the current density at the time of discharge increases, the ionic current in the direction along the negative electrode surface becomes dominant, and the precipitated alkali metal is cut and easily released from the negative electrode, and the current density at the time of discharge decreases. If too much, Li formed on the surface of the precipitated alkali metal
It is considered that the film of F is hardly broken.
【００２０】[0020]
【実施例】次に、本発明を実施例に基づき具体的に説明
する。Next, the present invention will be specifically described based on examples.
【００２１】《実施例１〜５および比較例１〜２》表１
に示す空孔率を有する各種ポリオレフィン系多孔質フィ
ルムをセパレータとして用いて図１に示すような扁平型
電池を組み立て、その充放電効率を測定した。電池の電
解液には、エチレンカーボネートとジエチルカーボネー
トとを１：１の体積比で混合した溶媒に、ＬｉＰＦ6を
１モル／リットルの濃度で溶解したものを用いた。<< Examples 1 to 5 and Comparative Examples 1 and 2 >> Table 1
A flat battery as shown in FIG. 1 was assembled using various polyolefin-based porous films having the porosity shown in FIG. 1 as separators, and the charge / discharge efficiency was measured. As the electrolyte solution of the battery, a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / liter in a solvent obtained by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 was used.
【００２２】図１中、負極集電体１は銅箔であり、封口
板２にスポット溶接されている。負極（試験極）３は、
直径１６.８ｍｍ、厚さ８０μｍのリチウム箔を打ち抜
いたものであり、負極集電体１に圧着されている。打ち
抜いたリチウム箔の電気容量は約３６ｍＡｈであるが、
試験の精度を向上させるために、各リチウム箔の重量を
測定し、その値から正確な電気容量Ｑexを求めた。正極
集電体４はステンレス網であり、正極缶５にスポット溶
接されている。正極（対極）６には、直径１６.８ｍ
ｍ、厚さ１ｍｍのリチウム金属箔を用いている。電池
は、アルゴンガス雰囲気下で、負極（試験極）３を配置
した封口板２を転地した後、セパレータ７をセットし、
前記電解液を１５０マイクロリットル注入し、ガスケッ
ト８を介して正極缶５をかぶせ、正極缶５の周縁部を封
口板２にかしめる手順で組み立てた。In FIG. 1, a negative electrode current collector 1 is a copper foil and is spot-welded to a sealing plate 2. The negative electrode (test electrode) 3
It is formed by punching a lithium foil having a diameter of 16.8 mm and a thickness of 80 μm, and is pressed to the negative electrode current collector 1. The electric capacity of the punched lithium foil is about 36 mAh,
In order to improve the accuracy of the test, the weight of each lithium foil was measured, and an accurate electric capacity Qex was determined from the value. The positive electrode current collector 4 is a stainless steel net, and is spot-welded to the positive electrode can 5. The positive electrode (counter electrode) 6 has a diameter of 16.8 m.
m, a 1 mm thick lithium metal foil is used. In the battery, the separator 7 is set after the sealing plate 2 on which the negative electrode (test electrode) 3 is disposed under an argon gas atmosphere,
150 microliters of the electrolytic solution was injected, the positive electrode can 5 was covered with the gasket 8, and the periphery of the positive electrode can 5 was crimped to the sealing plate 2.
【００２３】得られた扁平型電池の試験極に０.２ｍＡ
／ｃｍ2の電流密度でリチウムを１５時間かけて析出さ
せ、析出したリチウムを１.０ｍＡ／ｃｍ2の電流密度で
３時間かけて溶解させるサイクル（これは電池の負極に
対する充電・放電サイクルに相当する。）を１４回行っ
た後、１５回目に１.０ｍＡ／ｃｍ2の電流密度で電池の
電圧が−１Ｖになるまで析出したリチウムを溶解させた
ときの放電容量Ｑres を測定し、式： 充放電効率（％）＝〔［３−｛（Ｑex−Ｑres）／１
５｝］／３〕×１００ から充放電効率を算出した。結果を表１に示す。充放電
効率の値は、５個の電池の平均値である。The test electrode of the obtained flat battery had a current of 0.2 mA.
/ Lithium was precipitated over 15 hours at a current density of cm 2, precipitated cycles for lithium dissolved over 3 hours at a current density of 1.0 mA / cm 2 (which corresponds to a charge-discharge cycle for the negative electrode of the battery Is performed 14 times, and the discharge capacity Qres at the time of dissolving lithium deposited until the voltage of the battery becomes -1 V at a current density of 1.0 mA / cm 2 at the 15th time is measured. Charge / discharge efficiency (%) = [[3-｛(Qex-Qres) / 1
The charge / discharge efficiency was calculated from 5 °] / 3] × 100. Table 1 shows the results. The value of the charge / discharge efficiency is an average value of five batteries.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１は、セパレータの空孔率が４０％以上
の場合に、電池の充放電効率が実用レベルの充放電効率
として受け入れられている９８％以上になることを示し
ている。一方、セパレータの空孔率が４５％を超える
と、充放電効率が低下する傾向が見られる。これは、一
部のデンドライトがセパレータ内に食い込んで溶解が困
難になり始めたためと考えられる。セパレータの空孔率
が６０％以上になると、一部の電池が内部短絡を起こし
ていることからも、このことが示唆される。Table 1 shows that when the porosity of the separator is 40% or more, the charge / discharge efficiency of the battery becomes 98% or more, which is accepted as a practical level of charge / discharge efficiency. On the other hand, if the porosity of the separator exceeds 45%, the charge / discharge efficiency tends to decrease. This is considered to be because some dendrites began to bite into the separator and became difficult to dissolve. When the porosity of the separator is 60% or more, this is suggested from the fact that some of the batteries have an internal short circuit.
【００２６】《比較例３〜４》電解液として、エチレン
カーボネートとジエチルカーボネートとを１：１の体積
比で混合した溶媒に、表２に示す種々の塩を１モル／リ
ットルの濃度で溶解したものを用い、セパレータとし
て、空孔率３５％のポリオレフィン系多孔質フィルムを
用いたこと以外は、実施例１と同様にして扁平型電池を
組み立て、評価した。結果を表２に示す。Comparative Examples 3 and 4 Various salts shown in Table 2 were dissolved at a concentration of 1 mol / liter in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 as an electrolytic solution. A flat battery was assembled and evaluated in the same manner as in Example 1, except that a polyolefin-based porous film having a porosity of 35% was used as a separator. Table 2 shows the results.
【００２７】[0027]
【表２】 [Table 2]
【００２８】ＬｉＰＦ6およびＬｉＢＦ4は、負極活物質
であるリチウムと反応してＬｉＦの厚い表面皮膜を形成
するが、ＬｉＣｌＯ4は比較的薄い表面皮膜を形成する
ことが知られている。従って、ＬｉＰＦ6を用いた比較
例２の電池やＬｉＢＦ4を用いた比較例３の電池の充放
電効率は、ＬｉＣｌＯ4を用いた比較例４の電池より低
くなっている。このことは、アルカリ金属イオン伝導性
の電解質に用いる塩が負極内または負極上にＬｉＦを形
成させる塩である場合には、セパレータの空孔率が４０
％未満では、充分な充放電効率が得られないことを示し
ている。It is known that LiPF 6 and LiBF 4 react with lithium as a negative electrode active material to form a LiF thick surface film, whereas LiClO 4 forms a relatively thin surface film. Therefore, the charging and discharging efficiency of the battery of Comparative Example 2 using LiPF 6 and the battery of Comparative Example 3 using LiBF 4 are lower than the battery of Comparative Example 4 using LiClO 4 . This means that when the salt used for the alkali metal ion conductive electrolyte is a salt that forms LiF in or on the negative electrode, the porosity of the separator is 40%.
% Indicates that sufficient charge / discharge efficiency cannot be obtained.
【００２９】《実施例６〜９および比較例５〜６》これ
らの実施例は、リチウムイオン電池が充放電サイクルを
繰り返すことにより、負極の容量が劣化した場合（正極
の容量が負極の容量より大きくなった場合）や電解液の
枯渇などが原因で不均一な電極反応が起こり、負極の一
部のみが充放電反応に寄与する状態になった場合に相当
する。<< Examples 6 to 9 and Comparative Examples 5 to 6 >> In these examples, the capacity of the negative electrode was deteriorated by repeating the charge / discharge cycle of the lithium ion battery (the capacity of the positive electrode was smaller than the capacity of the negative electrode). This is equivalent to a case where a non-uniform electrode reaction occurs due to depletion of the electrolyte solution or the like, and only a part of the negative electrode becomes a state contributing to the charge / discharge reaction.
【００３０】グラファイト粉末９０重量部およびポリフ
ッ化ビニリデン系結着剤の粉末１０重量部をＮ−メチル
ピロリドンに分散させたものを銅箔上に塗布し、乾燥
後、ローラーにて圧延し、直径１６.８ｍｍ、厚さ１２
０μｍの円形に打ち抜いたものを負極（試験極）とし、
実施例１と同様の操作を行って扁平型電池を組み立て
た。90 parts by weight of graphite powder and 10 parts by weight of polyvinylidene fluoride-based binder powder dispersed in N-methylpyrrolidone are coated on a copper foil, dried, rolled by a roller, and rolled to a diameter of 16%. .8mm, thickness 12
The one punched out into a 0 μm circle is the negative electrode (test electrode),
A flat battery was assembled by performing the same operation as in Example 1.
【００３１】得られた電池の負極のグラファイトに対
し、リチウムイオンを０.２ｍＡ／ｃｍ2の電流密度で電
池の電圧が２０ｍＶになるまで吸蔵させ（これは電池の
充電に相当する。）、吸蔵されたリチウムイオンを１.
０ｍＡ／ｃｍ2の電流密度で電池の電圧が１Ｖになるま
で放出させる（これは電池の放電に相当する。）サイク
ルを５回繰り返したところ、負極の電気容量が２.８ｍ
Ａｈ／ｃｍ2の一定値になった。The graphite of the negative electrode of the obtained battery was occluded with lithium ions at a current density of 0.2 mA / cm 2 until the battery voltage became 20 mV (this corresponds to charging of the battery). 1.
The battery was discharged at a current density of 0 mA / cm 2 until the voltage of the battery reached 1 V (this corresponds to the discharge of the battery). The cycle was repeated 5 times, and the electric capacity of the negative electrode was 2.8 m.
It became a constant value of Ah / cm 2 .
【００３２】次に、負極からリチウムイオンを放出させ
た状態で扁平型電池を分解し、負極を取り出し、これを
アルカリ金属を活物質とする負極として用いて改めて前
記と同様の扁平型電池を組み立てた。セパレータには、
表３に示す空孔率を有する各種ポリオレフィン系多孔質
フィルムを用いた。改めて組み立てた扁平型電池の負極
に対し、リチウムイオンを総電気容量が６.８ｍＡｈ／
ｃｍ2になるまで０.２ｍＡ／ｃｍ2の電流密度で吸蔵さ
せ、１.０ｍＡ／ｃｍ2の電流密度で電池の電圧が１Ｖに
なるまで負極からリチウムイオンを放出させたときの電
気容量Ｑdisを測定し、式： 充放電効率（％）＝（Ｑdis／６.８）×１００ から充放電効率を算出した。また、同じ充放電サイクル
を１５回繰り返し、１５回目に１.０ｍＡ／ｃｍ2の電流
密度で電池の電圧が１Ｖになるまで負極からリチウムイ
オンを放出させたときの充放電効率も同様に算出した。
結果を充放電効率の１サイクルあたりの劣化率とともに
表３に示す。Next, the flat battery is disassembled in a state where lithium ions are released from the negative electrode, the negative electrode is taken out, and this is used as a negative electrode containing an alkali metal as an active material. Was. For the separator,
Various polyolefin-based porous films having the porosity shown in Table 3 were used. The total electric capacity of the negative electrode of the newly assembled flat battery was 6.8 mAh /
until the cm 2 is occluded at a current density of 0.2 mA / cm 2, the capacitance Qdis when the voltage of the battery at a current density of 1.0 mA / cm 2 was shown releasing lithium ions from the negative electrode until 1V The charge and discharge efficiency was calculated from the formula: charge and discharge efficiency (%) = (Qdis / 6.8) × 100. The same charge / discharge cycle was repeated 15 times, and the charge / discharge efficiency when lithium ions were released from the negative electrode at the 15th time at a current density of 1.0 mA / cm 2 until the voltage of the battery became 1 V was similarly calculated. .
The results are shown in Table 3 together with the rate of deterioration of the charge / discharge efficiency per cycle.
【００３３】[0033]
【表３】 [Table 3]
【００３４】表３から、充放電効率が充分に高く、劣化
率の小さい電池は、セパレータの空孔率が４０％以上の
電池であり、セパレータの空孔率が４５％の電池の劣化
率が最も小さいことがわかる。From Table 3, it can be seen that a battery having sufficiently high charge / discharge efficiency and a small deterioration rate is a battery having a separator porosity of 40% or more, and a battery having a separator porosity of 45% has a low deterioration rate. It turns out that it is the smallest.
【００３５】《実施例１０》空孔率が４５％のセパレー
タを用いた実施例２の扁平型電池を用い、０.２ｍＡ／
ｃｍ2の電流密度で負極にリチウムを析出させた後、電
析および溶解密度を３.０ｍＡｈ／ｃｍ2に固定して、電
流密度を０.０５〜５.０ｍＡ／ｃｍ2の間で変化させて
負極からリチウムを溶解させたこと以外は、実施例２と
同様の操作を行って各充放電効率を求めた。Example 10 The flat battery of Example 2 using a separator having a porosity of 45% was used, and 0.2 mA /
After depositing lithium on the negative electrode at a current density of 2 cm 2 , the electrodeposition and dissolution density were fixed at 3.0 mAh / cm 2 , and the current density was varied between 0.05 and 5.0 mA / cm 2. Each charge and discharge efficiency was determined by performing the same operation as in Example 2 except that lithium was dissolved from the negative electrode.
【００３６】図２は、リチウムを溶解させるときの電流
密度と負極の充放電効率との関係を示している。図２か
ら、充放電効率は、リチウムを溶解させるときの電流密
度が０．２〜３．０ｍＡ／ｃｍ2のときに高い値とな
り、１.０ｍＡ／ｃｍ2近傍のときに最大になることがわ
かる。図２で電流密度が小さくなると充放電効率が低下
しているのは、析出したリチウムの表面に形成されたＬ
ｉＦの皮膜が厚く、小さい電流密度ではその皮膜が破壊
されないためと考えられる。一方、電流密度が大きくな
ると充放電効率が低下するのは、負極表面に沿ったイオ
ン電流が支配的となり、析出したデンドライトが寸断さ
れ、負極から遊離することが原因と考えられる。FIG. 2 shows the relationship between the current density when lithium is dissolved and the charge / discharge efficiency of the negative electrode. From Figure 2, the charge and discharge efficiency becomes a high value when the current density is 0.2~3.0mA / cm 2 when dissolving lithium, may become maximum when 1.0 mA / cm 2 near Understand. In FIG. 2, the lower the current density is, the lower the charging / discharging efficiency is due to the L formed on the surface of the deposited lithium.
This is probably because the iF film is thick and the film is not destroyed at a small current density. On the other hand, it is considered that the reason why the charge / discharge efficiency decreases as the current density increases is that the ion current along the negative electrode surface becomes dominant, and the deposited dendrite is cut off and released from the negative electrode.
【００３７】《実施例１１》空孔率が４５％のセパレー
タを用いた実施例２の扁平型電池を用い、電流密度を
０.１〜４.０ｍＡ／ｃｍ2の間で変化させて負極にリチ
ウムを析出させた後、電析および溶解密度を３.０ｍＡ
ｈ／ｃｍ2に固定して、１.０ｍＡ／ｃｍ2の電流密度で
負極からリチウムを溶解させたこと以外は、実施例２と
同様の操作を行って各充放電効率を求めた。Example 11 Using the flat battery of Example 2 using a separator having a porosity of 45%, the current density was changed between 0.1 and 4.0 mA / cm 2 to form a negative electrode. After depositing lithium, the deposition and dissolution density were 3.0 mA.
h / cm 2 , and each charge / discharge efficiency was determined in the same manner as in Example 2 except that lithium was dissolved from the negative electrode at a current density of 1.0 mA / cm 2 .
【００３８】図３は、リチウムを析出させるときの電流
密度と負極の充放電効率との関係を示している。図３か
ら、充放電効率は、リチウムを析出させるときの電流密
度が０.４ｍＡ／ｃｍ2以下のときに高い値となることが
わかる。図３で電流密度が大きくなると充放電効率が低
下しているのは、析出したリチウムの形態が、太いフィ
ブリル状から細い針状に変化したためと考えられる。FIG. 3 shows the relationship between the current density when depositing lithium and the charge / discharge efficiency of the negative electrode. FIG. 3 shows that the charge / discharge efficiency becomes high when the current density when depositing lithium is 0.4 mA / cm 2 or less. In FIG. 3, the reason why the charge / discharge efficiency decreases as the current density increases is considered that the form of the deposited lithium changes from a thick fibril shape to a thin needle shape.
【００３９】《実施例１２〜１６および比較例７〜８》
負極として、貫通孔を有する圧延銅箔（穴径：０.３ｍ
ｍ、穴配列：千鳥格子、空孔率：５０％）の集電体にリ
チウム箔を圧入したものを用い、セパレータとして、表
４に示す空孔率を有する各種ポリオレフィン系多孔質フ
ィルムを用いたこと以外は、実施例１と同様の操作を行
って電池を組み立て、評価した。ここで、貫通孔を有す
る圧延銅箔を集電体として用いたのは、リチウム箔を圧
延銅箔に圧着することにより、入手時から存在するリチ
ウム箔の表面の皮膜を圧延銅箔の穴のエッジ部分で破壊
するためである。結果を表４に示す。充放電効率の値
は、５個の電池の平均値である。<< Examples 12 to 16 and Comparative Examples 7 to 8 >>
Rolled copper foil with through holes (hole diameter: 0.3 m) as negative electrode
m, hole arrangement: houndstooth check, porosity: 50%) using a lithium collector pressed into a current collector, and using various polyolefin-based porous films having porosity shown in Table 4 as a separator. A battery was assembled and evaluated by performing the same operation as in Example 1 except that the battery was not used. Here, the rolled copper foil having a through-hole was used as the current collector because the lithium foil was pressed against the rolled copper foil, so that the film on the surface of the lithium foil existing from the time of acquisition was formed in the hole of the rolled copper foil. This is to break at the edge. Table 4 shows the results. The value of the charge / discharge efficiency is an average value of five batteries.
【００４０】[0040]
【表４】 [Table 4]
【００４１】表１と表４との比較から、集電体として貫
通孔を有する金属箔を用いることにより、電池の充放電
効率がさらに向上することがわかる。これは、金属箔の
穴のエッジ部分で入手時から存在するリチウム箔の表面
の皮膜が破壊され、リチウムの析出点が多数生じ、一析
出点でのデンドライトの縦方向への成長が抑制され、デ
ンドライトの寸断や遊離が低減したためと考えられる。From a comparison between Tables 1 and 4, it can be seen that the use of a metal foil having a through hole as a current collector further improves the charge / discharge efficiency of the battery. This is because the film on the surface of the lithium foil existing from the time of acquisition is destroyed at the edge of the hole in the metal foil, a large number of lithium deposition points are generated, and the growth of dendrites at one deposition point in the vertical direction is suppressed, This is probably because dendrite shredding and separation were reduced.
【００４２】なお、アルカリ金属としてリチウム以外の
アルカリ金属やアルカリ金属を主成分とする合金、例え
ばリチウム−アルミニウム合金を使用して電池を組み立
て、前記各実施例と同様の操作を行って評価したとこ
ろ、リチウムを用いた場合と同様の効果を得ることがで
きた。A battery was assembled using an alkali metal other than lithium or an alloy containing an alkali metal as a main component, for example, a lithium-aluminum alloy, and evaluated by performing the same operation as in each of the above embodiments. And the same effect as in the case of using lithium could be obtained.
【００４３】[0043]
【発明の効果】本発明によれば、負極内または負極上に
ＬｉＦを形成させる電解質を用いても、４０％以上の空
孔率を有するセパレータを用いるため、さらには特定の
電流密度で充電・放電を行うため、特には貫通孔を有す
る金属箔集電体にアルカリ金属を圧入したものからなる
負極を用いるため、負極上でのデンドライトの発生を抑
制し、デンドライトを効果的に溶解（消失）させること
ができる。従って、負極の充放電効率が向上し、充放電
サイクルの寿命が長く、信頼性の高い非水電解質二次電
池を得ることができる。According to the present invention, even if an electrolyte for forming LiF in or on the negative electrode is used, a separator having a porosity of 40% or more is used. In order to perform discharge, in particular, to use a negative electrode made of a metal foil current collector having a through hole into which an alkali metal is pressed, the generation of dendrites on the negative electrode is suppressed, and the dendrites are effectively dissolved (disappeared). Can be done. Therefore, the charge / discharge efficiency of the negative electrode is improved, the life of the charge / discharge cycle is long, and a highly reliable nonaqueous electrolyte secondary battery can be obtained.
【図１】本発明の非水電解質二次電池の一例である扁平
型電池の縦断面図である。FIG. 1 is a longitudinal sectional view of a flat battery which is an example of a non-aqueous electrolyte secondary battery of the present invention.
【図２】リチウムを溶解させるときの電流密度と負極の
充放電効率との関係を示す図である。FIG. 2 is a diagram showing a relationship between current density when lithium is dissolved and charge and discharge efficiency of a negative electrode.
【図３】リチウムを析出させるときの電流密度と負極の
充放電効率との関係を示す図である。FIG. 3 is a diagram showing a relationship between current density when depositing lithium and charge / discharge efficiency of a negative electrode.
１ 負極集電体 ２ 封口板 ３ 負極 ４ 正極集電体 ５ 正極缶 ６ 正極 ７ セパレータ ８ ガスケット REFERENCE SIGNS LIST 1 negative electrode current collector 2 sealing plate 3 negative electrode 4 positive electrode current collector 5 positive electrode can 6 positive electrode 7 separator 8 gasket
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H014 AA02 AA07 BB12 EE01 EE05 EE10 HH02 HH04 5H029 AJ05 AJ12 AJ14 AL07 AL12 AM03 AM04 AM05 AM07 AM12 CJ16 CJ23 DJ04 DJ07 HJ09 HJ17 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H014 AA02 AA07 BB12 EE01 EE05 EE10 HH02 HH04 5H029 AJ05 AJ12 AJ14 AL07 AL12 AM03 AM04 AM05 AM07 AM12 CJ16 CJ23 DJ04 DJ07 HJ09 HJ17
Claims (6)
解質と、空孔率が４０％以上のセパレータと、アルカリ
金属を活物質とする負極とからなる非水電解質二次電
池。1. A non-aqueous electrolyte secondary battery comprising a positive electrode, an alkali metal ion-conductive electrolyte, a separator having a porosity of 40% or more, and a negative electrode containing an alkali metal as an active material.
負極内または負極上にフッ化リチウムを形成する塩を含
んでいる請求項１記載の非水電解質二次電池。2. An alkali metal ion conductive electrolyte,
The non-aqueous electrolyte secondary battery according to claim 1, further comprising a salt forming lithium fluoride in or on the negative electrode.
し、放電時に負極上のアルカリ金属が溶解する請求項１
または２記載の非水電解質二次電池。3. The method according to claim 1, wherein the alkali metal precipitates on the negative electrode during charging, and the alkali metal on the negative electrode dissolves during discharging.
Or the non-aqueous electrolyte secondary battery according to 2.
電時にアルカリ金属イオンを吸蔵し、放電時にアルカリ
金属イオンを放出する材料からなる請求項１〜３のいず
れかに記載の非水電解質二次電池。4. The non-aqueous electrolyte according to claim 1, wherein the negative electrode containing an alkali metal as an active material is made of a material that absorbs alkali metal ions during charging and releases alkali metal ions during discharging. Next battery.
ルカリ金属を貫通孔を有する金属箔集電体に圧入したも
のからなる請求項２記載の非水電解質二次電池。5. The non-aqueous electrolyte secondary battery according to claim 2, wherein the negative electrode containing an alkali metal as an active material is formed by press-fitting the alkali metal into a metal foil current collector having a through hole.
ｍＡ／ｃｍ2以下の電流密度で析出させ、放電時に負極
上のアルカリ金属を０.２〜３.０ｍＡ／ｃｍ2の電流密
度で溶解させることを特徴とする請求項１または２記載
の非水電解質二次電池の充放電方法。6. The method according to claim 6, wherein an alkali metal is added on the negative electrode during charging.
mA / cm 2 is deposited in the following current densities, nonaqueous of claim 1 or 2, wherein the negative electrode of an alkaline metal at the time of discharge, characterized in that dissolving at a current density of 0.2~3.0mA / cm 2 A method for charging and discharging an electrolyte secondary battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23757899A JP2001068162A (en) | 1999-08-24 | 1999-08-24 | Nonaqueous electrolyte secondary battery and its charging discharging method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23757899A JP2001068162A (en) | 1999-08-24 | 1999-08-24 | Nonaqueous electrolyte secondary battery and its charging discharging method |
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| Publication Number | Publication Date |
|---|---|
| JP2001068162A true JP2001068162A (en) | 2001-03-16 |
Family
ID=17017404
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23757899A Withdrawn JP2001068162A (en) | 1999-08-24 | 1999-08-24 | Nonaqueous electrolyte secondary battery and its charging discharging method |
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| Country | Link |
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