JP2001307773A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JP2001307773A JP2001307773A JP2000118186A JP2000118186A JP2001307773A JP 2001307773 A JP2001307773 A JP 2001307773A JP 2000118186 A JP2000118186 A JP 2000118186A JP 2000118186 A JP2000118186 A JP 2000118186A JP 2001307773 A JP2001307773 A JP 2001307773A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- battery
- positive electrode
- aqueous electrolyte
- lithium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水電解質電池に関す
るものであり、特に高温放置時に電池膨れを生じるるこ
となく、過充電時の安全性にも優れる非水電解質電池に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte battery which does not swell when left at high temperatures and which is excellent in safety during overcharge.
【０００２】[0002]
【従来の技術】近年の電子技術のめざましい進歩は、電
子機器の小形・軽量化を次々と実現させている。それに
伴い、電源である電池に対しても、一層の小型化、軽量
化、高エネルギー密度化が求められるようになってい
る。2. Description of the Related Art In recent years, remarkable progress in electronic technology has realized a reduction in size and weight of electronic devices one after another. Along with this, there is an increasing demand for batteries that are power sources to be further reduced in size, weight, and energy density.
【０００３】従来、一般用途の電池としては、鉛電池、
ニッケルカドミウム電池等の水溶液系電池が主流であっ
た。しかし、これらの水溶液系電池は、サイクル特性に
は優れるものの、電池重量やエネルギー密度の点では十
分に満足できるものとは言えなかった。Conventionally, batteries for general use include lead batteries,
Aqueous batteries such as nickel cadmium batteries were the mainstream. However, although these aqueous batteries are excellent in cycle characteristics, they cannot be said to be sufficiently satisfactory in terms of battery weight and energy density.
【０００４】そこで、最近、電池電圧が高く、高いエネ
ルギー密度を有し、サイクル特性にも優れた非水電解質
電池が使用され始めている。非水電解質電池の代表的な
ものとしては、リチウムイオンの可逆的インターカレー
ションが可能な物質を電極材料に用いたリチウムイオン
電池がある。Therefore, recently, nonaqueous electrolyte batteries having a high battery voltage, a high energy density, and excellent cycle characteristics have begun to be used. A typical nonaqueous electrolyte battery is a lithium ion battery using a material capable of reversible lithium ion intercalation as an electrode material.
【０００５】[0005]
【発明が解決しようとする課題】リチウムイオン電池
は、エネルギー密度、充放電サイクル特性に優れること
から、比較的消費電力の大きい携帯用通信端末機器の電
源として使用され、広範に普及してきている。Lithium-ion batteries have been used widely as power sources for portable communication terminals with relatively high power consumption because of their excellent energy density and charge / discharge cycle characteristics, and have been widely used.
【０００６】ところが、リチウムイオン電池において
は、過充電時に電解質や活物質の分解等の異常反応が起
こり、電池の発熱や破損に至る場合がある。このため、
過充電時における熱暴走を防止するために、正極合剤中
に炭酸リチウムを添加して電気化学的な分解反応による
ＣＯ2ガスの発生を利用して、電池に装着される電流遮
断素子を作動させる方法が提案されている（特開平４−
３２８２７８号、特開平４−３２９２６８号等参照）。
なお、正極に炭酸リチウムを添加した電池は、電流遮断
素子ではなく、電池の内圧上昇によって開弁する安全弁
であっても、上記と同様にＣＯ2ガスの発生により容易
に安全弁を作動することにより、過充電時における熱暴
走を防止することができる。However, in a lithium ion battery, an abnormal reaction such as decomposition of an electrolyte or an active material occurs at the time of overcharging, and the battery may generate heat or be damaged. For this reason,
To prevent thermal runaway during overcharging, add lithium carbonate to the positive electrode mixture and use the generation of CO 2 gas due to the electrochemical decomposition reaction to activate the current cutoff element attached to the battery A method has been proposed (Japanese Unexamined Patent Publication No.
328278 and JP-A-4-329268).
The battery obtained by adding lithium carbonate to the positive electrode is not a current cut-off device, even safety valve which opens by internal pressure increase of the battery by easily operating the safety valve by the generation of the same manner as described above CO 2 gas In addition, thermal runaway during overcharge can be prevented.
【０００７】しかしながら、上記のように炭酸リチウム
を添加した正極を備えた電池においては、高温環境下で
充放電された場合や充電状態で放置されただけで、ＣＯ
2ガスが多量に発生するために電池が膨れたり、さらに
は電池の電流遮断素子や安全弁が作動するといった悪影
響の出ることがあった。However, in the battery provided with the positive electrode to which lithium carbonate is added as described above, when the battery is charged / discharged in a high-temperature environment or left in a charged state, the CO
Since a large amount of the two gases was generated, the battery might swell, and furthermore, adverse effects such as the operation of the battery's current cutoff element and the operation of the safety valve might occur.
【０００８】本発明は、上記のような従来の課題を解決
するためになされたものであり、過充電時の安全性を確
保するため、正極合剤に炭酸リチウムを添加するととも
に、非水電解液中にプロパンスルトンを添加して、高温
放置時等における電池の膨れを抑制することにより、安
全性と信頼性を兼ね備えた非水電解質電池を提供するこ
とを目的としている。The present invention has been made to solve the above-mentioned conventional problems. In order to ensure safety during overcharge, lithium carbonate is added to a positive electrode mixture and non-aqueous electrolyte is added. It is an object of the present invention to provide a non-aqueous electrolyte battery having both safety and reliability by adding propane sultone to a liquid and suppressing swelling of the battery when left at a high temperature or the like.
【０００９】[0009]
【課題を解決するための手段】すなわち、本発明にかか
る第一の発明は、非水電解質電池において、正極に炭酸
リチウムを含有するとともに、非水電解液にプロパンス
ルトンを含有することを特徴とする。That is, a first invention according to the present invention is characterized in that, in a non-aqueous electrolyte battery, the positive electrode contains lithium carbonate and the non-aqueous electrolyte contains propane sultone. I do.
【００１０】また、本発明にかかる第二の発明は、上
記、電解液にプロパンスルトンを含有した非水電解質電
池において、正極合剤中の炭酸リチウム含有量が、正極
活物質１００重量部に対して１重量部以上、５重量部以
下であることを特徴とする。In a second aspect of the present invention, in the above nonaqueous electrolyte battery containing propane sultone in the electrolytic solution, the content of lithium carbonate in the positive electrode mixture is based on 100 parts by weight of the positive electrode active material. And not more than 1 part by weight and not more than 5 parts by weight.
【００１１】さらに、本発明にかかる第三の発明は、上
記、炭酸リチウムを含有した正極合剤を備えた非水電解
質電池において、プロパンスルトンの添加量が、電解液
量に対して０．２重量％以上、５重量％以下であること
を特徴とする。Further, the third invention according to the present invention provides a non-aqueous electrolyte battery provided with the above-described positive electrode mixture containing lithium carbonate, wherein the amount of propane sultone added is 0.2 to the amount of the electrolyte. It is not less than 5% by weight and not more than 5% by weight.
【００１２】[0012]
【発明の実施の形態】上述のごとく、本発明の特徴は、
非水電解質電池において、正極に炭酸リチウムを含有す
るとともに、非水電解液にプロパンスルトンを含有する
ことにある。DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, the features of the present invention are as follows.
In a non-aqueous electrolyte battery, a positive electrode contains lithium carbonate and a non-aqueous electrolyte contains propane sultone.
【００１３】本発明の非水電解質電池において使用され
る正極活物質としては、リチウムイオンを吸蔵・放出で
きる物質であればよく、金属酸化物（ＬｉＣｏＯ2、Ｌ
ｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＭｎＯ2、ＭｏＯ2、Ｃｕ
Ｏ、Ｃｒ2Ｏ3、ＣｒＯ3、Ｖ2Ｏ5、ＮｉＯＯＨなど）、
金属硫化物（ＦｅＳ、ＴｉＳ2、又はＭｏＳ2など）、金
属セレン化物（ＴｉＳｅ2など）等が例示される。The positive electrode active material used in the non-aqueous electrolyte battery of the present invention may be any material capable of inserting and extracting lithium ions, and may be a metal oxide (LiCoO 2 , LCo).
iNiO 2 , LiMn 2 O 4 , MnO 2 , MoO 2 , Cu
O, Cr 2 O 3 , CrO 3 , V 2 O 5 , NiOOH, etc.),
Examples thereof include metal sulfides (such as FeS, TiS 2 , or MoS 2 ) and metal selenides (such as TiSe 2 ).
【００１４】また、正極導電剤としては、アセチレンブ
ラック、ケッチェンブラック、ファーネスブラック、グ
ラファイト等を単体、もしくはこれらを組み合わせての
使用が例示される。As the positive electrode conductive agent, use of acetylene black, Ketjen black, furnace black, graphite, or the like alone or in combination thereof is exemplified.
【００１５】さらに、結着剤としては、ポリフッ化ビニ
リデン、ポリテトラフルオロエチレン、ゴム系高分子も
しくはこれらとセルロース系高分子との混合物またはポ
リフッ化ビニリデンを主体とするコポリマー等が例示さ
れる。Further, examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, a rubber-based polymer, a mixture of these with a cellulose-based polymer, and a copolymer mainly containing polyvinylidene fluoride.
【００１６】一方、負極活物質としては、リチウム金
属、またはリチウムアルミニウム合金や熱分解炭素、コ
ークス類、天然黒鉛や人造黒鉛等のグラファイト類、有
機高分子化合物焼成体、炭素繊維、活性炭などリチウム
を吸蔵・放出する炭素材料、またはポリピロールやポリ
アセチレンのようなポリマー材料を用いることも可能で
ある。On the other hand, as the negative electrode active material, lithium such as lithium metal, lithium aluminum alloy, pyrolytic carbon, coke, graphite such as natural graphite or artificial graphite, organic polymer compound fired body, carbon fiber, activated carbon and the like are used. It is also possible to use carbon materials that occlude and release, or polymeric materials such as polypyrrole and polyacetylene.
【００１７】非水電解質に用いる溶媒としては、エチレ
ンカーボネート、プロピレンカーボネート、ジエチルカ
ーボネート、ジメチルカーボネート、メチルエチルカー
ボネートなどの炭酸エステルやγ-ブチルラクトン、
１，２ジメトキシエタン、テトラヒドロフラン、２−メ
チルテトラヒドロフラン、プロピオン酸メチル等の有機
溶媒を単独または２種以上混合して使用しても良い。Examples of the solvent used for the non-aqueous electrolyte include carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate, and γ-butyl lactone.
Organic solvents such as 1,2 dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, and methyl propionate may be used alone or in combination of two or more.
【００１８】非水電解質の溶質としてのリチウム塩に
は、ＬｉＣｌＯ4、ＬｉＡｓＦ6、ＬｉＰＦ6、ＬｉＢ
Ｆ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2等を単独
または２種以上混合して使用することができる。The lithium salt as a solute of the non-aqueous electrolyte includes LiClO 4 , LiAsF 6 , LiPF 6 , LiB
F 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2, etc. can be used alone or in combination of two or more.
【００１９】[0019]
【実施例】以下、本発明を実施例に基づいて詳細に説明
するが、下記実施例により何ら限定されるものではな
く、その要旨を変更しない範囲において適宜変更して実
施することが可能であることは言うまでもない。 ［実施例］ （正極）： 活物質であるＬｉＣｏＯ2１００重量部に
対して、炭酸リチウムをそれぞれ０．５重量部、１．０
重量部、３．０重量部、５．０重量部及び６．５重量部
と変化させて混合し、さらに炭素系導電剤としてアセチ
レンブラックを３重量部、結着剤としてポリフッ化ビニ
リデン（ＰＶｄＦ）を４重量部を加え、そして、これら
の混合物に分散溶媒としてのＮＭＰ（Ｎ−メチルピロリ
ドン）を加えて混練し、正極ペーストを得た。次に、こ
の正極ペーストをアルミニウム箔よりなる電極基体に塗
布し、乾燥させ、炭酸リチウム添加量の異なる５種類の
リチウム電池用正極を得た。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following embodiments, and can be carried out with appropriate changes within the scope of the invention. Needless to say. [Example] (Positive electrode): Lithium carbonate was added in an amount of 0.5 part by weight and 1.0 part by weight with respect to 100 parts by weight of LiCoO 2 as an active material.
Parts by weight, 3.0 parts by weight, 5.0 parts by weight, and 6.5 parts by weight, and further mixed with 3 parts by weight of acetylene black as a carbon-based conductive agent, and polyvinylidene fluoride (PVdF) as a binder. Was added to the mixture, and NMP (N-methylpyrrolidone) as a dispersion solvent was added to the mixture and kneaded to obtain a positive electrode paste. Next, this positive electrode paste was applied to an electrode substrate made of an aluminum foil and dried to obtain five types of positive electrodes for lithium batteries having different amounts of lithium carbonate added.
【００２０】（負極）： ピッチの炭素化過程で生ずる
メソフェーズ小球体を原料としたメソカーボンマイクロ
ビーズをリチウムイオンのインターカレーション材と
し、ポリフッ化ビニリデン（ＰＶｄＦ）を結着剤として
混練し、適宜ＮＭＰを添加してペーストとしたものを、
銅箔からなる電極基体に塗布し、乾燥させ、負極を作製
した。なお、このときのメソカーボンマイクロビーズと
して、粒子径が５〜５０μｍ、比表面積が１〜１０ｍ2
／ｇのものを用いた。(Negative electrode): Mesocarbon microbeads made of mesophase spheres generated in the carbonization process of pitch are used as lithium ion intercalation material, and kneaded with polyvinylidene fluoride (PVdF) as a binder. The paste made by adding NMP,
The composition was applied to an electrode substrate made of copper foil and dried to produce a negative electrode. The mesocarbon microbeads at this time had a particle diameter of 5 to 50 μm and a specific surface area of 1 to 10 m 2.
/ G.
【００２１】（非水電解液）： エチレンカーボネート
とジエチルカーボネートとの体積比１：１の混合溶媒
に、ＬｉＰＦ6を１モル／リットル溶解したもの（以
下、Ａ液という）９９．９重量％に対して、プロパンス
ルトン（以下、Ｂ液という）０．１重量％混合した非水
電解液を調整した。同様に、Ａ液とＢ液の混合比をそれ
ぞれ９９．８対０．２、９９．５対０．５、９８．５対
１．５、９６．５対３．５、９５．０対５．０及び９
４．０対６．０とした非水電解液を調整した。(Non-aqueous electrolyte): A solution in which 1 mol / l of LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 (hereinafter referred to as solution A) to 99.9% by weight. On the other hand, a non-aqueous electrolyte mixed with 0.1% by weight of propane sultone (hereinafter referred to as solution B) was prepared. Similarly, the mixing ratios of solution A and solution B were 99.8: 0.2, 99.5: 0.5, 98.5: 1.5, 96.5: 3.5, 95.0: 5, respectively. 0.0 and 9
A non-aqueous electrolyte having a ratio of 4.0 to 6.0 was prepared.
【００２２】（セパレータ）： 厚さ２５μｍ、空孔率
４０％であるポリエチレン微多孔膜をセパレータとして
使用した。セパレータについても、特に制限されず、従
来から使用されている種々のセパレータを用いることが
できる。(Separator): A microporous polyethylene membrane having a thickness of 25 μm and a porosity of 40% was used as a separator. The separator is not particularly limited, and various types of conventionally used separators can be used.
【００２３】（電池）： 上記正負両極、セパレータ、
電解液を巻回して電極群を構成し、幅３０ｍｍ×高さ４
８ｍｍ×厚さ５ｍｍの角型電池容器に収納し、さらに非
水電解液を注入した上でその注液口を封口して、非水電
解質電池を作製した。この電池の概略図を図１に示す。
この電池の主な構成要素は、正極３と負極４とセパレー
タ５を巻回した電極群２、電池ケース６、安全弁８、電
解液（図示せず）等である。また、本実施例において作
製した電池の種類は、炭酸リチウム量の異なる正極５種
類とプロパンスルトンの添加量が異なる電解液の７種類
の組み合わせとなり、計３５種類である。 ［比較例１］正極に炭酸リチウムを添加しないことを除
いては、実施例と同様の手順により電池を作製した。す
なわち、電解液中の上記Ａ液とＢ液の重量比だけが異な
る７種類の電池を作製した。 ［比較例２］電解液中の上記Ａ液とＢ液の重量比が１０
０対０、すなわち、プロパンスルトンが添加されていな
い非水電解液を用いたことを除いては、実施例と同様の
手順により電池を作製した。すなわち、正極への炭酸リ
チウム添加量だけが異なる５種類の電池を作製した。 ［比較例３］正極に炭酸リチウムを添加せず、さらに非
水電解液にプロパンスルトンを添加していないことを除
いては、実施例と同様の手順により電池を作製した。(Battery): Both positive and negative electrodes, separator,
Electrode solution is wound to form an electrode group, width 30 mm × height 4
The battery was housed in a square battery container of 8 mm x 5 mm in thickness, further filled with a non-aqueous electrolyte, and the inlet was closed to prepare a non-aqueous electrolyte battery. A schematic diagram of this battery is shown in FIG.
The main components of this battery are an electrode group 2 in which a positive electrode 3, a negative electrode 4, and a separator 5 are wound, a battery case 6, a safety valve 8, an electrolyte (not shown), and the like. In addition, the types of batteries manufactured in this example are a combination of five types of positive electrodes having different amounts of lithium carbonate and seven types of electrolytes having different amounts of propane sultone added, that is, a total of 35 types. Comparative Example 1 A battery was manufactured in the same procedure as in the example except that lithium carbonate was not added to the positive electrode. That is, seven types of batteries having different weight ratios of the solution A and the solution B in the electrolytic solution were produced. [Comparative Example 2] The weight ratio of the above solution A and solution B in the electrolytic solution was 10
A battery was fabricated in the same procedure as in the example except that 0 to 0, that is, a non-aqueous electrolyte solution to which propane sultone was not added was used. That is, five types of batteries differing only in the amount of lithium carbonate added to the positive electrode were manufactured. [Comparative Example 3] A battery was fabricated in the same manner as in Example except that lithium carbonate was not added to the positive electrode and propane sultone was not added to the nonaqueous electrolyte.
【００２４】（初期容量試験）： 上記実施例と比較例
の電池（各１０個）を、下記条件において充放電を行
い、電池の初期容量を測定した。なお、充放電時の周囲
温度は２５℃とした。 充電条件： ５７０ｍＡ定電流充電−終止電圧４．２Ｖ その後、４．２Ｖ定電圧充電 × ５．０ｈ 放電条件： ５７０ｍＡ定電流放電−終止電圧３．０Ｖ （高温放置前後の電池厚み変化測定）： 上記実施例と
比較例の電池（各５個）を、下記充電条件において充電
した後、６０℃の恒温槽内に３０日間放置した。放置前
の充電直後と、３０日間放置後における電池厚さを測定
し、その差をもって電池厚み変化量を算出した。 充電条件： ５７０ｍＡ定電流充電−終止電圧４．２Ｖ その後、４．２Ｖ定電圧充電 × ５．０ｈ なお、充電時の周囲温度は２５℃とした。 （過充電試験）： 上記実施例と従来例の電池（各５
個）を、下記条件での過充電試験に供した。なお、過充
電時の周囲温度は２５℃とした。 過充電条件： ３．０Ａ定電流充電 × ３．０ｈ（連
続） そして、この過充電試験において、電池に漏液、発煙等
の異常の発生が見られるかどうかを観察した。(Initial Capacity Test): The batteries (10 batteries each) of the above Examples and Comparative Examples were charged and discharged under the following conditions, and the initial capacities of the batteries were measured. The ambient temperature during charging and discharging was 25 ° C. Charging conditions: 570 mA constant current charge-end voltage 4.2 V, then 4.2 V constant voltage charge × 5.0 h Discharge conditions: 570 mA constant current discharge-end voltage 3.0 V (measurement of battery thickness change before and after high temperature storage): The batteries of the example and the comparative example (each 5 batteries) were charged under the following charging conditions, and then left in a 60 ° C constant temperature bath for 30 days. The battery thickness was measured immediately after charging before standing and after standing for 30 days, and the difference in battery thickness was calculated from the difference. Charging conditions: 570 mA constant current charge-final voltage 4.2 V, then 4.2 V constant voltage charge × 5.0 h The ambient temperature during charging was 25 ° C. (Overcharge test): The batteries of the above example and the conventional example (5 for each)
Were subjected to an overcharge test under the following conditions. The ambient temperature during overcharging was 25 ° C. Overcharge condition: 3.0 A constant current charge × 3.0 h (continuous) Then, in this overcharge test, it was observed whether or not abnormalities such as liquid leakage and smoke were observed in the battery.
【００２５】実施例ならびに各比較例における、電池の
初期容量試験の結果を表１、表２および表３に示す。正
極への炭酸リチウムの添加量を増やすほど、正極板の容
量は減少するが、電極多孔度の調整等により、本試験電
池はいずれも５７０ｍＡｈになるように設計されたもの
である。表１、表２からプロパンスルトンの添加量が電
解液の重量に対して５重量％までなら容量劣化はない
が、６重量％になると容量劣化が大きくなる。これよ
り、プロパンスルトンの配合比は電解液量の５重量％以
下であることが好ましい。Tables 1, 2 and 3 show the results of the initial capacity test of the batteries in the examples and comparative examples. As the amount of lithium carbonate added to the positive electrode increases, the capacity of the positive electrode plate decreases. However, by adjusting the electrode porosity and the like, each of the test batteries was designed to have a capacity of 570 mAh. From Tables 1 and 2, there is no capacity deterioration when the amount of propane sultone added is up to 5% by weight with respect to the weight of the electrolytic solution, but when the amount becomes 6% by weight, the capacity deterioration becomes large. Accordingly, the mixing ratio of propane sultone is preferably 5% by weight or less based on the amount of the electrolytic solution.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】次に、実施例ならびに各比較例における、
高温放置試験の結果を表４、表５および表６に示す。表
４、表６から、炭酸リチウムの添加量が多くなるほど、
電池厚みが大きくなる傾向にある。これは、ＣＯ2ガス
の発生量が多くなることにより、電池の膨れが大きくな
ったものと考えられる。そして、表４、表６から、プロ
パンスルトンの配合比を０．２重量％以上にすると、Ｃ
Ｏ2ガスの発生による電池の膨れが小さくなることがわ
かった。これは、プロパンスルトンの添加により電解液
の分解が抑制され、 ＣＯ2ガスの発生が抑えられたため
と考えられる。しかし、炭酸リチウムの添加量が６．５
重量部になると、プロパンスルトン添加の有無に関わら
ず、電池の膨れが大きくなる。以上のことから、炭酸リ
チウムの添加量は５重量部以下、プロパンスルトンの配
合比は全電解液量の０．２重量％以上であることが好ま
しい。Next, in Examples and Comparative Examples,
The results of the high-temperature storage test are shown in Tables 4, 5 and 6. From Tables 4 and 6, as the amount of lithium carbonate added increases,
Battery thickness tends to increase. This is considered to be due to the fact that the amount of generated CO 2 gas increased, and the swelling of the battery increased. From Tables 4 and 6, when the mixing ratio of propane sultone is set to 0.2% by weight or more, C
It was found that swelling of the battery due to generation of O 2 gas was reduced. This is probably because the addition of propane sultone suppressed the decomposition of the electrolytic solution and suppressed the generation of CO 2 gas. However, the amount of lithium carbonate added was 6.5.
When the amount is in parts by weight, the swelling of the battery increases irrespective of whether propane sultone is added or not. From the above, it is preferable that the addition amount of lithium carbonate is 5 parts by weight or less, and the mixing ratio of propane sultone is 0.2% by weight or more of the total electrolyte solution amount.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【表５】 [Table 5]
【００３２】[0032]
【表６】 [Table 6]
【００３３】さらに、実施例ならびに各比較例における
過充電試験の結果を表７、表８および表９に示す。過充
電試験において，表中の○は異常がなかったもの，×は
漏液または発煙したものを表す。Tables 7, 8 and 9 show the results of the overcharge test in the examples and comparative examples. In the overcharge test, ○ in the table indicates that there was no abnormality, and X indicates that the liquid leaked or smoked.
【００３４】[0034]
【表７】 [Table 7]
【００３５】[0035]
【表８】 [Table 8]
【００３６】[0036]
【表９】 [Table 9]
【００３７】表７、表８および表９から、炭酸リチウム
が無添加、あるいは添加量が０．５重量部では、プロパ
ンスルトン添加の有無にかかわらず、電池はすべて漏液
または発煙に至った。また、炭酸リチウム添加量が１重
量部以上においては、過充電時において電池が熱暴走を
起こす前に、電気化学的な分解反応によるＣＯ2ガスの
発生により、安全弁が正常に作動し、いずれも漏液また
は発煙までは至らなかった。この結果から、炭酸リチウ
ムの添加量は１重量部以上であることが好ましいと考え
られる。As can be seen from Tables 7, 8 and 9, when lithium carbonate was not added or the addition amount was 0.5 part by weight, all of the batteries leaked or smoked regardless of whether propane sultone was added or not. When the amount of lithium carbonate added is 1 part by weight or more, the safety valve operates normally due to the generation of CO 2 gas due to the electrochemical decomposition reaction before the battery undergoes thermal runaway during overcharging. No leakage or fuming occurred. From this result, it is considered that the addition amount of lithium carbonate is preferably 1 part by weight or more.
【００３８】以上の結果から明らかなように、炭酸リチ
ウム添加量が正極活物質１００重量部に対して１重量部
以上、５重量部以下であり、且つ、プロパンスルトン添
加量が電解液量の０．２重量％以上、５重量％以下の時
に、高温放置時に電池の膨れ小さく、しかも安全性にも
優れた電池を提供することが可能となる。As is clear from the above results, the addition amount of lithium carbonate is 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the positive electrode active material, and the addition amount of propane sultone is 0% of the electrolyte amount. When the content is 0.2% by weight or more and 5% by weight or less, it becomes possible to provide a battery which is less swelled when left at high temperatures and which is excellent in safety.
【００３９】本実施例においては、リチウムイオン電池
における例を示したが、電解液を含浸するポリマー電解
質を用いた非水電解質電池においても同等の効果が得ら
れる。In this embodiment, an example of a lithium ion battery is shown, but the same effect can be obtained in a non-aqueous electrolyte battery using a polymer electrolyte impregnated with an electrolyte.
【００４０】[0040]
【発明の効果】本発明にかかる第一の発明は、非水電解
質電池において、正極に炭酸リチウムを含有するととも
に、電解液にプロパンスルトンを含有することを特徴と
する。According to a first aspect of the present invention, a nonaqueous electrolyte battery is characterized in that the positive electrode contains lithium carbonate and the electrolyte contains propane sultone.
【００４１】また、本発明にかかる第二の発明は、上
記、電解液にプロパンスルトンを含有した非水電解質電
池において、正極合剤中の炭酸リチウム含有量が、正極
活物質１００重量部に対して１重量部以上、５重量部以
下であることを特徴とする。The second invention according to the present invention is directed to a non-aqueous electrolyte battery containing the above-mentioned electrolyte solution containing propane sultone, wherein the lithium carbonate content in the positive electrode mixture is based on 100 parts by weight of the positive electrode active material. And not more than 1 part by weight and not more than 5 parts by weight.
【００４２】さらに、本発明にかかる第三の発明は、上
記、炭酸リチウムを含有した正極合剤を備えた非水電解
質電池において、プロパンスルトンの添加量が、電解液
量に対して０．２重量％以上、５重量％以下であること
を特徴とする。Further, according to a third aspect of the present invention, in the above-mentioned nonaqueous electrolyte battery provided with the positive electrode mixture containing lithium carbonate, the amount of propane sultone added is 0.2 to the amount of the electrolyte. It is not less than 5% by weight and not more than 5% by weight.
【００４３】以上、詳述したように、本発明は、従来の
非水電解質電池と比較して、正極に炭酸リチウムを添加
し、さらに電解液中にプロパンスルトンを添加すること
により、高温放置時において電池が膨れることなく、過
充電時の安全性にも優れた電池を提供することを可能に
した。As described in detail above, the present invention is different from the conventional nonaqueous electrolyte battery in that lithium carbonate is added to the positive electrode and propane sultone is further added to the electrolyte to allow the battery to be left at high temperatures. Thus, it has become possible to provide a battery which does not swell and which is excellent in safety during overcharge.
【図１】 本発明の一つの実施例である電池の概略構造
を示す図である。FIG. 1 is a diagram showing a schematic structure of a battery according to one embodiment of the present invention.
１ 非水電解質電池 ２ 電極群 ３ 正極 ４ 負極 ５ セパレータ ６ 電池ケース ７ 蓋 ８ 安全弁 ９ 正極端子 １０ 正極集電リード １１ 金属箔 DESCRIPTION OF SYMBOLS 1 Non-aqueous electrolyte battery 2 Electrode group 3 Positive electrode 4 Negative electrode 5 Separator 6 Battery case 7 Lid 8 Safety valve 9 Positive electrode terminal 10 Positive electrode current collecting lead 11 Metal foil
Claims (3)
る正極と、負極と、非水電解液を備える非水電解質電池
において、正極に炭酸リチウムを含有するとともに、非
水電解液にプロパンスルトンを含有することを特徴とす
る非水電解質電池。1. A non-aqueous electrolyte battery comprising a positive electrode having an active material capable of inserting and extracting lithium, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode contains lithium carbonate and the non-aqueous electrolyte contains propane sultone. A non-aqueous electrolyte battery comprising:
量部に対して１重量部以上、５重量部以下含有されるこ
とを特徴とする請求項１記載の非水電解質電池。2. The nonaqueous electrolyte battery according to claim 1, wherein the lithium carbonate is contained in an amount of 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the positive electrode active material.
０．２重量％以上、５重量％以下含有されることを特徴
とする請求項１または請求項２記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the propane sultone is contained in the non-aqueous electrolyte in an amount of 0.2% by weight or more and 5% by weight or less.
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|---|---|---|---|
| JP2000118186A JP3448544B2 (en) | 2000-04-19 | 2000-04-19 | Non-aqueous electrolyte battery |
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Cited By (4)
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| JP2008277106A (en) * | 2007-04-27 | 2008-11-13 | Gs Yuasa Corporation:Kk | Nonaqueous electrolyte battery and battery system |
| US9023537B2 (en) | 2010-04-09 | 2015-05-05 | Sony Corporation | Battery |
| US9350049B2 (en) | 2013-11-28 | 2016-05-24 | Gs Yuasa International Ltd. | Electric storage device and electric storage apparatus |
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| US9350049B2 (en) | 2013-11-28 | 2016-05-24 | Gs Yuasa International Ltd. | Electric storage device and electric storage apparatus |
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|---|---|
| JP3448544B2 (en) | 2003-09-22 |
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