JPH11204143A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JPH11204143A JPH11204143A JP10003958A JP395898A JPH11204143A JP H11204143 A JPH11204143 A JP H11204143A JP 10003958 A JP10003958 A JP 10003958A JP 395898 A JP395898 A JP 395898A JP H11204143 A JPH11204143 A JP H11204143A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- secondary battery
- aqueous electrolyte
- electrolyte secondary
- battery
- 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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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
(57)【要約】
【課題】 初回充電時におけるガス発生に起因した電池
内圧の上昇を抑え、高温での充放電特性が向上した非水
電解液二次電池を提供することにある。
【解決手段】 リチウム金属酸化物を含んだ正極と、炭
素材料を含んだ負極と、電解液とが電池ケース内に収納
された非水電解液二次電池において、電池ケース内に一
般式ＭＯ・Ａｌ2 Ｏ3 ・ｍＳｉＯ2 ・ｎＨ2 Ｏ（但し、
Ｍはアルカリ金属２原子またはアルカリ土類金属１原
子、ｍ及びｎは組成比）で表わされる吸着剤を添加し、
初回充電時に発生したガスを吸着させる。(57) [Problem] To provide a non-aqueous electrolyte secondary battery that suppresses a rise in battery internal pressure due to gas generation at the time of initial charging and has improved charge / discharge characteristics at high temperatures. SOLUTION: In a nonaqueous electrolyte secondary battery in which a positive electrode containing a lithium metal oxide, a negative electrode containing a carbon material, and an electrolyte are housed in a battery case, a general formula MO. Al 2 O 3 .mSiO 2 .nH 2 O (however,
M is 2 atoms of alkali metal or 1 atom of alkaline earth metal, and m and n are adsorbents represented by composition ratios),
The gas generated during the first charge is adsorbed.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高温での充放電特
性が良好で各種電子機器の電源として適する非水電解液
二次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 secondary battery having good charge / discharge characteristics at high temperatures and suitable as a power source for various electronic devices.
【０００２】[0002]
【従来の技術】現在、各種電子機器の電源として利用さ
れている非水電解液二次電池であるリチウム二次電池
は、炭素材料を含んだ負極と、ＬｉＭＯ2 （Ｍ＝Ｃｏ、
Ｎｉ）またはＬｉＭｎ2 Ｏ4 等のリチウム金属酸化物を
含んだ正極と、電解液とを電池ケース内に収納してい
る。 2. Description of the Related Art At present, a lithium secondary battery, which is a non-aqueous electrolyte secondary battery used as a power source for various electronic devices, includes a negative electrode containing a carbon material, a LiMO 2 (M = Co,
A positive electrode containing a lithium metal oxide such as Ni) or LiMn 2 O 4 and an electrolyte are housed in a battery case.
【０００３】上記電解液の非水溶媒には、環状炭酸エス
テルのプロピレンカーボネート（ＰＣ）、ＥＣ（エチレ
ンカーボネート）、鎖状炭酸エステルのジメチルカーボ
ネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭ
Ｃ）、ジエチルカーボネート（ＤＥＣ）などが用いら
れ、また溶質には、六弗化リン酸リチウム（ＬｉＰ
Ｆ6 ）やホウ弗化リチウム（ＬｉＢＦ4 ）などが用いら
れる。The non-aqueous solvents of the above electrolyte include cyclic carbonate propylene carbonate (PC), EC (ethylene carbonate), chain carbonate dimethyl carbonate (DMC), and ethyl methyl carbonate (EM).
C), diethyl carbonate (DEC) and the like, and the solute is lithium hexafluorophosphate (LiP
F 6 ) or lithium borofluoride (LiBF 4 ) is used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、現在使
用されている非水電解液二次電池は、電解液の種類によ
っては初回充電時に電解液の分解に起因すると思われる
ガスの発生が認められ、そのガス発生量も大きく、しか
も電解液の種類に依存する。即ち、電池内圧が３ｋｇ／
ｃｍ2 程度の大きさまで上昇する。このため、電池ケー
スの変形や漏液、延いては安全機構（電流遮断機構・安
全弁）が作動する恐れがある。However, in the non-aqueous electrolyte secondary batteries currently used, depending on the type of the electrolyte, generation of gas which is considered to be caused by decomposition of the electrolyte at the time of the first charge is recognized, The amount of generated gas is large, and depends on the type of electrolyte. That is, the battery internal pressure is 3 kg /
It rises to the size of about cm 2 . For this reason, there is a risk that the battery case will be deformed or leak, and eventually the safety mechanism (current cutoff mechanism / safety valve) will operate.
【０００５】また、電解液の分解に起因する電池内圧の
上昇により、内部抵抗上昇や充放電特性の低下があっ
た。特に高温（約５０℃）では、さらに電池内圧が上昇
するので、充放電特性の低下が顕著であった。ノートブ
ック型パソコンなどの携帯電子機器の電源は、電池の使
用環境が高温になる場合があり特に問題となる。[0005] In addition, an increase in the internal pressure of the battery due to decomposition of the electrolytic solution causes an increase in internal resistance and a decrease in charge / discharge characteristics. In particular, at high temperatures (about 50 ° C.), the internal pressure of the battery further increased, so that the charge / discharge characteristics were significantly reduced. The power supply of a portable electronic device such as a notebook personal computer is particularly problematic because the operating environment of the battery may be high.
【０００６】そこで、本発明の目的は、上記課題を解決
し、初回充電時に、ガス発生に起因する電池内圧の上昇
を抑え、高温での充放電特性が向上した非水電解液二次
電池を提供することにある。Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a non-aqueous electrolyte secondary battery in which the rise in battery internal pressure due to gas generation during the first charge is suppressed and the charge / discharge characteristics at high temperatures are improved. To provide.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するた
め、本発明の非水電解液二次電池は、リチウム金属酸化
物を含んだ正極と、炭素材料を含んだ負極と、電解液と
が電池ケース内に収納された非水電解液二次電池におい
て、電池ケース内に一般式ＭＯ・Ａｌ2 Ｏ3 ・mＳｉＯ
2 ・n Ｈ2 Ｏ（但し、Ｍはアルカリ金属２原子またはア
ルカリ土類金属１原子を表わし、ｍ及びｎは組成比を表
わす。）で表わされる吸着剤を添加したものである（請
求項１）。電池ケース内に、一般式ＭＯ・Ａｌ2 Ｏ3 ・
m ＳｉＯ2・n Ｈ2 Ｏで表わされる吸着剤（商品名はモ
レキュラーシーブ、以下モレキュラーシーブと称す。）
を添加することにより、初回充電時に発生したガスが吸
着される。このため、電池内圧の上昇が抑えられ、且つ
高温での充放電特性が向上する。In order to achieve the above object, a nonaqueous electrolyte secondary battery of the present invention comprises a positive electrode containing a lithium metal oxide, a negative electrode containing a carbon material, and an electrolyte. In a non-aqueous electrolyte secondary battery housed in a battery case, the general formula MO.Al 2 O 3 .mSiO
An adsorbent represented by 2 · n H 2 O (where M represents 2 atoms of an alkali metal or 1 atom of an alkaline earth metal, and m and n represent composition ratios) is added. ). In the battery case, the general formula MO.Al 2 O 3.
Adsorbent represented by mSiO 2 · nH 2 O (trade name is molecular sieve, hereinafter referred to as molecular sieve)
Is added, the gas generated at the time of the first charge is adsorbed. For this reason, an increase in battery internal pressure is suppressed, and the charge / discharge characteristics at high temperatures are improved.
【０００８】上記電解液の溶媒は、環状炭酸エステルと
鎖状炭酸エステルとの混合溶媒であるのが好ましい（請
求項２）。このうち環状炭酸エステルは、プロピレンカ
ーボネート、エチレンカーボネートのうち少なくとも一
種以上であればよい（請求項３）。溶媒として、環状炭
酸エステルと鎖状炭酸エステルとを混合する理由は、鎖
状エステルを用いると高温での充放電特性が良いためで
ある。特に、置換基にメチル基を含む鎖状炭酸エステル
を用いると（請求項４）、高温での充放電特性を一層向
上させることができる。このような鎖状炭酸エステルと
しては、ジメチルカーボネート、エチルメチルカーボネ
ートのうち少なくとも一種以上を用いればよい（請求項
５）。[0008] The solvent of the electrolytic solution is preferably a mixed solvent of a cyclic carbonate and a chain carbonate (claim 2). Of these, the cyclic carbonate may be at least one of propylene carbonate and ethylene carbonate (claim 3). The reason why the cyclic carbonate and the chain carbonate are mixed as the solvent is that the use of the chain ester provides good charge / discharge characteristics at high temperatures. In particular, when a chain carbonate containing a methyl group as a substituent is used (claim 4), the charge / discharge characteristics at high temperatures can be further improved. As such a chain carbonate, at least one of dimethyl carbonate and ethyl methyl carbonate may be used (claim 5).
【０００９】上記電解液の溶質としては、六弗化リン酸
リチウムを用いるのがよい（請求項６）。電解液の溶媒
にメチル基を有する鎖状炭酸カーボネートを含み、溶質
に六弗化リン酸リチウムを使用することで、高温での充
放電特性をより良く向上させることができる。As the solute of the electrolytic solution, it is preferable to use lithium hexafluorophosphate. By using a chain carbonate having a methyl group in the solvent of the electrolytic solution and using lithium hexafluorophosphate as the solute, the charge / discharge characteristics at high temperatures can be further improved.
【００１０】なお、電池ケース内に吸着剤のモレキュラ
ーシーブを添加する場所は、正極、負極、あるいはセパ
レータ中のいずれか一つに含ませる形態でもよいし、電
池ケース内のデッドスペースに配置する形態でもよい。
モレキュラーシーブを正極や負極に含ませる形態で添加
する場合、活物質量を減少させることになるので、好ま
しくは電池ケース内のデッドスペースに配置する形態が
良く、その添加量は例えば角形電池１４３４４８タイプ
（厚さ１４mm×幅３４mm×高さ４８mm）では０．５ｇ〜
１ｇの範囲が好ましく、円筒形電池１８６５０タイプで
は０．１ｇ程度の添加量でも効果がある。The location where the molecular sieve of the adsorbent is added to the battery case may be in the form of being included in any one of the positive electrode, the negative electrode, the separator, or in the dead space in the battery case. May be.
When the molecular sieve is added in the form of being included in the positive electrode or the negative electrode, the amount of the active material is reduced. Therefore, it is preferable to dispose the molecular sieve in the dead space in the battery case. (14mm thick x 34mm wide x 48mm high) 0.5g ~
A range of 1 g is preferable. In the case of the 18650 type cylindrical battery, an addition amount of about 0.1 g is effective.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実施形態を実施例
を中心に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described mainly with reference to examples.
【００１２】（１）試験電池 リチウム金属酸化物を含んだ正極と、炭素材料を含んだ
負極と、溶媒と溶質を混合した非水電解液とからなるリ
チウム二次電池であって、厚さ１４ｍｍ×幅３４ｍｍ×
高さ４８ｍｍの角形電極のリチウム二次電池を作製し
た。(1) Test Battery A lithium secondary battery comprising a positive electrode containing a lithium metal oxide, a negative electrode containing a carbon material, and a non-aqueous electrolyte mixed with a solvent and a solute, and having a thickness of 14 mm. × width 34mm ×
A lithium secondary battery having a square electrode with a height of 48 mm was manufactured.
【００１３】正極板は、コバルト酸リチウムと、結着剤
であるポリ弗化ビニリデンと、導電剤であるグラファイ
トとを、重量比が９０：５：５の割合で混合し、ペース
ト状にしたものを、厚み２０μｍのアルミニウム箔の両
面に塗布し、乾燥・圧延した後、幅３８ｍｍに裁断した
ものを用いた。The positive electrode plate is obtained by mixing lithium cobaltate, polyvinylidene fluoride as a binder, and graphite as a conductive agent at a weight ratio of 90: 5: 5 to form a paste. Was applied to both surfaces of an aluminum foil having a thickness of 20 μm, dried and rolled, and then cut into a width of 38 mm.
【００１４】負極板は、炭素材料と、結着剤であるポリ
弗化ビニリデンと、重量比が９５：５の割合で混合し、
ペースト状にしたものを、厚み１０μｍの銅箔両面に塗
布し、乾燥・圧延した後、幅４０ｍｍに裁断したものを
用いた。The negative electrode plate is prepared by mixing a carbon material and polyvinylidene fluoride as a binder at a weight ratio of 95: 5.
The paste was applied to both surfaces of a copper foil having a thickness of 10 μm, dried and rolled, and then cut into a width of 40 mm.
【００１５】上記正極板と上記負極板とを、幅４４ｍ
ｍ、厚さ２５μｍのポリエチレン微多孔膜からなるセパ
レータを介して長円スパイラル状に巻いた巻回群を、角
形電池ケース（厚さ１４ｍｍ×幅３４ｍｍ×高さ４８ｍ
ｍ）に挿入する。この角形電池ケースに対する蓋板に
は、予め安全弁と正極端子を作製しておく。そして、こ
の蓋板と角形電池ケースとをレーザー溶接することによ
り、角形電池ケースを密封する。The positive electrode plate and the negative electrode plate are set to a width of 44 m.
m, a winding group wound in an elliptical spiral shape with a separator made of a microporous polyethylene film having a thickness of 25 μm in a rectangular battery case (14 mm thick × 34 mm wide × 48 m high)
m). A safety valve and a positive electrode terminal are prepared in advance on the lid plate for the rectangular battery case. Then, the prismatic battery case is sealed by laser welding the lid plate and the prismatic battery case.
【００１６】モレキュラーシーブは、上記の蓋板と角形
電池ケースをレーザー溶接する前に、角形ケース内のデ
ッドスペースに入れる形で添加した。The molecular sieve was added to the above-mentioned cover plate and the dead space in the rectangular case before laser welding the lid plate and the rectangular battery case.
【００１７】下記の表１中において、〜は試作電池
の番号であり、このうち試作電池、、及びが本
発明の実施例のものである。これらの試作電池〜の
電解液の組成は欄外に示す通りである。In Table 1 below, 〜 denotes the number of the prototype battery, and among them, the prototype battery and those of the embodiment of the present invention. The compositions of the electrolyte solutions of these prototype batteries are as shown in the margin.
【００１８】但し、上下の数値欄のうち下欄が本発明の
実施例の電池の数値データであり、上欄は電池内に吸着
剤のモレキュラーシーブが添加されていない場合を比較
用に示したものである。吸着剤を添加した場合と吸着剤
を添加しない場合との差を分かり易くするため、同じ試
作番号の電池として分類されている。また、本発明の実
施例１〜実施例４については、表１の下欄中の数値枠の
右上に※１〜※４を付して他と区別した。後に述べる表
２〜表５についても同様である。However, the lower column of the upper and lower numerical columns is the numerical data of the battery of the embodiment of the present invention, and the upper column shows the case where the molecular sieve of the adsorbent is not added in the battery for comparison. Things. To make it easier to see the difference between the case where the adsorbent is added and the case where no adsorbent is added, the batteries are classified as having the same prototype number. Further, Examples 1 to 4 of the present invention are distinguished from the others by attaching * 1 to * 4 at the upper right of the numerical boxes in the lower column of Table 1. The same applies to Tables 2 to 5 described later.
【００１９】[0019]
【表１】 [Table 1]
【００２０】（実施例１）第１の実施例としての試作電
池の電解液には、環状炭酸エステルのプロピレンカー
ボネートＰＣと鎖状炭酸エステルのジメチルカーボネー
トＤＭＣとを、容積比が１：１で混合した溶媒を用い
た。溶質にはＬｉＰＦ6 を用いた。この溶質の溶質濃度
は１ｍｏｌ／リットルとした。吸着剤のモレキュラーシ
ーブ（実施例、比較例とも和光純薬工業合成ゼオライト
Ｆ−９を用いた。）は１グラムを添加した。Example 1 The electrolyte of a prototype battery as a first example was prepared by mixing propylene carbonate PC as a cyclic carbonate and dimethyl carbonate DMC as a chain carbonate in a volume ratio of 1: 1. The solvent used was used. LiPF 6 was used as a solute. The solute concentration of this solute was 1 mol / liter. One gram of the molecular sieve as an adsorbent (in Examples and Comparative Examples, zeolite F-9 synthesized by Wako Pure Chemical Industries, Ltd. was used) was added.
【００２１】（実施例２）第２の実施例としての試作電
池の電解液には、環状炭酸エステルのプロピレンカー
ボネートＰＣと鎖状炭酸エステルのエチルメチルカーボ
ネートＥＭＣとを、容積比が１：１で混合した溶媒を用
いた。溶質にはＬｉＰＦ6 を１ｍｏｌ／リットルの溶質
濃度で用いた。吸着剤のモレキュラーシーブは１グラム
を添加した。(Embodiment 2) The electrolyte of the prototype battery as the second embodiment was composed of cyclic carbonate propylene carbonate PC and chain carbonate ethyl methyl carbonate EMC at a volume ratio of 1: 1. A mixed solvent was used. As the solute, LiPF 6 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram.
【００２２】（実施例３）第３の実施例としての試作電
池の電解液には、環状炭酸エステルのエチレンカーボ
ネートＥＣと鎖状炭酸エステルのジメチルカーボネート
ＤＭＣとを、容積比が１：１で混合した溶媒を用いた。
溶質にはＬｉＰＦ6 を１ｍｏｌ／リットルの溶質濃度で
用いた。吸着剤のモレキュラーシーブは１グラムを添加
した。(Embodiment 3) The electrolyte of a prototype battery as a third embodiment was prepared by mixing ethylene carbonate EC of cyclic carbonate and dimethyl carbonate DMC of chain carbonate at a volume ratio of 1: 1. The solvent used was used.
As the solute, LiPF 6 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram.
【００２３】（実施例４）第４の実施例としての試作電
池の電解液には、環状炭酸エステルのエチレンカーボ
ネートＥＣと鎖状炭酸エステルのエチルメチルカーボネ
ートＥＭＣとを、容積比が１：１で混合した溶媒を用い
た。溶質にはＬｉＰＦ6 を１ｍｏｌ／リットルの溶質濃
度で用いた。吸着剤のモレキュラーシーブは１グラムを
添加した。(Embodiment 4) The electrolyte of the prototype battery as the fourth embodiment was prepared by mixing ethylene carbonate EC of cyclic carbonate and ethyl methyl carbonate EMC of chain carbonate in a volume ratio of 1: 1. A mixed solvent was used. As the solute, LiPF 6 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram.
【００２４】（比較例１）第１の比較例としての試作電
池の電解液には、環状炭酸エステルのプロピレンカー
ボネートＰＣと鎖状炭酸エステルのジエチルカーボネー
トＤＥＣとを、容積比が１：１で混合した溶媒を用い
た。溶質にはＬｉＰＦ6 を１ｍｏｌ／リットルの溶質濃
度で用いた。吸着剤のモレキュラーシーブは１グラムを
添加した。この比較例１は置換基にメチル基を含まない
点で実施例１〜実施例４のものと異なる。(Comparative Example 1) The electrolyte of the prototype battery as the first comparative example was prepared by mixing propylene carbonate PC of cyclic carbonate and diethyl carbonate DEC of chain carbonate in a volume ratio of 1: 1. The solvent used was used. As the solute, LiPF 6 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram. Comparative Example 1 is different from Examples 1 to 4 in that the substituent does not contain a methyl group.
【００２５】（比較例２）第２の比較例としての試作電
池の電解液には、環状炭酸エステルのエチレンカーボ
ネートＥＣと鎖状炭酸エステルのジエチルカーボネート
ＤＥＣとを、容積比が１：１で混合した溶媒を用いた。
溶質にはＬｉＰＦ6 を１ｍｏｌ／リットルの溶質濃度で
用いた。吸着剤のモレキュラーシーブは１グラムを添加
した。この比較例２も、置換基にメチル基を含まない点
で実施例１〜実施例４のものと異なる。(Comparative Example 2) The electrolyte of a prototype battery as a second comparative example was prepared by mixing ethylene carbonate EC of cyclic carbonate and diethyl carbonate DEC of chain carbonate at a volume ratio of 1: 1. The solvent used was used.
As the solute, LiPF 6 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram. Comparative Example 2 also differs from Examples 1 to 4 in that the substituent does not contain a methyl group.
【００２６】（比較例３）第３の比較例としての試作電
池の電解液には、環状炭酸エステルのエチレンカーボ
ネートＥＣと鎖状炭酸エステルのジメチルカーボネート
ＤＭＣとを、容積比が１：１で混合した溶媒を用いた。
溶質にはＬｉＢＦ4 を１ｍｏｌ／リットルの溶質濃度で
用いた。吸着剤のモレキュラーシーブは１グラムを添加
した。この比較例３は、溶質にＬｉＰＦ6 ではなくＬｉ
ＢＦ4 を用いている点で実施例１〜実施例４のものと異
なる。(Comparative Example 3) The electrolyte of a prototype battery as a third comparative example was prepared by mixing ethylene carbonate EC of cyclic carbonate and dimethyl carbonate DMC of chain carbonate in a volume ratio of 1: 1. The solvent used was used.
As a solute, LiBF 4 was used at a solute concentration of 1 mol / liter. The adsorbent molecular sieve added 1 gram. In Comparative Example 3, LiPF 6 was used instead of LiPF 6
In that with BF 4 differs from that of Examples 1 to 4.
【００２７】（２）試験方法 （ａ）上記の試作電池〜について、初回充電を以下
の条件で行った。即ち、定電流・定電圧充電で電流値１
００ｍＡを流し、充電時間は４５時間とした。この時に
電池内圧の変化を測定した。表１に電池内圧の量大値を
示す。但し、上下の数値欄のうち、下欄が吸着剤のモレ
キュラーシーブを添加している場合の数値データであ
り、上欄は電池内に吸着剤のモレキュラーシーブが添加
されていない比較用の数値データである。後に述べる表
２〜表５についても同様である。(2) Test method (a) Initial charging was performed on the above-mentioned prototype batteries to under the following conditions. That is, the current value is 1 with constant current and constant voltage charging.
00 mA was passed, and the charging time was 45 hours. At this time, the change in battery internal pressure was measured. Table 1 shows the maximum value of the battery internal pressure. However, in the upper and lower numerical columns, the lower column is the numerical data when the molecular sieve of the adsorbent is added, and the upper column is the numerical data for comparison where the molecular sieve of the adsorbent is not added to the battery. It is. The same applies to Tables 2 to 5 described later.
【００２８】表１より、電池内圧はモレキュラーシーブ
を添加することにより低下することが判る。Table 1 shows that the internal pressure of the battery is reduced by the addition of molecular sieve.
【００２９】（ｂ）また、初回充電終了時の電池ケース
厚さ方向の変形量も測定した。この結果を表２に示す。
表２より、モレキュラーシーブを添加すると、電池ケー
スの膨らみも小さくなることが分かる。(B) The amount of deformation in the thickness direction of the battery case at the end of the first charge was also measured. Table 2 shows the results.
Table 2 shows that the addition of the molecular sieve also reduces the swelling of the battery case.
【００３０】[0030]
【表２】 [Table 2]
【００３１】（ｃ）表３に、高温（４５℃）での充放電
サイクルにおける１００サイクル後の電池放電容量の容
量維持率（％）を示す。この充放電は次の条件によっ
た。(C) Table 3 shows the capacity retention rate (%) of the battery discharge capacity after 100 cycles in a charge / discharge cycle at a high temperature (45 ° C.). This charge / discharge was performed under the following conditions.
【００３２】 条件：定電流定電圧充電１ＣｍＡ、４．１V 、３時間 定電流放電１ＣｍＡ、３．０Ｖ ここで、容量維持率（％）とは、次式により与えられる
ものをいう。 容量維持率＝（サイクル中の放電容量／サイクル前の放
電容量）×１００Conditions: constant current constant voltage charging 1 CmA, 4.1 V, 3 hours constant current discharging 1 CmA, 3.0 V Here, the capacity retention ratio (%) means a value given by the following equation. Capacity retention rate = (discharge capacity during cycle / discharge capacity before cycle) × 100
【００３３】[0033]
【表３】 [Table 3]
【００３４】この表３から分かるように、サイクル特性
の向上には、電解液の溶媒にジメチルカーボネートなど
のメチル基を有する鎖状炭酸カーボネートを含み、且
つ、溶質が六弗化リン酸リチウムＬｉＰＦ6 を含んだも
の、即ち、実施例１〜実施例４（試作電池）が
効果的であった。なお、正極活物質のリチウム金属酸化
物は、コバルト酸リチウム（ＬｉＣｏＯ2 ）である。As can be seen from Table 3, in order to improve the cycle characteristics, the solvent of the electrolytic solution contains a chain carbonate having a methyl group such as dimethyl carbonate, and the solute is lithium hexafluorophosphate LiPF 6. , That is, Examples 1 to 4 (prototype batteries) were effective. The lithium metal oxide of the positive electrode active material is lithium cobalt oxide (LiCoO 2 ).
【００３５】（ｄ）表４には、マンガン酸リチウム（Ｌ
ｉＭｎ2 Ｏ4 ）を正極活物質に用いた場合での容量維持
率を、また、表５には、ニッケル酸リチウム（ＬｉＮｉ
Ｏ2）を正極活物質に用いた場合での容量維持率を示
す。(D) Table 4 shows that lithium manganate (L
iMn 2 O 4 ) is used as the positive electrode active material, and Table 5 shows the capacity retention ratio.
The capacity retention ratio when O 2 ) is used as the positive electrode active material is shown.
【００３６】[0036]
【表４】 [Table 4]
【表５】 表４、表５から明らかなように、マンガン酸リチウム又
はニッケル酸リチウムを正極活物質に用いた場合でも、
コバルト酸リチウムを用いた場合と同様な効果が得られ
た。即ち、高温（４５℃）でのサイクル特性の向上に
は、電解液の溶媒にジメチルカーボネートなどのメチル
基を有する鎖状カーボネートを含み、且つ、溶質が六弗
化リン酸リチウムを含んだもの、即ち、実施例１〜実施
例４（試作電池）が効果的であった。[Table 5] As is clear from Tables 4 and 5, even when lithium manganate or lithium nickelate is used for the positive electrode active material,
The same effect as in the case of using lithium cobaltate was obtained. That is, in order to improve the cycle characteristics at a high temperature (45 ° C.), the solvent of the electrolytic solution contains a chain carbonate having a methyl group such as dimethyl carbonate, and the solute contains lithium hexafluorophosphate. That is, Examples 1 to 4 (prototype batteries) were effective.
【００３７】[0037]
【発明の効果】以上説明したように本発明によれば、次
のような優れた効果が得られる。As described above, according to the present invention, the following excellent effects can be obtained.
【００３８】（１）請求項１に記載の発明によれば、電
池ケース内に、一般式ＭＯ・Ａｌ2Ｏ3 ・m ＳｉＯ2 ・n
Ｈ2 Ｏで表わされる吸着剤であるモレキュラーシーブ
を添加したので、モレキュラーシーブにより初回充電時
に発生したガスが吸着される。このため、初回充電時で
のガス発生に伴う電池内圧上昇を抑制し、且つ、高温で
の充放電特性を向上させることができる。(1) According to the first aspect of the present invention, the general formula MO.Al 2 O 3 .m SiO 2 .n is provided in the battery case.
Since molecular sieve, which is an adsorbent represented by H 2 O, was added, the gas generated at the time of the first charge is adsorbed by the molecular sieve. For this reason, it is possible to suppress an increase in the internal pressure of the battery due to the generation of gas at the time of the first charge, and to improve the charge / discharge characteristics at high temperatures.
【００３９】（２）請求項２に記載の発明によれば、上
記電解液の溶媒が、環状炭酸エステルに鎖状炭酸エステ
ルを混合させた溶媒であるため、溶媒に環状炭酸エステ
ルのみを用いた場合に比べ、高温での充放電特性が良い
非水電解液二次電池が得られる。(2) According to the second aspect of the present invention, since the solvent of the electrolytic solution is a mixture of a cyclic carbonate and a chain carbonate, only the cyclic carbonate is used as the solvent. As compared with the case, a non-aqueous electrolyte secondary battery having good charge / discharge characteristics at high temperatures can be obtained.
【００４０】（３）請求項３に記載の発明によれば、環
状炭酸エステルを、プロピレンカーボネート、エチレン
カーボネートのうち少なくとも一種以上と特定したの
で、高温での充放電特性に優れた非水電解液二次電池が
得られる。(3) According to the third aspect of the invention, since the cyclic carbonate is specified as at least one of propylene carbonate and ethylene carbonate, the non-aqueous electrolyte having excellent charge / discharge characteristics at high temperatures. A secondary battery is obtained.
【００４１】（４）請求項４に記載の発明によれば、上
記鎖状炭酸エステルのうちでも置換基にメチル基を含む
ものに特定したので、更に高温での充放電特性に優れた
非水電解液二次電池が得られる。(4) According to the fourth aspect of the present invention, among the above-mentioned chain carbonate esters, those having a methyl group as a substituent are specified, so that the non-aqueous solution further excellent in charge / discharge characteristics at a high temperature. An electrolyte secondary battery is obtained.
【００４２】（５）請求項５に記載の発明によれば、上
記置換基にメチル基を含む鎖状炭酸エステルとして、ジ
メチルカーボネート、エチルメチルカーボネートのうち
少なくとも一種以上を含むものに特定したので、実際に
高温での充放電特性が優れた非水電解液二次電池を得る
ことができる。(5) According to the fifth aspect of the present invention, the chain carbonate containing a methyl group as the substituent is specified to contain at least one of dimethyl carbonate and ethyl methyl carbonate. In fact, a non-aqueous electrolyte secondary battery having excellent charge / discharge characteristics at high temperatures can be obtained.
【００４３】（６）請求項６に記載の発明によれば、上
記電解液の溶質として、六弗化リン酸リチウムを用いる
構成としたので、例えば、電解液の溶媒にメチル基を有
する鎖状炭酸カーボネートを含み、溶質に六弗化リン酸
リチウムを使用することで、高温での充放電特性をより
良く向上させた実際的な非水電解液二次電池を得ること
ができる。(6) According to the sixth aspect of the invention, since lithium hexafluorophosphate is used as the solute of the electrolytic solution, for example, a chain having a methyl group in the solvent of the electrolytic solution is used. By using lithium carbonate hexafluoride as a solute containing carbonate carbonate, it is possible to obtain a practical non-aqueous electrolyte secondary battery in which the charge / discharge characteristics at high temperatures are further improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 吉郎 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiro Harada 5-36-11 Shimbashi, Minato-ku, Tokyo Inside Fuji Electric Chemical Co., Ltd.
Claims (6)
素材料を含んだ負極と、非水電解液とを電池ケース内に
収納した非水電解液二次電池において、 電池ケース内に一般式ＭＯ・Ａｌ2 Ｏ3 ・m ＳｉＯ2 ・
n Ｈ2 Ｏ（但し、Ｍはアルカリ金属２原子またはアルカ
リ土類金属１原子、ｍ及びｎは組成比）で表わされる吸
着剤を添加したことを特徴とする非水電解液二次電池。A non-aqueous electrolyte secondary battery containing a positive electrode containing a lithium metal oxide, a negative electrode containing a carbon material, and a non-aqueous electrolyte in a battery case. MO ・ Al 2 O 3・ m SiO 2・
n H 2 O (where, M is an alkali metal 2 atoms or alkaline earth metal 1 atom, m and n composition ratio) non-aqueous electrolyte secondary battery, characterized in that the addition of adsorbent represented by.
と鎖状炭酸エステルとの混合溶媒であることを特徴とす
る請求項１記載の非水電解液二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the solvent of the electrolyte is a mixed solvent of a cyclic carbonate and a chain carbonate.
ーボネート、エチレンカーボネートのうち少なくとも一
種以上であることを特徴とする請求項２記載の非水電解
液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 2, wherein the cyclic carbonate is at least one of propylene carbonate and ethylene carbonate.
ル基を含むことを特徴とする請求項２記載の非水電解液
二次電池。4. The non-aqueous electrolyte secondary battery according to claim 2, wherein said chain carbonate includes a methyl group as a substituent.
ボネート、エチルメチルカーボネートのうち少なくとも
一種以上であることを特徴とする請求項２記載の非水電
解液二次電池。5. The non-aqueous electrolyte secondary battery according to claim 2, wherein the chain carbonate is at least one of dimethyl carbonate and ethyl methyl carbonate.
ウムであることを特徴とする請求項１、２、３、４又は
５記載の非水電解液二次電池。6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the solute of the electrolyte is lithium hexafluorophosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10003958A JPH11204143A (en) | 1998-01-12 | 1998-01-12 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10003958A JPH11204143A (en) | 1998-01-12 | 1998-01-12 | Non-aqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11204143A true JPH11204143A (en) | 1999-07-30 |
Family
ID=11571620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10003958A Pending JPH11204143A (en) | 1998-01-12 | 1998-01-12 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11204143A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000013251A1 (en) * | 1998-08-31 | 2000-03-09 | Hitachi, Ltd. | Lithium secondary cell and device |
| EP1107336A3 (en) * | 1999-11-30 | 2001-09-19 | Sony Corporation | Nonaqueous electrolyte battery |
| JP2003036850A (en) * | 2001-07-23 | 2003-02-07 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
| JP2003077549A (en) * | 2001-08-31 | 2003-03-14 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
| US9812745B2 (en) | 2012-12-28 | 2017-11-07 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device |
-
1998
- 1998-01-12 JP JP10003958A patent/JPH11204143A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000013251A1 (en) * | 1998-08-31 | 2000-03-09 | Hitachi, Ltd. | Lithium secondary cell and device |
| EP1107336A3 (en) * | 1999-11-30 | 2001-09-19 | Sony Corporation | Nonaqueous electrolyte battery |
| US7776465B1 (en) | 1999-11-30 | 2010-08-17 | Sony Corporation | Nonaqueous electrolyte battery |
| JP2003036850A (en) * | 2001-07-23 | 2003-02-07 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
| JP2003077549A (en) * | 2001-08-31 | 2003-03-14 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
| US9812745B2 (en) | 2012-12-28 | 2017-11-07 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device |
| US10044076B2 (en) | 2012-12-28 | 2018-08-07 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device |
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