JPH11238513A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH11238513A JPH11238513A JP10040403A JP4040398A JPH11238513A JP H11238513 A JPH11238513 A JP H11238513A JP 10040403 A JP10040403 A JP 10040403A JP 4040398 A JP4040398 A JP 4040398A JP H11238513 A JPH11238513 A JP H11238513A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- positive electrode
- negative electrode
- phosphorus compound
- organic phosphorus
- 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.)
- Granted
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
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は非水電解質電池に関
するもので、さらに詳しく言えば、高温特性および高温
下での保存性、安全性が向上でき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 capable of improving high-temperature characteristics, storage stability at high temperatures, and safety.
【０００２】[0002]
【従来の技術】近年、高性能化、小型化が進む電子機器
用電源、電力貯蔵用電源、電気自動車用電源として、高
起電力、高エネルギー密度が得られる種々の非水電解質
電池が注目されている。2. Description of the Related Art In recent years, various non-aqueous electrolyte batteries capable of obtaining a high electromotive force and a high energy density have been attracting attention as power supplies for electronic devices, power storage power supplies, and electric vehicle power supplies that have been improved in performance and miniaturization. ing.
【０００３】このような非水電解質電池には、正極と負
極に、固有の電位水準においてリチウムを吸蔵または放
出、吸蔵および放出が可能な材料を活物質として使用
し、電解質に非水系の液体を使用した液系のものと電解
質に固体またはゲルを使用した高分子系のものがある。In such a nonaqueous electrolyte battery, a material capable of occluding or releasing lithium at a specific potential level is used as an active material for a positive electrode and a negative electrode, and a nonaqueous liquid is used as an electrolyte. There are liquid type used and polymer type using solid or gel as the electrolyte.
【０００４】上記した非水電解質電池のうち、電解質に
非水系の液体を使用した液系のものは、電解質に固体ま
たはゲルを使用した高分子系のものよりリチウムイオン
伝導性が良好であるため、高率放電を必要とする負荷に
広く用いられているが、このような高率放電は電池温度
の上昇や内圧の上昇の原因になり、それによって電池が
設置される周囲温度が上昇し、漏液や可燃性ガスが発生
するといった危険性があるため、高温下での保存性、安
全性に配慮する必要がある。Among the non-aqueous electrolyte batteries described above, a liquid battery using a non-aqueous liquid as an electrolyte has a better lithium ion conductivity than a polymer battery using a solid or gel as an electrolyte. Widely used for loads that require high-rate discharge, such high-rate discharge causes an increase in battery temperature and internal pressure, thereby increasing the ambient temperature where the battery is installed, Because of the danger of liquid leakage and the generation of flammable gas, it is necessary to consider storage stability and safety at high temperatures.
【０００５】一方、電解質に固体またはゲルを使用した
高分子系のものは、高率放電用には多用されていなかっ
たが、液系のものより安全性が高いことから、徐々にこ
のような用途に適したものが普及してきており、液系の
ものと同様の配慮が必要になってきている。On the other hand, polymer-based electrolytes using solids or gels as electrolytes have not been widely used for high-rate discharges, but because of their higher safety than liquid-based electrolytes, such electrolytes are gradually used. The thing suitable for a use is spreading, and the same consideration as a liquid thing is needed.
【０００６】上記した非水電解質電池は、正極がＬｉＣ
ｏＯ2 ，ＬｉＭｎ2 Ｏ4 などの正極活物質、黒鉛やカー
ボンブラックなどの導電助剤、ポリフッ化ビニリデンな
どの結着剤からなる正極合剤をアルミニウムなどからな
る正極集電体上に担持したものであり、負極が炭素材料
や遷移金属酸化物などの負極活物質、ポリフッ化ビニリ
デンなどの結着剤からなる負極合剤を銅などからなる負
極集電体上に担持したものであり、これらが隔離体を介
して配されてなる。In the above nonaqueous electrolyte battery, the positive electrode is LiC
A positive electrode active material such as oO 2 or LiMn 2 O 4 , a conductive additive such as graphite or carbon black, and a positive electrode mixture comprising a binder such as polyvinylidene fluoride supported on a positive electrode current collector made of aluminum or the like The negative electrode is a negative electrode active material such as a carbon material or a transition metal oxide, and a negative electrode mixture comprising a binder such as polyvinylidene fluoride supported on a negative electrode current collector made of copper or the like. It is arranged via an isolator.
【０００７】そして、電解質に非水系の液体を使用した
液系のものは、隔離体が多孔性ポリエチレンフィルムか
らなるセパレータであり、このセパレータ、前記正極お
よび負極に、プロピレンカーボネート、エチレンカーボ
ネートなどの環状炭酸エステルやジエチルカーボネー
ト、ジメチルカーボネートなどの鎖状炭酸エステルのよ
うなエステル類、ジメトキシエタンなどの鎖状エーテ
ル、テトラヒドロフランなどの環状エーテルなどのエー
テル類、γ−ブチルラクトンなどのラクトン類などから
なる混合溶媒に、過塩素酸リチウム（ＬｉＣｌＯ4 ）、
４フッ化硼酸リチウム（ＬｉＢＦ4 ）、６フッ化燐酸リ
チウム（ＬｉＰＦ6 ）、トリフルオロメタンスルホン酸
リチウム（ＬｉＣＦ3 ＳＯ3 ）のようなリチウム塩を溶
解させた電解液が含浸されてなる。In a liquid system using a non-aqueous liquid as an electrolyte, a separator in which a separator is made of a porous polyethylene film, and the separator, the positive electrode and the negative electrode are provided with a cyclic material such as propylene carbonate or ethylene carbonate. Mixtures composed of esters such as chain carbonates such as carbonates, diethyl carbonate and dimethyl carbonate, chain ethers such as dimethoxyethane, ethers such as cyclic ethers such as tetrahydrofuran, and lactones such as γ-butyl lactone. Lithium perchlorate (LiClO 4 ) as a solvent,
An electrolyte in which a lithium salt such as lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), or lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is dissolved is impregnated.
【０００８】また、電解質に固体またはゲルを使用した
高分子系のものは、隔離体がポリエチレンオキシドまた
はポリアクリロニトリルなどのポリマー溶媒と前記エス
テル類、前記エーテル類、前記ラクトン類などを混合し
た混合溶媒に前記リチウム塩を溶解したポリマー溶液を
多孔性ポリエチレンフィルムなどに含浸して得た高分子
固体電解質や高分子ゲル電解質であり、この高分子固体
電解質や高分子ゲル電解質は前記正極および負極中にも
含有されてなる。[0008] In the case of a high-molecular type electrolyte using a solid or gel as an electrolyte, the separator is a mixed solvent in which a polymer solvent such as polyethylene oxide or polyacrylonitrile is mixed with the esters, ethers, lactones and the like. A polymer solid electrolyte or a polymer gel electrolyte obtained by impregnating a polymer solution in which the lithium salt is dissolved in a porous polyethylene film or the like, and the polymer solid electrolyte or the polymer gel electrolyte is contained in the positive electrode and the negative electrode. Is also contained.
【０００９】[0009]
【発明が解決しようとする課題】上記のような非水電解
質電池では、溶媒であるエステル類、エーテル類、ラク
トン類は高温下において耐酸化性が低下するため、周囲
温度が６０〜８０℃の雰囲気下で電池を動作させたり、
このような雰囲気下で電池を放置すると、放電容量の低
下が大きくなるという問題があった。In the above-mentioned non-aqueous electrolyte battery, the solvents such as esters, ethers and lactones have low oxidation resistance at high temperatures, and therefore have an ambient temperature of 60 to 80 ° C. Operating the battery in an atmosphere,
If the battery is left in such an atmosphere, there is a problem that the discharge capacity is greatly reduced.
【００１０】[0010]
【課題を解決するための手段】上記課題を解決するた
め、請求項１記載の発明は、正極と負極とが隔離体を介
して配されてなる非水電解質電池において、正極、負
極、隔離体の少なくとも一つが、芳香族有機リン化合物
を含有することを特徴とするものであり、これにより、
高温下において正極中で電解液、高分子固体電解質、高
分子ゲル電解質に含まれるエステル類、エーテル類、ラ
クトン類が酸化され、劣化するのを抑制することができ
るとともに、正極から活性酸素が発生するほどの異常な
高温下においては活性酸素の強い酸化力を失活させるこ
とができる。In order to solve the above-mentioned problems, the invention according to claim 1 is directed to a non-aqueous electrolyte battery in which a positive electrode and a negative electrode are arranged via an isolator. At least one of which is characterized by containing an aromatic organic phosphorus compound, whereby
Ester, ethers, and lactones contained in the electrolyte, polymer solid electrolyte, and polymer gel electrolyte can be oxidized and degraded in the positive electrode at high temperatures, and active oxygen can be generated from the positive electrode. Under an abnormally high temperature, the strong oxidizing power of active oxygen can be deactivated.
【００１１】また、請求項２記載の発明は、請求項１記
載の非水電解質電池において、芳香族有機リン化合物は
酸化物またはハロゲン化物であることを特徴とするもの
であり、これにより、エステル類、エーテル類、ラクト
ン類の酸化を効率よく抑制することができる。According to a second aspect of the present invention, in the nonaqueous electrolyte battery according to the first aspect, the aromatic organic phosphorus compound is an oxide or a halide. , Ethers and lactones can be efficiently suppressed from being oxidized.
【００１２】また、請求項３記載の発明は、請求項１ま
たは２記載の非水電解質電池において芳香族有機リン化
合物の含有量は正極、負極、隔離体中に含まれる電解
液、高分子固体電解質、高分子ゲル電解質の重量の０．
１〜５％であることを特徴とするものであり、これによ
り、電池の充電効率や放電容量を低下させることなく、
エステル類、エーテル類、ラクトン類の酸化を抑制する
ことができる。According to a third aspect of the present invention, there is provided the nonaqueous electrolyte battery according to the first or second aspect, wherein the content of the aromatic organic phosphorus compound is a positive electrode, a negative electrode, an electrolytic solution contained in the separator, a polymer solid. 0% of the weight of the electrolyte and polymer gel electrolyte.
1 to 5%, thereby reducing the charging efficiency and discharge capacity of the battery.
Oxidation of esters, ethers and lactones can be suppressed.
【００１３】[0013]
【発明の実施の形態】以下、本発明をその実施の形態に
基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on its embodiments.
【００１４】本発明の実施の形態に係る非水電解質電池
の特徴は、正極、負極、隔離体の少なくとも一つに、芳
香族有機リン化合物を含有させたことである。A feature of the nonaqueous electrolyte battery according to the embodiment of the present invention is that at least one of the positive electrode, the negative electrode, and the separator contains an aromatic organic phosphorus compound.
【００１５】前記芳香族有機リン化合物としては、ジフ
ェニルフォスフィン、トリフェニルフォスフィン、トリ
オルトトリルフォスフィン、メタトリルフォスフィン、
パラトリルフォスフィン、ジシクロヘキシルフェニルフ
ォスフィン、ジフェニルシクロヘキシルフォスフィンが
あり、特にトリフェニルフォスフィンオキシドのような
酸化物やジフェニルフォスフィナスクロライドのような
ハロゲン化物が好ましい。The aromatic organic phosphorus compound includes diphenylphosphine, triphenylphosphine, triorthotolylphosphine, metatolylphosphine,
There are paratolylphosphine, dicyclohexylphenylphosphine, and diphenylcyclohexylphosphine, and an oxide such as triphenylphosphine oxide and a halide such as diphenylphosphine chloride are particularly preferable.
【００１６】また、前記芳香族有機リン化合物の含有量
は正極、負極、隔離体中に含まれる電解液、高分子固体
電解質、高分子ゲル電解質の重量の１〜１０％とするの
がよく、より好ましくは３〜１０％とするのがよい。こ
のことは、芳香族有機リン化合物の含有量が１％以下で
あると高温下でエステル類、エーテル類、ラクトン類が
酸化され、劣化するのを抑制できなくなることに基づく
ものであり、１０％以上であると電池の充電効率や放電
容量が低下することに基づくものである。The content of the aromatic organic phosphorus compound is preferably 1 to 10% of the weight of the electrolyte solution, the solid polymer electrolyte, and the polymer gel electrolyte contained in the positive electrode, the negative electrode, and the separator. More preferably, it is 3 to 10%. This is based on the fact that when the content of the aromatic organic phosphorus compound is 1% or less, esters, ethers, and lactones are oxidized at high temperatures and cannot be suppressed from deteriorating. This is based on the fact that the charging efficiency and discharge capacity of the battery decrease.
【００１７】[0017]
【実施例】図１は本発明の実施例および比較例に係る非
水電解質電池の断面図である。FIG. 1 is a sectional view of a nonaqueous electrolyte battery according to an example of the present invention and a comparative example.
【００１８】図１に示した非水電解質電池は、正極活物
質、導電助剤および結着剤からなる正極合剤１がアルミ
ニウム製の正極集電体２上に担持された正極、負極活物
質および結着剤からなる負極合剤３が銅製の負極集電体
４上に担持された負極、前記正、負極間に介在させた隔
離体５からなる。The nonaqueous electrolyte battery shown in FIG. 1 has a positive electrode mixture 1 comprising a positive electrode active material, a conductive auxiliary agent and a binder supported on an aluminum positive electrode current collector 2, and a negative electrode active material. A negative electrode mixture 3 comprising a binder is supported on a negative electrode current collector 4 made of copper, and a separator 5 is interposed between the positive and negative electrodes.
【００１９】（実施例１）正極活物質としてのＬｉＣｏ
Ｏ2 が８５重量％、導電助剤としてのカーボンブラック
が１０重量％、結着剤としてのポリフッ化ビニリデンが
５重量％からなる正極合剤１をアルミニウム製の正極集
電体２上に担持した合剤の厚さが約１００μｍの正極、
負極活物質としての黒鉛が９５重量％、結着剤としての
ポリフッ化ビニリデンが５重量％からなる負極合剤３を
銅製の負極集電体４上に担持した合剤の厚さが約１００
μｍの負極、前記正、負極間に介在させた隔離体５から
なり、前記隔離体５が多孔性ポリエチレンフィルムから
なるセパレータであり、このセパレータと前記正極、負
極とに、リチウム塩としての１モルのＬｉＰＦ4 を、溶
媒としてのエチレンカーボネートとジメチルカーボネー
トとの混合溶媒に溶解した電解液が含浸されるととも
に、前記電解液中には芳香族有機リン化合物としてのジ
フェニルフォスフィンを５重量％含有させたものであ
る。こうして得られた電池の容量は１０００ｍＡｈであ
る。(Example 1) LiCo as a positive electrode active material
A positive electrode mixture 1 composed of 85% by weight of O 2, 10% by weight of carbon black as a conductive additive, and 5% by weight of polyvinylidene fluoride as a binder was supported on a positive electrode current collector 2 made of aluminum. A cathode having a mixture thickness of about 100 μm,
A negative electrode mixture 3 comprising 95% by weight of graphite as a negative electrode active material and 5% by weight of polyvinylidene fluoride as a binder is supported on a negative electrode current collector 4 made of copper with a thickness of about 100%.
μm, a separator 5 interposed between the positive and negative electrodes, wherein the separator 5 is a separator made of a porous polyethylene film. Of LiPF 4 in a mixed solvent of ethylene carbonate and dimethyl carbonate as a solvent is impregnated, and 5% by weight of diphenylphosphine as an aromatic organic phosphorus compound is contained in the electrolyte. It is a thing. The capacity of the battery thus obtained is 1000 mAh.
【００２０】（実施例２）隔離体５が約１０万の平均分
子量をもったポリアクリロニトリル１重量部に、前述し
た電解液５重量部を含浸した厚さが約３０μｍの高分子
ゲル電解質であり、この高分子ゲル電解質中に３重量％
のジフェニルフォスフィンを含有させたものであり、正
極活物質としてのＬｉＣｏＯ2 が６７重量％、導電助剤
としてのアセチレンブラックが８重量％、前記高分子ゲ
ル電解質が２５重量％からなる正極合剤１をアルミニウ
ム製の正極集電体２上に担持した合剤の厚さが約１００
μｍの正極、負極活物質としての黒鉛が８０重量％、前
記高分子ゲル電解質が２０重量％からなる負極合剤３を
銅製の負極集電体４上に担持した合剤の厚さが約１００
μｍの負極、前記正、負極間に前記隔離体５を介在させ
たものである。こうして得られた電池の容量は１０００
ｍＡｈである。(Example 2) The separator 5 is a polymer gel electrolyte having a thickness of about 30 μm in which 1 part by weight of polyacrylonitrile having an average molecular weight of about 100,000 is impregnated with 5 parts by weight of the above-mentioned electrolytic solution. 3% by weight in this polymer gel electrolyte
A positive electrode mixture comprising 67% by weight of LiCoO 2 as a positive electrode active material, 8% by weight of acetylene black as a conductive aid, and 25% by weight of the polymer gel electrolyte 1 is supported on a positive electrode current collector 2 made of aluminum and has a thickness of about 100
The negative electrode mixture 3 comprising 80% by weight of graphite as a positive electrode and negative electrode active material and 20% by weight of the polymer gel electrolyte on a negative electrode current collector 4 made of copper has a thickness of about 100 μm.
The separator 5 is interposed between the negative electrode of μm and the positive and negative electrodes. The capacity of the battery thus obtained is 1000
mAh.
【００２１】（実施例３）隔離体５が約５０００の平均
分子量をもったポリエチレンオキシドの架橋体１重量部
に、前述した電解液２重量部を含浸した厚さが約３０μ
ｍの高分子固体電解質であり、この高分子固体電解質中
に１重量％のジフェニルフォスフィンを含有させたもの
であり、正極活物質としてのＬｉＣｏＯ2 が６７重量
％、導電助剤としてのアセチレンブラックが８重量％、
前記高分子固体電解質が２５重量％からなる正極合剤１
をアルミニウム製の正極集電体２上に担持した合剤の厚
さが約１００μｍの正極、負極活物質としての黒鉛が８
０重量％、前記高分子ゲル電解質が２０重量％からなる
負極合剤３を銅製の負極集電体４上に担持した合剤の厚
さが約１００μｍの負極、前記正、負極間に前記隔離体
５を介在させたものである。こうして得られた電池の容
量は１０００ｍＡｈである。Example 3 A separator 5 was prepared by impregnating 1 part by weight of a crosslinked polyethylene oxide having an average molecular weight of about 5,000 with 2 parts by weight of the above-mentioned electrolytic solution to a thickness of about 30 μm.
m, a solid polymer electrolyte containing 1% by weight of diphenylphosphine, 67% by weight of LiCoO 2 as a positive electrode active material, and acetylene black as a conductive additive. Is 8% by weight,
Positive electrode mixture 1 comprising 25% by weight of the polymer solid electrolyte
Of a mixture having a thickness of about 100 μm and a graphite serving as a negative electrode active material having a thickness of about 100 μm, on a positive electrode current collector 2 made of aluminum.
A negative electrode mixture 3 comprising 0% by weight and 20% by weight of the polymer gel electrolyte is supported on a negative electrode current collector 4 made of copper, and the thickness of the mixture is about 100 μm. The body 5 is interposed. The capacity of the battery thus obtained is 1000 mAh.
【００２２】（比較例１）電解液中に芳香族有機リン化
合物としてのジフェニルフォスフィンを含有させていな
いこと以外は実施例１と同じのものである。Comparative Example 1 The same as Example 1 except that diphenylphosphine as an aromatic organic phosphorus compound was not contained in the electrolytic solution.
【００２３】（比較例２）高分子ゲル電解質中に芳香族
有機リン化合物としてのジフェニルフォスフィンを含有
させていないこと以外は実施例２と同じのものである。Comparative Example 2 The same as Example 2 except that diphenylphosphine as an aromatic organic phosphorus compound was not contained in the polymer gel electrolyte.
【００２４】（比較例３）高分子固体電解質中に芳香族
有機リン化合物としてのジフェニルフォスフィンを含有
させていないこと以外は実施例３と同じのものである。Comparative Example 3 The same as Example 3 except that diphenylphosphine as an aromatic organic phosphorus compound was not contained in the solid polymer electrolyte.
【００２５】上記した実施例１〜３に係る非水電解質電
池および比較例１〜３に係る非水電解質電池を、周囲温
度６０℃の雰囲気下で１か月間放置し、放置後の各電池
の自己放電量を調査し、結果を表１に示す。The nonaqueous electrolyte batteries according to Examples 1 to 3 and the nonaqueous electrolyte batteries according to Comparative Examples 1 to 3 were allowed to stand for one month in an atmosphere at an ambient temperature of 60 ° C. The amount of self-discharge was investigated, and the results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１から、実施例１〜３に係る非水電解質
電池は、自己放電量が１５〜２０％であり、比較例１〜
３に係る非水電解質電池より小さくなることがわかっ
た。From Table 1, it can be seen that the non-aqueous electrolyte batteries according to Examples 1 to 3 have a self-discharge amount of 15 to 20% and Comparative Examples 1 to 5.
3 was smaller than the non-aqueous electrolyte battery according to Example 3.
【００２８】次に、上記した実施例１〜３に係る非水電
解質電池および比較例１〜３に係る非水電解質電池につ
いて充放電サイクル試験を行い、各電池の放電容量の変
化を調査した結果を図２に示す。なお、充放電サイクル
は、周囲温度が６０℃の雰囲気下で、充電を０．２Ｃの
定電流で終止電圧が４．２Ｖまでとし、放電を０．２Ｃ
の定電流で終止電圧が２．７Ｖまでとした。Next, charge-discharge cycle tests were performed on the non-aqueous electrolyte batteries according to Examples 1 to 3 and the non-aqueous electrolyte batteries according to Comparative Examples 1 to 3, and the change in the discharge capacity of each battery was examined. Is shown in FIG. In the charge / discharge cycle, in an atmosphere at an ambient temperature of 60 ° C., charging was performed at a constant current of 0.2 C, the final voltage was set to 4.2 V, and discharging was performed at a rate of 0.2 C.
And the final voltage was set to 2.7 V.
【００２９】図２から、実施例１〜３に係る非水電解質
電池は、比較例１〜３に係る非水電解質電池より放電容
量の低下が小さいことがわかった。From FIG. 2, it was found that the non-aqueous electrolyte batteries according to Examples 1 to 3 exhibited a smaller decrease in discharge capacity than the non-aqueous electrolyte batteries according to Comparative Examples 1 to 3.
【００３０】上記した実施例１〜３に係る非水電解質電
池および比較例１〜３に係る非水電解質電池電池を、満
充電状態にして周囲温度を２５０℃まで上昇させた時の
状況を調査し、結果を表２に示す。The situation when the ambient temperature was raised to 250 ° C. with the non-aqueous electrolyte batteries according to Examples 1 to 3 and the non-aqueous electrolyte batteries according to Comparative Examples 1 to 3 being fully charged was investigated. The results are shown in Table 2.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表２から、実施例１〜３に係る非水電解質
電池は、比較例１〜３に係る非水電解質電池のような異
常が発生しないことがわかった。From Table 2, it was found that the non-aqueous electrolyte batteries according to Examples 1 to 3 did not cause an abnormality unlike the non-aqueous electrolyte batteries according to Comparative Examples 1 to 3.
【００３３】上記した実施例では、芳香族有機リン化合
物は電解液、高分子ゲル電解質または高分子固体電解質
中に含有させているが、正極および／または負極中に含
有させてもよい。特に、正極中に含有させると、高温下
において正極中で電解液または電解質が酸化されて劣化
するのを抑制することができるとともに、上述した異常
な高温下においては正極から発生する活性酸素の酸化力
を失活させることができるので、発火に至るといった危
険性を回避することができる。In the above embodiment, the aromatic organic phosphorus compound is contained in the electrolytic solution, the polymer gel electrolyte or the polymer solid electrolyte, but may be contained in the positive electrode and / or the negative electrode. In particular, when contained in the positive electrode, it is possible to prevent the electrolyte or the electrolyte from being oxidized and degraded in the positive electrode at high temperatures, and to oxidize active oxygen generated from the positive electrode at abnormal abnormal high temperatures. Since the force can be deactivated, the danger of firing can be avoided.
【００３４】また、上記した実施例では、芳香族有機リ
ン化合物としてジフェニルフォスフィンを用いたもので
あるが、前述した酸化物やハロゲン化物であっても同様
の効果が得られる。In the above-described embodiment, diphenylphosphine is used as the aromatic organic phosphorus compound. However, the same effects can be obtained with the above-mentioned oxides and halides.
【００３５】[0035]
【発明の効果】上記した如く、各請求項記載の発明は、
正極、負極、隔離体の少なくとも一つに芳香族有機リン
化合物を含有させたことにより、高温特性および高温下
での保存性、安全性を向上させることができるので、こ
のような雰囲気下で非水電解質電池を使用する際の信頼
性の向上に寄与することができる。As described above, the invention described in each claim is
By including an aromatic organic phosphorus compound in at least one of the positive electrode, the negative electrode, and the separator, high-temperature characteristics, storage stability at high temperatures, and safety can be improved. This can contribute to improvement of reliability when using the water electrolyte battery.
【図１】本発明の実施例および比較例に係る非水電解質
電池の断面図である。FIG. 1 is a cross-sectional view of a non-aqueous electrolyte battery according to an example of the present invention and a comparative example.
【図２】本発明の実施例および比較例に係る非水電解質
電池の充放電サイクル特性を調査した図である。FIG. 2 is a diagram illustrating the charge / discharge cycle characteristics of nonaqueous electrolyte batteries according to Examples and Comparative Examples of the present invention.
１ 正極合剤 ２ 正極集電体 ３ 負極合剤 ４ 負極集電体 ５ 隔離体 DESCRIPTION OF SYMBOLS 1 Positive electrode mixture 2 Positive electrode collector 3 Negative electrode mixture 4 Negative electrode collector 5 Isolator
Claims (3)
なる非水電解質電池において、正極、負極、隔離体の少
なくとも一つが、芳香族有機リン化合物を含有すること
を特徴とする非水電解質電池。1. A non-aqueous electrolyte battery in which a positive electrode and a negative electrode are arranged via an isolator, wherein at least one of the positive electrode, the negative electrode, and the isolator contains an aromatic organic phosphorus compound. Water electrolyte battery.
て、芳香族有機リン化合物は酸化物またはハロゲン化物
であることを特徴とする非水電解質電池。2. The non-aqueous electrolyte battery according to claim 1, wherein the aromatic organic phosphorus compound is an oxide or a halide.
において、芳香族有機リン化合物の含有量は正極、負
極、隔離体中に含まれる電解液、高分子固体電解質、高
分子ゲル電解質の重量の１〜１０％であることを特徴と
する非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the content of the aromatic organic phosphorus compound is selected from the group consisting of a positive electrode, a negative electrode, an electrolyte contained in the separator, a polymer solid electrolyte, and a polymer gel electrolyte. Non-aqueous electrolyte battery characterized by being 1 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04040398A JP4438103B2 (en) | 1998-02-23 | 1998-02-23 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04040398A JP4438103B2 (en) | 1998-02-23 | 1998-02-23 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11238513A true JPH11238513A (en) | 1999-08-31 |
| JP4438103B2 JP4438103B2 (en) | 2010-03-24 |
Family
ID=12579711
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04040398A Expired - Fee Related JP4438103B2 (en) | 1998-02-23 | 1998-02-23 | Non-aqueous electrolyte battery |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002198090A (en) * | 2000-12-25 | 2002-07-12 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte secondary cell |
| KR100791426B1 (en) | 2000-06-16 | 2008-01-07 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Oil clearing sheet for makeup |
| WO2012117826A1 (en) * | 2011-03-03 | 2012-09-07 | 株式会社豊田中央研究所 | Nonaqueous-electrolyte halogen cell |
-
1998
- 1998-02-23 JP JP04040398A patent/JP4438103B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100791426B1 (en) | 2000-06-16 | 2008-01-07 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Oil clearing sheet for makeup |
| JP2002198090A (en) * | 2000-12-25 | 2002-07-12 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte secondary cell |
| WO2012117826A1 (en) * | 2011-03-03 | 2012-09-07 | 株式会社豊田中央研究所 | Nonaqueous-electrolyte halogen cell |
| JP2012195269A (en) * | 2011-03-03 | 2012-10-11 | Toyota Central R&D Labs Inc | Nonaqueous electrolyte halogen battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4438103B2 (en) | 2010-03-24 |
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