JPH11260404A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH11260404A JPH11260404A JP10060738A JP6073898A JPH11260404A JP H11260404 A JPH11260404 A JP H11260404A JP 10060738 A JP10060738 A JP 10060738A JP 6073898 A JP6073898 A JP 6073898A JP H11260404 A JPH11260404 A JP H11260404A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- polymer
- polycyclic alicyclic
- solid electrolyte
- polymer gel
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム電池、リ
チウムイオン電池等の非水電解質電池に関するものであ
る。特に耐高温性に優れ、高温下での安全性に優れた電
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 such as a lithium battery and a lithium ion battery. Particularly, the present invention relates to a battery having excellent high-temperature resistance and excellent safety at high temperatures.
【０００２】[0002]
【従来の技術】リチウム、リチウム合金、リチウム挿入
化合物を負極とする、リチウム一次電池、二次電池の電
解質は、非水系の溶媒や高分子にリチウム塩を溶解した
ものである。電解液を構成する主たる溶媒は、プロピレ
ンカーボネイト（ＰＣ）、エチレンカーボネイト（Ｅ
Ｃ）などの環状炭酸エステル、ジエチルカーボネイト
（ＤＥＣ）、ジメチルカーボネイト（ＤＭＣ）等の鎖状
炭酸エステル、ジメトキシエタン等の鎖状エーテル、テ
トラヒドロフラン（ＴＨＦ）等の環状エーテル、ガンマ
ブチロラクトン（γＢＬ）等のラクトン類であり、一般
的にこれらの混合物である。このような溶剤に過塩素酸
リチウム（ＬｉＣｌＯ4 ）、４フッ化ホウ酸リチウム
（ＬｉＢＦ4 ）、６フッ化燐酸リチウム（ＬｉＰ
Ｆ6 ）、リチウムトリフロロメタスルフォネート（Ｌｉ
ＣＦ3 ＳＯ3 ）等のリチウム塩が溶解した溶液を電解液
としている。2. Description of the Related Art An electrolyte of a lithium primary battery or a secondary battery using lithium, a lithium alloy or a lithium insertion compound as a negative electrode is obtained by dissolving a lithium salt in a non-aqueous solvent or polymer. The main solvents constituting the electrolytic solution are propylene carbonate (PC) and ethylene carbonate (E
Cyclic carbonates such as C), chain carbonates such as diethyl carbonate (DEC) and dimethyl carbonate (DMC), chain ethers such as dimethoxyethane, cyclic ethers such as tetrahydrofuran (THF), and gamma butyrolactone (γBL). Lactones, generally a mixture thereof. Such solvents include lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), and lithium hexafluorophosphate (LiP
F 6 ), lithium trifluorometasulfonate (Li
A solution in which a lithium salt such as CF 3 SO 3 ) is dissolved is used as an electrolyte.
【０００３】また、高分子固体電解質や高分子ゲル電解
質において、高分子材料としては、ポリエチレンオキシ
ド（ＰＥＯ）骨格、ポリシロキサン骨格のものやポリア
クリロニトリル（ＰＡＮ）などがある。高分子固体電解
質の可塑剤やゲル電解質の溶剤には、前記のエステル、
エーテル、ラクトン系の溶剤等がある。In the polymer solid electrolyte and the polymer gel electrolyte, examples of the polymer material include those having a polyethylene oxide (PEO) skeleton, a polysiloxane skeleton, and polyacrylonitrile (PAN). In the plasticizer of the polymer solid electrolyte or the solvent of the gel electrolyte, the ester,
Examples include ether and lactone solvents.
【０００４】[0004]
【発明が解決しようとする課題】上記従来の非水電解質
電池には以下の課題があった。即ち、上記電解液の主溶
媒たる炭酸エステル、エーテル、ラクトン類は、いずれ
も高温下での耐酸化性が十分とはいえず、電池を６０〜
８０℃等の高温下で動作させたり、放置した時の容量低
下が大きい。また、２００℃を超える異常な高温下に置
かれた時に、発火燃焼の危険性がある等である。The above-mentioned conventional non-aqueous electrolyte battery has the following problems. That is, the carbonates, ethers, and lactones, which are the main solvents of the electrolytic solution, do not have sufficient oxidation resistance at high temperatures.
When operated at a high temperature such as 80 ° C. or left unattended, the capacity is greatly reduced. Further, there is a danger of ignition and combustion when placed at an abnormally high temperature exceeding 200 ° C.
【０００５】[0005]
【課題を解決するための手段】本発明では上記課題を解
決するため、電解液、高分子ゲル電解質または高分子固
体電解質が、添加剤として多環形脂環式炭化水素または
その誘導体を含有するか、さらに望ましくは電解液の主
たる溶媒、または高分子固体電解質、ゲル電解質を構成
する主たる溶媒および高分子材料が多環形脂環式炭化水
素またはその誘導体である。中でもモノテルペン類また
はその誘導体を含む電解質が高温下での安定性に優れ、
かつ難燃性に於いても従来の電解液より優れていること
を見い出し本発明に至った。多環形脂環式炭化水素がど
のように作用するのかは明かではないが、高温下では電
解質内に発生したラジカルが電解質の分解劣化や発火の
要因になると考えられ、前記多環形脂環式炭化水素は発
生したラジカルを捕捉し不活性な形に変えてしまう働き
をするのではないかと考えられる。According to the present invention, in order to solve the above-mentioned problems, an electrolyte, a polymer gel electrolyte or a polymer solid electrolyte contains a polycyclic alicyclic hydrocarbon or a derivative thereof as an additive. More preferably, the main solvent of the electrolytic solution, or the main solvent and the polymer material constituting the solid polymer electrolyte and the gel electrolyte are polycyclic alicyclic hydrocarbons or derivatives thereof. Among them, electrolytes containing monoterpenes or derivatives thereof have excellent stability at high temperatures,
In addition, they have found that they are superior to conventional electrolytes in flame retardancy, and have reached the present invention. It is not clear how the polycyclic alicyclic hydrocarbons act, but it is thought that radicals generated in the electrolyte at high temperatures may cause degradation and ignition of the electrolyte, and the above-mentioned polycyclic alicyclic hydrocarbons may be affected. It is thought that hydrogen acts to trap generated radicals and convert them to an inactive form.
【０００６】[0006]
【発明の実施の形態】図１は本発明電池の１例を示す断
面図である。図１において、１は正極である。正極はコ
バルト酸リチウム（ＬｉＣｏＯ2 ）やマンガン酸リチウ
ム（ＬｉＭｎ2 Ｏ4 ）等の活物質、黒鉛やカーボンブラ
ック等の導電助材、ポリフッ化ビニリデン（ＰＶＤＦ）
等の結着剤、後述の電解液とで構成される。または、Ｐ
ＶＤＦに代えて結着剤と電解質の両方の機能を兼ねる高
分子ゲル電解質もしくは高分子固体電解質で構成され
る。正極１はアルミニウム（Ａｌ）箔等の集電体３上に
担持されている。２は負極である。負極は各種炭素材料
や遷移金属酸化物材料等のリチウム挿入可能な材料から
成る活物質材料、ＰＶＤＦ等の結着剤、電解液とで構成
される。または、正極と同様にＰＶＤＦに代えて高分子
ゲル電解質もしくは高分子固体電解質で構成される。負
極２は銅箔等の集電体４上に担持されている。５は電解
液を含有する微孔性のポリエチレン（ＰＥ）フィルムや
後述の高分子固体電解質フィルムや高分子ゲル電解質か
ら成るセパレータである。FIG. 1 is a sectional view showing an example of the battery of the present invention. In FIG. 1, reference numeral 1 denotes a positive electrode. The positive electrode is an active material such as lithium cobalt oxide (LiCoO 2 ) or lithium manganate (LiMn 2 O 4 ), a conductive auxiliary material such as graphite or carbon black, polyvinylidene fluoride (PVDF)
Etc., and an electrolytic solution described later. Or P
Instead of VDF, it is composed of a polymer gel electrolyte or a polymer solid electrolyte having both functions of a binder and an electrolyte. The positive electrode 1 is supported on a current collector 3 such as an aluminum (Al) foil. 2 is a negative electrode. The negative electrode is composed of an active material made of a lithium-insertable material such as various carbon materials and transition metal oxide materials, a binder such as PVDF, and an electrolyte. Alternatively, similarly to the positive electrode, it is composed of a polymer gel electrolyte or a polymer solid electrolyte instead of PVDF. The negative electrode 2 is supported on a current collector 4 such as a copper foil. Reference numeral 5 denotes a separator made of a microporous polyethylene (PE) film containing an electrolyte, a polymer solid electrolyte film described later, or a polymer gel electrolyte.
【０００７】電解液は、支持塩としての各種のリチウム
塩を後述の非水系の溶剤に溶解させた溶液である。ここ
で適用されるリチウム塩としては、ＬｉＣＦ3 ＳＯ3 、
ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）
2 、ＬｉＮ（ＣＦ3 ＳＯ2 ）（Ｃ4 Ｆ9 ＳＯ2 ）、Ｌｉ
Ｃ（ＣＦ3 ＳＯ2 ）3 、ＬｉＢＦ4 、ＬｉＰＦ6 等であ
る。電解液の溶剤は、前記の炭酸エチレン、炭酸プロピ
レン、炭酸ジエチルや炭酸ジメチルなどである。高分子
ゲル電解質の高分子成分は、ポリフッ化ビニリデン、ポ
リ６フッ化プロピレン等のフッ素樹脂やポリアクリロニ
トリル等である。高分子ゲル電解質は、これらの高分子
成分と前記電解液成分で構成されたゲルである。高分子
固体電解質の高分子成分は、ポリエチレンオキシド、ポ
リシロキサン、ポリフォスファゼン等である。高分子固
体電解質は、これら極性を有する高分子に前記リチウム
塩を溶解させたものである。高分子固体電解質において
は、可塑剤として炭酸プロピレン、炭酸エチレン、γブ
チロラクトン等を添加する場合もある。The electrolytic solution is a solution in which various lithium salts as supporting salts are dissolved in a non-aqueous solvent described later. As the lithium salt applied here, LiCF 3 SO 3 ,
LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 )
2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), Li
C (CF 3 SO 2 ) 3 , LiBF 4 , LiPF 6 and the like. The solvent of the electrolytic solution is the above-mentioned ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate or the like. The polymer component of the polymer gel electrolyte is a fluororesin such as polyvinylidene fluoride, polypropylene hexafluoride, or polyacrylonitrile. The polymer gel electrolyte is a gel composed of these polymer components and the electrolyte component. The polymer component of the polymer solid electrolyte is polyethylene oxide, polysiloxane, polyphosphazene, or the like. The polymer solid electrolyte is obtained by dissolving the lithium salt in a polymer having these polarities. In the polymer solid electrolyte, propylene carbonate, ethylene carbonate, γ-butyrolactone, or the like may be added as a plasticizer.
【０００８】第一の実施の形態は、電解液、高分子ゲル
電解質または高分子固体電解質が、多環形脂環式炭化水
素またはその誘導体を添加剤として含有する。具体的に
は、ピネン、カンフェン、ボルネンやフェンケン、ビシ
クロオクタン、ビシクロオクタエンまたはこれらの骨格
を有するエステルやエーテル化合物である。誘導体の例
としては、脂環式化合物のアルキルアセテート、炭酸エ
ステル、アルキルエーテル等である。中でもモノテルペ
ン類に属するピネンやカンフェンまたはその誘導体であ
るノピルアセテート等が好適である。これら添加剤の電
解液、高分子ゲル電解質、高分子固体電解質中の含有率
は１〜１０重量％が適当であり、更には２〜６重量％が
望ましい。In the first embodiment, the electrolyte, the polymer gel electrolyte or the polymer solid electrolyte contains a polycyclic alicyclic hydrocarbon or a derivative thereof as an additive. Specifically, it is pinene, camphene, bornene, fenken, bicyclooctane, bicyclooctaene, or an ester or ether compound having a skeleton of these. Examples of the derivative include an alicyclic compound such as alkyl acetate, carbonate, and alkyl ether. Among them, pinene and camphene belonging to monoterpenes or nopyr acetate which is a derivative thereof are preferable. The content of these additives in the electrolyte solution, polymer gel electrolyte and polymer solid electrolyte is suitably from 1 to 10% by weight, and more preferably from 2 to 6% by weight.
【０００９】第二の実施の形態は、電解液の主溶剤、高
分子ゲル電解質を構成する主たる液体成分、可塑剤含有
形高分子固体電解質の主たる可塑剤が多環形脂環式炭化
水素またはその誘導体である。具体的にはピネンのアセ
テート等である。溶剤全体に占める多環形脂環式炭化水
素の誘導体比率は少なくとも６０ｖｏｌ．％であり、更
には８０ｖｏｌ．％以上が望ましい。副溶剤としては、
前述のＰＣ，ＥＣ等の環状エステル、鎖状エステル、ブ
チロラクトン、環状エーテル、鎖状エーテルが適用でき
る。リチウム塩の濃度は０．５〜２．０Ｍ／ｌが適当で
ある。In the second embodiment, the main solvent of the electrolytic solution, the main liquid component constituting the polymer gel electrolyte, and the main plasticizer of the plasticizer-containing polymer solid electrolyte are polycyclic alicyclic hydrocarbons or polycyclic alicyclic hydrocarbons. It is a derivative. Specifically, it is a pinene acetate or the like. The derivative ratio of the polycyclic alicyclic hydrocarbon in the whole solvent is at least 60 vol. %, And 80 vol. % Or more is desirable. As a co-solvent,
The aforementioned cyclic esters such as PC and EC, chain esters, butyrolactone, cyclic ethers and chain ethers can be used. The concentration of the lithium salt is suitably 0.5 to 2.0 M / l.
【００１０】第三の実施の形態は、高分子固体電解質や
高分子ゲル電解質を構成する高分子材料が、多環形脂環
式骨格構造を有する成分を含む。高分子材料が多環形脂
環式炭化水素またはその誘導体単独で成る高分子でもよ
いし、高分子ゲル電解質においては従来のフッ素樹脂や
ポリアクリロニトリルとの共重合体もしくは混合物でも
よい。高分子固体電解質においては、従来のポリエチレ
ンオキシド等との共重合体もしくは混合物でもよい。高
分子を構成する多環形脂環式炭化水素またはその誘導体
の比率は４０重量％以上が適当である。さらには、６０
重量％以上が望ましい。高分子構成要素として適用され
る多環形脂環式炭化水素の誘導体の具体例を挙げると、
両末端にアクリレート基を有するテルペンの誘導体やペ
ンダントとして脂環式炭化水素の誘導体基を有するビニ
ル重合体である。その他多環形脂環式炭化水素が複数箇
連なった構造を有する化合物等である。高分子固体電解
質は可塑材を含有するタイプも可能であり、主たる可塑
材には前記電解液の溶剤で記述した、多環形脂環式炭化
水素の誘導体が適用される。In the third embodiment, the polymer material constituting the polymer solid electrolyte or the polymer gel electrolyte contains a component having a polycyclic alicyclic skeleton structure. The polymer material may be a polymer consisting of a polycyclic alicyclic hydrocarbon or a derivative thereof alone, or a polymer gel electrolyte may be a copolymer or a mixture with a conventional fluororesin or polyacrylonitrile. In the polymer solid electrolyte, a copolymer or a mixture with a conventional polyethylene oxide or the like may be used. The proportion of the polycyclic alicyclic hydrocarbon or its derivative constituting the polymer is suitably at least 40% by weight. Furthermore, 60
% By weight or more is desirable. To give specific examples of derivatives of polycyclic alicyclic hydrocarbon applied as a polymer component,
It is a terpene derivative having an acrylate group at both terminals or a vinyl polymer having an alicyclic hydrocarbon derivative group as a pendant. Other examples include compounds having a structure in which a plurality of polycyclic alicyclic hydrocarbons are linked. The polymer solid electrolyte may be of a type containing a plasticizer, and a derivative of the polycyclic alicyclic hydrocarbon described in the solvent of the electrolytic solution is applied to the main plasticizer.
【００１１】液体状の電解液の溶剤が多環形脂環式炭化
水素である場合を例に説明すると、正極は８５重量％の
ＬｉＣｏＯ2 と１０重量％のカーボンブラック、５重量
％のＰＶＤＦから成り、Ａｌ箔集電体上に担持されてい
る。合材層の厚さは約１００μｍである。負極は黒鉛９
５重量％とＰＶＤＦ５重量％から成り、Ｃｕ箔集電体上
に担持されている。合剤層の厚さは約１００μｍであ
る。セパレータは厚さ２５μｍのＰＥ製微孔性フィルム
である。電解液は濃度が１ＭのＬｉＰＦ6 を溶解させた
テルペン誘導体の溶液である。テルペン誘導体の誘導体
の例としてはピネンの誘導体の１種のノピルアセテート
があげられる。In the case where the solvent of the liquid electrolyte is a polycyclic alicyclic hydrocarbon, for example, the positive electrode is composed of 85% by weight of LiCoO 2 , 10% by weight of carbon black, and 5% by weight of PVDF. , On an aluminum foil current collector. The thickness of the mixture layer is about 100 μm. The negative electrode is graphite 9
It consists of 5% by weight and 5% by weight of PVDF and is supported on a Cu foil current collector. The thickness of the mixture layer is about 100 μm. The separator is a PE microporous film having a thickness of 25 μm. The electrolyte is a solution of a terpene derivative in which LiPF 6 having a concentration of 1 M is dissolved. An example of a derivative of a terpene derivative is one kind of nopyr acetate of a derivative of pinene.
【００１２】高分子固体電解質および高分子ゲル電解質
を例に説明する。高分子材料の例としてはテルペンジフ
ェノールジアクリレートの重合物があげられる。高分子
固体電解質はＬｉＰＦ6 １０重量％、前記高分子９０重
量％から成る固溶体である。高分子ゲル電解質は、前記
１ＭのＬｉＰＦ6 のノピルアセテート溶液７０重量％、
テルペンジフェノールジアクリレートの重合物３０重量
％から成る高分子ゲルである。正極はＬｉＣｏＯ2 ６７
重量％、アセチレンブラック８重量％、高分子固体電解
質または高分子ゲル電解質重量２５％から成る複合電極
で、Ａｌ箔製正極集電体上に担持されている。合剤層の
厚さは約１００μｍである。負極は黒鉛８０重量％、高
分子固体電解質または高分子ゲル電解質２０重量から成
る複合電極でＣｕ箔製負極集電体上に担持されている。
合剤層の厚さは約１００μｍである。セパレータは厚さ
約３０μｍの高分子固体電解質または高分子ゲル電解質
のフィルムである。表１は本発明に係る電池と従来電池
の６０℃、１ヶ月放置時の自己放電量を比較した表であ
る。The polymer solid electrolyte and the polymer gel electrolyte will be described as examples. Examples of the polymer material include a polymer of terpene diphenol diacrylate. The polymer solid electrolyte is a solid solution composed of 10% by weight of LiPF 6 and 90% by weight of the polymer. The polymer gel electrolyte contains 70% by weight of the above-mentioned 1 M LiPF 6 nopyr acetate solution,
This is a polymer gel comprising 30% by weight of a polymer of terpene diphenol diacrylate. The positive electrode is LiCoO 2 67
The composite electrode is composed of 25% by weight, 8% by weight of acetylene black, and 25% by weight of a polymer solid electrolyte or a polymer gel electrolyte, and is supported on a positive electrode current collector made of Al foil. The thickness of the mixture layer is about 100 μm. The negative electrode is a composite electrode composed of 80% by weight of graphite and 20% by weight of a polymer solid electrolyte or a polymer gel electrolyte, and is supported on a negative electrode current collector made of Cu foil.
The thickness of the mixture layer is about 100 μm. The separator is a polymer solid electrolyte or polymer gel electrolyte film having a thickness of about 30 μm. Table 1 is a table comparing the self-discharge amount of the battery according to the present invention and the conventional battery at 60 ° C. for one month.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１において電池の基本構成は正極がＬｉ
ＣｏＯ2 、負極が黒鉛で全て同じであるが、電解質を異
にする。ＡおよびＢは電解液が液状の電池である。Ａは
本発明に係る電池で電解液の組成は１ＭのＬｉＰＦ6 を
溶解させたノピルアセテート溶液である。Ｂは従来電池
で電解液の組成は１ＭのＬｉＰＦ6 を溶解させたＥＣ／
ＤＭＣ／ＤＥＣ混合溶液である。ＣおよびＤは高分子ゲ
ル電解質電池である。Ｃは本発明に係る電池で電解質の
組成は１ＭのＬｉＰＦ6 を溶解させたノピルアセテート
溶液を含んだテルペンジフェニールジアクリレートを重
合させたものである。Ｄは従来電池で電解質の組成は１
ＭのＬｉＰＦ6 を溶解させたＥＣ／ＤＭＣ／ＤＥＣ混合
溶液を含んだＰＡＮである。ＥおよびＦは高分子固体電
解質電池である。Ｅは本発明に係る電池で電解質の組成
はＬｉＰＦ6 １０重量％を含んだテルペンジフェノール
ジアクリレート９０重量％を重合させたものである。Ｆ
は従来電池で電解質の組成はＬｉＰＦ6 １０重量％を含
んだＰＥＯ９０重量％からなるものである。In Table 1, the basic structure of the battery is such that the positive electrode is Li
CoO 2 and graphite are all the same for graphite but the electrolyte is different. A and B are batteries in which the electrolyte is liquid. A is a battery according to the present invention, and the composition of the electrolyte is a nopyr acetate solution in which 1M LiPF 6 is dissolved. B is a conventional battery, and the composition of the electrolyte was EC / in which 1 M LiPF 6 was dissolved.
It is a DMC / DEC mixed solution. C and D are polymer gel electrolyte batteries. C is a battery according to the present invention, in which the composition of the electrolyte is obtained by polymerizing terpene diphenyl diacrylate containing a nopyr acetate solution in which 1M LiPF 6 is dissolved. D is a conventional battery and the composition of the electrolyte is 1
PAN containing an EC / DMC / DEC mixed solution in which M LiPF 6 is dissolved. E and F are polymer solid electrolyte batteries. E is a battery according to the present invention, in which the composition of the electrolyte is obtained by polymerizing 90% by weight of terpene diphenol diacrylate containing 10% by weight of LiPF 6 . F
Is a conventional battery in which the composition of the electrolyte is 90% by weight of PEO containing 10% by weight of LiPF 6 .
【００１５】表１から明らかな如く、本発明電池は、従
来電池に比べて自己放電性能に優れている。As is clear from Table 1, the battery of the present invention has better self-discharge performance than the conventional battery.
【００１６】図２は液体の電解液を有する本発明に係る
電池Ａと従来電池Ｂを温度６０℃で充放電を繰り返した
時のサイクル特性を示した図である。充電レートは０．
２Ｃ、充電終止電圧は４．２Ｖ、放電レートは０．２
Ｃ、放電終止電圧は２．７Ｖとした。電池の区分は表１
で示した区分と同一である。図１より、本発明に係る電
池Ａは、従来電池Ｂに比べてサイクル経過に伴う容量低
下が小さく、優れた特性を有していることがわかる。FIG. 2 is a graph showing cycle characteristics when the battery A according to the present invention having a liquid electrolyte and the conventional battery B are repeatedly charged and discharged at a temperature of 60 ° C. The charging rate is 0.
2C, charge end voltage is 4.2V, discharge rate is 0.2
C, the discharge end voltage was 2.7 V. See Table 1 for battery categories.
It is the same as the category indicated by. From FIG. 1, it can be seen that the battery A according to the present invention has a smaller capacity decrease with the passage of cycles and has excellent characteristics as compared with the conventional battery B.
【００１７】図３は高分子ゲル電解質および高分子固体
電解質を有する本発明に係る電池Ｃ、Ｅと従来電池Ｄ、
Ｆの温度６０℃での充放電サイクル特性を比較した図で
ある。充電、放電ともに条件は図１で示したのと同一で
ある。また、電池区分は表１で示したのと同一である。
ＣとＤおよびＥとＦを比較して明かな如く、本発明に係
る電池はサイクルの経過に伴う容量の低下が小さく、優
れた特性を有している。FIG. 3 shows batteries C and E according to the present invention and a conventional battery D having a polymer gel electrolyte and a polymer solid electrolyte, respectively.
FIG. 9 is a diagram comparing charge-discharge cycle characteristics of F at a temperature of 60 ° C. The conditions for both charging and discharging are the same as those shown in FIG. The battery classification is the same as that shown in Table 1.
As is clear from comparison between C and D and between E and F, the battery according to the present invention has a small decrease in capacity with the passage of cycles and has excellent characteristics.
【００１８】表２は本発明に係る電池と従来電池をフル
充電状態にして２５０℃に昇温した時の安全性の比較を
示した表である。電池の容量は全て１０００ｍＡｈであ
る。電池の区分は前記の表１と同じである。Table 2 shows a comparison of safety when the battery according to the present invention and the conventional battery are fully charged and the temperature is raised to 250 ° C. All batteries have a capacity of 1000 mAh. The battery classification is the same as in Table 1 above.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２から明らかな如く、本発明電池は、従
来電池に比べて高い安全性を有している。As apparent from Table 2, the battery of the present invention has higher safety than the conventional battery.
【００２１】[0021]
【発明の効果】 本発明に係る非水電解質電池
は、高温での充放電性能、高温での放置性能、および異
常な高温にさらされた時の安全性に優れるもので、工業
的価値の高いものである。EFFECT OF THE INVENTION The nonaqueous electrolyte battery according to the present invention has excellent industrial value because it is excellent in charge / discharge performance at high temperatures, leaving performance at high temperatures, and safety when exposed to abnormal high temperatures. Things.
【図１】本発明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 the present invention.
【図２】本発明に係る非水電解液二次電池と従来の二次
電池の６０℃における充放電サイクル特性を比較した図
である。FIG. 2 is a diagram comparing charge / discharge cycle characteristics at 60 ° C. of a nonaqueous electrolyte secondary battery according to the present invention and a conventional secondary battery.
【図３】本発明に係る高分子ゲル電解質および高分子固
体電解質を有する二次電池と従来の二次電池の６０℃に
於ける充放電サイクル特性を比較した図である。FIG. 3 is a diagram comparing charge / discharge cycle characteristics at 60 ° C. of a secondary battery having a polymer gel electrolyte and a polymer solid electrolyte according to the present invention and a conventional secondary battery.
Claims (5)
固体電解質が、多環形脂環式炭化水素またはその誘導体
を含むことを特徴とする非水電解質電池。1. A non-aqueous electrolyte battery, wherein the electrolyte, the polymer gel electrolyte or the polymer solid electrolyte contains a polycyclic alicyclic hydrocarbon or a derivative thereof.
が、電解液、高分子ゲル電解質の溶剤成分、または高分
子固体電解質の可塑剤成分であ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 method according to claim 1, wherein the polycyclic alicyclic hydrocarbon or a derivative thereof is a solvent component of an electrolytic solution, a polymer gel electrolyte, or a plasticizer component of a polymer solid electrolyte. Water electrolyte battery.
質を構成する高分子材料が、多環形脂環式炭化水素また
はその誘導体を成分として含むことを特徴とする請求項
１記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the polymer material constituting the polymer gel electrolyte or the polymer solid electrolyte contains a polycyclic alicyclic hydrocarbon or a derivative thereof as a component. .
で表わされる基本構造を有することを特徴とする請求項
１記載の非水電解質電池。 【化１】 【化２】 【化３】 【化４】 【化５】 4. The non-aqueous electrolyte battery according to claim 1, wherein the polycyclic alicyclic hydrocarbon has a basic structure represented by the following chemical formula. Embedded image Embedded image Embedded image Embedded image Embedded image
テルまたはエーテルであることを特徴とする請求項１記
載の非水電解質電池。5. The non-aqueous electrolyte battery according to claim 1, wherein the derivative of the polycyclic alicyclic hydrocarbon is an ester or an ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06073898A JP4359942B2 (en) | 1998-03-12 | 1998-03-12 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06073898A JP4359942B2 (en) | 1998-03-12 | 1998-03-12 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11260404A true JPH11260404A (en) | 1999-09-24 |
| JP4359942B2 JP4359942B2 (en) | 2009-11-11 |
Family
ID=13150911
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06073898A Expired - Fee Related JP4359942B2 (en) | 1998-03-12 | 1998-03-12 | Non-aqueous electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP4359942B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002222663A (en) * | 2001-01-26 | 2002-08-09 | Mitsubishi Chemicals Corp | Electrolyte solution and secondary cell |
| JP2010027616A (en) * | 1999-06-30 | 2010-02-04 | Panasonic Corp | Nonaqueous electrolyte secondary battery, charging control system of nonaqueous electrolyte secondary battery, and equipment using the same |
| KR20180088143A (en) * | 2017-01-26 | 2018-08-03 | 서울대학교산학협력단 | Solid polymer electrolyte and lithium battery comprising the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07335218A (en) * | 1994-06-07 | 1995-12-22 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JPH1139941A (en) * | 1997-07-17 | 1999-02-12 | Asahi Glass Co Ltd | Polymer electrolyte and lithium battery |
| JPH1196832A (en) * | 1997-09-19 | 1999-04-09 | Asahi Glass Co Ltd | Polymer electrolyte and lithium battery |
-
1998
- 1998-03-12 JP JP06073898A patent/JP4359942B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07335218A (en) * | 1994-06-07 | 1995-12-22 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JPH1139941A (en) * | 1997-07-17 | 1999-02-12 | Asahi Glass Co Ltd | Polymer electrolyte and lithium battery |
| JPH1196832A (en) * | 1997-09-19 | 1999-04-09 | Asahi Glass Co Ltd | Polymer electrolyte and lithium battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010027616A (en) * | 1999-06-30 | 2010-02-04 | Panasonic Corp | Nonaqueous electrolyte secondary battery, charging control system of nonaqueous electrolyte secondary battery, and equipment using the same |
| JP2002222663A (en) * | 2001-01-26 | 2002-08-09 | Mitsubishi Chemicals Corp | Electrolyte solution and secondary cell |
| KR20180088143A (en) * | 2017-01-26 | 2018-08-03 | 서울대학교산학협력단 | Solid polymer electrolyte and lithium battery comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4359942B2 (en) | 2009-11-11 |
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