JPH0765855A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH0765855A JPH0765855A JP5239126A JP23912693A JPH0765855A JP H0765855 A JPH0765855 A JP H0765855A JP 5239126 A JP5239126 A JP 5239126A JP 23912693 A JP23912693 A JP 23912693A JP H0765855 A JPH0765855 A JP H0765855A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- substance
- lithium battery
- electrolyte
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム電池、特にリ
チウム二次電池に関し、繰り返し充放電性能の改良に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium battery, in particular a lithium secondary battery, and relates to improvement of repetitive charge / discharge performance.
【０００２】[0002]
【従来の技術】最近のマイクロエレクトロニクス化は、
各種電子機器のメモリーバックアップ用電源に代表され
るように、電池の電子機器内収納、エレクトロニクス素
子および回路との一体化に伴って、電池の小型化、軽量
化、薄型化とさらに高エネルギー密度を有する電池とが
強く要望されている。近年、一次電池の分野では、既に
リチウム電池などの小型、軽量の電池が実用化されてい
るが、その用途分野は限られたものである。2. Description of the Related Art Recent microelectronics is
As represented by memory backup power supplies for various electronic devices, battery storage in electronic devices and integration with electronic elements and circuits have made batteries smaller, lighter, thinner, and have a higher energy density. There is a strong demand for batteries that have them. In recent years, in the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use, but their fields of use are limited.
【０００３】そこで、従来の鉛電池、ニッケル−カドミ
ウム電池に代わる電池として、より小型軽量化が可能な
非水電解液を用いた二次電池がより注目されているが、
電極活物質のサイクル特性、自己放電特性などの実用特
性をより向上させるために現在も多くの研究機関で検討
されている。Therefore, as a battery replacing the conventional lead battery and nickel-cadmium battery, a secondary battery using a non-aqueous electrolyte, which can be made smaller and lighter, is receiving more attention.
Many research institutions are currently studying it in order to further improve practical characteristics such as cycle characteristics and self-discharge characteristics of electrode active materials.
【０００４】従来、基板や機器への電池の装着に関し、
円筒型、ボタン型といった電池形状は、機器内の体積利
用率の点で効率的とはいえず、電池は、電子機器のデザ
インを制限する大きな因子となっていた。薄型フィルム
状電池は、機器内のデッドスペースを有効に利用できる
こと、電池の形状を任意に決定できることから、電子機
器のデザインは、もはや電池に制限されることがなくな
るという点で注目されている。Conventionally, regarding the mounting of the battery on the substrate and the equipment,
The battery shape such as the cylindrical type and the button type is not efficient in terms of volume utilization in the device, and the battery has been a major factor limiting the design of electronic devices. The thin film battery has attracted attention because the dead space in the device can be effectively used and the shape of the battery can be arbitrarily determined, so that the design of the electronic device is no longer limited to the battery.
【０００５】薄型フィルム状電池の生産に当たっては、
高分子固体電解質を用いることが、電池の注液工程を無
くせることから、製造工程が大きく簡略化できるという
特徴がある。In producing a thin film battery,
The use of the polymer solid electrolyte has a feature that the manufacturing process can be greatly simplified because the liquid injection process of the battery can be eliminated.
【０００６】二次電池の電極材料としては、安全性の
面、ハイレート性能の面、サイクル可逆性の面から炭素
材料を負極に用いることが有効であり、すでに製品化さ
れている。この炭素材料の性能を充分に引き出すため
に、種々の電解液組成が検討されてきたが、毒性、安全
性の点で問題の少ない材料として、リチウム塩としては
六フッ化燐酸リチウムが注目されてきた。しかしなが
ら、この材料は環境への暴露に対して極めて不安定であ
るため、純度向上技術、取扱い中に水分の混入を避ける
技術が重要になってきた。As a secondary battery electrode material, it is effective to use a carbon material for the negative electrode from the viewpoint of safety, high rate performance and cycle reversibility, and it has already been commercialized. Various electrolytic solution compositions have been studied in order to bring out the full performance of this carbon material, but lithium hexafluorophosphate has been attracting attention as a lithium salt as a material with few problems in terms of toxicity and safety. It was However, since this material is extremely unstable when exposed to the environment, a technique for improving the purity and a technique for avoiding mixing of water during handling have become important.
【０００７】[0007]
【発明が解決しようとする課題】薄型フィルム電池の製
造には、注液工程がない代わりに高分子固体電解質もま
たシートとして扱う。このことは、リチウム塩を含んだ
材料がラインに流れることを意味する。ここに、先に述
べたような、環境への暴露に対して不安定な材料を用い
ようとするとき上記のような工程は不利な点として働
く。すなわち、フッ素化物を持った物質は、例えば水分
が混入すると、容易にフッ化水素を発生する。発生した
フッ化水素は電池系の活物質であるリチウムイオンと反
応し、ＬｉＦとなって不活性化する。例えば六フッ化燐
酸リチウムでは、 ＬｉＰＦ6 ＋ Ｈ2 Ｏ → ＰＦ5 ＋ ＬｉＯＨ ＋ ＨＦ （１）In the production of thin film batteries, the solid polymer electrolyte is also treated as a sheet instead of the injection process. This means that the material containing the lithium salt flows through the line. Here, the process described above acts as a disadvantage when trying to use a material that is unstable to environmental exposure as described above. That is, a substance having a fluorinated substance easily generates hydrogen fluoride when, for example, water is mixed. The generated hydrogen fluoride reacts with lithium ions, which are the active material of the battery system, and becomes LiF to be inactivated. For example, in lithium hexafluorophosphate, LiPF 6 + H 2 O → PF 5 + LiOH + HF (1)
【０００８】この問題は、インターカレーションまたは
インサーション型電極を正負極ともに採用する電池系の
場合、とりわけ深刻である。すなわち、一方の極に金属
リチウムのように活物質を過剰に持つことが許される電
極を具備する系と違い、正極と負極に含まれるリチウム
のトータル量が限定されており、この量が崩れることは
充放電性能に直接大きな影響を与えるからである。This problem is particularly serious in the case of a battery system in which an intercalation or insertion type electrode is used for both positive and negative electrodes. That is, unlike a system including an electrode that is allowed to have an excessive amount of active material such as metallic lithium in one electrode, the total amount of lithium contained in the positive electrode and the negative electrode is limited, and this amount may collapse. Is because it directly affects the charge and discharge performance.
【０００９】さらに、高分子固体電解質に用いるポリマ
ーや、電解液に用いる溶媒にフッソ原子を含んだ材料を
用いる場合、それらから次のような反応によって水素原
子が引き抜かれ、フッ化水素の発生に至る場合がある。 ＬｉＰＦ6 ＋ −Ｈ → ＰＦ5 ＋ −Ｌｉ ＋ ＨＦ （２）Further, when a polymer containing a fluorine atom is used for a polymer used for a polymer solid electrolyte or a solvent used for an electrolytic solution, hydrogen atoms are extracted from them by the following reaction to generate hydrogen fluoride. It may reach. LiPF 6 + -H → PF 5 + -Li + HF (2)
【００１０】一例を挙げれば、熱・光・電子線硬化によ
りポリマーを架橋させる場合に比較的一般に用いられる
アクリレート末端基は、引き抜かれ易い水素原子を持っ
ている。また、リチウム塩がフッ素原子を持っている場
合についてこれまで述べたが、ポリマーがフッ素原子を
持っている場合には、ポリマーから引き抜かれたフッ素
原子が起因して、フッ化水素の発生に至る場合がある。As one example, the acrylate end group, which is relatively commonly used when a polymer is crosslinked by heat, light, or electron beam curing, has a hydrogen atom that is easily abstracted. Also, although the case where the lithium salt has a fluorine atom has been described so far, when the polymer has a fluorine atom, the fluorine atom extracted from the polymer causes hydrogen fluoride to be generated. There are cases.
【００１１】これらの反応によって生成したフッ化水素
は、充放電中に活物質であるリチウムイオンと結合する
ため、電池容量を低下させる原因となる。The hydrogen fluoride produced by these reactions binds with lithium ions as an active material during charging and discharging, which causes a decrease in battery capacity.
【００１２】[0012]
【課題を解決するための手段】本発明は上記目的を達成
するべく、電気化学的にリチウムイオンを放出−吸蔵す
る活物質を主体とする電極を正極および負極とし、フッ
素化物を含む電解質を用いた電池に於いて、また、フッ
素化物を持ったリチウム塩を溶解している電解質を用い
た電池に於いて、また、六フッ化リン酸リチウムを溶解
している電解質を用いた電池に於いて、電池内に孤立電
子対を持った窒素、リン、硫黄原子のうち少なくとも１
以上を含む物質を含んでいることを特徴とするリチウム
電池である。また、前記孤立電子対を持った物質がアミ
ン類であるリチウム電池である。また、前記アミン類の
添加量がモル分子量でリチウム塩のモル分子量と同等以
下、好ましくはリチウム塩のモル分子量の１／１０以下
であるリチウム電池である。また、前記孤立電子対を持
った物質がピリジン環を含有する物質であるリチウム電
池である。また、前記孤立電子対を持った物質がポリビ
ニルピリジンであるリチウム電池である。また、電解質
が高分子固体電解質であるリチウム電池である。In order to achieve the above object, the present invention uses a positive electrode and a negative electrode which are mainly composed of an active material that electrochemically releases and stores lithium ions, and uses an electrolyte containing a fluorinated compound. In a battery using an electrolyte in which a lithium salt having a fluorinated compound is dissolved, and in a battery using an electrolyte in which lithium hexafluorophosphate is dissolved. , At least one of nitrogen, phosphorus and sulfur atoms with lone electron pairs in the battery
A lithium battery containing a substance containing the above. A lithium battery in which the substance having the lone electron pair is amines. Further, the lithium battery is one in which the addition amount of the amines is equal to or less than the molar molecular weight of the lithium salt in terms of molar molecular weight, and is preferably 1/10 or less of the molar molecular weight of the lithium salt. A lithium battery in which the substance having a lone electron pair is a substance containing a pyridine ring. A lithium battery in which the substance having the lone electron pair is polyvinyl pyridine. In addition, it is a lithium battery in which the electrolyte is a polymer solid electrolyte.
【００１３】ここで、電解質とは、リチウム塩を溶解し
てなる電解液や固体電解質のことをいう。Here, the electrolyte means an electrolytic solution or a solid electrolyte in which a lithium salt is dissolved.
【００１４】[0014]
【作用】フッ化水素が発生する環境下で、例えば窒素原
子上に孤立電子対を持った物質があると、次の反応によ
りフッ化水素は直ちにトラップされ、リチウムイオンを
攻撃する能力を失う。よって、上記のような機構でリチ
ウム電池の性能が低下することを防ぐ。 ＨＦ ＋ −Ｎ： → −ＮＨ−ＦIn the environment where hydrogen fluoride is generated, for example, if there is a substance having a lone electron pair on the nitrogen atom, hydrogen fluoride is immediately trapped by the next reaction and loses the ability to attack lithium ions. Therefore, it is possible to prevent the performance of the lithium battery from being deteriorated by the above mechanism. HF + -N: → -NH-F
【００１５】窒素、リン、硫黄原子上に孤立電子対を持
った物質としては、トリエチルアミン、ポリビニルピリ
ジン、トリエチルフォスフィン、トリフェニルフォスフ
ィン、ジエチルスルフィド等が挙げられるが、これらに
限定するものではない。これらの物質は共に、強い電子
供与性を持っているために上式のようにフッ化水素をト
ラップする作用が強い。Examples of the substance having a lone pair of electrons on nitrogen, phosphorus and sulfur atoms include, but are not limited to, triethylamine, polyvinylpyridine, triethylphosphine, triphenylphosphine and diethyl sulfide. . Since both of these substances have a strong electron donating property, they have a strong action of trapping hydrogen fluoride as in the above formula.
【００１６】この作用は、ＬｉＰＦ6 を塩とした場合に
とりわけ効果が高いが、ＬｉＢＦ4、ＬｉＣＦ3 Ｓ
Ｏ3 、ＬｉＮ（ＣＦ3 ＳＯ2)2 等を塩に用いた場合、あ
るいはテトラフルオロエチレン、ナフィオン等をバイン
ダーや高分子固体電解質を構成するためのポリマーに用
いた場合にも適用できる。また、孤立電子対を持った物
質を電極バインダーとして用いてもよい。This action is particularly effective when LiPF 6 is used as a salt, but LiBF 4 , LiCF 3 S
It is also applicable when O 3 , LiN (CF 3 SO 2 ) 2 or the like is used as a salt, or when tetrafluoroethylene, Nafion or the like is used as a binder or a polymer for forming a polymer solid electrolyte. Further, a substance having a lone electron pair may be used as the electrode binder.
【００１７】このとき、アミン類を例に挙げれば、これ
に含まれる窒素原子の数は、発生すると考えられる遊離
フッ素の最大量を越える必要はなく、逆に大量の添加
は、電極の充放電効率の低下、集電体の腐食を引き起こ
し、電池寿命を低下させる原因となる。また、例えば使
用しているリチウム塩の全量が分解するということは実
際の生産工程に用いる低湿度雰囲気下では現実にはな
く、リチウム塩のごく一部が上記のような反応に寄与す
るのであるから、当量添加したとしても、まだ余剰であ
る。At this time, taking amines as an example, the number of nitrogen atoms contained in the amine need not exceed the maximum amount of free fluorine that is considered to be generated. It causes a decrease in efficiency, corrosion of the current collector, and a decrease in battery life. Further, for example, the fact that the entire amount of the lithium salt used is decomposed is not realistic under the low humidity atmosphere used in the actual production process, and only a part of the lithium salt contributes to the reaction as described above. Therefore, even if the equivalent amount is added, there is still excess.
【００１８】トリエチルアミンの添加量をどこまで減ら
しても効果を発揮するかについては生産工程雰囲気水分
量にもよるが、モル分子量でリチウム塩のモル分子量の
１／１０乃至１／１００の範囲で発明者らが実験したと
ころでは、トリエチルアミンの充分な添加効果が発揮さ
れ、かつ上記のような過剰添加の欠点も見いだされなか
った。添加量が１／１０を越えると、サイクル容量カー
ブにやや遜色がみられた。これは、過剰の添加が負極活
物質の初期効率を低下させたことに起因するものと考え
られる。The extent to which the amount of triethylamine added can be reduced to obtain the effect depends on the water content in the atmosphere of the production process, but the inventor has a molar molecular weight in the range of 1/10 to 1/100 of the molar molecular weight of the lithium salt. In the experiments conducted by them, a sufficient effect of adding triethylamine was exhibited, and the above-mentioned drawbacks of excessive addition were not found. When the added amount exceeded 1/10, the cycle capacity curve was slightly dissimilar. It is considered that this is because the excessive addition reduced the initial efficiency of the negative electrode active material.
【００１９】先に述べたように、電解質が高分子固体電
解質である場合には、液式電池のように注液、すなわち
リチウム塩の導入を最終工程に持ってくることが困難で
あるため、より一層本発明の作用が効果的に発揮され
る。As described above, when the electrolyte is a polymer solid electrolyte, it is difficult to bring the solution, that is, the introduction of the lithium salt, to the final step like a liquid battery, The effect of the present invention is more effectively exhibited.
【００２０】[0020]
【実施例】実施例により、さらに詳細に説明する。以下
の実施例および比較例の実験に用いられた雰囲気は、露
点−２０℃の水分量を持つ空気雰囲気であり、リチウム
電池の組立を行うにはこの水分量では多すぎて一般に不
適当とされている雰囲気である。EXAMPLES The present invention will be described in more detail with reference to examples. The atmosphere used in the experiments of the following examples and comparative examples is an air atmosphere having a moisture content of dew point -20 ° C, and this moisture content is too large for assembling a lithium battery and is generally considered unsuitable. It is a vibrant atmosphere.
【００２１】（実施例１）γ−ブチロラクトンに１モル
／ｌのＬｉＰＦ6 を溶解させた電解液に重量平均分子量
１，０００のポリエチレンオキシドジアクリレートを
３：１の重量比で混合したものを調製した。これを以降
「モノマー液」と称する。リチウムコバルト酸化物とカ
ーボンを１０：１の割合で混合しておいたものと、０．
０２モル／ｌのトリエチルアミンを添加したモノマー液
とを１：１の重量比で混ぜ合わせ、ペースト状とし、ア
ルミニウム箔上に約３０μｍの厚みに塗布後、電子線を
照射し、正極を得た。Example 1 A mixture was prepared by mixing polyethylene oxide diacrylate having a weight average molecular weight of 1,000 at a weight ratio of 3: 1 with an electrolytic solution prepared by dissolving 1 mol / l of LiPF 6 in γ-butyrolactone. did. This is hereinafter referred to as "monomer liquid". Lithium cobalt oxide and carbon mixed at a ratio of 10: 1, and.
A monomer solution containing 02 mol / l of triethylamine was mixed at a weight ratio of 1: 1 to form a paste, which was applied on an aluminum foil to a thickness of about 30 μm and then irradiated with an electron beam to obtain a positive electrode.
【００２２】得られた正極上に、０．０２モル／ｌのト
リエチルアミンを添加したモノマー液を約３０μｍの厚
みに塗布後、電子線を照射し、セパレータ層を形成させ
た。On the obtained positive electrode, a monomer solution containing 0.02 mol / l of triethylamine was applied to a thickness of about 30 μm and then irradiated with an electron beam to form a separator layer.
【００２３】ピッチ系カーボンと、０．０２モル／ｌの
トリエチルアミンを添加したモノマー液とを１：１の重
量比で混ぜ合わせ、ペースト状とし、銅箔上に約３０μ
ｍの厚みに塗布後、電子線を照射し、負極を得、先に得
られた正極／セパレータ二層成形品と貼り合わせ、周囲
をシールし、フィルム電池とした。電極作用面積は３３
ｃｍ2 である。Pitch-based carbon and a monomer solution containing 0.02 mol / l of triethylamine were mixed at a weight ratio of 1: 1 to form a paste, and about 30 μm was formed on a copper foil.
After being applied to a thickness of m, an electron beam was irradiated to obtain a negative electrode, which was attached to the positive electrode / separator two-layer molded product obtained above and the periphery was sealed to obtain a film battery. Electrode working area is 33
cm 2 .
【００２４】この電池を、０．５ｍＡ／ｃｍ2 の電流密
度で４．３Ｖから２．７Ｖの間で放電−充電を繰り返す
サイクル試験を行った。サイクルにともなう放電容量の
変化を図１中の（１）のカーブで示す。This battery was subjected to a cycle test in which discharge-charging was repeated between 4.3 V and 2.7 V at a current density of 0.5 mA / cm 2 . The change of the discharge capacity with the cycle is shown by the curve (1) in FIG.
【００２５】（実施例２）上記実施例１において、０．
０２モル／ｌのトリエチルアミンを添加したモノマー液
の代わりに、重量平均分子量２，４００のポリビニルピ
リジン１ミリモル／ｌを溶解したモノマー液を用いたこ
と以外は実施例１と全く同様に作製したフィルム電池を
同様のサイクル試験に供した。サイクルにともなう放電
容量の変化を図１中の（２）のカーブで示す。(Embodiment 2) In the above-mentioned Embodiment 1, 0.
A film battery produced in exactly the same manner as in Example 1 except that a monomer solution in which 1 mmol / l of polyvinylpyridine having a weight average molecular weight of 2,400 was dissolved was used in place of the monomer solution in which 02 mol / l of triethylamine was added. Was subjected to the same cycle test. The curve of (2) in FIG. 1 shows the change of the discharge capacity with the cycle.
【００２６】（比較例）上記実施例１において、いづれ
の部分にもトリエチルアミンを添加しなかったこと以外
は実施例１と全く同様に作製したフィルム電池を同様の
サイクル試験に供した。サイクルにともなう放電容量の
変化を図１中の（３）のカーブで示す。Comparative Example A film battery prepared in exactly the same manner as in Example 1 except that triethylamine was not added to any of the parts in Example 1 was subjected to the same cycle test. The change of the discharge capacity with the cycle is shown by the curve (3) in FIG.
【００２７】[0027]
【発明の効果】図１に示すように、高分子固体電解質の
製造工程から固体電解質原料中に孤立電子対を持った物
質を添加しておいたものは、長期の繰り返し充放電サイ
クルに対し、高容量が安定に得られ、本発明の効果は大
である。なお、本発明では、正極及び負極に用いる電極
活物質材料の種類、固体電解質を形成するポリマー材料
の種類、リチウム塩の含有量、電池サイズについては限
定しない。As shown in FIG. 1, when a substance having a lone electron pair is added to the solid electrolyte raw material from the manufacturing process of the polymer solid electrolyte, it is A high capacity can be stably obtained, and the effect of the present invention is great. In the present invention, the types of electrode active material materials used for the positive and negative electrodes, the types of polymer materials forming the solid electrolyte, the lithium salt content, and the battery size are not limited.
【図１】カード型二次電池の充放電サイクル試験によっ
て得られた、サイクル数に対する放電容量の推移のカー
ブであり、（１）、（２）はそれぞれ本発明の実施例
１、２により作製された電池、（３）は比較例に示す方
法で作製された電池によるものである。FIG. 1 is a curve of a change in discharge capacity with respect to the number of cycles, which is obtained by a charge / discharge cycle test of a card type secondary battery, and (1) and (2) are produced by Examples 1 and 2 of the present invention, respectively. The prepared battery, (3), is a battery manufactured by the method shown in the comparative example.
Claims (8)
する活物質を主体とする電極を正極および負極とし、フ
ッ素化物を含む電解質を用いた電池に於いて、電池内に
孤立電子対を持った窒素、リン、硫黄原子のうち少なく
とも１以上を含む物質を含んでいることを特徴とするリ
チウム電池。1. A battery using an electrolyte containing a fluorinated compound, wherein an electrode mainly composed of an active material that electrochemically releases and stores lithium ions is used as a positive electrode and a negative electrode, and an isolated electron pair is present in the battery. A lithium battery containing a substance containing at least one of nitrogen, phosphorus and sulfur atoms.
する活物質を主体とする電極を正極および負極とし、フ
ッ素化物を持ったリチウム塩を溶解している電解質を用
いた電池に於いて、電池内に孤立電子対を持った窒素、
リン、硫黄原子のうち少なくとも１以上を含む物質を含
んでいることを特徴とするリチウム電池。2. A battery using an electrolyte in which a lithium salt having a fluorinated compound is dissolved, the positive electrode and the negative electrode are electrodes mainly composed of an active material that electrochemically releases and stores lithium ions. Nitrogen with a lone pair of electrons in the battery,
A lithium battery comprising a substance containing at least one of phosphorus and sulfur atoms.
ムである請求項２記載のリチウム電池。3. The lithium battery according to claim 2, wherein the lithium salt is lithium hexafluorophosphate.
である請求項１乃至３記載のリチウム電池。4. The lithium battery according to claim 1, wherein the substance having a lone electron pair is an amine.
チウム塩のモル分子量と同等以下である請求項４記載の
リチウム電池。5. The lithium battery according to claim 4, wherein the addition amount of the amines is equal to or less than the molar molecular weight of the lithium salt in terms of molar molecular weight.
環を含有する物質である請求項１乃至３記載のリチウム
電池。6. The lithium battery according to claim 1, wherein the substance having a lone electron pair is a substance containing a pyridine ring.
ピリジンである請求項１乃至３記載のリチウム電池。7. The lithium battery according to claim 1, wherein the substance having a lone electron pair is polyvinyl pyridine.
求項１乃至７記載のリチウム電池。8. The lithium battery according to claim 1, wherein the electrolyte is a solid polymer electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23912693A JP3292220B2 (en) | 1993-08-30 | 1993-08-30 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23912693A JP3292220B2 (en) | 1993-08-30 | 1993-08-30 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0765855A true JPH0765855A (en) | 1995-03-10 |
| JP3292220B2 JP3292220B2 (en) | 2002-06-17 |
Family
ID=17040177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23912693A Expired - Fee Related JP3292220B2 (en) | 1993-08-30 | 1993-08-30 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3292220B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093462A (en) * | 2000-07-14 | 2002-03-29 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| US6767671B2 (en) | 2000-07-14 | 2004-07-27 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| JP2008218326A (en) * | 2007-03-07 | 2008-09-18 | Nec Corp | Electric storage device |
| JP2009054462A (en) * | 2007-08-28 | 2009-03-12 | Furukawa Battery Co Ltd:The | Lithium-ion secondary battery |
| JP2012009284A (en) * | 2010-06-24 | 2012-01-12 | Fdk Corp | Lithium-ion secondary battery |
| CN108832149A (en) * | 2018-06-15 | 2018-11-16 | 中国计量大学 | Lithium-sulfur cell electrolyte of one kind and lithium-sulfur cell |
| JP2019186078A (en) * | 2018-04-12 | 2019-10-24 | 三井化学株式会社 | Nonaqueous electrolytic solution for battery, and lithium secondary battery |
| US10476107B2 (en) | 2016-07-28 | 2019-11-12 | Panasonic Intellectual Property Management Co., Ltd. | Battery |
-
1993
- 1993-08-30 JP JP23912693A patent/JP3292220B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093462A (en) * | 2000-07-14 | 2002-03-29 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| US6767671B2 (en) | 2000-07-14 | 2004-07-27 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| JP2008218326A (en) * | 2007-03-07 | 2008-09-18 | Nec Corp | Electric storage device |
| JP2009054462A (en) * | 2007-08-28 | 2009-03-12 | Furukawa Battery Co Ltd:The | Lithium-ion secondary battery |
| JP2012009284A (en) * | 2010-06-24 | 2012-01-12 | Fdk Corp | Lithium-ion secondary battery |
| US10476107B2 (en) | 2016-07-28 | 2019-11-12 | Panasonic Intellectual Property Management Co., Ltd. | Battery |
| JP2019186078A (en) * | 2018-04-12 | 2019-10-24 | 三井化学株式会社 | Nonaqueous electrolytic solution for battery, and lithium secondary battery |
| CN108832149A (en) * | 2018-06-15 | 2018-11-16 | 中国计量大学 | Lithium-sulfur cell electrolyte of one kind and lithium-sulfur cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3292220B2 (en) | 2002-06-17 |
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