JPH06275279A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH06275279A JPH06275279A JP5084130A JP8413093A JPH06275279A JP H06275279 A JPH06275279 A JP H06275279A JP 5084130 A JP5084130 A JP 5084130A JP 8413093 A JP8413093 A JP 8413093A JP H06275279 A JPH06275279 A JP H06275279A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- binder
- pvp
- battery
- graphite powder
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は黒鉛粉末を負極材料とし
て使用したリチウム二次電池に係わり、詳しくは黒鉛粉
末と負極集電体との密着性を向上させ、これによりサイ
クル特性を向上させることを目的とした結着剤の改良に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using graphite powder as a negative electrode material. More specifically, it improves the adhesion between the graphite powder and the negative electrode current collector, thereby improving the cycle characteristics. The present invention relates to improvement of a binder for the purpose.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池の負極材料として、充電時に樹枝状の
リチウムが電析せず内部短絡などの心配がないこと、容
量の大きい電池が得られることなどの理由から、黒鉛が
新素材として脚光を浴びつつある。2. Description of the Related Art In recent years,
As a negative electrode material for lithium secondary batteries, graphite is in the spotlight as a new material because dendritic lithium does not deposit during charging and there is no risk of internal short-circuiting, and batteries with large capacities can be obtained. It's starting.
【０００３】而して、従来、黒鉛を素材とする電極は、
例えばポリフッ化ビニリデン（ＰＶｄＦ）のＮ−メチル
ピロリドン（ＮＭＰ）溶液に黒鉛粉末を分散混合してス
ラリーとし、このスラリーを銅、ステンレス（ＳＵ
Ｓ）、ニッケル等の負極集電体（芯体；板や箔）上に塗
布し、乾燥することにより作製されていた。Thus, conventionally, the electrodes made of graphite are
For example, graphite powder is dispersed and mixed in a N-methylpyrrolidone (NMP) solution of polyvinylidene fluoride (PVdF) to form a slurry, and the slurry is prepared from copper and stainless steel (SU).
S), nickel, or the like was applied on a negative electrode current collector (core; plate or foil) and dried.
【０００４】しかしながら、ＰＶｄＦを結着剤として使
用した場合、黒鉛粉末と負極集電体との密着性が悪くて
黒鉛粉末が負極から脱落し易いため、サイクル寿命が総
じて短いなどの問題が指摘されていた。However, when PVdF is used as a binder, the adhesion between the graphite powder and the negative electrode current collector is poor, and the graphite powder easily falls off from the negative electrode, so that problems such as a short cycle life are pointed out. Was there.
【０００５】本発明は、かかる事情に鑑みなされたもの
であって、その目的とするところは、黒鉛粉末と負極集
電体との密着性が良い、サイクル寿命の長いリチウム二
次電池を提供するにある。The present invention has been made in view of the above circumstances, and an object thereof is to provide a lithium secondary battery having good adhesion between graphite powder and a negative electrode current collector and a long cycle life. It is in.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウム二次電池（以下、「本発明電
池」と称する。）は、黒鉛粉末をポリイミド（ＰＩ）と
ポリビニルピロリドン（ＰＶＰ）との複合体からなる結
着剤で結着してなる結着体が負極として使用されてな
る。In order to achieve the above object, a lithium secondary battery according to the present invention (hereinafter referred to as "the battery of the present invention") comprises graphite powder, polyimide (PI) and polyvinylpyrrolidone (PVP). ) Is used as the negative electrode.
【０００７】本発明電池においては、負極の結着剤とし
てＰＩとＰＶＰとの複合体が使用される。因みに、ＰＩ
一種単独を使用した場合は、銅、ステンレス、ニッケル
等の集電体金属との密着性については問題は無いもの
の、黒鉛粉末同士の結着性が悪く、一方ＰＶＰ単独を使
用した場合は、黒鉛粉末同士の結着性については問題は
無いものの、集電体金属との密着性が悪い。また、ＰＩ
は電解液に溶出しないが、ＰＶＰは溶出する。In the battery of the present invention, a composite of PI and PVP is used as a binder for the negative electrode. By the way, PI
When using one kind alone, there is no problem in adhesion with the collector metal such as copper, stainless steel, nickel, etc., but the binding property between graphite powders is poor, while when using PVP alone, graphite Although there is no problem with the binding property between the powders, the adhesion with the current collector metal is poor. In addition, PI
Does not elute in the electrolyte, but PVP does.
【０００８】本発明における結着剤は、上記したＰＩと
ＰＶＰとの単なる混合物ではなく、ＰＩとＰＶＰとの複
合体である。複合体中のＰＩとＰＶＰとの好適な重量比
は１：１〜１：５である。The binder in the present invention is not a mere mixture of PI and PVP as described above, but a complex of PI and PVP. The preferred weight ratio of PI to PVP in the complex is 1: 1 to 1: 5.
【０００９】ＰＩとＰＶＰとの単なる混合物が集電体金
属との密着性及び黒鉛粉末同士の結着性に関して混合比
率に応じた中間的特性しか示さないのに対して、本発明
におけるＰＩとＰＶＰとの複合体は、前記各物性に関し
てそれらを単独使用した場合以上の優れた特性を示すと
ともに、電解液に溶出することもない。While a simple mixture of PI and PVP exhibits only intermediate properties according to the mixing ratio with respect to the adhesion with the current collector metal and the binding property between graphite powders, PI and PVP in the present invention. The complex with and shows excellent properties with respect to the above physical properties as compared with the case where they are used alone, and does not elute into the electrolytic solution.
【００１０】本発明における複合体は、例えばポリアミ
ド酸のＮＭＰ溶液にさらにＰＶＰを溶かしたものを加熱
処理することにより得られる。この加熱処理により、ポ
リアミド酸が縮合（脱水縮合）してＰＩに変わるのであ
る。The composite of the present invention can be obtained, for example, by heat treating a solution of PVP in an NMP solution of polyamic acid. By this heat treatment, the polyamic acid is condensed (dehydrated condensation) and converted into PI.
【００１１】本発明における複合体は、ＰＩのイミド化
率が８０％以上のものが好ましい。ＰＩのイミド化率が
８０％未満の場合は、集電体金属との密着性が良くな
い。ここに、イミド化率とは、ＰＩ前駆体１００モルに
対する生成したＰＩのモル数である。The complex of the present invention preferably has a PI imidization ratio of 80% or more. When the imidization ratio of PI is less than 80%, the adhesion to the current collector metal is poor. Here, the imidization ratio is the number of moles of generated PI with respect to 100 moles of PI precursor.
【００１２】イミド化率８０％以上の複合体は、例えば
ポリアミド酸及びＰＶＰのＮＭＰ溶液を１００〜４００
°Ｃの温度で１時間以上加熱処理することにより得るこ
とができる。因みに、３５０°Ｃで加熱処理する場合
は、加熱処理時間約１時間でＰＩのイミド化率が８０％
となり、また約３時間で全てのポリアミド酸がＰＩとな
る（イミド化率１００％）。The composite having an imidization ratio of 80% or more is prepared by using, for example, 100 to 400 NMP solutions of polyamic acid and PVP.
It can be obtained by heat treatment at a temperature of ° C for 1 hour or more. By the way, when the heat treatment is performed at 350 ° C, the imidation ratio of PI is 80% in the heat treatment time of about 1 hour.
In addition, all the polyamic acid becomes PI in about 3 hours (imidization ratio 100%).
【００１３】本発明における負極は、黒鉛粉末を上述し
た結着剤としての複合体で結着してなる結着体である。
負極（結着体）中の結着剤の含有比率は０．１〜５重量
％が好ましい。結着剤の含有比率が０．１重量％未満の
場合は、集電体金属との密着性及び黒鉛粉末同士の結着
性が不充分となり、また５重量％を越えた場合は、内部
抵抗の増大に因る充放電効率の低下を招く。The negative electrode in the present invention is a binder obtained by binding graphite powder with the above-mentioned composite as a binder.
The content ratio of the binder in the negative electrode (binder) is preferably 0.1 to 5% by weight. If the content of the binder is less than 0.1% by weight, the adhesion with the current collector metal and the binding between the graphite powders will be insufficient, and if it exceeds 5% by weight, the internal resistance will be low. This leads to a decrease in charge / discharge efficiency due to the increase of
【００１４】上述した如く、本発明は負極の結着剤とし
てＰＩとＰＶＰとの複合体を使用した点に特徴がある。
それゆえ、電解液等の電池を構成する他の部材について
は特に制限されず、リチウム二次電池用として従来使用
され、或いは提案されている種々の材料を制限無く使用
することが可能である。As described above, the present invention is characterized in that the composite of PI and PVP is used as the binder for the negative electrode.
Therefore, other members constituting the battery such as the electrolytic solution are not particularly limited, and various materials conventionally used or proposed for lithium secondary batteries can be used without limitation.
【００１５】たとえば、電解液としては、プロピレンカ
ーボネート、エチレンカーボネート、ビニレンカーボネ
ートなどの有機溶媒や、これらとジメチルカーボネー
ト、ジエチルカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、エトキシメトキシエタ
ンなどの低沸点溶媒との混合溶媒に、ＬｉＰＦ6 、Ｌｉ
ＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 などの電解液溶質を０．７
〜１．５Ｍ（モル／リットル）、就中１Ｍの割合で溶か
した溶液が例示される。For example, the electrolytic solution may be an organic solvent such as propylene carbonate, ethylene carbonate or vinylene carbonate, or dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane or ethoxymethoxyethane. In a mixed solvent with a low boiling point solvent such as LiPF 6 , Li
Electrolyte solutes such as ClO 4 and LiCF 3 SO 3 are added to 0.7
An example is a solution dissolved at a ratio of up to 1.5 M (mol / liter), especially 1 M.
【００１６】[0016]
【作用】本発明電池においては、負極の結着剤としてＰ
ＩとＰＶＰとの複合体が使用されているので、黒鉛粉末
と集電体金属との密着性及び黒鉛粉末同士の結着性が良
好であり、このため充放電を繰り返し行っても黒鉛粉末
の負極からの脱落が殆ど無い。In the battery of the present invention, P is used as a binder for the negative electrode.
Since the composite of I and PVP is used, the adhesion between the graphite powder and the current collector metal and the binding property between the graphite powders are good, so that even if charging and discharging are repeated, the graphite powder Almost no falling off from the negative electrode.
【００１７】[0017]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００１８】（実施例１）単３型（ＡＡ）のリチウム二
次電池（本発明電池）を作製した。Example 1 AA type (AA) lithium secondary battery (the battery of the present invention) was produced.
【００１９】〔正極〕正極活物質としてのＬｉＣｏＯ2
と導電剤としての人造黒鉛とを重量比９：１で混合して
得た混合物を、ＰＩの５重量％ＮＭＰ溶液に分散させて
スラリーを調製し、このスラリーをドクターブレード法
にて正極集電体としてのアルミニウム箔の両面に塗布し
た後、３５０°Ｃで２時間真空下で加熱処理して正極を
作製した。[Positive electrode] LiCoO 2 as a positive electrode active material
And a mixture of artificial graphite as a conductive agent in a weight ratio of 9: 1 are dispersed in a 5 wt% NMP solution of PI to prepare a slurry, and this slurry is collected by a doctor blade method for collecting positive electrode current. After applying on both sides of the aluminum foil as a body, it was heat-treated under vacuum at 350 ° C. for 2 hours to produce a positive electrode.
【００２０】〔負極〕ポリアミド酸及びＰＶＰをＮＭＰ
に溶かし、２重量％溶液（ポリアミド酸：１重量％、Ｐ
ＶＰ：１重量％）を調製した。次いで、この溶液に、天
然黒鉛と結着剤（樹脂固形分）との重量比が９９．５：
０．５となるように、天然黒鉛を混合分散させてスラリ
ーとした。このスラリーをドクターブレード法により負
極集電体としての銅箔の両面に塗布した後（塗布厚み：
３６μｍ）、３５０°Ｃで２時間真空下で加熱処理して
負極を作製した。なお、この加熱処理後のＰＩのイミド
化率を赤外線（ＩＲ）吸収スペクトルにより求めたとこ
ろ、８２％であった。[Negative electrode] NMP containing polyamic acid and PVP
2% by weight solution (polyamic acid: 1% by weight, P
VP: 1 wt%) was prepared. Next, in this solution, the weight ratio of natural graphite to the binder (resin solid content) is 99.5:
Natural graphite was mixed and dispersed to give a slurry of 0.5. After applying this slurry to both sides of a copper foil as a negative electrode current collector by the doctor blade method (application thickness:
36 μm) and 350 ° C. for 2 hours under vacuum to prepare a negative electrode. The imidation ratio of PI after the heat treatment was 82% as determined by infrared (IR) absorption spectrum.
【００２１】〔電解液〕エチレンカーボネートとジメチ
ルカーボネートとの等体積混合溶媒に、ＬｉＰＦ6 を１
Ｍの割合で溶かして電解液を調製した。[Electrolytic Solution] 1 volume of LiPF 6 was added to an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate.
An electrolyte solution was prepared by dissolving the electrolyte solution at a ratio of M.
【００２２】〔電池の作製〕以上の正負両極及び電解液
を用いて単３型の本発明電池ＢＡ１を作製した。なお、
セパレータとしては、ポリプロピレン製の微多孔膜（ポ
リプラスチックス社製、商品名「セルガード」）を使用
し、これに先の電解液を注液した。[Production of Battery] AA-type battery BA1 of the present invention was produced using the above-described positive and negative electrodes and the electrolytic solution. In addition,
As the separator, a polypropylene microporous film (manufactured by Polyplastics Co., trade name "Celgard") was used, and the above electrolytic solution was injected therein.
【００２３】図１は作製した本発明電池ＢＡ１を模式的
に示す断面図であり、図示の電池ＢＡ１は、正極１、負
極２、これら両電極を離間するセパレータ３、正極リー
ド４、負極リード５、正極外部端子６、負極缶７などか
らなる。正極１及び負極２は、非水系電解液を注入され
たセパレータ３を介して渦巻き状に巻き取られた状態で
負極缶７内に収容されており、正極１は正極リード４を
介して正極外部端子６に、また負極２は負極リード５を
介して負極缶７に接続され、電池内部で生じた化学エネ
ルギーを電気エネルギーとして外部へ取り出し得るよう
になっている。FIG. 1 is a sectional view schematically showing the produced battery BA1 of the present invention. The illustrated battery BA1 includes a positive electrode 1, a negative electrode 2, a separator 3 for separating these two electrodes, a positive electrode lead 4, and a negative electrode lead 5. , Positive electrode external terminal 6, negative electrode can 7 and the like. The positive electrode 1 and the negative electrode 2 are housed in the negative electrode can 7 in a spirally wound state via the separator 3 in which the non-aqueous electrolyte solution is injected, and the positive electrode 1 is connected to the outside of the positive electrode via the positive electrode lead 4. The terminal 6 and the negative electrode 2 are connected to the negative electrode can 7 via the negative electrode lead 5 so that chemical energy generated inside the battery can be taken out as electric energy to the outside.
【００２４】（比較例１）負極の作製において、ポリア
ミド酸及びＰＶＰの２重量％ＮＭＰ溶液に代えて、ＰＶ
ｄＦの５重量％ＮＭＰ溶液を使用したこと以外は実施例
１と同様にして、比較電池ＢＣ１を作製した。(Comparative Example 1) In the preparation of the negative electrode, a 2 wt% NMP solution of polyamic acid and PVP was used instead of PV.
A comparative battery BC1 was prepared in the same manner as in Example 1 except that a 5 wt% NMP solution of dF was used.
【００２５】（比較例２）負極の作製において、ポリア
ミド酸及びＰＶＰの２重量％ＮＭＰ溶液に代えて、ＰＶ
Ｐの５重量％ＮＭＰ溶液を使用したこと以外は実施例１
と同様にして、比較電池ＢＣ２を作製した。(Comparative Example 2) In the preparation of the negative electrode, a 2 wt% NMP solution of polyamic acid and PVP was used instead of PV.
Example 1 except that a 5 wt% NMP solution of P was used
A comparative battery BC2 was produced in the same manner as in.
【００２６】（比較例３）負極の作製において、ポリア
ミド酸及びＰＶＰの２重量％ＮＭＰ溶液に代えて、ＰＩ
の１重量％ＮＭＰ溶液を使用したこと以外は実施例１と
同様にして、比較電池ＢＣ３を作製した。COMPARATIVE EXAMPLE 3 In the preparation of the negative electrode, instead of the 2 wt% NMP solution of polyamic acid and PVP, PI was used.
A comparative battery BC3 was prepared in the same manner as in Example 1 except that the 1 wt% NMP solution of 1 was used.
【００２７】〔各電池のサイクル特性〕２００ｍＡで充
電終止電圧４．２Ｖまで充電した後、２００ｍＡで放電
終止電圧２．７５Ｖまで放電する工程を１サイクルとす
るサイクル試験を行い、各電池のサイクル特性を調べ
た。結果を図２に示す。[Cycle characteristics of each battery] A cycle test is performed in which one cycle includes a process of charging to 200 V at a charge end voltage of 4.2 V and then discharging at 200 mA to a discharge end voltage of 2.75 V. I checked. The results are shown in Figure 2.
【００２８】図２は、各電池のサイクル特性を、縦軸に
電池容量（ｍＡｈ）を、横軸にサイクル数（回）をとっ
て示したグラフである。FIG. 2 is a graph showing the cycle characteristics of each battery, with the vertical axis representing the battery capacity (mAh) and the horizontal axis representing the number of cycles (times).
【００２９】同図より、ＰＩとＰＶＰとの複合体を負極
の結着剤として使用した本発明電池ＢＡ１は、ＰＶｄＦ
を使用した比較電池ＢＣ１（従来電池）に比し、黒鉛粉
末の負極からの脱落が少ないため格段優れたサイクル特
性を有することが分かる。From the figure, the battery BA1 of the present invention using the composite of PI and PVP as the binder of the negative electrode is PVdF.
It can be seen that compared with the comparative battery BC1 (conventional battery) in which No. 1 is used, the graphite powder has less falling off from the negative electrode, and thus has significantly excellent cycle characteristics.
【００３０】また、本発明電池ＢＡ１は、ＰＶＰを単独
使用した比較電池ＢＣ２及びＰＩを単独使用した比較電
池ＢＣ３に比べても、明らかに優れたサイクル特性を有
することが分かる。Further, it can be seen that the battery BA1 of the present invention has obviously excellent cycle characteristics as compared with the comparative battery BC2 using PVP alone and the comparative battery BC3 using PI alone.
【００３１】〔剥離強度〕実施例１及び比較例１〜３で
作製した各負極について、剥離強度をバネ秤を使用して
測定した。負極の表面に約０．５ｃｍ2 のヒモ付き両面
テープを貼着し、バネ秤のフックでそのヒモをかけて引
っ張り、テープが黒鉛粉末とともに集電体から引き剥が
れるときの荷重（ｋｇ／ｇ）を剥離強度とした。結果を
次の表１に示す。[Peeling Strength] The peeling strength of each negative electrode produced in Example 1 and Comparative Examples 1 to 3 was measured using a spring balance. A double-sided tape with a strap of about 0.5 cm 2 was attached to the surface of the negative electrode, and the strap was pulled with the hook of a spring balance to pull it, and the tape was peeled off from the current collector together with the graphite powder (kg / g). Was defined as the peel strength. The results are shown in Table 1 below.
【００３２】[0032]
【表１】 [Table 1]
【００３３】同表より、本発明において使用するＰＩと
ＰＶＰとの複合体は、従来のＰＶｄＦよりも優れた密着
性及び結着性を有することはもとより、ＰＩ単独又はＰ
ＶＰ単独を使用した場合と比べても格段優れていること
が分かる。From the table, it can be seen that the composite of PI and PVP used in the present invention has excellent adhesion and binding properties as compared with the conventional PVdF, as well as PI alone or P
It can be seen that it is far superior to the case of using VP alone.
【００３４】叙上の実施例では、本発明電池を単３型電
池に適用する場合について説明したが、本発明は電池形
状に特に制限はなく、扁平型、角型など、種々の形状の
リチウム二次電池に適用し得るものである。In the above examples, the case where the battery of the present invention is applied to an AA type battery has been described. However, the present invention is not particularly limited in battery shape, and lithium batteries having various shapes such as flat type and square type can be used. It can be applied to a secondary battery.
【００３５】[0035]
【発明の効果】本発明電池は、負極の黒鉛粉末の結着剤
としてＰＩとＰＶＰとの複合体が使用されているので、
黒鉛粉末の負極からの脱落が殆ど起こらず、そのためサ
イクル特性に優れるなど、本発明は優れた特有の効果を
奏する。The battery of the present invention uses a composite of PI and PVP as a binder for the graphite powder of the negative electrode.
The present invention has excellent peculiar effects such as almost no fall of graphite powder from the negative electrode and therefore excellent cycle characteristics.
【図１】単３型の本発明電池の断面図である。FIG. 1 is a sectional view of an AA battery of the present invention.
【図２】実施例１及び比較例１〜３で作製した各リチウ
ム二次電池のサイクル特性を示すグラフである。FIG. 2 is a graph showing cycle characteristics of each lithium secondary battery produced in Example 1 and Comparative Examples 1 to 3.
ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ BA1 Inventive battery 1 Positive electrode 2 Negative electrode 3 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目18番地 三洋 電機株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Toshihiko Saito 2-18 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (4)
ルピロリドン（ＰＶＰ）との複合体からなる結着剤で結
着してなる結着体が負極として使用されていることを特
徴とするリチウム二次電池。1. A lithium secondary battery characterized in that a binder obtained by binding graphite powder with a binder comprising a composite of polyimide (PI) and polyvinylpyrrolidone (PVP) is used as a negative electrode. Next battery.
０．１〜５重量％であり、当該結着剤中のポリイミド
（ＰＩ）とポリビニルピロリドン（ＰＶＰ）との重量比
が１：１〜１：５である請求項１記載のリチウム二次電
池。2. The content ratio of the binder in the binder is 0.1 to 5% by weight, and the weight ratio of polyimide (PI) and polyvinylpyrrolidone (PVP) in the binder is The lithium secondary battery according to claim 1, which has a ratio of 1: 1 to 1: 5.
０〜１００％である請求項１記載のリチウム二次電池。3. The imidization ratio of the polyimide (PI) is 8
The lithium secondary battery according to claim 1, which is 0 to 100%.
を１００〜４００°Ｃの温度で１時間以上加熱処理する
ことにより縮合させて得られたものである請求項３記載
のリチウム二次電池。4. The lithium secondary battery according to claim 3, wherein the polyimide (PI) is obtained by condensation of polyamic acid by heat treatment at a temperature of 100 to 400 ° C. for 1 hour or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08413093A JP3238980B2 (en) | 1993-03-17 | 1993-03-17 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08413093A JP3238980B2 (en) | 1993-03-17 | 1993-03-17 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06275279A true JPH06275279A (en) | 1994-09-30 |
| JP3238980B2 JP3238980B2 (en) | 2001-12-17 |
Family
ID=13821931
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08413093A Expired - Lifetime JP3238980B2 (en) | 1993-03-17 | 1993-03-17 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3238980B2 (en) |
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1993
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