JPH0992331A - Polymer solid electrolyte lithium secondary battery - Google Patents
Polymer solid electrolyte lithium secondary batteryInfo
- Publication number
- JPH0992331A JPH0992331A JP7242787A JP24278795A JPH0992331A JP H0992331 A JPH0992331 A JP H0992331A JP 7242787 A JP7242787 A JP 7242787A JP 24278795 A JP24278795 A JP 24278795A JP H0992331 A JPH0992331 A JP H0992331A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- polymer solid
- hydrocarbon group
- polymer
- negative electrode
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高分子固体電解質
リチウム二次電池に関するものである。TECHNICAL FIELD The present invention relates to a polymer solid electrolyte lithium secondary battery.
【０００２】[0002]
【従来の技術】電解液の液漏れを防止できる電池とし
て、固体からなる電解質を用いた固体電解質電池が知ら
れている。特に高分子化合物からなる電解質を用いた高
分子固体電解質電池は、電池反応を行うためのイオンの
伝導性が高い上、電解質が柔軟性に富んでいるため電解
質の薄膜化が可能になり、電池の厚みを薄くできる。ま
た、高分子化合物の分子設計を行うことにより各種の機
能性を得ることができる等の長所を有している。2. Description of the Related Art As a battery capable of preventing electrolyte leakage, a solid electrolyte battery using a solid electrolyte is known. In particular, a polymer solid electrolyte battery using an electrolyte composed of a polymer compound has high ion conductivity for carrying out a battery reaction, and since the electrolyte is flexible, it is possible to make the electrolyte into a thin film. Can be made thinner. Further, it has an advantage that various functionalities can be obtained by designing the molecule of the polymer compound.
【０００３】高分子固体電解質電池において、負極活物
質としてリチウムを用いると、高いエネルギーを有する
二次電池（高分子固体電解質リチウム二次電池）を得る
ことができる。しかしながら、負極活物質として純リチ
ウムを用いると、リチウムの針状結晶が負極活物質上に
析出するいわゆるデンドライトが生じる。デンドライト
が正極板に達すると電池が短絡し、電池性能が著しく低
下する。またこのような短絡が生じると過大な電流が流
れて電池が発熱し、電池の封口部に不良が生じたり、電
解質が揮発するおそれがある。そのため、電池内圧が上
昇して、最悪の場合には、電池が破裂して爆発する。When lithium is used as the negative electrode active material in the polymer solid electrolyte battery, a secondary battery having high energy (polymer solid electrolyte lithium secondary battery) can be obtained. However, when pure lithium is used as the negative electrode active material, so-called dendrite in which needle-like crystals of lithium are deposited on the negative electrode active material occurs. When the dendrite reaches the positive electrode plate, the battery is short-circuited and the battery performance is significantly reduced. Further, when such a short circuit occurs, an excessive current may flow and the battery may generate heat, which may cause a defect in the sealing portion of the battery or volatilize the electrolyte. Therefore, the internal pressure of the battery rises, and in the worst case, the battery bursts and explodes.
【０００４】そこで、負極活物質としてＬｉ−Ａｌ等の
リチウム合金を用いることが提案された。負極活物質と
してＬｉ合金を用いると電池の充電時にＬｉの合金化反
応が起こり、デンドライトの成長が抑制される。しかし
ながら、リチウムは合金にすると堅くなるため、電池の
形状が制限されてしまう。またリチウム合金を用いて
も、短絡を十分に防止することはできなかった。Therefore, it has been proposed to use a lithium alloy such as Li-Al as the negative electrode active material. When a Li alloy is used as the negative electrode active material, an Li alloying reaction occurs at the time of charging the battery, and dendrite growth is suppressed. However, lithium alloys harden, which limits the shape of the battery. Moreover, even if a lithium alloy is used, a short circuit cannot be sufficiently prevented.
【０００５】そこで、このようなデンドライトによる短
絡を防止するために、リチウムイオンの吸蔵、放出が可
能な炭素材を負極材として用いることが提案された。Therefore, in order to prevent such a short circuit due to dendrites, it has been proposed to use a carbon material capable of inserting and extracting lithium ions as a negative electrode material.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、高分子
固体電解質を用いた電池は、負極材である炭素材料にリ
チウムイオンが吸蔵されにくく、電解質に非水電解液を
用いた電池に比べて、容量が低く、充放電サイクル特性
も低い。これは、高分子電解質から炭素材料（負極材）
にリチウムイオンがスムーズに受け渡されないためであ
ると思われる。However, the battery using the polymer solid electrolyte is less likely to occlude lithium ions in the carbon material as the negative electrode material, and has a higher capacity than the battery using the non-aqueous electrolyte solution as the electrolyte. Is low and the charge / discharge cycle characteristics are also low. This is from polymer electrolyte to carbon material (negative electrode material)
It seems that lithium ions are not delivered smoothly.
【０００７】本発明の目的は、負極材である炭素材料に
リチウムイオンが吸蔵されやすく、高容量で、充放電サ
イクル寿命の長い高分子固体電解質リチウム二次電池を
提供することにある。An object of the present invention is to provide a polymer solid electrolyte lithium secondary battery which has a high capacity and a long charge / discharge cycle life, in which lithium ions are easily occluded in a carbon material as a negative electrode material.
【０００８】[0008]
【課題を解決するための手段】本発明は、炭素材料を負
極材として用いるリチウム二次電池を対象にする。本発
明では、芳香族炭化水素基及び複素芳香族炭化水素基の
少なくとも一つを有する高分子化合物からなる高分子固
体電解質を用いる。なお芳香族炭化水素基及び複素芳香
族炭化水素基は単環であってもよく、多環であってもよ
い。芳香族炭化水素基としては、スチリル基、フェニル
基、トリル基、ナフチル基、アントラニル基、ピレニル
基、ビフェニル基、フルオレニル基、フェナンスレニル
基、ビスフェノールＡ残基等がある。また複素芳香族炭
化水素基としては、ベンゾフラニル基、キノリニル基、
アクリジニル基等がある。またここでいう高分子固体電
解質とは、単に電解質層を形成する高分子固体電解質だ
けでなく、正極材層及び負極材層に含まれている高分子
固体電解質も含むものである。The present invention is directed to a lithium secondary battery using a carbon material as a negative electrode material. In the present invention, a polymer solid electrolyte composed of a polymer compound having at least one of an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group is used. The aromatic hydrocarbon group and the heteroaromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the aromatic hydrocarbon group include styryl group, phenyl group, tolyl group, naphthyl group, anthranyl group, pyrenyl group, biphenyl group, fluorenyl group, phenanthrenyl group and bisphenol A residue. As the heteroaromatic hydrocarbon group, a benzofuranyl group, a quinolinyl group,
There is an acridinyl group and the like. Further, the polymer solid electrolyte referred to herein includes not only the polymer solid electrolyte forming the electrolyte layer but also the polymer solid electrolyte contained in the positive electrode material layer and the negative electrode material layer.
【０００９】芳香族炭化水素基及び複素芳香族炭化水素
基のようにベンゼン環及びベンゼン環に類似した環を有
する基は、炭素材料（負極材）と分子構造が似ているた
め、炭素材料（負極材）と密着しやすい。そこで本発明
のように、芳香族炭化水素基及び複素芳香族炭化水素基
の少なくとも一つを有する高分子化合物からなる高分子
固体電解質を用いると、高分子固体電解質と炭素材料
（負極材）との密着性が高くなって、高分子固体電解質
と炭素材料（負極材）との間におけるリチウムイオンの
受け渡しがスムーズになる。A group having a benzene ring or a ring similar to a benzene ring, such as an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group, has a molecular structure similar to that of the carbon material (negative electrode material), and therefore the carbon material ( It is easy to adhere to the negative electrode material). Therefore, as in the present invention, when a polymer solid electrolyte composed of a polymer compound having at least one of an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group is used, a polymer solid electrolyte and a carbon material (negative electrode material) are obtained. And the adhesion of lithium ions between the polymer solid electrolyte and the carbon material (negative electrode material) becomes smooth.
【００１０】また、高分子固体電解質を芳香族炭化水素
基及び複素芳香族炭化水素基を有さない高分子化合物で
形成し、炭素材料の表面のみを芳香族炭化水素基及び複
素芳香族炭化水素基の少なくとも一つを有する高分子化
合物で覆っても同じような効果を得られるが、この場
合、炭素材料の表面を芳香族炭化水素基及び複素芳香族
炭化水素基の少なくとも一つを有する高分子化合物で覆
う必要があり、電池の製造が繁雑になる。本発明では、
高分子固体電解質全体を芳香族炭化水素基及び複素芳香
族炭化水素基の少なくとも一つを有する高分子化合物で
形成することにより、このような繁雑さをなくして、電
池の製造を容易にしている。Further, the polymer solid electrolyte is formed of a polymer compound having neither an aromatic hydrocarbon group nor a heteroaromatic hydrocarbon group, and only the surface of the carbon material is an aromatic hydrocarbon group or a heteroaromatic hydrocarbon. A similar effect can be obtained by covering with a polymer compound having at least one of the groups, but in this case, the surface of the carbon material has a high content of at least one of an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group. It needs to be covered with molecular compounds, which complicates battery manufacturing. In the present invention,
By forming the entire polymer solid electrolyte with a polymer compound having at least one of an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group, such complication can be eliminated and battery manufacturing is facilitated. .
【００１１】芳香族炭化水素基は炭素材との親和性が良
好なため、炭素材に密着しやすい。そのため、高分子化
合物として芳香族炭化水素基を側鎖に有するものを用い
ると、電極反応がスムーズに進み、電池特性が向上する
利点がある。Since the aromatic hydrocarbon group has a good affinity with the carbon material, it easily adheres to the carbon material. Therefore, when a polymer compound having an aromatic hydrocarbon group in its side chain is used, there is an advantage that the electrode reaction proceeds smoothly and the battery characteristics are improved.
【００１２】高分子化合物として、メトキシオリゴエチ
レンオキシポリフォスファゼンの側鎖のメチル基を芳香
族炭化水素基に置換したものを用いると、電極反応がス
ムーズに進む上、主鎖のポリフォスファゼンがリチウム
イオンの伝導性が高いことから、電池特性が大きく向上
する利点がある。When methoxy oligoethylene oxy polyphosphazene having a side chain methyl group substituted with an aromatic hydrocarbon group is used as the polymer compound, the electrode reaction proceeds smoothly and the main chain polyphosphazene is Since the lithium ion conductivity is high, there is an advantage that the battery characteristics are greatly improved.
【００１３】[0013]
（実施例１）図１は偏平形高分子固体電解質リチウム二
次電池に適用した本発明の実施例の断面図である。本実
施例の電池は正極集電体１の片面上に形成された正極活
物質層２と、負極集電体３の片面上に形成された負極活
物質層４とが高分子固体電解質層５を介して積層された
構造を有している。(Example 1) FIG. 1 is a sectional view of an example of the present invention applied to a flat type polymer solid electrolyte lithium secondary battery. In the battery of the present embodiment, the positive electrode active material layer 2 formed on one surface of the positive electrode current collector 1 and the negative electrode active material layer 4 formed on one surface of the negative electrode current collector 3 have the solid polymer electrolyte layer 5 It has a structure of being laminated via.
【００１４】本実施例の高分子固体電解質リチウム二次
電池は次のようにして製造した。The polymer solid electrolyte lithium secondary battery of this example was manufactured as follows.
【００１５】最初にメトキシオリゴエチレンオキシポリ
フォスファゼン（ＭＥＰ）の側鎖のメチル基をスチリル
基に置換したものを１，２−ジメトキシエタン（ＤＭ
Ｅ）に溶解した溶液（以下、単にスチリル基含有ＭＥＰ
／ＤＭＥと言う）からなる高分子固体電解質溶液を次の
ようにして作った。まずジクロロフォスファゼン３量体
をチッ素置換したガラス封管中で２５０℃で約８時間加
熱する熱開環重合を行った。これにより、重合率３０％
のポリジクロロホスファゼンができる。次にこれをガラ
ス製昇華装置に入れ、１１０℃、５mmHgで約４時間昇華
して未重合のジクロロフォスファゼンを除去し、高純度
のポリジクロロホスファゼンを得た。次にオリゴエチレ
ングリコールモノメチルエーテル１モルと、スチレンに
オリゴエチレングリコールをマイケル付加させたオリゴ
エチレングリコールモノスチリルエーテル１モルとを混
合した混合物と、ナトリウム４０ｇを裁断してＴＨＦ溶
液に分散させた分散溶液とを用意した。そしてこの分散
溶液中に前述の混合物を徐々に滴下し、室温において４
時間、５５℃において２時間反応させてアルコラート溶
液を作った。First, 1,2-dimethoxyethane (DM) was prepared by substituting the methyl group of the side chain of methoxyoligoethyleneoxypolyphosphazene (MEP) with a styryl group.
E) dissolved in solution (hereinafter, simply styryl group-containing MEP
/ DME) was prepared as follows. First, the dichlorophosphazene trimer was subjected to thermal ring-opening polymerization by heating at 250 ° C. for about 8 hours in a glass sealed tube substituted with nitrogen. This gives a polymerization rate of 30%
Polydichlorophosphazene can be obtained. Next, this was placed in a glass sublimation apparatus and sublimated at 110 ° C. and 5 mmHg for about 4 hours to remove unpolymerized dichlorophosphazene to obtain high-purity polydichlorophosphazene. Next, a mixture of 1 mol of oligoethylene glycol monomethyl ether and 1 mol of oligoethylene glycol monostyryl ether obtained by Michael-adding oligoethylene glycol to styrene, and a dispersion solution in which 40 g of sodium was cut and dispersed in a THF solution. And prepared. Then, the above mixture was gradually added dropwise to this dispersion solution, and the mixture was mixed at room temperature with 4
The alcoholate solution was prepared by reacting at 55 ° C. for 2 hours.
【００１６】次に前述のポリジクロロホスファゼン１０
０ｇを２リットルのトルエンに溶解した。その後、この
溶解中に２０〜３０℃において、前述のアルコラート溶
液を滴下した後、約６０℃で８時間の置換反応を行っ
た。置換反応完了後、希塩酸により中和してから、減圧
濃縮後、水を加えて限外ろ過装置により脱塩及び未反応
原料の除去を行った。次に水を濃縮除去してから、ＤＭ
Ｅを加えて、共沸脱水により水を５０〜１００ｐｐｍま
で更に除去した。その後、脱水したＤＭＥとＬｉＣｌＯ
4 を溶解したＤＭＥとを加えてスチリル基含有ＭＥＰ／
ＤＭＥを完成した。スチリル基含有ＭＥＰ／ＤＭＥに含
まれるスチリル基含有ＭＥＰ（高分子固体電解質）は次
の式を有している。Next, the above-mentioned polydichlorophosphazene 10
0 g was dissolved in 2 liters of toluene. Then, after adding the above-mentioned alcoholate solution at 20-30 degreeC during this melt | dissolution, the substitution reaction was performed at about 60 degreeC for 8 hours. After the substitution reaction was completed, the reaction mixture was neutralized with dilute hydrochloric acid, concentrated under reduced pressure, water was added, and desalting and removal of unreacted raw materials were performed by an ultrafiltration device. Next, water is concentrated and removed, and then DM
E was added to further remove water to 50-100 ppm by azeotropic dehydration. Then dehydrated DME and LiClO
DME in which 4 was dissolved and styryl group-containing MEP /
DME completed. The styryl group-containing MEP (polymer solid electrolyte) contained in the styryl group-containing MEP / DME has the following formula.
【００１７】[0017]
【化１】 このようにスチリル基含有ＭＥＰは、ＭＥＰの側鎖のメ
チル基がスチリル基に置換された構造を有している。Embedded image As described above, the styryl group-containing MEP has a structure in which the methyl group on the side chain of the MEP is substituted with the styryl group.
【００１８】次に正極板を作った。まず、ＬｉＣｏＯ2
粉末とカーボンブラックとを１８：１５の重量比で混合
してから真空乾燥した。次にこれとスチリル基含有ＭＥ
Ｐ／ＤＭＥ（高分子固体電解質溶液）とをドライボック
ス中で混合してからＤＭＥを揮発させた。その後、これ
を混練したものをロールプレスでステンレス箔からなる
正極集電体１に、該正極集電体１の周縁部を残すように
正極集電体シ−ト状に貼り付けて正極材層２を形成した
正極板（１５ｍＡｈ）を完成した。Next, a positive electrode plate was prepared. First, LiCoO 2
The powder and carbon black were mixed in a weight ratio of 18:15 and then vacuum dried. Next, this and styryl group-containing ME
P / DME (polymer solid electrolyte solution) was mixed in a dry box, and then DME was volatilized. Then, the kneaded product is roll-pressed to a positive electrode current collector 1 made of stainless steel foil and attached in a positive electrode current collector sheet shape so as to leave a peripheral portion of the positive electrode current collector 1, and a positive electrode material layer. The positive electrode plate (15 mAh) on which No. 2 was formed was completed.
【００１９】次に負極板を作った。まず、日本黒鉛製の
黒鉛粉末（ＪＳＰ）とスチリル基含有ＭＥＰ／ＤＭＥ
（高分子固体電解質溶液）とを７０：３０の重量比で混
合してからＤＭＥを揮発させた。その後、これを混練し
たものをロールプレスでステンレス箔からなる負極集電
体３に、該負極集電体３の周縁部を残すようにシ−ト状
に貼り付けて負極材層４を形成した負極板（１５ｍＡ
ｈ）を完成した。Next, a negative electrode plate was prepared. First, graphite powder (JSP) made by Nippon Graphite and styryl group-containing MEP / DME
(Polymer solid electrolyte solution) was mixed at a weight ratio of 70:30, and then DME was volatilized. Then, the kneaded material was roll-pressed to a negative electrode current collector 3 made of stainless steel foil and attached in a sheet shape so as to leave a peripheral portion of the negative electrode current collector 3 to form a negative electrode material layer 4. Negative electrode plate (15 mA
h) was completed.
【００２０】次に正極板の正極材層の上に前述のスチリ
ル基含有ＭＥＰ／ＤＭＥ（高分子固体電解質溶液）を塗
布してからＤＭＥを揮発させて高分子固体電解質半部を
形成すると共に、正極集電体１の周縁部にポリオレフィ
ン系樹脂からなる封止材半部を熱溶着して電池の正極板
側半部を作った。次に負極板の負極材層４の上にもスチ
リル基含有ＭＥＰ／ＤＭＥを塗布してからＤＭＥを揮発
させて高分子固体電解質半部を形成すると共に、負極集
電体の周縁部にポリオレフィン系樹脂からなる封止材半
部を熱溶着して電池の負極板側半部を作った。Next, the aforementioned styryl group-containing MEP / DME (polymer solid electrolyte solution) is applied onto the positive electrode material layer of the positive electrode plate, and then DME is volatilized to form a polymer solid electrolyte half portion. Half of the sealing material made of polyolefin resin was heat-welded to the peripheral portion of the positive electrode current collector 1 to form the half of the positive electrode plate side of the battery. Next, the styryl group-containing MEP / DME is also applied on the negative electrode material layer 4 of the negative electrode plate, and then DME is volatilized to form a polymer solid electrolyte half part, and at the same time, a polyolefin-based material is applied to the peripheral part of the negative electrode current collector. Half of the sealing material made of resin was heat-welded to form the half of the battery on the negative electrode plate side.
【００２１】次に電池の正極板側半部と電池の負極板側
半部とを接合して封止材半部を相互に溶着させて本実施
例の高分子固体電解質リチウム二次電池を完成した。Next, the positive electrode plate side half of the battery and the negative electrode plate side half of the battery are joined and the sealing material half is welded to each other to complete the solid polymer electrolyte lithium secondary battery of this embodiment. did.
【００２２】（実施例２）本実施例の電池は、下記の式
に示すようにスチリル基の代りにフェニル基でＭＥＰの
側鎖のメチル基を置換した高分子化合物で高分子固体電
解質を形成したもので、その他は、実施例１と同じ構造
を有している。(Example 2) In the battery of this example, a polymer solid electrolyte is formed by a polymer compound in which a methyl group on the side chain of MEP is substituted with a phenyl group instead of a styryl group as shown in the following formula. Other than that, it has the same structure as the first embodiment.
【００２３】[0023]
【化２】 本実施例の電池は、「スチレンにオリゴエチレングリコ
ールをマイケル付加させたオリゴエチレングリコールモ
ノスチリルエーテル」の代りに「フェノールにエチレン
オキシドを付加させたオリゴエチレングリコールモノフ
ェニルエーテル」を用い、その他は実施例１と同様にし
て製造した。Embedded image In the battery of this example, "oligoethylene glycol monophenyl ether obtained by adding ethylene oxide to phenol" was used in place of "oligoethylene glycol monostyryl ether obtained by Michael addition of oligoethylene glycol to styrene". It was produced in the same manner as 1.
【００２４】（実施例３）本実施例の電池は、下記の式
に示すようにスチリル基の代りにナフチル基でＭＥＰの
側鎖のメチル基を置換した高分子化合物で高分子固体電
解質を形成したもので、その他は、実施例１と同じ構造
を有している。(Embodiment 3) In the battery of this embodiment, a polymer solid electrolyte is formed by a polymer compound in which a methyl group on the side chain of MEP is replaced with a naphthyl group instead of a styryl group as shown in the following formula. Other than that, it has the same structure as the first embodiment.
【００２５】[0025]
【化３】 本実施例の電池は、フェノールの代りにナフトールを用
い、その他は実施例２と同様にして製造した。Embedded image The battery of this example was manufactured in the same manner as in Example 2 except that naphthol was used instead of phenol.
【００２６】（実施例４）本実施例の電池は、下記の
（Ａ）の式と（Ｂ）の式の共重合体からなる高分子化合
物で高分子固体電解質を形成したもので、その他は、実
施例１と同じ構造を有している。(Example 4) The battery of this example is one in which a polymer solid electrolyte is formed from a polymer compound composed of the copolymers of the formulas (A) and (B) below. , Has the same structure as that of the first embodiment.
【００２７】[0027]
【化４】 本実施例で用いる高分子固体電解質は次のようにして作
った。まずオリゴエチレングリコールモノフェニルエー
テル［ＨＯ（ＣＨ2 ＣＨ2 Ｏ）m Ｃ6 Ｈ5 ］０．１モル
とオリゴエチレングリコールモノメチルエーテル［ＨＯ
（ＣＨ2 ＣＨ2Ｏ）ｌＣＨ3 ］０．１モルとトリエチル
アミン２．２モルとの混合物をトルエンに溶解した。こ
れに、氷冷下において、メタクリル酸クロリド２．２モ
ルのトルエン溶液を滴下した。滴下後、徐々に昇温して
光を遮った状態でハイドロキノンモノメチルエーテルを
１重量％添加して５０℃で６時間反応を行った。反応
後、水洗、脱水、濃縮を行い、これに約０．５％のベン
ゾイルパーオキシドを添加してから、８０〜１００℃で
５〜１５分加熱重合して高分子固体電解質を完成した。Embedded image The polymer solid electrolyte used in this example was prepared as follows. First, 0.1 mol of oligoethylene glycol monophenyl ether [HO (CH 2 CH 2 O) m C 6 H 5 ] and oligoethylene glycol monomethyl ether [HO
A mixture of 0.1 mol of (CH 2 CH 2 O) 1 CH 3 ] and 2.2 mol of triethylamine was dissolved in toluene. To this, a toluene solution of 2.2 mol of methacrylic acid chloride was added dropwise under ice cooling. After the dropping, 1% by weight of hydroquinone monomethyl ether was added while the temperature was gradually raised and the light was shielded, and the reaction was carried out at 50 ° C. for 6 hours. After the reaction, the product was washed with water, dehydrated and concentrated, and about 0.5% of benzoyl peroxide was added thereto, followed by heat polymerization at 80 to 100 ° C. for 5 to 15 minutes to complete a solid polymer electrolyte.
【００２８】（実施例５）本実施例の電池は、下記の
（Ａ）の式と（Ｂ）の式の共重合体からなる高分子化合
物で高分子固体電解質を形成したもので、その他は、実
施例１と同じ構造を有している。(Embodiment 5) The battery of this embodiment is one in which a polymer solid electrolyte is formed of a polymer compound composed of the copolymers of the formulas (A) and (B) below. , Has the same structure as that of the first embodiment.
【００２９】[0029]
【化５】 本実施例で用いる高分子固体電解質は、オリゴエチレン
グリコールモノフェニルエーテルの代りにオリゴエチレ
ングリコールモノ（Ｎ−メチル−Ｎ−フェニルアミノエ
チル）エーテルを用い、その他は、実施例４と同様にし
て作った。Embedded image The solid polymer electrolyte used in this example was prepared in the same manner as in Example 4, except that oligoethylene glycol mono (N-methyl-N-phenylaminoethyl) ether was used instead of oligoethylene glycol monophenyl ether. It was
【００３０】（実施例６）本実施例の電池は、下記の
（Ａ）の式と（Ｂ）の式の共重合体からなる高分子化合
物で高分子固体電解質を形成したもので、その他は、実
施例１と同じ構造を有している。(Example 6) The battery of this example is one in which a polymer solid electrolyte is formed from a polymer compound composed of the copolymers of the formulas (A) and (B) below. , Has the same structure as that of the first embodiment.
【００３１】[0031]
【化６】 本実施例で用いる高分子固体電解質は、４−（エンドメ
トキシ−オリゴエチレンオキシ）スチレンとメタクリル
酸エンドメトキシオリゴエチレングリコールエステルと
を共重合させて作った。[Chemical 6] The polymer solid electrolyte used in this example was produced by copolymerizing 4- (endomethoxy-oligoethyleneoxy) styrene and methacrylic acid endomethoxyoligoethylene glycol ester.
【００３２】（比較例１）本比較例の電池は、下記の式
に示すようにＭＥＰ（スチリル基を含有しないもの）で
高分子固体電解質を形成したもので、その他は、実施例
１と同じ構造を有している。(Comparative Example 1) The battery of this comparative example is the same as that of Example 1 except that the polymer solid electrolyte is formed of MEP (containing no styryl group) as shown in the following formula. It has a structure.
【００３３】[0033]
【化７】 次に上記各電池に２５μA/cm2 の電流密度で４．２Ｖま
で行う充電と、同じ電流密度で２．８Ｖまで行う放電と
を繰り返し、各電池の充放電特性を調べた。図２はその
測定結果を示している。本図より上記実施例１〜６の電
池は、比較例１の電池に比べて容量が高く、しかも充放
電サイクル寿命を延ばせることが分る。なお、上記実施
例では、側鎖に芳香族炭化水素基を有する高分子化合物
からなる高分子固体電解質を用いた電池の例を示した
が、本発明はこれに限定されるものではなく、下記式に
示すように主鎖に芳香族炭化水素基を有する高分子化合
物からなる高分子固体電解質を用いても構わない。[Chemical 7] Next, the charging and discharging characteristics of each battery were examined by repeating charging to each battery at a current density of 25 μA / cm 2 up to 4.2 V and discharging at the same current density up to 2.8 V. FIG. 2 shows the measurement results. It can be seen from this figure that the batteries of Examples 1 to 6 have higher capacities than the batteries of Comparative Example 1 and can extend the charge / discharge cycle life. In the above examples, an example of a battery using a polymer solid electrolyte made of a polymer compound having an aromatic hydrocarbon group in the side chain is shown, but the present invention is not limited to this, and A solid polymer electrolyte composed of a polymer compound having an aromatic hydrocarbon group in the main chain as shown in the formula may be used.
【００３４】[0034]
【化８】 Embedded image
【化９】 また本発明は、下記式に示すエンド−２−ピリジルオキ
シ−オリゴエチレンオキシメタクリレートように複素芳
香族炭化水素基を有する高分子化合物からなる高分子固
体電解質を用いても構わない。Embedded image Further, in the present invention, a polymer solid electrolyte composed of a polymer compound having a heteroaromatic hydrocarbon group such as endo-2-pyridyloxy-oligoethyleneoxymethacrylate represented by the following formula may be used.
【００３５】[0035]
【化１０】 また本発明は、下記（Ａ）の式と（Ｂ）の式の共重合体
に示すように芳香族炭化水素基と複素芳香族炭化水素基
の両方を有する高分子化合物からなる高分子固体電解質
を用いても構わない。Embedded image The present invention also provides a solid polymer electrolyte comprising a polymer compound having both an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group as shown in the copolymers of the following formulas (A) and (B). May be used.
【００３６】[0036]
【化１１】 なお本実施例では、負極材の炭素材料として黒鉛を用い
たが、炭素材料はリチウムイオンを吸蔵、放出できるも
のえあれば、他のものを用いても構わない。Embedded image In this example, graphite was used as the carbon material of the negative electrode material, but other carbon materials may be used as long as they can store and release lithium ions.
【００３７】以下、明細書に記載した複数の発明の中で
いくつかの発明についてその構成を示す。The structure of some of the inventions described in the specification will be shown below.
【００３８】（１） 炭素材料を負極材として用いる高
分子固体電解質リチウム二次電池において、メトキシオ
リゴエチレンオキシポリフォスファゼンの側鎖にあるメ
チル基をスチリル基に置換したものを高分子固体電解質
として用いることを特徴とする高分子固体電解質リチウ
ム二次電池。(1) Polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material, wherein a methyl group in the side chain of methoxyoligoethyleneoxypolyphosphazene is replaced with a styryl group as a polymer solid electrolyte. A polymer solid electrolyte lithium secondary battery characterized by being used.
【００３９】（２） 炭素材料を負極材として用いる高
分子固体電解質リチウム二次電池において、メトキシオ
リゴエチレンオキシポリフォスファゼンの側鎖にあるメ
チル基をフェニル基に置換したものを高分子固体電解質
として用いることを特徴とする高分子固体電解質リチウ
ム二次電池。(2) A polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material, in which a methyl group in the side chain of methoxyoligoethyleneoxypolyphosphazene is replaced with a phenyl group as a polymer solid electrolyte. A polymer solid electrolyte lithium secondary battery characterized by being used.
【００４０】（３） 炭素材料を負極材として用いる高
分子固体電解質リチウム二次電池において、メトキシオ
リゴエチレンオキシポリフォスファゼンの側鎖にあるメ
チル基をナフチル基に置換したものを高分子固体電解質
として用いることを特徴とする高分子固体電解質リチウ
ム二次電池。(3) Polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material. A polymer solid electrolyte obtained by substituting a methyl group in the side chain of methoxyoligoethyleneoxypolyphosphazene with a naphthyl group. A polymer solid electrolyte lithium secondary battery characterized by being used.
【００４１】（４） 炭素材料を負極材として用いる高
分子固体電解質リチウム二次電池において、式（Ａ）と
式（Ｂ）との共重合体からなる高分子化合物を高分子固
体電解質として用いることを特徴とする高分子固体電解
質リチウム二次電池。(4) Polymer solid electrolyte using a carbon material as a negative electrode material In a lithium secondary battery, a polymer compound comprising a copolymer of formula (A) and formula (B) is used as a polymer solid electrolyte. Polymer solid electrolyte lithium secondary battery characterized by:
【００４２】[0042]
【化１２】 （５） 炭素材料を負極材として用いる高分子固体電解
質リチウム二次電池において、式（Ａ）と式（Ｂ）との
共重合体からなる高分子化合物を高分子固体電解質とし
て用いることを特徴とする高分子固体電解質リチウム二
次電池。[Chemical 12] (5) In a polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material, a polymer compound comprising a copolymer of formula (A) and formula (B) is used as a polymer solid electrolyte. Polymer solid electrolyte lithium secondary battery.
【００４３】[0043]
【化１３】 （６） 炭素材料を負極材として用いる高分子固体電解
質リチウム二次電池において、式（Ａ）と式（Ｂ）との
共重合体からなる高分子化合物を高分子固体電解質とし
て用いることを特徴とする高分子固体電解質リチウム二
次電池。Embedded image (6) In a polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material, a polymer compound comprising a copolymer of formula (A) and formula (B) is used as a polymer solid electrolyte. Polymer solid electrolyte lithium secondary battery.
【００４４】[0044]
【化１４】 Embedded image
【００４５】[0045]
【発明の効果】芳香族炭化水素基及び複素芳香族炭化水
素基のようにベンゼン環及びベンゼン環に類似した環を
有する基は、炭素材料（負極材）と分子構造が似ている
ため、炭素材料（負極材）と密着しやすい。本発明によ
れば、芳香族炭化水素基及び複素芳香族炭化水素基の少
なくとも一つを有する高分子化合物からなる高分子固体
電解質を用いるので、高分子固体電解質と炭素材料（負
極材）と密着性が高くなって、高分子固体電解質と炭素
材料（負極材）との間におけるリチウムイオンの受け渡
しがスムーズになる。そのため、本発明によれば、高容
量で、サイクル寿命の長い電池を得ることができる。EFFECTS OF THE INVENTION A group having a benzene ring or a ring similar to a benzene ring, such as an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group, has a molecular structure similar to that of a carbon material (negative electrode material), and therefore has a carbon Easily adheres to the material (negative electrode material). According to the present invention, since the solid polymer electrolyte composed of the polymer compound having at least one of the aromatic hydrocarbon group and the heteroaromatic hydrocarbon group is used, the solid polymer electrolyte and the carbon material (negative electrode material) are adhered to each other. As a result, the lithium ion is smoothly transferred between the polymer solid electrolyte and the carbon material (negative electrode material). Therefore, according to the present invention, a battery having a high capacity and a long cycle life can be obtained.
【図１】 本発明の実施例の高分子固体電解質リチウム
二次電池の断面図である。FIG. 1 is a cross-sectional view of a polymer solid electrolyte lithium secondary battery of an example of the present invention.
【図２】 試験に用いた電池のサイクル寿命特性を示す
図である。FIG. 2 is a diagram showing cycle life characteristics of a battery used in a test.
１ 正極集電体 ２ 正極活物質層 ３ 負極集電体 ４ 負極活物質層 ５ 高分子固体電解質層 1 Positive Electrode Current Collector 2 Positive Electrode Active Material Layer 3 Negative Electrode Current Collector 4 Negative Electrode Active Material Layer 5 Polymer Solid Electrolyte Layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小牧 昭夫 東京都新宿区西新宿二丁目１番１号 新神 戸電機株式会社内 (72)発明者 笹岡 三千雄 徳島県徳島市川内町加賀須野463番地 大 塚化学株式会社徳島研究所内 (72)発明者 中長 偉文 徳島県徳島市川内町加賀須野463番地 大 塚化学株式会社徳島研究所内 (72)発明者 犬伏 昭嘉 徳島県徳島市川内町加賀須野463番地 大 塚化学株式会社徳島研究所内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Akio Komaki 2-1-1, Nishi-Shinjuku, Shinjuku-ku, Tokyo Within Shinjin Todenki Co., Ltd. (72) Inventor Michio Sasaoka 463 Kagasuno, Kawauchi-cho, Tokushima, Tokushima Prefecture Otsuka Chemical Co., Ltd.Tokushima Research Institute (72) Inventor Weibun Nakano 463, Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima Research Institute (72) Inventor, Akiyoshi Inubushi, Kagasuno, Tokushima City 463 Otsuka Chemical Co., Ltd. Tokushima Laboratory
Claims (3)
体電解質リチウム二次電池において、 芳香族炭化水素基及び複素芳香族炭化水素基の少なくと
も一つを有する高分子化合物からなる高分子固体電解質
を用いることを特徴とする高分子固体電解質リチウム二
次電池。1. A polymer solid electrolyte lithium secondary battery using a carbon material as a negative electrode material, comprising a polymer solid electrolyte comprising a polymer compound having at least one of an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group. A polymer solid electrolyte lithium secondary battery characterized by being used.
素基を側鎖に有していることを特徴とする請求項１に記
載の高分子固体電解質リチウム二次電池。2. The polymer solid electrolyte lithium secondary battery according to claim 1, wherein the polymer compound has the aromatic hydrocarbon group in a side chain.
ゴエチレンオキシポリフォスファゼンの側鎖のメチル基
を芳香族炭化水素基に置換したものを用いることを特徴
とする請求項２に記載の高分子固体電解質リチウム二次
電池。3. The polymer solid according to claim 2, wherein the polymer compound is methoxyoligoethyleneoxypolyphosphazene having a side chain methyl group substituted with an aromatic hydrocarbon group. Electrolyte lithium secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24278795A JP3524651B2 (en) | 1995-09-21 | 1995-09-21 | Polymer solid electrolyte lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24278795A JP3524651B2 (en) | 1995-09-21 | 1995-09-21 | Polymer solid electrolyte lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0992331A true JPH0992331A (en) | 1997-04-04 |
| JP3524651B2 JP3524651B2 (en) | 2004-05-10 |
Family
ID=17094293
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24278795A Expired - Fee Related JP3524651B2 (en) | 1995-09-21 | 1995-09-21 | Polymer solid electrolyte lithium secondary battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8227135B2 (en) * | 2005-03-29 | 2012-07-24 | Toyota Motor Corporation | Electrolytes to enhance oxygen reduction reaction (ORR) in the cathode layer of PEM fuel cell |
-
1995
- 1995-09-21 JP JP24278795A patent/JP3524651B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8227135B2 (en) * | 2005-03-29 | 2012-07-24 | Toyota Motor Corporation | Electrolytes to enhance oxygen reduction reaction (ORR) in the cathode layer of PEM fuel cell |
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|---|---|
| JP3524651B2 (en) | 2004-05-10 |
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