JPH07320724A - Solid electrolyte battery - Google Patents
Solid electrolyte batteryInfo
- Publication number
- JPH07320724A JPH07320724A JP6131429A JP13142994A JPH07320724A JP H07320724 A JPH07320724 A JP H07320724A JP 6131429 A JP6131429 A JP 6131429A JP 13142994 A JP13142994 A JP 13142994A JP H07320724 A JPH07320724 A JP H07320724A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- polymer
- negative electrode
- electrolyte
- electrolyte battery
- 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.)
- Pending
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)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は固体電解質電池に係わ
り、詳しくは高率（大電流）での放電容量（高率放電容
量）が大きい固体電解質電池を得ることを目的とした、
負極材料の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolyte battery, and more specifically, to obtain a solid electrolyte battery having a high discharge capacity (high rate discharge capacity) at a high rate (large current).
The present invention relates to improvements in negative electrode materials.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
固体電解質電池が、漏液の心配が無いためにポジション
フリーであること、電解液の注液を必要としないために
電池の組立が容易であることなどの液体電解質電池には
無い利点があることから、注目されている。2. Description of the Related Art In recent years,
There are advantages that liquid electrolyte batteries do not have, such as solid electrolyte batteries that are position-free because there is no risk of liquid leakage, and battery assembly is easy because electrolyte injection is not required. It has been attracting attention.
【０００３】しかしながら、固体電解質のイオン伝導性
（導電率）が液体電解質のそれに比べて低く、また固体
電解質と負極の界面の接触抵抗が液体電解質と負極のそ
れに比べて大きいため、従来の固体電解質電池には、高
率放電（大電流放電）した場合、容量が低下するという
問題があった。このため、現在実用化されている固体電
解質電池は、心臓のペースメーカーの電源用に使用され
ているリチウム電池のみである。However, the ionic conductivity (conductivity) of the solid electrolyte is lower than that of the liquid electrolyte, and the contact resistance at the interface between the solid electrolyte and the negative electrode is higher than that of the liquid electrolyte and the negative electrode. The battery has a problem that its capacity decreases when it is discharged at a high rate (large current discharge). Therefore, the only solid electrolyte battery that has been put into practical use at present is the lithium battery used for the power supply of the pacemaker of the heart.
【０００４】固体電解質そのもののイオン伝導性につい
ては、例えば電解質塩の他にイオン伝導性に優れた非プ
ロトン性溶媒（液体）を高分子重合体に含有せしめてゲ
ル化することなどによりある程度改善することができる
が、固体電解質と負極の界面の接触抵抗については、有
効な解決手段が見出されていないのが実情である。The ionic conductivity of the solid electrolyte itself is improved to some extent by, for example, adding an aprotic solvent (liquid) having excellent ionic conductivity to the high molecular weight polymer in addition to the electrolyte salt to cause gelation. However, as for the contact resistance at the interface between the solid electrolyte and the negative electrode, no effective solution has been found.
【０００５】本発明は、かかる実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、固体電解質と負極
の界面の接触抵抗の小さい、すなわち高率放電容量の大
きい固体電解質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 solid electrolyte battery having a small contact resistance at the interface between the solid electrolyte and the negative electrode, that is, a large high rate discharge capacity. 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
の本発明に係る固体電解質電池（以下、「本発明電池」
と称する。）は、正極と、リチウムを吸蔵及び放出する
ことが可能な炭素材料を用いた負極と、高分子固体電解
質又は高分子ゲル状電解質とを備える固体電解質電池で
あって、前記炭素材料のｃ軸方向の結晶子の大きさ（Ｌ
ｃ）が３００Å以上であり、且つ格子面（００２）面に
おけるｄ値（ｄ002 ）が３．３７Å以下であるものであ
る。なお、高分子ゲル状電解質を用いた電池は、厳密に
はゲル状電解質電池とすべきかも知れないが、高分子ゲ
ル状電解質は見掛け上固形であるので、本明細書ではこ
れをも固体電解質電池に含める。Means for Solving the Problems A solid electrolyte battery according to the present invention for achieving the above object (hereinafter referred to as "the present battery")
Called. ) Is a solid electrolyte battery comprising a positive electrode, a negative electrode using a carbon material capable of inserting and extracting lithium, and a polymer solid electrolyte or a polymer gel electrolyte, wherein the c-axis of the carbon material is Size of crystallite in the direction (L
c) is 300 Å or more, and the d value (d 002 ) on the lattice plane (002) plane is 3.37 Å or less. The battery using the polymer gel electrolyte may be strictly a gel electrolyte battery, but since the polymer gel electrolyte is apparently solid, this is also referred to as a solid electrolyte in this specification. Include in battery.
【０００７】本発明電池においては、負極材料として、
ｃ軸方向の結晶子の大きさ（Ｌｃ）が３００Å以上であ
り、且つ格子面（００２）面におけるｄ値（ｄ002 ）が
３．３７Å以下である炭素材料が用いられる。Ｌｃが３
００Å未満又はｄ002 が３．３７Åを越えると、固体電
解質と負極との接合性が悪くなるため、両者の界面の接
触抵抗が大きくなり、高率放電容量が低下する。In the battery of the present invention, as the negative electrode material,
A carbon material having a crystallite size (Lc) in the c-axis direction of 300 Å or more and a d value (d 002 ) of 3.37 Å or less on the lattice plane (002) plane is used. Lc is 3
If it is less than 00 Å or d 002 exceeds 3.37 Å, the bondability between the solid electrolyte and the negative electrode deteriorates, so that the contact resistance at the interface between the two increases and the high rate discharge capacity decreases.
【０００８】高分子固体電解質としては、リチウムイオ
ン及び強酸のアニオンからなる電解質塩（イオン性物
質）と、酸素又は窒素を含有する高分子重合体とからな
るものが好ましい。リチウムイオン及び強酸のアニオン
からなる電解質塩の具体例としては、過塩素酸リチウム
（ＬｉＣｌＯ4 ）、トリフルオロメタンスルホン酸リチ
ウム（ＬｉＣＦ3 ＳＯ3 ）、六フッ化リン酸リチウム
（ＬｉＰＦ6 ）、四フッ化ホウ酸リチウム（ＬｉＢ
Ｆ4 ）、六フッ化ヒ酸リチウム（ＬｉＡｓＦ6 ）、六フ
ッ化アンチモン酸リチウム（ＬｉＳｂＦ6 ）、リチウム
トリフルオロメタンスルホン酸イミド〔ＬｉＮ（ＣＦ3
ＳＯ2 ）2 〕が、また酸素又は窒素を含有する高分子重
合体の具体例としては、ポリエチレンオキシド、ポリプ
ロピレンオキシド、ポリエチレンイミンが、それぞれ挙
げられる。The solid polymer electrolyte is preferably composed of an electrolyte salt (ionic substance) composed of a lithium ion and an anion of a strong acid, and a polymer polymer containing oxygen or nitrogen. Specific examples of the electrolyte salt composed of lithium ions and anions of strong acids include lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), and tetrafluoride. Lithium borate (LiB
F 4), lithium hexafluoroarsenate (LiAsF 6), lithium hexafluoro antimonate (LiSbF 6), lithium trifluoromethanesulfonate imide [LiN (CF 3
SO 2 ) 2 ], and specific examples of the high molecular weight polymer containing oxygen or nitrogen include polyethylene oxide, polypropylene oxide, and polyethyleneimine.
【０００９】高分子ゲル状電解質としては、リチウムイ
オン及び強酸のアニオンからなる電解質塩と、酸素又は
窒素を含有する高分子重合体と、非プロトン性溶媒とか
らなるものが好ましい。電解質塩、及び、酸素又は窒素
を含有する高分子重合体としては、先に挙げたものが例
示される。また、非プロトン性溶媒としては、エチレン
カーボネート（ＥＣ）、プロピレンカーボネート（Ｐ
Ｃ）、ブチレンカーボネート（ＢＣ）、γ−ブチロラク
トン（γ−ＢＬ）、スルホラン（ＳＬ）、１，２−ジメ
トキシエタン（ＤＭＥ）、１，２−ジエトキシエタン
（ＤＥＥ）、エトキシメトキシエタン（ＥＭＣ）、テト
ラヒドロフラン（ＴＨＦ）、２−メチルテトラヒドロフ
ラン（２Ｍ−ＴＨＦ）、１，３−ジオキソラン（ＤＯＸ
Ｌ）、４−メチル−１，３−ジオキソラン（４Ｍ−ＤＯ
ＸＬ）が例示される。The polymer gel electrolyte is preferably composed of an electrolyte salt containing a lithium ion and an anion of a strong acid, a polymer containing oxygen or nitrogen, and an aprotic solvent. Examples of the electrolyte salt and the high molecular weight polymer containing oxygen or nitrogen include those mentioned above. Further, as the aprotic solvent, ethylene carbonate (EC), propylene carbonate (P
C), butylene carbonate (BC), γ-butyrolactone (γ-BL), sulfolane (SL), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EMC) , Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2M-THF), 1,3-dioxolane (DOX)
L), 4-methyl-1,3-dioxolane (4M-DO
XL) is illustrated.
【００１０】[0010]
【作用】一般に高率放電においては、正極側に近い負極
の表面の炭素材料のみが充放電に関与し、極板内部の炭
素材料は充放電に関与しにくい。しかし、本発明電池に
おいては、Ｌｃ及びｄ002 が特定の範囲にある炭素材料
が負極材料として用いられているので、理由は定かでな
いが固体電解質と負極との接合性が向上して両者の界面
の接触抵抗が小さくなり、高率放電時の負極の利用率の
低下が抑制されて、高率放電容量が低下しにくくなる。In general, in high-rate discharge, only the carbon material on the surface of the negative electrode near the positive electrode side participates in charging / discharging, and the carbon material inside the electrode plate hardly participates in charging / discharging. However, in the battery of the present invention, a carbon material having Lc and d 002 in a specific range is used as the negative electrode material, so the reason why the solid electrolyte and the negative electrode are improved in bonding property is not clear. The contact resistance becomes low, the decrease in the utilization factor of the negative electrode during high-rate discharge is suppressed, and the high-rate discharge capacity is less likely to decrease.
【００１１】[0011]
【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。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１２】〔正極の作製〕正極活物質としてのコバル
ト酸リチウム（ＬｉＣｏＯ2 ）粉末と、導電剤としての
黒鉛粉末と、結着剤としてのＰＴＦＥ（ポリテトラフル
オロエチレン）とを重量比８：１：１で混合して正極合
剤を調製し、これを円板状に成形し、１００°Ｃで真空
乾燥して、正極を作製した。[Production of Positive Electrode] Lithium cobalt oxide (LiCoO 2 ) powder as a positive electrode active material, graphite powder as a conductive agent, and PTFE (polytetrafluoroethylene) as a binder in a weight ratio of 8: 1. 1 to prepare a positive electrode mixture, which was molded into a disk shape and vacuum dried at 100 ° C. to prepare a positive electrode.
【００１３】〔負極の作製〕種々のＬｃ及びｄ002 を有
する負極材料としての黒鉛粉末と、結着剤としてのＰＴ
ＦＥとを重量比９：１で混合して負極合剤を調製し、こ
れを円板状に成形し、１００°Ｃで真空乾燥して、負極
を作製した。[Production of Negative Electrode] Graphite powder as a negative electrode material having various Lc and d 002 , and PT as a binder.
A negative electrode mixture was prepared by mixing FE with a weight ratio of 9: 1, formed into a disk shape, and vacuum dried at 100 ° C. to prepare a negative electrode.
【００１４】〔固体電解質の作製〕８０°Ｃで予め真空
乾燥した平均分子量６００００のポリエチレンオキシド
と、ＬｉＣｌＯ4 （ポリエチレンオキシド中のエチレン
オキシド単位１０モル部に対して１モル部）とをアセト
ニトリルに溶かして溶液を調製し、この溶液をステンレ
ス鋼製のシャーレ上にキャストし、減圧乾燥してアセト
ニトリルを除去した後、１００°Ｃで加熱乾燥して、高
分子固体電解質を作製した。[Preparation of Solid Electrolyte] Polyethylene oxide having an average molecular weight of 60,000 previously vacuum-dried at 80 ° C. and LiClO 4 (1 part by mole with respect to 10 parts by mole of ethylene oxide unit in polyethylene oxide) were dissolved in acetonitrile. A solution was prepared, cast on a stainless steel petri dish, dried under reduced pressure to remove acetonitrile, and then dried by heating at 100 ° C. to prepare a polymer solid electrolyte.
【００１５】〔固体電解質電池の組立〕上記の正極、各
負極及び固体電解質を用いて、直径２０ｍｍ、厚さ２．
５ｍｍの扁平型固体電解質電池Ａ１〜Ａ１４（理論容
量：９０ｍＡｈ）を組み立てた。各固体電解質電池の負
極に用いた炭素材料のＬｃ及びｄ002 を表１に示す。[Assembly of Solid Electrolyte Battery] Using the above positive electrode, each negative electrode and the solid electrolyte, the diameter was 20 mm and the thickness was 2.
5 mm flat type solid electrolyte batteries A1 to A14 (theoretical capacity: 90 mAh) were assembled. Table 1 shows Lc and d 002 of the carbon material used for the negative electrode of each solid electrolyte battery.
【００１６】[0016]
【表１】 [Table 1]
【００１７】〈高率放電容量〉固体電解質電池Ａ１〜Ａ
１４について、室温（２５°Ｃ）下にて、１０ｍＡで
４．２Ｖまで充電した後、１０ｍＡで２Ｖまで放電し
て、高率放電容量を求めた。結果を図１に示す。<High rate discharge capacity> Solid electrolyte batteries A1 to A
Regarding No. 14, at room temperature (25 ° C.), it was charged to 4.2 V at 10 mA and then discharged to 2 V at 10 mA to obtain a high rate discharge capacity. The results are shown in Fig. 1.
【００１８】図１は、縦軸に放電容量（ｍＡｈ）を、ま
た横軸にｄ002 （Å）をとって示したグラフであり、同
図より、Ｌｃ及びｄ002 が本発明で規制する範囲内にあ
る炭素材料を負極に使用した固体電解質電池Ａ１〜Ａ６
（本発明電池）は、Ｌｃ及びｄ002 が上記範囲を外れる
炭素材料を負極に使用した固体電解質電池Ａ７〜Ａ１４
と比較して、高率放電容量が格段大きいことが分かる。FIG. 1 is a graph in which the vertical axis represents discharge capacity (mAh) and the horizontal axis represents d 002 (Å). From the figure, the ranges in which Lc and d 002 are regulated by the present invention are shown. Solid electrolyte batteries A1 to A6 using the carbon material therein as a negative electrode
(Invention battery) is a solid electrolyte battery A7 to A14 in which a carbon material having Lc and d 002 out of the above range is used for the negative electrode.
It can be seen that the high rate discharge capacity is much larger than that of
【００１９】[0019]
【発明の効果】負極と固体電解質の界面の接触抵抗が小
さいので、高率放電容量が大きい。Since the contact resistance at the interface between the negative electrode and the solid electrolyte is small, the high rate discharge capacity is large.
【図１】実施例で作製した各固体電解質電池の放電容量
を示したグラフである。FIG. 1 is a graph showing the discharge capacity of each solid electrolyte battery produced in an example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山崎 幹也 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikiya Yamazaki 2-5-5 Keihan Hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-5 Keihan-hondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (4)
が可能な炭素材料を用いた負極と、高分子固体電解質又
は高分子ゲル状電解質とを備える固体電解質電池であっ
て、前記炭素材料のｃ軸方向の結晶子の大きさ（Ｌｃ）
が３００Å以上であり、且つ格子面（００２）面におけ
るｄ値（ｄ002 ）が３．３７Å以下であることを特徴と
する固体電解質電池。1. A solid electrolyte battery comprising a positive electrode, a negative electrode using a carbon material capable of inserting and extracting lithium, and a polymer solid electrolyte or a polymer gel electrolyte, which comprises: Crystallite size in the c-axis direction (Lc)
Is 300 Å or more, and the d value (d 002 ) on the lattice plane (002) plane is 3.37 Å or less.
及び強酸のアニオンからなる電解質塩と、酸素又は窒素
を含有する高分子重合体とからなる請求項１記載の固体
電解質電池。2. The solid electrolyte battery according to claim 1, wherein the polymer solid electrolyte comprises an electrolyte salt composed of a lithium ion and an anion of a strong acid, and a polymer polymer containing oxygen or nitrogen.
ン及び強酸のアニオンからなる電解質塩と、酸素又は窒
素を含有する高分子重合体と、非プロトン性溶媒とから
なる請求項１記載の固体電解質電池。3. The solid according to claim 1, wherein the polymer gel electrolyte comprises an electrolyte salt composed of a lithium ion and a strong acid anion, a polymer containing oxygen or nitrogen, and an aprotic solvent. Electrolyte battery.
ド、ポリプロピレンオシキド又はポリエチレンイミンで
ある請求項２又は３記載の固体電解質電池。4. The solid electrolyte battery according to claim 2 or 3, wherein the high molecular polymer is polyethylene osquid, polypropylene osquid or polyethylene imine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6131429A JPH07320724A (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6131429A JPH07320724A (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07320724A true JPH07320724A (en) | 1995-12-08 |
Family
ID=15057758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6131429A Pending JPH07320724A (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07320724A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0729194A3 (en) * | 1995-02-02 | 1996-09-18 | Hitachi Ltd |
-
1994
- 1994-05-20 JP JP6131429A patent/JPH07320724A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0729194A3 (en) * | 1995-02-02 | 1996-09-18 | Hitachi Ltd |
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