JP2664477B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2664477B2 JP2664477B2 JP1127303A JP12730389A JP2664477B2 JP 2664477 B2 JP2664477 B2 JP 2664477B2 JP 1127303 A JP1127303 A JP 1127303A JP 12730389 A JP12730389 A JP 12730389A JP 2664477 B2 JP2664477 B2 JP 2664477B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- aqueous electrolyte
- negative electrode
- solute
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は非水系電解液電池に関し、特にその非水系電
解液の溶質に関するものである。The present invention relates to a non-aqueous electrolyte battery, and more particularly to a solute of the non-aqueous electrolyte.
（ロ） 従来の技術 リチウム又はリチウム合金等を負極に用いた非水系電
解液電池は、高エネルギー密度で低自己放電率であると
いう特徴を有する。近年、この種電池が広く普及するに
つれて、この種電池の低温特性の改善が望まれている。(B) Conventional technology A non-aqueous electrolyte battery using lithium or a lithium alloy or the like as a negative electrode is characterized by a high energy density and a low self-discharge rate. In recent years, with the widespread use of this type of battery, it has been desired to improve the low-temperature characteristics of this type of battery.
そこで電解液の溶質として、非水系溶媒に対する溶解
度が高く、低温放電時に負極上にリチウムが析出するこ
とのないトリフルオロメタンスルホン酸リチウム（LiCF
3SO3）を用いることにより、この種電池の低温放電特性
を改良することが提案されている（例えば特公昭61−51
387号公報、特公昭63−52749号公報等参照）。Therefore, as a solute of the electrolyte, lithium trifluoromethanesulfonate (LiCF), which has high solubility in non-aqueous solvents and does not deposit lithium on the negative electrode during low-temperature discharge,
By using 3 SO 3), it has been proposed to improve the low-temperature discharge characteristics of each type cell (e.g. Japanese Patent Publication 61-51
387, Japanese Patent Publication No. 63-52749, etc.).
（ハ） 発明が解決しようとする課題 しかしながら、上記トリフルオロメタンスルホン酸リ
チウム（LiCF3SO3）を溶質として用いた場合は、LiCF3S
O3からイオン化したフッ素と活性な負極のリチウムとが
電池の保存中に反応して、負極表面に不働態であるフッ
化リチウムの被膜が生成する。このため、電池の内部抵
抗が増大し、長期保存後の低温放電特性が悪くなるとい
う問題を有していた。(C) Problems to be Solved by the Invention However, when the above-mentioned lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is used as a solute, LiCF 3 S
Fluorine ionized from O 3 reacts with active lithium of the negative electrode during storage of the battery to form a passive lithium fluoride film on the negative electrode surface. For this reason, there has been a problem that the internal resistance of the battery increases and the low-temperature discharge characteristics after long-term storage deteriorate.
そこで本発明はかかる問題点に鑑みてなされたもので
あって、低温放電特性、特に長期保存後の低温放電特性
の改善された非水系電解液電池を提供しようとするもの
である。The present invention has been made in view of such a problem, and an object of the present invention is to provide a non-aqueous electrolyte battery having improved low-temperature discharge characteristics, particularly low-temperature discharge characteristics after long-term storage.
（ニ） 課題を解決するための手段 本発明の非水系電解液電池は、リチウム或いはリチウ
ム合金よりなる負極と、正極と、溶媒及び溶質からなる
非水系電解液とを有する電池において、前記溶質とし
て、トリフルオロメタンスルホン酸リチウムを除くトリ
ハロゲン化メタンスルホン酸リチウムを用いたことを特
徴とするものである。(D) Means for Solving the Problems A non-aqueous electrolyte battery of the present invention is a battery having a negative electrode made of lithium or a lithium alloy, a positive electrode, and a non-aqueous electrolyte made of a solvent and a solute. And lithium trihalogenated methanesulfonate except lithium trifluoromethanesulfonate.
また前記溶質としては、LiCF2ClSO3、LiCFCl2SO3、Li
CCl3SO3、LiCF2BrSO3、LiCFBr2SO3及びLiCBr3SO3からな
る群より選択された少なくとも１つを用いるのが好まし
い。Further, as the solute, LiCF 2 ClSO 3 , LiCFCl 2 SO 3 , LiCF 2
It is preferable to use at least one selected from the group consisting of CCl 3 SO 3 , LiCF 2 BrSO 3 , LiCFBr 2 SO 3 and LiCBr 3 SO 3 .
（ホ） 作用 トリフルオロメタンスルホン酸リチウム（LiCF3SO3）
は、電池の長期保存中において、分子中のフッ素（Ｆ）
がイオン化してフッ素イオンとなり、負極のリチウムと
反応して、負極表面にフッ化リチウムの不働態被膜を生
成させる。その結果、電池の内部抵抗が増大し、保存後
の電池特性が低下してしまう。(E) Action Lithium trifluoromethanesulfonate (LiCF 3 SO 3 )
Indicates that fluorine (F) in the molecule during long-term storage of the battery
Ionizes into fluorine ions, reacts with lithium of the negative electrode, and forms a passive film of lithium fluoride on the negative electrode surface. As a result, the internal resistance of the battery increases, and the battery characteristics after storage deteriorate.
そこで、化学式LiCF3SO3のフッ素（Ｆ）の少なくとも
１つを、塩素（Cl）、臭素（Br）等のフッ素以外のハロ
ゲンで置換する、即ちトリフルオロメタンスルホン酸リ
チウム以外のトリハロゲン化メタンスルホン酸リチウム
を、非水系電解液の溶質として用いることにより、フッ
素イオンとリチウムとの前記反応が抑制され、保存後の
電池特性、特に低温放電特性の劣化を抑えることができ
る。Therefore, at least one of fluorine (F) in the chemical formula LiCF 3 SO 3 is replaced with a halogen other than fluorine such as chlorine (Cl) and bromine (Br), that is, a trihalogenated methanesulfone other than lithium trifluoromethanesulfonate. By using lithium oxide as a solute of the non-aqueous electrolyte, the above-mentioned reaction between fluorine ions and lithium is suppressed, and deterioration of battery characteristics after storage, particularly low-temperature discharge characteristics, can be suppressed.
この理由は、フッ素より電気陰性度の小さいハロゲン
である塩素や臭素を少なくとも１つでも有するトリハロ
ゲン化メタンスルホン酸リチウムは、ハロゲンと炭素と
の結合が、イオン結合性から共有結合性に近くなり、そ
の分子構造が安定化することに基づくものであると考え
られる。そしてこのような現象は、トリハロゲン化メタ
ンスルホン酸リチウムにおけるトリハロゲンが全てフッ
素であるF3の場合を除いたもの、即ち、F2Cl、FCl2、Cl
3、F2Br2,FBr2,Br3等とした場合において観察される。This is because lithium trihalide lithium methanesulfonate, which has at least one of chlorine and bromine, which are halogens having electronegativity lower than that of fluorine, has a bond between a halogen and carbon that is closer to a covalent bond than an ionic bond. This is considered to be based on the stabilization of the molecular structure. And such a phenomenon excludes the case where F 3 in which all trihalogens in the trihalogenated lithium methanesulfonate are fluorine, that is, F 2 Cl, FCl 2 , Cl 2
3, is observed in case of the F 2 Br 2, FBr 2, Br 3 or the like.
（ヘ） 実施例 以下に、本発明の比較例との対比に言及し、詳述す
る。以下に用いた電池は、第１図に示す如く、扁平型の
非水系電解液電池を用いた。(F) Examples Hereinafter, the present invention will be described in detail with reference to comparison with comparative examples. As shown in FIG. 1, a flat non-aqueous electrolyte battery was used as the battery used below.
（実施例１） 第１図に、本発明電池の縦断面図を示す。第１図中、
２はリチウム金属からなる負極であって、負極集電体７
の内面に圧着されており、この負極集電体７はフェライ
ト系ステンレス鋼（SUS430）からなる断面略コ字状の負
極缶５の内底面に固着されている。上記負極缶５の周端
は、ポリプロピレン製の絶縁パッキング８の内部に固定
されており、絶縁パッキング８の外周には、ステンレス
製の上記負極缶５とは反対方向に断面略コ字状をなす正
極缶４が固定されている。この正極缶４の内底面には、
正極集電体６が固定されており、この正極集電体６の内
面には正極１が固定されている。この正極１と前記負極
２との間には、電解液が含浸されたセパレータ３が介挿
されている。ところで、前記正極１は、350〜430℃の温
度範囲で熱処理した二酸化マンガンを活物質として用い
ており、この活物質と、導電剤としてカーボン粉末と、
結着剤としてフッ素樹脂粉末とを、それぞれ85:10:5の
重量比で、混合している。そして、次にこの混合物を加
圧成形した後、250〜350℃で熱処理して、正極１を作製
した。(Example 1) FIG. 1 shows a longitudinal sectional view of the battery of the present invention. In FIG.
Reference numeral 2 denotes a negative electrode made of lithium metal, and a negative electrode current collector 7
The negative electrode current collector 7 is fixed to the inner bottom surface of the negative electrode can 5 made of ferritic stainless steel (SUS430) and having a substantially U-shaped cross section. The peripheral end of the negative electrode can 5 is fixed inside a polypropylene insulating packing 8, and the outer periphery of the insulating packing 8 has a substantially U-shaped cross section in a direction opposite to the stainless steel negative electrode can 5. The positive electrode can 4 is fixed. On the inner bottom surface of the positive electrode can 4,
The positive electrode current collector 6 is fixed, and the positive electrode 1 is fixed to the inner surface of the positive electrode current collector 6. A separator 3 impregnated with an electrolytic solution is interposed between the positive electrode 1 and the negative electrode 2. By the way, the positive electrode 1 uses manganese dioxide heat-treated at a temperature range of 350 to 430 ° C. as an active material. This active material, carbon powder as a conductive agent,
Fluororesin powder as a binder is mixed in a weight ratio of 85: 10: 5, respectively. Then, the mixture was press-molded, and then heat-treated at 250 to 350 ° C. to produce a positive electrode 1.
一方、前記負極２は、リチウムを所定寸法に打ち抜く
ことにより、作製したものである。On the other hand, the negative electrode 2 is manufactured by punching lithium into a predetermined size.
そして非水系電解液としては、非水系の溶媒としての
プロピレンカーボネート及び1.2−ジメトキシエタンと
の混合溶液に、溶質としてのLiCF2SO3（トリフルオロメ
タンスルホン酸リチウムを除くトリハロゲン化メタンス
ルホン酸リチウム）を、１モル／溶解させたものを用
いた。As a non-aqueous electrolytic solution, a mixed solution of propylene carbonate and 1.2-dimethoxyethane as non-aqueous solvents and LiCF 2 SO 3 as a solute (lithium trihalogenated methanesulfonate except lithium trifluoromethanesulfonate) are used. Was dissolved at 1 mol / mol.
これらを用いて、外径20mm、厚み2.5mm、電池容量130
mAHを有する、本発明電池Ａを作製した。Using these, outer diameter 20mm, thickness 2.5mm, battery capacity 130
Inventive battery A having mAH was prepared.
（実施例２） 非水系電解液の溶質として、LiCl3SO3を用いた他は、
上記実施例と同様にして、本発明電池Ｂを作製した。(Example 2) Except that LiCl 3 SO 3 was used as a solute of the non-aqueous electrolyte,
Battery B of the present invention was produced in the same manner as in the above example.
（実施例３） 非水系電解液の溶質として、LiCBr3SO3を用いた他
は、上記実施例１と同様にして、本発明電池Ｃを作製し
た。Example 3 A battery C of the present invention was produced in the same manner as in Example 1 except that LiCBr 3 SO 3 was used as a solute of the nonaqueous electrolytic solution.
（比較例） 非水系電解液の溶質として、LiCF3SO3を用いた他は、
上記実施例１と同様にして、比較電池Ｘを作製した。(Comparative Example) Except that LiCF 3 SO 3 was used as the solute of the non-aqueous electrolyte,
A comparative battery X was produced in the same manner as in Example 1 above.
◎ 実験１ 上記本発明電池Ａ〜Ｃ及び比較電池Ｘを用い、初期低
温放電特性及び保存後の低温放電特性を、それぞれ調べ
た。その結果を、第２図及び第３図に示す。実 験 Experiment 1 Using the batteries A to C of the present invention and the comparative battery X, the initial low-temperature discharge characteristics and the low-temperature discharge characteristics after storage were examined. The results are shown in FIGS. 2 and 3.
尚、第２図は電池組立後直ちに温度−20℃、負荷3KΩ
で放電したときの低温放電特性、第３図は電池組立後60
℃で３カ月保存（室温で４・５年間保存した場合に相
当）した後温度−20℃、負荷3KΩで放電したときの低温
放電特性を、それぞれ示す特性図である。Fig. 2 shows a temperature of -20 ° C and a load of 3KΩ immediately after battery assembly.
Low-temperature discharge characteristics when the battery was discharged at 60 ° C.
FIG. 4 is a characteristic diagram showing low-temperature discharge characteristics when the battery is stored at -20 ° C. for 3 months (corresponding to storage at room temperature for 4.5 years) and then discharged at a temperature of −20 ° C. and a load of 3 KΩ.
第２図及び第３図から明らかなように、本発明電池Ａ
〜Ｃと比較電池Ｘとは、初期の低温放電特性では同等の
値を示しているが、保存後の低温放電特性において、本
発明電池Ａ〜Ｃは、比較電池Ｘよりも優れていることが
認められる。As is clear from FIGS. 2 and 3, the battery A of the present invention was used.
-C and Comparative Battery X show the same value in the initial low-temperature discharge characteristics, but in the low-temperature discharge characteristics after storage, batteries A to C of the present invention are superior to Comparative Battery X. Is recognized.
◎ 実験２ 前記せる各電池を用い、高温保存前後の電池の内部抵
抗を測定した。実 験 Experiment 2 Using each of the batteries described above, the internal resistance of the batteries before and after high-temperature storage was measured.
その結果を、第１表に示す。 Table 1 shows the results.
第１表より、比較電池Ｘは、保存後に内部抵抗が著し
く増大していることがわかる。これに対し、本発明電池
Ａ〜Ｃは、保存後であっても、内部抵抗の増加が極めて
小さく抑制されていることがわかる。 Table 1 shows that the internal resistance of the comparative battery X significantly increased after storage. On the other hand, in the batteries A to C of the present invention, the increase in the internal resistance is suppressed to a very small value even after storage.
（ト） 発明の効果 以上の如く、本発明によれば、非水系電解液の溶質と
して、トリフルオロメタンスルホン酸リチウムを除くト
リハロゲン化メタンスルホン酸リチウムを用いているの
で、保存後の負極表面における不働態被膜の生成を抑制
することができ、保存後においても優れた低温放電特性
を有する非水系電解液電池を提供しうるものであり、そ
の工業的価値は極めて大きい。(G) Effect of the Invention As described above, according to the present invention, as the solute of the nonaqueous electrolyte, lithium trihalide methanesulfonate other than lithium trifluoromethanesulfonate is used. The present invention can provide a non-aqueous electrolyte battery that can suppress the formation of a passive film and has excellent low-temperature discharge characteristics even after storage, and its industrial value is extremely large.
第１図は本発明非水系電解液電池の縦断面図、第２図は
初期低温放電特性図、第３図は保存後の低温放電特性図
である。 １……正極、２……負極、３……セパレータ、４……正
極缶、５……負極缶、６……正極集電体、７……負極集
電体、８……絶縁パッキング A,B,C……本発明電池、Ｘ……比較電池。FIG. 1 is a longitudinal sectional view of the nonaqueous electrolyte battery of the present invention, FIG. 2 is an initial low-temperature discharge characteristic diagram, and FIG. 3 is a low-temperature discharge characteristic diagram after storage. DESCRIPTION OF SYMBOLS 1 ... Positive electrode, 2 ... Negative electrode, 3 ... Separator, 4 ... Positive electrode can, 5 ... Negative electrode can, 6 ... Positive electrode current collector, 7 ... Negative electrode current collector, 8 ... Insulating packing A, B, C: battery of the present invention, X: comparative battery.
Claims (2)
と、正極と、溶媒及び溶質からなる非水系電解液とを有
する電池において、 前記溶質として、トリフルオロメタンスルホン酸リチウ
ムを除くトリハロゲン化メタンスルホン酸リチウムを用
いたことを特徴とする非水系電解液電池。1. A battery comprising a negative electrode made of lithium or a lithium alloy, a positive electrode, and a non-aqueous electrolytic solution comprising a solvent and a solute, wherein the solute includes lithium trihalogenated methanesulfonate other than lithium trifluoromethanesulfonate. A non-aqueous electrolyte battery comprising:
CCl3SO3、LiCF2BrSO3、LiCFBr2SO3及びLiCBr3SO3からな
る群より選択された少なくとも１つであることを特徴と
する請求項記載の非水系電解液電池。2. The method according to claim 1, wherein the solute is LiCF 2 ClSO 3 , LiCFCl 2 SO 3 , LiCF 2
CCl 3 SO 3, LiCF 2 BrSO 3, LiCFBr 2 SO 3 and a non-aqueous electrolyte battery according to claim wherein the LiCBr 3 is at least one selected from the group consisting of SO 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1127303A JP2664477B2 (en) | 1989-05-19 | 1989-05-19 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1127303A JP2664477B2 (en) | 1989-05-19 | 1989-05-19 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02306544A JPH02306544A (en) | 1990-12-19 |
| JP2664477B2 true JP2664477B2 (en) | 1997-10-15 |
Family
ID=14956617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1127303A Expired - Fee Related JP2664477B2 (en) | 1989-05-19 | 1989-05-19 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2664477B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2026009859A1 (en) * | 2024-07-04 | 2026-01-08 | セントラル硝子株式会社 | Novel sulfonate, flame retardant, additive composition, resin composition, and molded article |
-
1989
- 1989-05-19 JP JP1127303A patent/JP2664477B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02306544A (en) | 1990-12-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |