JP2730983B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2730983B2 JP2730983B2 JP17598289A JP17598289A JP2730983B2 JP 2730983 B2 JP2730983 B2 JP 2730983B2 JP 17598289 A JP17598289 A JP 17598289A JP 17598289 A JP17598289 A JP 17598289A JP 2730983 B2 JP2730983 B2 JP 2730983B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- aqueous electrolyte
- negative electrode
- low
- 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 - Lifetime
Links
Classifications
-
- Y02E60/12—
Landscapes
- 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61-513
87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 61-513
No. 87, 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
する非水系電解液電池であって、前記溶質として、トリ
ハロゲン化メタンリン酸リチウム、トリハロゲン化メタ
ンホウ酸リチウムの少なくとも１つを用いたことを特徴
とするものである。(D) Means for Solving the Problems The present invention is a non-aqueous electrolyte 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, wherein the solute is , And at least one of lithium trihalogenated methanephosphate and lithium trihalogenated methaneborate is used.
（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、トリハロゲン化メタンリン酸リチウム、トリ
ハロゲン化メタンホウ酸リチウムを、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, by using lithium trihalide methanephosphate and lithium trihalide methaneborate as a solute of the non-aqueous electrolyte, the above-described reaction between fluorine ions and lithium is suppressed, and the battery characteristics after storage, especially the low-temperature discharge characteristics Degradation can be suppressed.
この理由は、トリハロゲン化メタンリン酸リチウム、
トリハロゲン化メタンホウ酸リチウムのリン酸基（−PO
3−P2O6）やホウ酸基（−BO2、−B4O6）が、分子内の結
合に関与せる電子を炭素原子側に押しやり、トリハロゲ
ン化メタンスルホン酸リチウムに比べて、分子内におけ
るハロゲンと炭素との結合を、イオン結合性から共有結
合性に近づける。その結果、分子構造が安定化し、フッ
素イオンを放出し難くなることに起因すると推定され
る。This is because lithium trihalogenated methanephosphate,
Phosphate group of lithium trihalogenated methaneborate (-PO
3 -P 2 O 6 ) and boric acid groups (-BO 2 , -B 4 O 6 ) push the electrons involved in the intramolecular bond to the carbon atom side, compared to lithium trihalide methanesulfonate. In addition, the bond between halogen and carbon in the molecule is made closer to covalent bond from ionic bond. As a result, it is presumed that the molecular structure is stabilized and fluorine ions are hardly released.
ここで、前記トリハロゲン化メタンリン酸リチウム、
トリハロゲン化メタンホウ酸リチウムの少なくとも１つ
としては、化学式Li2CF3SO3、Li3CF3P2O6、Li2CF3Bo2、
LiCF3B4O6で表されるもの等を用いることが可能であ
る。Here, the lithium trihalogenated methanephosphate,
At least one of the lithium trihalogenated methane borate has a chemical formula of Li 2 CF 3 SO 3 , Li 3 CF 3 P 2 O 6 , Li 2 CF 3 Bo 2 ,
It is possible to use one represented by LiCF 3 B 4 O 6 or the like.
更に、前記化学式においてフッ素（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
ゲンで置換した化合物を用いることができる。この場合
塩素や臭素は、フッ素より電気陰性度の小さいハロゲン
であるので、前記化学式における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より一層近くな
り、フッ素イオンとリチウムとの反応が効果的に抑制さ
れる。Further, a compound in which at least one of fluorine (F) in the above chemical formula is substituted with a halogen other than fluorine such as chlorine (Cl) or bromine (Br) can be used. In this case, chlorine or bromine is a halogen having a smaller electronegativity than fluorine, so that the bond between the halogen and carbon in the above chemical formula becomes closer to the covalent bond from the ionic bond, and the reaction between the fluorine ion and lithium is increased. Effectively suppressed.
（ヘ）実施例 以下に、本発明と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
非水系電解液電池である。(F) Example Hereinafter, the present invention will be described in detail with reference to a comparison between the present invention and a comparative example. The battery used below is a flat type non-aqueous electrolyte battery as shown in FIG.
（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、導電剤としてのカーボン粉末
と、結着剤としてのフッ素樹脂粉末とを、それぞれ85:1
0:5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, and fluororesin powder as a binder are used. , 85: 1 each
They are mixed at a weight ratio of 0: 5. Then, after this mixture is pressure-formed, it is heat-treated at 250 to 350 ° C.
Was prepared.
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（Li2CF3PO3（トリハロゲ
ン化メタンリン酸リチウム）を、１モル/l溶解させたも
のを用いた。As a non-aqueous electrolyte, a mixture of propylene carbonate and 1.2-dimethoxyethane as non-aqueous solvents was mixed with 1 mol / liter of (Li 2 CF 3 PO 3 (lithium trihalogenated methanephosphate)) as a solute. l Dissolved one was used.
これらを用いて外径20mm、厚み2.5mm、電池容量130AH
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 130AH
Inventive Battery A having the following formula:
（実施例２） 非水系電解液の溶質として、Li2CF3BO2（トリハロゲ
ン化メタンホウ酸リチウム）を用いた他は、上記実施例
１と同様にして、本発明電池Ｂを作製した。Example 2 A battery B of the present invention was produced in the same manner as in Example 1 except that Li 2 CF 3 BO 2 (lithium trihalogenated methane borate) was used as a solute of the nonaqueous electrolyte.
（比較例） 非水系電解液の溶質として、LiCF3SO3（トリハロゲン
化メタンスルホン酸リチウム）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 A comparative battery X was prepared in the same manner as in Example 1 except that LiCF 3 SO 3 (lithium trihalogenated methanesulfonate) was used as a solute of the nonaqueous electrolytic solution.
◎実験１ 上記本発明電池Ａ、Ｂ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。Experiment 1 Initial low-temperature discharge characteristics and low-temperature discharge characteristics after storage were examined using the batteries A and B of the present invention and the comparative battery X, respectively. 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℃、負極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 negative electrode of 3 KΩ 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 stored at 3 ° C. for 3 months (corresponding to storage for 4.5 years at room temperature) and then discharged at a temperature of −20 ° C. under 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、Ｂ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、Ｂは、比較電池Ｘより優れていることが
認められる。As is clear from FIGS. 2 and 3, the batteries A and B of the present invention and the comparative battery X show the same value in the initial low-temperature discharge characteristics, but show the low-temperature discharge characteristics after storage.
It is recognized that the batteries A and B of the present invention are superior to the comparative battery X.
◎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、Ｂは、保存後であっても、内部抵抗が極めて小さく
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. In contrast, it can be seen that the batteries A and B of the present invention have extremely low internal resistance 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、トリハロゲン化メタンリン酸リチウム、トリハロ
ゲン化メタンホウ酸リチウムのうちの少なくとも１つを
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) Effects of the Invention As described above, according to the present invention, since at least one of lithium trihalide methanephosphate and lithium trihalide methaneborate is used as a solute of the non-aqueous electrolyte solution, It is possible to provide a non-aqueous electrolyte battery having excellent low-temperature discharge characteristics even after storage by suppressing generation of a passive film on the surface of the negative electrode afterwards, 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……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: battery of the present invention; X: comparative battery.
Claims (1)
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、トリハロゲン化メタンリン酸リチウ
ム、トリハロゲン化メタンホウ酸リチウムの少なくとも
１つ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 electrolyte solution containing a solvent and a solute, wherein the solute includes lithium trihalide methanephosphate and lithium trihalide methaneborate. A non-aqueous electrolyte battery using at least one battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17598289A JP2730983B2 (en) | 1989-07-07 | 1989-07-07 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17598289A JP2730983B2 (en) | 1989-07-07 | 1989-07-07 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0340372A JPH0340372A (en) | 1991-02-21 |
| JP2730983B2 true JP2730983B2 (en) | 1998-03-25 |
Family
ID=16005635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17598289A Expired - Lifetime JP2730983B2 (en) | 1989-07-07 | 1989-07-07 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2730983B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016031316A1 (en) * | 2014-08-25 | 2016-03-03 | 宇部興産株式会社 | Non-aqueous liquid electrolyte, electricity storage device using same, and phosphorus compound used therein |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352547A (en) * | 1992-08-27 | 1994-10-04 | Hitachi Maxell, Ltd. | Organic electrolytic solution and organic electrolytic solution cell |
-
1989
- 1989-07-07 JP JP17598289A patent/JP2730983B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016031316A1 (en) * | 2014-08-25 | 2016-03-03 | 宇部興産株式会社 | Non-aqueous liquid electrolyte, electricity storage device using same, and phosphorus compound used therein |
| JPWO2016031316A1 (en) * | 2014-08-25 | 2017-08-31 | 宇部興産株式会社 | Non-aqueous electrolyte, power storage device using the same, and phosphorus compound used therefor |
| US10093688B2 (en) | 2014-08-25 | 2018-10-09 | Ube Industries, Ltd. | Non-aqueous liquid electrolyte, electricity storage device using same, and phosphorus compound used therein |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0340372A (en) | 1991-02-21 |
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