JPH06105612B2 - Non-aqueous electrolyte primary battery - Google Patents
Non-aqueous electrolyte primary batteryInfo
- Publication number
- JPH06105612B2 JPH06105612B2 JP63058601A JP5860188A JPH06105612B2 JP H06105612 B2 JPH06105612 B2 JP H06105612B2 JP 63058601 A JP63058601 A JP 63058601A JP 5860188 A JP5860188 A JP 5860188A JP H06105612 B2 JPH06105612 B2 JP H06105612B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- aqueous electrolyte
- negative electrode
- primary battery
- electrolyte primary
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
Description
【発明の詳細な説明】 イ．産業上の利用分野 本発明は非水電解液一次電池に関するものである。Detailed Description of the Invention a. TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte primary battery.
ロ．従来の技術 リチウム、ナトリウム或いはこれらの合金のようなアル
カリ軽金属を活物質とする負極を用いた非水電解液一次
電池は高エネルギー密度を有し、且つ自己放電が少ない
という利点を有する。B. 2. Description of the Related Art A non-aqueous electrolyte primary battery using a negative electrode using an alkali light metal such as lithium, sodium or an alloy thereof as an active material has advantages of high energy density and low self-discharge.
さて、近年に至ってはこの種電池の適用分野の拡大に伴
い電池特性の改善が要望されており、その一つとして低
温放電特性の向上が望まれている。そこで、低温放電特
性の改善のために溶質としてトリフルオロメタンスルホ
ン酸リチウム（LiCF3SO3）を用いることが提案されてい
る。Now, in recent years, along with the expansion of application fields of this type of battery, improvement of battery characteristics has been demanded, and as one of them, improvement of low temperature discharge characteristics is desired. Therefore, it has been proposed to use lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) as a solute in order to improve low-temperature discharge characteristics.
LiCF3SO3を溶質に用いると、初期の低温放電特性は改善
されるものの、長期保存後は低温放電特性が低下すると
いう問題がある。When LiCF 3 SO 3 is used as a solute, the initial low temperature discharge characteristics are improved, but the low temperature discharge characteristics deteriorate after long-term storage.
ハ．発明が解決しようとする課題 本発明は上記従来の問題に鑑み、初期及び保存後のいず
れの場合においても優れた低温放電特性を示す非水電解
液一次電池を提供することを目的とする。C. SUMMARY OF THE INVENTION In view of the above conventional problems, it is an object of the present invention to provide a non-aqueous electrolyte primary battery that exhibits excellent low-temperature discharge characteristics both in the initial stage and after storage.
ニ．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非水電解液一次
電池は、負極としてアルミニウムを0.1〜20.0重量％含
むリチウム−アルミニウム合金が用いられていることを
要旨とする。D. Means for Solving the Problems The non-aqueous electrolyte primary battery according to the present invention for achieving the above object is characterized in that a lithium-aluminum alloy containing 0.1 to 20.0% by weight of aluminum is used as a negative electrode. .
ホ．作用 負極にLiを用い、溶質にLiCF3SO3を用いた場合に、保存
後の低温放電特性が低下する理由は詳かではないが、次
のように考えられる。即ち、保存中にLiCF3SO3からイオ
ン化したフッ素が活性なLiと反応して、負極表面に不働
態であるフッ化リチウムの被膜が生成し内部抵抗が増大
することに起因すると考えられる。E. It is not clear why the low-temperature discharge characteristics after storage deteriorate when Li is used for the negative electrode and LiCF 3 SO 3 is used for the solute, but it is considered as follows. That is, it is considered that fluorine ionized from LiCF 3 SO 3 reacts with active Li during storage to form a passive film of lithium fluoride on the surface of the negative electrode to increase the internal resistance.
ここで本発明のように、負極として特にAlを0.1〜20.0
重量％含むLi−Al合金を用いるとLi単独に比してLi−Al
合金は活性度が低いため保存中に存在するフッ素イオン
とLi−Al合金とが反応し難く、そのため負極表面におけ
る不働態被膜の生成が抑えられ、保存後の低温放電特性
の低下が抑制される。Here, as in the present invention, particularly Al as a negative electrode 0.1 to 20.0
When a Li-Al alloy containing wt% is used, Li-Al is
Since the alloy has low activity, it is difficult for the fluorine ions present during storage to react with the Li-Al alloy, so the formation of the passive film on the negative electrode surface is suppressed, and the deterioration of low temperature discharge characteristics after storage is suppressed. .
ヘ．実施例 以下本発明の実施例について詳述する。F. Examples Examples of the present invention will be described in detail below.
350〜430℃の温度で熱処理した二酸化マンガンを活物質
とし、この活物質に導電剤としてのカーボン粉末及び結
着剤としてのフッ素樹脂粉末とを85:10:5の重量比で混
合した混合物を加圧成形した後、250〜350℃で熱処理し
たものを正極とする。Using a mixture of manganese dioxide heat-treated at a temperature of 350 to 430 ° C. as an active material, carbon powder as a conductive agent and fluororesin powder as a binder in a weight ratio of 85: 10: 5. After being pressure-molded, it is heat-treated at 250 to 350 ° C. to obtain a positive electrode.
負極はAlを2.0重量％含んだLi−Al合金を所定寸法に打
抜いたものである。The negative electrode is a Li-Al alloy containing 2.0% by weight of Al punched to a predetermined size.
非水電解液はプロピレンカーボネートと1,2ジメトキシ
エタンとの混合溶媒に、LiCF3SO3を１モル/l溶解したも
のである。The non-aqueous electrolyte is a mixture of propylene carbonate and 1,2 dimethoxyethane in which 1 mol / l of LiCF 3 SO 3 is dissolved.
そして、これらの要素を用いて径20.0mm、厚み2.5mm、
電池容量130mAHの本発明電池（Ａ）を作成した。And using these elements, diameter 20.0mm, thickness 2.5mm,
A battery (A) of the present invention having a battery capacity of 130 mAH was prepared.
次に、本発明電池の優位性を調べるために、負極として
Liを用いることを除いて他は本発明電池と同様の比較電
池（Ｂ）を作成した。Next, in order to investigate the superiority of the battery of the present invention, as a negative electrode
A comparative battery (B) similar to the battery of the present invention was prepared except that Li was used.
又、負極としてLiを用い、溶質として過塩素酸リチウム
を用いることを除いて他は本発明電池と同様の比較電池
（Ｃ）を作成した。A comparative battery (C) similar to the battery of the present invention was prepared except that Li was used as the negative electrode and lithium perchlorate was used as the solute.
第１図及び第２図は本発明電池と比較電池の低温放電特
性図であって、第１図は電池組立後、直ちに−20℃にお
いて3KΩの定抵抗で放電した時の初期特性、又第２図は
電池組立後、60℃で３ケ月間保存（室温で4.5年間保存
した場合にほぼ相当）したのち−20℃において3KΩの定
抵抗で放電した時の保存特性を夫々示す。1 and 2 are low-temperature discharge characteristic diagrams of the battery of the present invention and the comparative battery, and FIG. 1 shows initial characteristics when discharged at a constant resistance of 3 KΩ at −20 ° C. immediately after assembly of the battery, and Figure 2 shows the storage characteristics of the battery after it was stored at 60 ° C for 3 months (corresponding to storage at room temperature for 4.5 years) and then discharged at a constant resistance of 3KΩ at -20 ° C.
第１図の初期特性から溶質としてLiCF3SO3を用いると低
温特性が改善されるのがわかる。With LiCF 3 SO 3 as a solute from the initial characteristics of the first view can be seen that the low-temperature characteristic is improved.
又、第２図の保存特性から、溶質としてLiCF3SO3を用
い、負極としてLi−Al合金を用いると、保存後の低温放
電特性にも優れることがわかる。Further, from the storage characteristics of FIG. 2, it is found that when LiCF 3 SO 3 is used as the solute and a Li—Al alloy is used as the negative electrode, the low temperature discharge characteristics after storage are also excellent.
下表はこれら電池の保存前後の内部抵抗値を示す。The table below shows the internal resistance of these batteries before and after storage.
又、第３図は負極としてのLi−Al合金中のAl量と電池の
放電容量（−20℃で3KΩ定抵抗放電）との関係を示す図
であり、第３図からAl量としては0.1〜20.0重量％の範
囲が好ましいことがわかる。尚、第３図において実線は
初期特性、破線は保存特性である。 Further, FIG. 3 is a diagram showing the relationship between the amount of Al in the Li-Al alloy as the negative electrode and the discharge capacity of the battery (3 KΩ constant resistance discharge at −20 ° C.). It can be seen that a range of up to 20.0% by weight is preferable. In FIG. 3, the solid line shows the initial characteristic and the broken line shows the storage characteristic.
ト．発明の効果 上述した如く、負極としてAlを0.1〜20.0重量％含むLi
−Al合金を用いることにより、初期及び保存後のいずれ
の場合においても優れた低温放電特性を示す非水電解液
一次電池を得ることができるものであり、この種電池の
用途拡大に資するところ極めて大である。G. As described above, as the negative electrode, Li containing 0.1 to 20.0% by weight of Al is used.
By using the -Al alloy, it is possible to obtain a non-aqueous electrolyte primary battery exhibiting excellent low-temperature discharge characteristics in both the initial and storage cases, and it is extremely useful for expanding the applications of this type of battery. Is large.
第１図及び第２図は電池の低温放電特性図であって、第
１図は初期特性、第２図は保存特性である。第３図はLi
−Al合金中のAl量と電池の放電容量との関係を示す図で
ある。 Ａ…本発明電池、Ｂ、Ｃ…比較電池。1 and 2 are low temperature discharge characteristics of the battery, FIG. 1 shows initial characteristics, and FIG. 2 shows storage characteristics. Figure 3 shows Li
FIG. 3 is a diagram showing the relationship between the amount of Al in an Al alloy and the discharge capacity of a battery. A ... Inventive battery, B, C ... Comparative battery.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 昌利 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 (56)参考文献 特開 昭61−176074（ＪＰ，Ａ) 特開 昭61−218068（ＪＰ，Ａ) 特公 昭60−57188（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Masatoshi Takahashi, 2-18, Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (56) References JP 61-176074 (JP, A) JP 61 -218068 (JP, A) JP 60-57188 (JP, B2)
Claims (1)
極と、トリフルオロメタンスルホン酸リチウムを溶媒に
溶かしてなる非水電解液とを備えるものであって、前記
負極としてアルミニウムを0.1〜20.0重量％含むリチウ
ム−アルミニウム合金が用いられていることを特徴とす
る非水電解液一次電池。1. A positive electrode, a negative electrode using an alkali light metal as an active material, and a non-aqueous electrolytic solution prepared by dissolving lithium trifluoromethanesulfonate in a solvent, wherein the negative electrode contains 0.1 to 20.0 parts by weight of aluminum. % Lithium-aluminum alloy is used, a non-aqueous electrolyte primary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63058601A JPH06105612B2 (en) | 1988-03-11 | 1988-03-11 | Non-aqueous electrolyte primary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63058601A JPH06105612B2 (en) | 1988-03-11 | 1988-03-11 | Non-aqueous electrolyte primary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01232661A JPH01232661A (en) | 1989-09-18 |
| JPH06105612B2 true JPH06105612B2 (en) | 1994-12-21 |
Family
ID=13089033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63058601A Expired - Lifetime JPH06105612B2 (en) | 1988-03-11 | 1988-03-11 | Non-aqueous electrolyte primary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06105612B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2674686B1 (en) * | 1991-03-26 | 1996-12-13 | Alsthom Cge Alcatel | LITHIUM / BROMINE TRIFLUORIDE ELECTROCHEMICAL GENERATOR, INTENDED TO BE DISCHARGED AFTER PRIMING AND STORAGE. |
| CA2072488C (en) | 1991-08-13 | 2002-10-01 | Andrew Webber | Nonaqueous electrolytes |
| US5514491A (en) * | 1993-12-02 | 1996-05-07 | Eveready Battery Company, Inc. | Nonaqueous cell having a lithium iodide-ether electrolyte |
| US5432030A (en) * | 1993-12-02 | 1995-07-11 | Eveready Battery Company, Inc. | Li/FeS2 cell employing a solvent mixture of diox, DME and 3ME20X with a lithium-based solute |
| KR101381674B1 (en) | 2011-08-12 | 2014-04-04 | 주식회사 엘지화학 | Jelly-Roll of Improved Productivity and Battery Cell Comprising the Same |
| CN103290293B (en) * | 2013-06-05 | 2016-02-24 | 四川天齐锂业股份有限公司 | Lithium-aluminium alloy and production method thereof and purposes |
| US11168384B2 (en) * | 2019-07-26 | 2021-11-09 | Fmc Lithium Usa Corp. | Process of preparing a lithium aluminum alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6057188A (en) * | 1983-09-05 | 1985-04-02 | 株式会社栗本鉄工所 | Preheater of scrap for electric furnace |
| JPS60109182A (en) * | 1983-11-17 | 1985-06-14 | Sanyo Chem Ind Ltd | Secondary battery |
| FR2576712B1 (en) * | 1985-01-30 | 1988-07-08 | Accumulateurs Fixes | NON-AQUEOUS ELECTROCHEMICAL ELECTROCHEMICAL GENERATOR |
| JPH0763016B2 (en) * | 1985-03-22 | 1995-07-05 | ソニー株式会社 | Organic electrolyte battery |
| JPH0810605B2 (en) * | 1985-12-12 | 1996-01-31 | 日立マクセル株式会社 | Lithium secondary battery |
-
1988
- 1988-03-11 JP JP63058601A patent/JPH06105612B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01232661A (en) | 1989-09-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081221 Year of fee payment: 14 |