JPS63198260A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS63198260A JPS63198260A JP62030503A JP3050387A JPS63198260A JP S63198260 A JPS63198260 A JP S63198260A JP 62030503 A JP62030503 A JP 62030503A JP 3050387 A JP3050387 A JP 3050387A JP S63198260 A JPS63198260 A JP S63198260A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- electrolyte
- nonaqueous electrolyte
- lithium nitrate
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- -1 lithium tetrafluoroborate Chemical compound 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
Abstract
Description
【発明の詳細な説明】
イ、 産業上の利用分野
本発明はリチウム合金いはリチウム合金を活物質とする
負極と、正極と、溶媒と溶質とからなる非水電解液とを
備えた非水電解液電池に関するものである。[Detailed description of the invention] B. Industrial application field The present invention provides a non-aqueous electrolyte comprising a negative electrode using a lithium alloy or a lithium alloy as an active material, a positive electrode, and a non-aqueous electrolyte comprising a solvent and a solute. This invention relates to electrolyte batteries.
口、 従来の技術
この種電池は単位体積当りのエネルギー密度が高く、且
自己放電が小さいという利点がある。BACKGROUND OF THE INVENTION This type of battery has the advantage of high energy density per unit volume and low self-discharge.
ところで電解液を構成する溶質としては一般に過塩素酸
リチウムが用いられているが、過塩素酸リチウムを用い
た場合には低温特性に難があり、又過塩素酸リチウムは
非常に酸化力が犬であるため有機溶媒を酸化してしまう
という問題がある。By the way, lithium perchlorate is generally used as the solute that makes up the electrolyte, but when lithium perchlorate is used, it has poor low-temperature characteristics, and lithium perchlorate has very low oxidizing power. Therefore, there is a problem that the organic solvent is oxidized.
そこで、例えば特開昭５８−６６２６４号公報、特開昭
５８−１６３１７６号公報に開示されている三フッ化メ
タンスルホン酸リチウム、六フッ化すン酸すチウム或い
は四フッ化ホウ酸リチウムなどのフッ素を含むリチウム
塩を溶質としで用いると低温特性を改善しろると共に、
フッ素を含むリチウム塩は酸化作用がないため有機溶媒
を酸化するという問題を解消することができる。Therefore, for example, fluorine such as lithium trifluoromethanesulfonate, lithium hexafluorosulfonate, or lithium tetrafluoroborate disclosed in JP-A-58-66264 and JP-A-58-163176 Using a lithium salt containing as a solute improves the low temperature properties and
Lithium salts containing fluorine have no oxidizing effect and can solve the problem of oxidizing organic solvents.
ハ、 発明が解決しようとする問題点
しかしながらフッ素を含むリチウム塩を溶質に用いた場
合、電池缶材料が腐蝕し、電解液中に溶解した電池缶材
料が負極表面に析出して電圧降下、放電容量の減少など
を惹起し電池の保存特性を劣化させるという問題がある
。C. Problems to be Solved by the Invention However, when a fluorine-containing lithium salt is used as a solute, the battery can material corrodes, and the battery can material dissolved in the electrolyte is deposited on the negative electrode surface, resulting in voltage drop and discharge. There is a problem in that it causes a decrease in capacity and deteriorates the storage characteristics of the battery.
二、 問題点を解決するための手段
非水電解液を構成する溶質としてフッ素を含むリチウム
塩を用いる非水電解液電池において、電解液に硝酸リチ
ウムを添加する。2. Means for solving the problem In a nonaqueous electrolyte battery that uses a fluorine-containing lithium salt as a solute constituting the nonaqueous electrolyte, lithium nitrate is added to the electrolyte.
ホ、 作用
溶質としてフッ素を含むリチウム塩を用いた場合の電池
缶材料の腐蝕は、電池缶を構成するステンレス鋼表面に
形成されている不働態のクロム酸化膜の破壊が要因と考
えられる。そしてフッ素を含むリグラム塩は酸化作用が
ないため腐蝕現象が進行するのである。E. Corrosion of battery can materials when using a fluorine-containing lithium salt as a working solute is thought to be caused by the destruction of the passive chromium oxide film formed on the surface of the stainless steel that makes up the battery can. Since Ligram salt containing fluorine has no oxidizing effect, corrosion progresses.
しかしながら、本発明電池のように電解液に硝酸リチウ
ムを添加するとこの硝酸リチウムの酸化力により、電池
缶を構成するステンレス鋼表面に新たに不働態のクロム
酸化膜が形成きれ電池缶材料の腐蝕が抑制される。However, when lithium nitrate is added to the electrolyte as in the battery of the present invention, the oxidizing power of the lithium nitrate causes a new passive chromium oxide film to form on the stainless steel surface of the battery can, resulting in corrosion of the battery can material. suppressed.
へ 実施例 以下本発明の実施例について詳述する。Example Examples of the present invention will be described in detail below.
正極は３５０〜４３０°Ｃの温度で熱処理した二酸化マ
ンガン活物質に、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を８５：１０：５の重量比で
混合し、この混合物を加圧成形した後２５０〜３５０°
Ｃで熱処理したものである。又、負極はリチウム圧延板
を所定寸法に打抜いたものである。The positive electrode is made by mixing carbon powder as a conductive agent and fluororesin powder as a binder in a weight ratio of 85:10:5 with a manganese dioxide active material that has been heat-treated at a temperature of 350 to 430°C, and then adding this mixture. 250~350° after pressure forming
It was heat treated with C. Further, the negative electrode is made by punching a lithium rolled plate into a predetermined size.
而して非水電解液は、プロピレンカーボネートと１，２
ジメトキシエタンとの等体積混合溶媒に溶質として三フ
ッ化メタンスルホン酸リチウムを１モル／１２溶解した
ものであり、そしてこの非水電解液には硝酸リチウムが
０．１ｇ／β添加されている。尚、電池缶としてはステ
ンレス鋼（ｓｕｓ４ｓｏ）ヲ使用した。これらの要素を
用いて組立てた径２０．０ｍ１厚み０．２５ｍｍ、電池
容量１２０ｍＡＨ（７）本発明電池を（Ａ）とする。Therefore, the non-aqueous electrolyte contains propylene carbonate and 1,2
Lithium trifluoromethanesulfonate as a solute was dissolved at 1 mol/12 in a mixed solvent of equal volume with dimethoxyethane, and 0.1 g/β of lithium nitrate was added to this non-aqueous electrolyte. Note that stainless steel (sus4so) was used as the battery can. A battery of the present invention assembled using these elements and having a diameter of 20.0 m, a thickness of 0.25 mm, and a battery capacity of 120 mAH (7) is designated as (A).
又、硝酸リチウムの添加量を１．０ｇ／ｆとした以外は
本発明電池（Ａ）と同様の本発明電池（Ｂ）を作成した
。Further, a battery (B) of the present invention similar to the battery (A) of the present invention was prepared except that the amount of lithium nitrate added was 1.0 g/f.
更に、比較のために硝酸リチウムを添加しないことを除
いて他は本発明電池（Ａ）と同様の比較電池（Ｃ）を作
成した。Furthermore, for comparison, a comparative battery (C) was prepared which was the same as the battery of the present invention (A) except that lithium nitrate was not added.
第１図及び第２図は本発明電池と比較電池との放電特性
比較図を示し、第１図は電池組立後、直ちに室温におい
て５００Ωの定抵抗で放電した時の放電特性図であり、
又第２図は電池組立後、６０°Ｃで３ケ月保存したのち
室温において５００Ωの定抵抗で放電した時の放電特性
図である。1 and 2 show comparison diagrams of discharge characteristics between the battery of the present invention and a comparison battery, and FIG. 1 is a diagram of discharge characteristics when the battery is discharged at a constant resistance of 500Ω at room temperature immediately after assembly,
Moreover, FIG. 2 is a discharge characteristic diagram when the battery was stored at 60° C. for 3 months after assembly and then discharged at room temperature with a constant resistance of 500Ω.
第１図及び第２図から明らかなように、電池組立直後の
放電においては硝酸リチウムの有無による特性の差異は
認められないが、高温保存後における放電では顕著な差
異が認められた。As is clear from FIGS. 1 and 2, no difference in characteristics due to the presence or absence of lithium nitrate was observed in the discharge immediately after battery assembly, but a significant difference was observed in the discharge after high-temperature storage.
次に各電池の保存前と高温保存後における内部インピー
ダンスを下表に示す。尚、測定は１ ｋＨｚの周波数で
行なった。Next, the internal impedance of each battery before storage and after high temperature storage is shown in the table below. Note that the measurement was performed at a frequency of 1 kHz.
表
上表の結果から明らかなように、比較電池（Ｃ）では保
存後に内部インピーダンスが増大しているのに対し、本
発明電池（Ａ ）（Ｂ ）では保存後も内部インピーダ
ンスの増大はほとんどない。As is clear from the results in the table above, the internal impedance of the comparison battery (C) increases after storage, whereas the internal impedance of the batteries of the invention (A) and (B) hardly increases after storage. .
又、保存後の電池を分解したところ比較電池（Ｃ）はリ
チウム負極の表面が黒く変色していたが本発明電池（Ａ
）（Ｂ ）ではそのような現象は認められなかった。Furthermore, when the battery was disassembled after storage, the surface of the lithium negative electrode of the comparative battery (C) was found to be black and discolored, whereas the battery of the present invention (A)
) (B), no such phenomenon was observed.
更に、保存後の正極缶を金属顕微鏡で観察したところ、
比較電池（Ｃ）の場合にはかなりの孔蝕が認められたが
本発明電池（Ａ）（Ｂ）の場合にはほとんど腐蝕されて
いなかった。Furthermore, when we observed the cathode can after storage using a metallurgical microscope, we found that
Although considerable pitting corrosion was observed in the comparative battery (C), there was almost no corrosion in the batteries (A) and (B) of the present invention.
（ト）発明の効果
上述した如く、非水電解液を構成する溶質として特にフ
ッ素を含むリチウム塩を用いる非水電解液電池において
、電解液に硝酸リチウムを添加することによりこの種電
池特有の問題である電池缶材料の腐蝕現象を抑制するこ
とができるものであり、その工業的価値は極めて犬であ
る。(g) Effects of the invention As mentioned above, in non-aqueous electrolyte batteries that use lithium salts containing fluorine as the solute constituting the non-aqueous electrolyte, the addition of lithium nitrate to the electrolyte causes problems specific to this type of battery. It can suppress the corrosion phenomenon of battery can materials, and its industrial value is extremely high.
図面は電池電圧と放電時間との関係を示し、第１図は初
期放電特性図、第２図は６０°Ｃで３ケ月保存した後の
放電特性図である。
（Ａ＞（Ｂ）・・・本発明電池、（Ｃ）・・・比較電池
。The drawings show the relationship between battery voltage and discharge time; FIG. 1 is an initial discharge characteristic diagram, and FIG. 2 is a discharge characteristic diagram after storage at 60° C. for 3 months. (A>(B)...Battery of the present invention, (C)...Comparative battery.
Claims (1)
と、正極と、溶媒とフッ素を含むリチウム塩よりなる溶
質とからなる非水電解液とを備えるものであって、前記
電解液に硝酸リチウムを添加したことを特徴とする非水
電解液電池。(1) A device comprising a negative electrode using lithium or a lithium alloy as an active material, a positive electrode, and a non-aqueous electrolyte consisting of a solvent and a solute made of a lithium salt containing fluorine, the electrolyte containing lithium nitrate. A non-aqueous electrolyte battery characterized by the addition of additives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62030503A JPS63198260A (en) | 1987-02-12 | 1987-02-12 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62030503A JPS63198260A (en) | 1987-02-12 | 1987-02-12 | Nonaqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63198260A true JPS63198260A (en) | 1988-08-16 |
| JPH0432505B2 JPH0432505B2 (en) | 1992-05-29 |
Family
ID=12305619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62030503A Granted JPS63198260A (en) | 1987-02-12 | 1987-02-12 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63198260A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0215567A (en) * | 1988-07-01 | 1990-01-19 | Sanyo Electric Co Ltd | Nonaqueous type electrolyte battery |
| JPH0343960A (en) * | 1989-07-11 | 1991-02-25 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| FR2674518A1 (en) * | 1991-03-26 | 1992-10-02 | Centre Nat Rech Scient | FLUID ELECTROLYTES BASED ON LITHIUM SALT AMMONIACATES. |
| US20130202950A1 (en) * | 2012-02-07 | 2013-08-08 | Sb Limotive Co., Ltd. | Lithium Rechargeable Battery and Method of Making the Same |
| WO2014188503A1 (en) * | 2013-05-21 | 2014-11-27 | 株式会社日立製作所 | Electricity storage device and method for manufacturing same |
-
1987
- 1987-02-12 JP JP62030503A patent/JPS63198260A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0215567A (en) * | 1988-07-01 | 1990-01-19 | Sanyo Electric Co Ltd | Nonaqueous type electrolyte battery |
| JPH0715821B2 (en) * | 1988-07-01 | 1995-02-22 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| JPH0343960A (en) * | 1989-07-11 | 1991-02-25 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| FR2674518A1 (en) * | 1991-03-26 | 1992-10-02 | Centre Nat Rech Scient | FLUID ELECTROLYTES BASED ON LITHIUM SALT AMMONIACATES. |
| WO1992017911A1 (en) * | 1991-03-26 | 1992-10-15 | Centre National De La Recherche Scientifique (Cnrs) | Fluid electrolytes based on lithium salt ammines |
| US20130202950A1 (en) * | 2012-02-07 | 2013-08-08 | Sb Limotive Co., Ltd. | Lithium Rechargeable Battery and Method of Making the Same |
| US8916288B2 (en) * | 2012-02-07 | 2014-12-23 | Samsung Sdi Co., Ltd. | Lithium rechargeable battery and method of making the same |
| WO2014188503A1 (en) * | 2013-05-21 | 2014-11-27 | 株式会社日立製作所 | Electricity storage device and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0432505B2 (en) | 1992-05-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |