JPS63241866A - Nonaqueous electrolytic battery - Google Patents
Nonaqueous electrolytic batteryInfo
- Publication number
- JPS63241866A JPS63241866A JP7657387A JP7657387A JPS63241866A JP S63241866 A JPS63241866 A JP S63241866A JP 7657387 A JP7657387 A JP 7657387A JP 7657387 A JP7657387 A JP 7657387A JP S63241866 A JPS63241866 A JP S63241866A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- fluorine
- solute
- solvent
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000001590 oxidative 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PZNTXFRCVDEQCU-UHFFFAOYSA-M CS([O-])(=O)=O.[Li+].F.F.F Chemical compound CS([O-])(=O)=O.[Li+].F.F.F PZNTXFRCVDEQCU-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- YRKSRVPYWLKVMF-UHFFFAOYSA-M [Li+].[F-].F.F.F.F Chemical compound [Li+].[F-].F.F.F.F YRKSRVPYWLKVMF-UHFFFAOYSA-M 0.000 description 1
- USHGRFXQYJEHII-UHFFFAOYSA-M [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F Chemical compound [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F USHGRFXQYJEHII-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent 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
- FMZAYHNSJGQHCZ-UHFFFAOYSA-J tetralithium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Li+].[Li+].[Li+].[Li+] FMZAYHNSJGQHCZ-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 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
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
Abstract
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明はリチウムを活物質とする負橢と、金属の酸化物
、硫化物、ハロゲン化物などを活物質とする正極と、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] A. Field of Industrial Application The present invention relates to a negative electrode using lithium as an active material, a positive electrode using a metal oxide, sulfide, halide, etc. as an active material, and a non-aqueous electrolyte. The present invention relates to a non-aqueous electrolyte battery.
口 従来技術
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。By the way, lithium perchlorate is generally used as the solute constituting the electrolytic solution, but when lithium perchlorate is used, there are problems in low-temperature characteristics.
又、過塩素酸リチウムは非常に酸化力が大であるため、
有機溶媒を酸化してしまうという問題がある。In addition, lithium perchlorate has a very strong oxidizing power, so
There is a problem that the organic solvent is oxidized.
そこで１例えば特開昭５８−６６２６４号公報。For example, Japanese Patent Application Laid-Open No. 58-66264.
特開昭５８−１６３１７６号公報に開示されている三フ
ク化メタンスルホン酸すチワム、六７ツ化リン酸リチワ
ム或いは四７ツ化ホク酸リチクムなどのフッ素を含むリ
チウム塩全溶質として用いると低温特性を改善しつると
共に、７７累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。When used as a total solute, lithium salts containing fluorine such as lithium trifluoride methanesulfonate, lithium hexafluoride phosphate, or lithium tetrafluoride phosate disclosed in JP-A-58-163176 have a low temperature. In addition to improving the properties, the lithium salt containing 77-components has no oxidizing effect, so it 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、高温での保存において電池罐材料が腐蝕し、電解液
中に溶解した電池罐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 lithium salt containing fluorine is used as a solute, the battery can material corrodes during storage at high temperatures, and the battery can material dissolved in the electrolyte is deposited on the negative electrode surface. There is a problem in that it causes a voltage drop, a decrease in discharge capacity, etc., 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、電解液に水酸化リ
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 hydroxide 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電
纜材料の腐蝕は、電池Ｗ１を構成するステー ンレス
銅表面に形成されている不働態のクロム酸化膜の破壊が
装置と考えられる。そしてフッ素を含むリチウム塩は酸
化作用がないため腐蝕現象が進行するのである。Corrosion of electrical cable materials when a fluorine-containing lithium salt is used as a solute is thought to be caused by the destruction of the passive chromium oxide film formed on the stainless steel surface of the battery W1. Since fluorine-containing lithium salts have no oxidizing effect, corrosion progresses.
しかしながら１本発明電池のように電解液に水酸化リチ
ウムを添加すると、を電纜材料の表面に水酸化物の被膜
が形成され電電纜材料の腐蝕が抑制される。However, when lithium hydroxide is added to the electrolyte as in the battery of the present invention, a hydroxide film is formed on the surface of the wire material, thereby suppressing corrosion of the wire material.
へ実施例 以下本発明の実施例について詳述する。Examples Examples of the present invention will be described in detail below.
正橋は３５０〜４６０℃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℃で
熱処理したものである。父、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。Masahashi mixes carbon powder as a conductive agent and fluororesin powder as a binder in a weight ratio of 85:10:5 to a manganese dioxide active material that has been heat-treated at a temperature of 350 to 460°C, and then adds this mixture. After pressure molding, it was heat-treated at 250 to 350°C. The negative electrode was made by punching a rolled lithium 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／ｌ溶解したも
のであり、且この非水電解液に水酸化リチウムを添加し
た。Therefore, the non-aqueous electrolyte contains propylene carbonate and 1,2
Lithium trifluoromethanesulfonate was dissolved as a solute at 1 mol/l in a mixed solvent of equal volume with dimethoxyethane, and lithium hydroxide was added to this nonaqueous electrolyte.
電電纜としてはステンレス鋼（５ＵＳ４３０ ）を使用
し、これらの要素を用いて径２０．０ｍｍ、厚み２．５
ｍ、電池容量１３ＱｍＡＨの本発明電池を組立てた。尚
、電解液に添加する水酸化リチウムの添加ｉｉを０．１
ｇ／ｌとしたものを本発明電池（Ａ ’ ） 、 １
．０ ｇ ／ ｌとしたものを本発明電池（Ａ２）゛と
した。Stainless steel (5US430) is used as the electrical cable, and these elements are used to create a wire with a diameter of 20.0 mm and a thickness of 2.5 mm.
A battery of the present invention having a battery capacity of 13QmAH was assembled. In addition, the addition ii of lithium hydroxide added to the electrolyte was 0.1
g/l is the battery of the present invention (A'), 1
．． The battery with a concentration of 0 g/l was designated as the battery of the present invention (A2).
又、水酸化リチウムを添加せず、他は本発明電池と同様
の従来電池［Ｂｌを作成した。In addition, a conventional battery [Bl] was prepared which was the same as the battery of the present invention but without the addition of lithium hydroxide.
第１図及び第２因は本発明電池と従来電池との放電特性
比較図を示し、第１因は電池組立後、直ちに室温に〉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℃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。Figures 1 and 2 show comparison diagrams of discharge characteristics between the battery of the present invention and a conventional battery, and Figure 1 shows the discharge characteristics when the battery was assembled and then immediately brought to room temperature and discharged with a constant resistance of 500Ω. ,
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
の放電においては水酸化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 was observed depending on the presence or absence of lithium hydroxide 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１ＫＨ２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 1KH2.
表
°上表の結果から明らかなように、従来電池（Ｂｌ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（Ａ１ ） （Ａ２ ）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, while the internal impedance of conventional batteries (Bl) increases after storage,
In the batteries (A1) and (A2) of the present invention, there is almost no increase in internal impedance even after storage.
父、保存後の電池を分解したところ従来電池（Ｂｌはリ
チクム負操の表面が黒く変色していたが本発明ｔａＣＡ
１）（Ａｚ）ではそのような現象は認められなかった。When my father disassembled the battery after storage, the surface of the conventional battery (Bl was black and discolored)
No such phenomenon was observed in 1) (Az).
更に、保存後の正極罐を金属顕微鏡で観察したところ、
従来電池（Ｂｌの場合にはかなりの孔蝕が認められたが
本発明電池（ＡＩ ） （Ａ２ ）の場合に軟はとんど
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
In the case of the conventional battery (Bl), considerable pitting corrosion was observed, but in the case of the battery of the present invention (AI) (A2), the soft part was hardly corroded.
尚、水酸化リチウムの添７＋Ｄ量としては第１図及び第
２図から明らかなように０．１ｇ／ｊと１．０ｇ／Ｅに
ほとんど差異がな（０，１ｇ／／で充分に効果が期待で
きることがわかる。As is clear from Figures 1 and 2, there is almost no difference in the amount of addition 7+D of lithium hydroxide between 0.1 g/j and 1.0 g/E (0.1 g/J is sufficiently effective). I know what to expect.
又、実施例ではフッ素を含むリチウム塩として三フッ化
メタンスルホン酸すチクムの場合のみを例示したが、そ
の他に六フッ化すン酸すチクムや四フッ°化ホク酸リチ
ウムなども同様に使用しつる。Furthermore, in the examples, only the case of trifluoromethanesulfonate sulfonate was used as the fluorine-containing lithium salt, but other fluorine-containing sulfonate sulfonate, lithium tetrafluoride fluoride, etc. may also be used in the same manner. Vine.
（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訃いて
、！解散に水酸化リチウムを添加することにより、低温
特性に優れるという利点を維持し且ａ電纜材料の腐蝕現
象を抑制することができるものであり、七の工業的価値
は極めて大である。(g) Effects of the invention As mentioned above, the non-aqueous electrolyte battery uses a lithium salt containing fluorine as a solute constituting the non-aqueous electrolyte. By adding lithium hydroxide to the dissolution, it is possible to maintain the advantage of excellent low-temperature properties and to suppress the corrosion phenomenon of the a-wire material, and the industrial value of 7 is extremely large.
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℃で６ケ月保存した後の放
電特性内である。
（Ａ１ ）（Ａ２ ）・・・本発明電池、（Ｂ１・・・
従来電池。The drawings show the relationship between battery voltage and discharge time; FIG. 1 shows the initial discharge characteristics, and FIG. 2 shows the discharge characteristics after storage at 60° C. for 6 months. (A1) (A2)...Battery of the present invention, (B1...
Conventional battery.
Claims (1)
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つて、前記電解液に水酸化リチ
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 containing lithium 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, wherein lithium hydroxide is added to the electrolyte. A non-aqueous electrolyte battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7657387A JPS63241866A (en) | 1987-03-30 | 1987-03-30 | Nonaqueous electrolytic battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7657387A JPS63241866A (en) | 1987-03-30 | 1987-03-30 | Nonaqueous electrolytic battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63241866A true JPS63241866A (en) | 1988-10-07 |
Family
ID=13608984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7657387A Pending JPS63241866A (en) | 1987-03-30 | 1987-03-30 | Nonaqueous electrolytic battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241866A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282563A (en) * | 1991-03-08 | 1992-10-07 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte battery and manufacture thereof |
| EP0631340A2 (en) * | 1993-06-18 | 1994-12-28 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
-
1987
- 1987-03-30 JP JP7657387A patent/JPS63241866A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282563A (en) * | 1991-03-08 | 1992-10-07 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte battery and manufacture thereof |
| EP0631340A2 (en) * | 1993-06-18 | 1994-12-28 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
| EP0631340A3 (en) * | 1993-06-18 | 1997-02-05 | Hitachi Maxell | Organic electrolytic solution cell. |
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