JPH0317185B2 - - Google Patents
Info
- Publication number
- JPH0317185B2 JPH0317185B2 JP57115694A JP11569482A JPH0317185B2 JP H0317185 B2 JPH0317185 B2 JP H0317185B2 JP 57115694 A JP57115694 A JP 57115694A JP 11569482 A JP11569482 A JP 11569482A JP H0317185 B2 JPH0317185 B2 JP H0317185B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- thionyl chloride
- negative electrode
- present
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- 229920006393 polyether sulfone Polymers 0.000 claims description 19
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 208000028659 discharge Diseases 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明は、正極活物質に塩化チオニル、負極活
物質にリチウムを用いる塩化チオニル・リチウム
電池に於いて、その表面をポリエーテルサルフオ
ンフイルムで被覆した事を特徴とするリチウム負
極を用いた電池に関するものである。[Detailed Description of the Invention] The present invention is a thionyl chloride lithium battery using thionyl chloride as a positive electrode active material and lithium as a negative electrode active material, and is characterized in that the surface thereof is coated with a polyether sulfon film. This invention relates to a battery using a lithium negative electrode.
近年著しい電子技術の進歩による電子機器の多
様化に伴い、電池に対する性能要求も多様化し、
Ag2O／Zn、MnO2／Zn、−（CF−）ｎ／Li、
MnO2／Li等の各種電池が、それぞれの用途に応
じ大量に市場に供給されてきているが、塩化チオ
ニル・リチウム電池（SOCl2／Li電池）もまた、
その優秀なる性能、即ち、高いエネルギー密度、
出力密度、安定した高い電圧、優秀な貯蔵性能、
低温性能及び高率放電性能故に市場の注目を集め
ているものの一つである。 With the diversification of electronic devices due to remarkable advances in electronic technology in recent years, the performance requirements for batteries have also diversified.
Ag 2 O/Zn, MnO 2 /Zn, -(CF-)n/Li,
Various types of batteries such as MnO 2 /Li have been supplied to the market in large quantities depending on their purpose, but lithium thionyl chloride batteries (SOCl 2 /Li batteries) are also
Its excellent performance, namely high energy density,
power density, stable high voltage, excellent storage performance,
It is one of the products that is attracting attention in the market due to its low temperature performance and high rate discharge performance.
しかるにこの電池は、第１図に示す如くその構
造上活性金属であるリチウム負極が正極活物質で
あると共に電解質としても働く塩化チオニルと接
触している為、貯蔵中にリチウムが塩化チオニル
と反応し、その表面に高抵抗の塩化リチウムの不
動態被膜が生成し、長期貯蔵後の放電初期にこの
被膜の高抵抗に起因する著しい電圧降下（電圧遅
延）を起こし実使用上著しい不都合を与えるとい
う欠点があり、この電池の性能面での唯一の欠点
となつていた。 However, as shown in Figure 1, this battery has a structure in which the lithium negative electrode, which is an active metal, is in contact with thionyl chloride, which is the positive electrode active material and also acts as an electrolyte, so lithium reacts with thionyl chloride during storage. , a high-resistance passive film of lithium chloride is formed on its surface, and the high resistance of this film causes a significant voltage drop (voltage delay) at the beginning of discharge after long-term storage, resulting in significant inconvenience in actual use. This was the only drawback in terms of performance of this battery.
従来からこの種電圧遅延解消の為、多くの発
明、考案が為されており、例えばリチウム表面を
シアノアクリル酸メチル、シアノアクリル酸エチ
ルのフイルム等で被覆してから電池の状態で71℃
において「焼き込み」を行なつたり、或いはリチ
ウム表面を塩ビ−酢ビ共重合物のフイルムで被覆
し、更に塩化チオニル中に硫化リチウムを溶解し
その相乗効果を利用することにより、貯蔵中のリ
チウム表面への塩化チオニルの作用を妨げ、その
結果不動態膜の生成を防止し、電圧遅延を防止す
る等の方法が用いられてきた。しかしながらシア
ノアクリル酸メチル、シアノアクリル酸メチルは
市販の瞬間接着剤に用いられている如く非常に接
着性に富むため、その取り扱いが困難であり、ま
た塩ビ−酢ビ共重合体の被覆は、同物質の塩化チ
オニル溶液をリチウム上に塗布した後、塩化チオ
ニルのみを蒸発除去して形成させるが、塩化チオ
ニル自体は強い刺激臭と腐蝕性、毒性を有するた
め、その作業、設備が極めて面倒であり、さらに
硫化リチウムは非常に吸湿性に富むため、その保
管、取り扱いが極めて面倒であるという欠点を有
している。 Many inventions and ideas have been made to eliminate this kind of voltage delay. For example, the lithium surface is coated with a film of methyl cyanoacrylate or ethyl cyanoacrylate, and then the battery is heated to 71°C.
By performing "burning" on the lithium surface, or by coating the lithium surface with a film of vinyl chloride-vinyl acetate copolymer, and by dissolving lithium sulfide in thionyl chloride and utilizing the synergistic effect, the lithium during storage can be Methods have been used to prevent the action of thionyl chloride on the surface, thereby preventing the formation of a passive film and preventing voltage delay. However, methyl cyanoacrylate and methyl cyanoacrylate, which are used in commercially available instant adhesives, are extremely adhesive and difficult to handle. After applying a solution of the substance thionyl chloride on lithium, only thionyl chloride is removed by evaporation, but thionyl chloride itself has a strong pungent odor, corrosivity, and toxicity, so the work and equipment are extremely troublesome. Moreover, since lithium sulfide is highly hygroscopic, it has the disadvantage that its storage and handling are extremely troublesome.
本発明はこれらの欠点を解消するもので、簡単
な操作で被覆が可能で、且つ電圧遅延を有効に抑
制することができるリチウム表面の保護被膜に関
するものである。すなわち本発明は、接着性や吸
着性がなくて取り扱いが簡単なポリエーテルサル
フオンをリチウムに対し比較的安定で、且つ毒
性、腐蝕性、引火性のない低沸点溶媒（40℃）で
ある塩化メチレンに溶かして成る溶液中にリチウ
ムを単に浸漬し次いで乾燥するだけで得られるポ
リエーテルサルフオンフイルムで被覆したリチウ
ム負極を用いる事により、電池の状態で「焼き込
み」という煩雑な操作を行なうことなく、貯蔵中
の塩化チオニルとリチウムの反応を有効に防止
し、塩化リチウムの不動態膜の生成を抑制し、そ
の結果長期貯蔵後の電圧遅延を解消し良好なる放
電性能を有するSOCl2／Li電池を提供せんとする
ものである。 The present invention solves these drawbacks and relates to a protective coating for the surface of lithium that can be coated with a simple operation and that can effectively suppress voltage delay. In other words, the present invention uses polyether sulfone, which has no adhesive or adsorbing properties and is easy to handle, to chloride, which is a low boiling point solvent (40°C) that is relatively stable against lithium and is non-toxic, corrosive, and non-flammable. By using a lithium negative electrode coated with a polyether sulfon film obtained by simply immersing lithium in a solution prepared by dissolving it in methylene and then drying it, a complicated operation called "burning" is performed in the battery state. SOCl 2 /Li effectively prevents the reaction between thionyl chloride and lithium during storage, suppresses the formation of a passive film of lithium chloride, eliminates voltage delay after long-term storage, and has good discharge performance. The aim is to provide batteries.
以下本発明の一実施例を図面に基づき説明す
る。第１図は本発明によるポリエーテルサルフオ
ン被膜でその表面を覆つたリチウム負極を用いた
直径14mmφ、高さ29mmのSOCl2／Li電池の縦断面
図である。図中１はSuS304より成る正極ケース、
２はテフロンとアセチレンブラツクより成る正極
集電体、３はガラス不織布より成るセパレータ
ー、４は本発明のリチウム負極５はニツケルによ
り成る負極リード、６は正極活物質として働くと
共に電解液としても作用する1.5MのLiAlCl4を含
んだ塩化チオニル、７はSuS304製の負極端子で
注液管の役割も行なう先端は熔融封止されてお
り、SuS304製のケースフタ８とはガラス層９に
より絶縁、ハーメチツクシールされている。 An embodiment of the present invention will be described below based on the drawings. FIG. 1 is a longitudinal sectional view of an SOCl 2 /Li battery having a diameter of 14 mmφ and a height of 29 mm, using a lithium negative electrode whose surface is covered with a polyether sulfon film according to the present invention. 1 in the figure is a positive electrode case made of SuS304.
2 is a positive electrode current collector made of Teflon and acetylene black, 3 is a separator made of glass non-woven fabric, 4 is a lithium negative electrode 5 of the present invention is a negative electrode lead made of nickel, and 6 acts as a positive electrode active material and also acts as an electrolyte. Thionyl chloride containing 1.5M LiAlCl 4 , 7 is a negative electrode terminal made of SuS304, the tip which also serves as a liquid injection pipe is melt-sealed, and the case lid 8 made of SuS304 is insulated by a glass layer 9 and hermetically sealed. It has been sealed.
第２図は本発明によるリチウム負極の拡大断面
図であり、リチウム１０の外表面をポリエーテル
サルフオン１１で被覆したものであり、ドライボ
ツクス中にてポリエーテルサルフオンの５％塩化
メチレン溶液中にリチウムを浸漬後、直ちに引き
上げ乾燥するのみという簡単な操作により得られ
たものである。 FIG. 2 is an enlarged cross-sectional view of a lithium negative electrode according to the present invention, in which the outer surface of lithium 10 is coated with polyethersulfon 11, and the electrode is placed in a 5% methylene chloride solution of polyethersulfon in a dry box. It was obtained by a simple operation of immersing lithium in water and immediately pulling it up and drying it.
尚、ポリエーテルサルフオンの被覆は塩化メチ
レンに溶解させた任意の濃度のポリエーテルサル
フオン溶液中にリチウムを浸漬後乾燥することに
より容易に形成することができ、またポリエーテ
ルサルフオン塩化メチレン溶液は吸湿性接着性に
乏しいので通常大気中にて調整ができその取り扱
いは極めて容易である。 The polyether sulfon coating can be easily formed by immersing lithium in a polyether sulfon solution of any concentration dissolved in methylene chloride and then drying it. Because it has poor hygroscopic adhesive properties, it can usually be prepared in the atmosphere and is extremely easy to handle.
つぎに本実施例に基づくSOCl2／Li電池Ａと全
く処理していないリチウムを用いて作成した電池
Ｂをそれぞれ60℃で10日間貯蔵した時1KΩ負荷、
温度25℃で放電した時の放電初期特性の比較を第
３図に示す。これより明らかな如く、本発明に基
づく電池は放電初期の電圧遅延がなく良好な立上
がり特性を示すのが判る。 Next, when SOCl 2 /Li battery A based on this example and battery B made using completely untreated lithium were stored at 60°C for 10 days, the load was 1KΩ.
Figure 3 shows a comparison of the initial discharge characteristics when discharged at a temperature of 25°C. As is clear from this, the battery according to the present invention has no voltage delay at the initial stage of discharge and exhibits good start-up characteristics.
またポリエーテルサルフオンの膜厚と効果の関
係を間接的に調べる為、ポリエーテルサルフオン
の塩化メチレン溶液濃度を５％〜40％の範囲で変
えてそれぞれリチウムを浸漬乾燥させてその表面
に各種膜厚のポリエーテルサルフオン層を形成せ
しめ、本実施例に基づく構造の電池を作成し、前
述と同一の試験を行ない電圧遅延を調べた。 In addition, in order to indirectly investigate the relationship between the film thickness and the effect of polyether sulfon, we varied the concentration of polyether sulfon in methylene chloride solution in the range of 5% to 40%, immersed and dried lithium, and applied various types of polyether sulfon to the surface. A battery having a structure based on this example was prepared by forming a thick polyether sulfon layer, and the same test as described above was conducted to examine the voltage delay.
結果を第４図に示す。全範囲に亘つて電圧遅延
抑制効果が認められたが、特に好ましいのは５％
〜15％の濃度範囲であつた。 The results are shown in Figure 4. Voltage delay suppressing effects were observed over the entire range, but 5% is particularly preferable.
The concentration range was ~15%.
このことより、ポリエーテルサルフオン被膜の
厚みと電圧遅延抑制効果の間には何らかの関係が
ありそうであるが、ポリエーテルサルフオン自体
の塩化チオニル中でのリチウムの保護機構が明確
でないため、はつきりした事は判らない。 From this, it seems that there is some relationship between the thickness of the polyether sulfon coating and the voltage delay suppressing effect, but since the protection mechanism of polyether sulfon itself for lithium in thionyl chloride is not clear, I don't know what happened.
しかしながらポリエーテルサルフオンによる電
圧遅延抑制効果はその塗膜厚に関係なく明らかで
あることは一目瞭然である。 However, it is obvious that the voltage delay suppressing effect of polyether sulfon is obvious regardless of the coating thickness.
以上より明らかな如く、本発明は電圧遅延のな
いSOCl2／Li電池を容易に提供するものであり、
その工業的価値著しく大である。 As is clear from the above, the present invention easily provides an SOCl 2 /Li battery without voltage delay,
Its industrial value is extremely large.
第１図は本発明に基づくリチウムを用いた
SOCl2／Li電池の縦断面図。第２図は、本発明に
基づくポリエーテルサルフオン被膜を有するリチ
ウムの部分断面拡大図。第３図は本発明に基づく
電池Ａと従来の電池Ｂの放電曲線。第４図はポリ
エーテルサルフオンの塩化メチレン溶液濃度と30
秒目電圧の相関図。
４……リチウム負極、１０……リチウム、１１
……ポリエーテルサルフオン。
Figure 1 shows a sample using lithium according to the present invention.
Longitudinal cross-sectional view of SOCl 2 /Li battery. FIG. 2 is an enlarged partial cross-sectional view of lithium with a polyether sulfon coating according to the present invention. FIG. 3 shows the discharge curves of battery A according to the present invention and conventional battery B. Figure 4 shows the concentration of polyether sulfone in methylene chloride solution and 30
Correlation diagram of second voltage. 4...Lithium negative electrode, 10...Lithium, 11
...Polyether sulfon.
Claims (1)
たリチウムを負極活物質として用いることを特徴
とした塩化チオニル・リチウム電池。1. A thionyl chloride lithium battery characterized by using lithium whose surface is coated with polyether sulfone resin as a negative electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11569482A JPS598275A (en) | 1982-07-02 | 1982-07-02 | Thionyl chloride-lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11569482A JPS598275A (en) | 1982-07-02 | 1982-07-02 | Thionyl chloride-lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS598275A JPS598275A (en) | 1984-01-17 |
| JPH0317185B2 true JPH0317185B2 (en) | 1991-03-07 |
Family
ID=14668921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11569482A Granted JPS598275A (en) | 1982-07-02 | 1982-07-02 | Thionyl chloride-lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS598275A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0157878B1 (en) * | 1983-09-29 | 1990-01-31 | Medtronic, Inc. | Nonaqueous electrochemical cell |
| EP3480901B1 (en) | 2017-11-06 | 2020-02-19 | Schleifring GmbH | Vibration absorbing device for slip-ring brushes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5553073A (en) * | 1978-10-11 | 1980-04-18 | Catanzarite Vincent Owen | Lithium anode* thionyl chloride active cathode electrochemical battery coating |
-
1982
- 1982-07-02 JP JP11569482A patent/JPS598275A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5553073A (en) * | 1978-10-11 | 1980-04-18 | Catanzarite Vincent Owen | Lithium anode* thionyl chloride active cathode electrochemical battery coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS598275A (en) | 1984-01-17 |
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