JPS63236256A - Organic electrolytic solution battery - Google Patents
Organic electrolytic solution batteryInfo
- Publication number
- JPS63236256A JPS63236256A JP6931087A JP6931087A JPS63236256A JP S63236256 A JPS63236256 A JP S63236256A JP 6931087 A JP6931087 A JP 6931087A JP 6931087 A JP6931087 A JP 6931087A JP S63236256 A JPS63236256 A JP S63236256A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrolytic solution
- carbon
- carbon black
- separator
- 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
- 239000008151 electrolyte solution Substances 0.000 title abstract 4
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000005486 organic electrolyte Substances 0.000 claims description 12
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- -1 polypropylene Polymers 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KQGNOMIWXOGHDR-UHFFFAOYSA-N [C].[Li].[C] Chemical compound [C].[Li].[C] KQGNOMIWXOGHDR-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/06—Electrodes for primary cells
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、有機電解液を使用する、例えば、ぶつ化炭素
−リチウム電池の正極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improvements in positive electrodes, for example for carbon-lithium carbon batteries, using organic electrolytes.
従来の技術
この種の負極活物質として、リチウム、マグネシウム等
の軽金属を用い、正極活物質としてぶつ化炭素を用いた
有機電解液電池は、放電電圧の安定性と長期信頼性に優
れている。しかし反面、ぶつ化炭素は導電性が悪いため
、電池の内部抵抗が大きくなる。この問題を解決するた
めに従来は、比表面積が７０〜１ｏＯｒｒＩ！／ｇのカ
ーボンブラックを導電剤とし、このカーボンブラックを
ふっ素樹脂等の結着剤とともにぶつ化炭素と混合して、
正極を形成していた。BACKGROUND OF THE INVENTION This type of organic electrolyte battery using light metals such as lithium, magnesium, etc. as a negative electrode active material and carbon dioxide as a positive electrode active material has excellent discharge voltage stability and long-term reliability. However, on the other hand, since carbon dioxide has poor conductivity, the internal resistance of the battery increases. Conventionally, to solve this problem, the specific surface area was set at 70 to 10OrrI! /g of carbon black is used as a conductive agent, and this carbon black is mixed with carbonized carbon along with a binder such as a fluororesin.
It formed the positive electrode.
発明が解決しようとする問題点
しかしながら、このような従来の有機電解液電池では、
ふり化炭素が電解液をはじきやすく、さらに、カーボン
ブラックの電解液保持能力が少ないため、正極として電
解液を十分には保持することができず、このため、正極
が安定した反応を行なうことができない。また、カーボ
ンブラックの正極混入時において、初−ポンプラックの
組織がばらばらになるため、導電性が減少する。これら
のため、従来の有機電解液電池は、放電維持電圧特性（
ＣＣＶ特性）を向上させにくいという問題点があった。Problems to be Solved by the Invention However, in such conventional organic electrolyte batteries,
Carbon fluoride easily repels the electrolyte, and carbon black has a low ability to retain the electrolyte, so the positive electrode cannot sufficiently retain the electrolyte, making it difficult for the positive electrode to perform stable reactions. Can not. Furthermore, when carbon black is mixed into the positive electrode, the structure of the first pump rack becomes fragmented, resulting in a decrease in conductivity. For these reasons, conventional organic electrolyte batteries have a discharge sustaining voltage characteristic (
There was a problem in that it was difficult to improve the CCV characteristics.
本発明は、このような問題点を解決するもので、ＣＣｖ
特性を向上させることができる有機電解液電池を提供す
るものである。The present invention solves these problems, and CCv
An object of the present invention is to provide an organic electrolyte battery whose characteristics can be improved.
問題点を解決するための手段
このような従来の問題点を解決するために本発明は、ふ
り化炭素を活物質とする正極に、活性炭と中空のシェル
状粒子からなるカーボンブランクとを混入したものであ
る。Means for Solving the Problems In order to solve these conventional problems, the present invention mixes activated carbon and a carbon blank made of hollow shell-like particles into a positive electrode whose active material is carbon fluoride. It is something.
作用
上記構成によれば、カーボンブラックの粒子が中空のシ
ェル状粒子であるため、有機電解液の保持性がよく、こ
の中空のシェル状粒子からなるカーボンブラックと、さ
らに活性炭を正極に混入するため、正極の有機電解液保
持力を向上させることができ、正極と有機電解液との実
際の反応面積を増やすことができるとともに、正極内に
おける導電性を向上させることができる。その結果、電
池のＣＣＶ特性を向上させることができる。Effect According to the above configuration, since the carbon black particles are hollow shell-like particles, they have good retention of the organic electrolyte, and since the carbon black made of the hollow shell-like particles and activated carbon are further mixed into the positive electrode. , the organic electrolyte holding power of the positive electrode can be improved, the actual reaction area between the positive electrode and the organic electrolyte can be increased, and the conductivity within the positive electrode can be improved. As a result, the CCV characteristics of the battery can be improved.
実施例
以下、本発明の一実施例を図にもとづいて説明する０
図において、１は内面にニッケル鍍金を施したステンレ
ス鋼からなる有底円筒形状の正極缶である。この正極缶
１の内底部分には、導電性炭素塗膜２を塗布している。EXAMPLE Hereinafter, an example of the present invention will be described with reference to the drawings. In the drawings, reference numeral 1 denotes a bottomed cylindrical positive electrode can made of stainless steel whose inner surface is nickel plated. A conductive carbon coating film 2 is applied to the inner bottom portion of the positive electrode can 1 .
この導電性炭素塗膜２の上には正極３を設けており、こ
の正極３は、ふっ化炭素を９０重量パーセント（ｗｔ％
）、中空のシェル状粒子からなる比表面積９ｏｏｒｒ？
／！のカーボンブラック６ ｅｓ ｗ ｔ％、比表面積
２０００♂／ｇの活性炭粉末’ｉｉＩｗｔ％、ふっ素樹
脂等の結着剤’１４ｗｔ％混合して形成されている。前
記正極３の上には、ポリプロピレン不織布からなるセパ
レータ４を設けている。このセパレータ４の上には、金
属リチウムからなる負極５を設けている。この負極６の
上部には、封口板６を圧着固定している。A positive electrode 3 is provided on this conductive carbon coating film 2, and this positive electrode 3 contains 90% by weight (wt%) of fluorocarbon.
), the specific surface area of hollow shell-like particles is 9oorr?
/! It is formed by mixing 6 es wt% of carbon black, 11wt% of activated carbon powder with a specific surface area of 2000♂/g, and 14 wt% of a binder such as a fluororesin. A separator 4 made of polypropylene nonwoven fabric is provided on the positive electrode 3. On this separator 4, a negative electrode 5 made of metallic lithium is provided. A sealing plate 6 is crimped and fixed to the upper part of this negative electrode 6.
この封口板６の周縁部は、絶縁体からなるガスケツドア
を介して正極缶１にかしめられておジ、封口板６が負極
６．セパレータ４．正極３を正極缶１の内部方向に付勢
している。なお、電解液には、ｒ−ブチロラクトンとジ
メトキシエタンとの混合有機溶媒にほうふつ化リチウム
全溶解させたものを用い、電池の外径を２３電、高さ２
２．０間とした０
以上のように構成した電池人と、正極に活性炭を混入し
てないことの他は電池人と同構成の電池Ｂと、比表面積
了Ｏｒｎ’／ダのアセチレンブラック１ｏｗｔ％、ふっ
化炭素ａ ｓ ｗｔ％、結着剤ｓｗｔ％とから形成した
正極を用いた従来の電池Ｃとを試作し、それぞれの電池
について、試作直後と保存後とで３００Ω定抵抗負荷、
２０℃におけるＣＣＶ特性値全測定した結果を表に示す
。なお、保存条件としては、温度６０℃で３０日間とし
た。The peripheral edge of the sealing plate 6 is caulked to the positive electrode can 1 via a gasket door made of an insulator, and the sealing plate 6 is attached to the negative electrode 6. Separator 4. The positive electrode 3 is urged toward the inside of the positive electrode can 1. The electrolyte used was one in which lithium fluoride was completely dissolved in a mixed organic solvent of r-butyrolactone and dimethoxyethane.
A battery constructed as above, a battery B having the same structure as the battery except that activated carbon was not mixed in the positive electrode, and acetylene black 1 ow with a specific surface area of 2.0. %, fluorocarbon a s wt %, and a binder s wt %.For each battery, a 300Ω constant resistance load was applied immediately after the prototype production and after storage.
The results of all measurements of CCV characteristic values at 20°C are shown in the table. Note that the storage conditions were a temperature of 60° C. for 30 days.
表
表から明らかなように、本実施例における電池人は、電
池Ｂ、Ｃに比べてＣＯＷ特性が優れている。As is clear from the table, the battery in this example has better COW characteristics than batteries B and C.
なお、実施例では比表面積が９ｏｏ１１１！／ｆのカー
ボンブランクについて述べた７％、９００ ｒｒ？／’
９以上の比表面積を有するカーボンブラックについて
も検討を行なったが、同様な効果が得られた。In addition, in the example, the specific surface area is 9oo111! /f carbon blank mentioned 7%, 900 rr? /'
Carbon black having a specific surface area of 9 or more was also investigated, and similar effects were obtained.
まｋ、正極の導電性を得るためのカーボンブラックの適
量は３〜９ｗｔ％で十分であり、従来のカーボンブラッ
クの量より少なくすることができる。The appropriate amount of carbon black for obtaining conductivity of the positive electrode is sufficient at 3 to 9 wt%, and can be lower than the conventional amount of carbon black.
そして、正極に混入する活性炭粉末量は５〜２０ｗｔ％
が最も良い結果であった。The amount of activated carbon powder mixed into the positive electrode is 5 to 20 wt%.
was the best result.
なお、このような粉末を均一に分散させ、均一な正極を
得るには作業上の注意を必要とするが、本発明者等の検
討では、カーボンブラックと活性炭を有機溶媒中でそれ
ぞれを分散混合した後、スラリー状態でふっ化炭素と、
そｎぞれを添加練合することにより均質で電気抵抗の安
定した正極が得らｎることが明らかとなった。Although it is necessary to be careful when working to uniformly disperse such powder and obtain a uniform positive electrode, the present inventors have investigated the method of dispersing and mixing carbon black and activated carbon in an organic solvent. After that, with fluorocarbon in slurry state,
It has become clear that a homogeneous positive electrode with stable electrical resistance can be obtained by adding and kneading each of them.
また、この正極を使用した電池のＣＣｖ特性のばらつき
度合は従来電池に比べ約捧であった。Furthermore, the degree of variation in CCv characteristics of batteries using this positive electrode was about 100% compared to conventional batteries.
発明の効果
以上の説明から明らかなように本発明は、ぶつ化炭素を
活物質とする正極に、活性炭と中空のシエル状粒子から
なるカーボンブラックとを混入したことにより、カーボ
ンブラックと活性炭の相乗効果のため、正極の電解液保
持力を向上させることができ、正極の実際の反応面積を
増やせるとともに正極の導電性を向上させることができ
る。その結果、ＣＣＶ特性の優れた有機電解液電池を得
ることができる。Effects of the Invention As is clear from the above explanation, the present invention has a positive electrode containing carbon dioxide as an active material, mixed with activated carbon and carbon black consisting of hollow shell-shaped particles. As a result, the electrolyte holding power of the positive electrode can be improved, the actual reaction area of the positive electrode can be increased, and the conductivity of the positive electrode can be improved. As a result, an organic electrolyte battery with excellent CCV characteristics can be obtained.
図は本発明の一実施例における有機電解液電池の縦断面
図である。
１・・・・・・正極Ｌ ３・・・・・・正極、４・・・
・・・セパレータ、６・・・・・・負極、６・・・・・
・封口板、Ｔ・・・・・・ガスケット。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名／−
−−正極お
３−正 極
４−でパレータ
５− 負 極
６− 付口抜
７−・−ガスケットThe figure is a longitudinal cross-sectional view of an organic electrolyte battery according to an embodiment of the present invention. 1...Positive electrode L 3...Positive electrode, 4...
...Separator, 6...Negative electrode, 6...
・Sealing plate, T...Gasket. Name of agent: Patent attorney Toshio Nakao and 1 other person/-
--Positive electrode 3-Positive electrode 4- and pallet 5- Negative electrode 6- With opening 7-・-Gasket
Claims (1)
介して対向し、ふっ化炭素を活物質とする正極と、前記
負極および正極に接触する有機電解液とを備え、前記正
極に、活性炭と中空のシェル状粒子からなるカーボンブ
ラックとを混入した有機電解液電池。A negative electrode having a light metal as an active material, a positive electrode facing the negative electrode with a separator in between and having fluorocarbon as an active material, and an organic electrolyte in contact with the negative electrode and the positive electrode. An organic electrolyte battery mixed with carbon black consisting of hollow shell-like particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6931087A JPS63236256A (en) | 1987-03-24 | 1987-03-24 | Organic electrolytic solution battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6931087A JPS63236256A (en) | 1987-03-24 | 1987-03-24 | Organic electrolytic solution battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63236256A true JPS63236256A (en) | 1988-10-03 |
Family
ID=13398858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6931087A Pending JPS63236256A (en) | 1987-03-24 | 1987-03-24 | Organic electrolytic solution battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63236256A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100330633B1 (en) * | 1993-09-30 | 2002-10-25 | 스미또모 가가꾸 고교 가부시끼가이샤 | Lithium secondary battery |
-
1987
- 1987-03-24 JP JP6931087A patent/JPS63236256A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100330633B1 (en) * | 1993-09-30 | 2002-10-25 | 스미또모 가가꾸 고교 가부시끼가이샤 | Lithium secondary battery |
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