JPS62249355A - Inorganic nonaqueous electrolyte battery - Google Patents
Inorganic nonaqueous electrolyte batteryInfo
- Publication number
- JPS62249355A JPS62249355A JP61091026A JP9102686A JPS62249355A JP S62249355 A JPS62249355 A JP S62249355A JP 61091026 A JP61091026 A JP 61091026A JP 9102686 A JP9102686 A JP 9102686A JP S62249355 A JPS62249355 A JP S62249355A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- carbon
- battery
- carbon black
- stiffness value
- 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 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000004898 kneading Methods 0.000 abstract description 8
- 238000005087 graphitization Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract 2
- 239000006230 acetylene black Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003115 supporting electrolyte 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
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は無機非水電解液電池に係わり、さらに詳しく
はその正極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to inorganic non-aqueous electrolyte batteries, and more particularly to improvements in positive electrodes thereof.
従来、リチウム、ナトリウムなどのアルカリ金属を負極
とし、塩化チオニル、塩化スルフリル、塩化ホスホリル
などのオキシハロゲン化物を正極活物質および電解液の
溶媒とする無機非水電解液電池においては、正極にはア
セチレンブラックを主成分とし、このアセチレンブラッ
クとポリテトラフルオロエチレンと黒鉛を混練した配合
剤で作製した炭素多孔質成形体が用いられていた（たと
えば特願昭５８−１２１５６３号公報）。Conventionally, in inorganic nonaqueous electrolyte batteries in which alkali metals such as lithium and sodium are used as the negative electrode and oxyhalides such as thionyl chloride, sulfuryl chloride, and phosphoryl chloride are used as the positive electrode active material and the electrolyte solvent, acetylene is used as the positive electrode. A carbon porous molded body made of a mixture of black as a main component and acetylene black, polytetrafluoroethylene, and graphite has been used (for example, Japanese Patent Application No. 121563/1982).
上記炭素多孔質成形体正極の炭素質は正極活物質である
オキシハロゲン化物を還元するための触媒として働くも
のであるが、炭素多孔質成形体正極の作製にあたって、
炭素質としてアセチレンブラックを用いるのは、アセチ
レンブラックは一般のカーボンブラックに比べて揮発性
物質などの不純物が少なく、不純物が正極活物質のオキ
シハロゲン化物と反応して電池容量を低下させることが
少ないからである。The carbon material of the above-mentioned carbon porous molded positive electrode acts as a catalyst for reducing the oxyhalide which is the positive electrode active material, but in preparing the carbon porous molded positive electrode,
Acetylene black is used as the carbon material because it contains fewer impurities such as volatile substances than ordinary carbon black, and impurities are less likely to react with the oxyhalide of the positive electrode active material and reduce battery capacity. It is from.
しかしながら、上記正極の主成分であるアセチレンブラ
ックは、機械的強度が弱く、混練によってその鎖状構造
が破壊されて、正極内の電子伝導性が低下し、その結果
、電池の内部抵抗が大き（なって放電容量が低下すると
いう問題があった。However, acetylene black, which is the main component of the positive electrode, has weak mechanical strength, and its chain structure is destroyed by kneading, reducing the electronic conductivity within the positive electrode. As a result, the internal resistance of the battery increases ( Therefore, there was a problem that the discharge capacity decreased.
本発明は上述した従来技術の問題点を解決するもので、
炭素多孔質成形体正極を、揮発性物質が少なく、黒鉛化
度が太き（、かつ大きな鎮状構造を有するカーボンブラ
ックを主成分とする配合剤で作製することによって目的
を達成したものである。The present invention solves the problems of the prior art described above.
This goal was achieved by creating a carbon porous molded positive electrode with a compound containing carbon black as the main component, which contains less volatile substances, has a high degree of graphitization (and has a large slag structure). .
すなわち、本発明は、揮発性物質が０．２重量％以下で
、ＣｕＫα線によるＸ線回折で回折角２６．９’付近の
炭素（００２）の半価幅が４．９°であり、アブソープ
シジンスティフネス（＾ｂｓｏｒｐｔｉｏｎ ５ｔｉｆ
ｆｉｎｅｓｓ ）値が３３ｃｄ／ ５ ｇ 〜４０ａＪ
／ ５ ｇのカーボンブラックを主成分とする配合剤で
炭素多孔質成形体正極を作製することによって、正極作
製にあたっての混練による電子伝導性の低下を防止して
、電子伝導性が高い正極を得たものである。That is, in the present invention, the volatile substance is 0.2% by weight or less, the half-width of carbon (002) near the diffraction angle of 26.9' is 4.9° in X-ray diffraction using CuKα rays, and the Soapsygin Stiffness (^bsorption 5tif)
finess) value is 33cd/5g ~ 40aJ
By producing a carbon porous molded positive electrode with a compounding material containing / 5 g of carbon black as a main component, a decrease in electronic conductivity due to kneading during positive electrode production can be prevented, and a positive electrode with high electronic conductivity can be obtained. It is something that
本発明で用いるカーボンブラックは、上記のように、揮
発性物質が０．２重量％以下で、揮発性物質の含有量が
アセチレンブラックと同程度であって、通常のカーボン
ブランク（揮発性物質の含有量は通常０．５〜１７．０
重量％）より少ないので、正極とした場合に不純物によ
る副反応が少な（、またＣｕＫα線によるＸ線回折で回
折角２６．９°付近の炭素（００２）の半価幅が４．９
°と通常のカーボンブラックよりも小さく、結晶性が良
好で黒鉛化度が大きく、かつアブソーブションスティフ
ネス値（アブソーブションスティフネス値とは、試料５
ｇにアセトンを１０％含有するアセトン水溶液を加え団
塊状になった時の液量をいう）が３３ｃｄ／５ｇ〜４０
ｃｄ１５ｇでアセチレンブラックのアブソーブションス
ティフネス値３１ｃｍ３／５ｇより大きく、アセチレン
ブラックと同様に鎖状構造ををし、かつその鎖状構造が
上記アブソープションスティフネス値からも明らかなよ
うにアセチレンブラックより発達している。したがって
、このカーボンブラックを用いて正極を作製した場合は
、不純物による副反応が少なく、またアセチレンブラッ
クと同様に鎖状構造を有しており、かつ、後に第３図に
基づいて詳述するように、同じ時間粉砕した場合のアブ
ソープションスティフネス値が常にアセチレンブラック
より大きく、したがって同時間の粉砕では常にアセチレ
ンブランクより大きな鎖状構造を有しているので、アセ
チレンブラックを用いる場合に比べて電子伝導性の高い
正極を得ることができる。また、同様に第３１）ｉ！ｌ
に示されるように、このカーボンブラックは、アセチレ
ンブランクに比べて混練による鎮状構造の破壊率が少な
く、混線による電子伝導性の喪失が少ないので、混線を
アセチレンブランクの場合より長く行うことができ、少
量のポリテトラフルオロエチレンの使用でも、長時間混
練によりポリテトラフルオロエチレンの結着作用を充分
に発揮させることができる。したがって、このカーボン
ブラックを主成分とする配合剤を用いた場合には、アセ
チレンブラックを用いる場合に比べて機械的強度の大き
い正極を得ることができる。As mentioned above, the carbon black used in the present invention has a volatile substance content of 0.2% by weight or less, the content of volatile substances is about the same as that of acetylene black, and the carbon black used in the present invention is The content is usually 0.5-17.0
(% by weight), so there are fewer side reactions due to impurities when used as a positive electrode (Also, in X-ray diffraction with CuKα rays, the half width of carbon (002) at a diffraction angle of around 26.9° is 4.9
° and smaller than normal carbon black, good crystallinity, high graphitization degree, and absorption stiffness value (absorption stiffness value refers to sample 5
The amount of liquid when an acetone aqueous solution containing 10% acetone is added to g to form a lump) is 33 cd/5 g to 40
CD15g is greater than the absorption stiffness value of acetylene black, 31cm3/5g, and it has a chain structure similar to acetylene black, and the chain structure is more developed than acetylene black, as is clear from the above absorption stiffness value. ing. Therefore, when a positive electrode is produced using this carbon black, there are fewer side reactions due to impurities, and it has a chain structure like acetylene black, and as will be explained in detail later based on Figure 3. In addition, the absorption stiffness value is always larger than that of acetylene black when milled for the same time, and therefore it always has a larger chain structure than acetylene blank when milled for the same time. A highly conductive positive electrode can be obtained. Similarly, 31) i! l
As shown in , this carbon black has a lower rate of destruction of the silane structure due to kneading than an acetylene blank, and less loss of electronic conductivity due to cross-talk, so cross-crossing can be carried out for a longer period of time than with an acetylene blank. Even if a small amount of polytetrafluoroethylene is used, the binding effect of polytetrafluoroethylene can be fully exhibited by long-time kneading. Therefore, when a compounding agent containing carbon black as a main component is used, a positive electrode having greater mechanical strength can be obtained than when acetylene black is used.
上記のごと＜、揮発性物質が０．２ 重量％以下で、Ｃ
ｕＫｏｔ線によるＸ線回折で回折角２６．９°付近の炭
素（００２）の半価幅が４．９°であり、アブソーブシ
ョンスティフネス値が３３ｃｄ／５ｇ〜４０−７５ｇと
いう特性を持つカーボンブラックとしては、たとえばベ
ルギー国のセデマ社よりエンサグリ・スーパーＳ （Ｅ
ＮＳＡＧＲＩ・５ＵＰＩ！ＲＳ）の商品名で市販されて
いるカーボンブラックをその一例としてあげることがで
きる。As above, volatile substances are 0.2% by weight or less, C
As a carbon black that has the characteristics that the half width of carbon (002) near the diffraction angle of 26.9° is 4.9° in X-ray diffraction using uKot rays, and the absorption stiffness value is 33cd/5g to 40-75g. For example, Ensagri Super S (E
NSAGRI・5UPI! An example of such carbon black is commercially available under the trade name RS.
第３図に上記エンサグリ・スーパーＳとアセチレンブラ
ックをボールミルで粉砕したときの粉砕時間とアブソー
プションスティフネス値との関係を示す。なお、粉砕に
使用されたボールミルは直径５０ｍ＋ｗ、内部有効長さ
５００＋ｗ＋ｗで、直径１３ＩＩＩＩ１）の磁性ボール
が６０個入れられており、粉砕はこのボールミル内に試
料をそれぞれ１０ｇずつ入れ、ボールミルを回転速度２
５ｒｐ＋＊で回転させることによって行われた。なお、
第３図において、曲線■は上記エンサグリ・スーパーＳ
の粉砕時間に伴うアブソープションスティフネス値の変
化を表し、曲線■はアセチレンブラックの粉砕時間に伴
うアブソープションステイフネス値の変化を表す。第３
図に示すように、同じ粉砕時間で比較した場合のエンサ
グリ・スーパーＳのアブソープションスティフネス値は
常にアセチレンブラックより大きく、エンサグリ・スー
パーＳの方がアセチレンブランクより常に大きな鎖状構
造を保有している。また、混練によるアブソープション
スティフネス値の低下も、エンサグリ・スーパーＳの方
がアセチレンブラックより若干少なく、強度的にもエン
サグリ・スーパーＳの方がアセチレンブラックより優れ
ている。FIG. 3 shows the relationship between the grinding time and the absorption stiffness value when the Ensagri Super S and acetylene black were ground in a ball mill. The ball mill used for pulverization has a diameter of 50 m + w, an internal effective length of 500 + w + w, and contains 60 magnetic balls with a diameter of 13 III 1). For pulverization, 10 g of each sample is placed in this ball mill, and the ball mill is rotated at a rotation speed. 2
This was done by rotating at 5 rp+*. In addition,
In Figure 3, the curve ■ is the Ensagri Super S
The curve ■ represents the change in the absorption stiffness value with the grinding time of acetylene black, and the curve ■ represents the change in the absorption stiffness value with the grinding time of acetylene black. Third
As shown in the figure, the absorption stiffness value of Ensagri Super S is always larger than that of acetylene black when compared at the same grinding time, and Ensagri Super S always has a larger chain structure than acetylene blank. There is. Furthermore, the reduction in absorption stiffness value due to kneading is slightly lower for Ensagri Super S than for acetylene black, and Ensagri Super S is also superior to acetylene black in terms of strength.
本発明においては、上記特定のカーボンブランクを主成
分とし、通常、これに強度向上の目的で黒鉛と結着剤と
してのポリテトラフルオロエチレンを加え、さらにメチ
ルアルコール、水などの揮発性成分を添加して混練し、
得られた混練物を押出成形機で押出成形し、乾燥して揮
発性成分を除去することによって炭素多孔質成形体正極
が得られる。In the present invention, the above-mentioned specific carbon blank is the main component, and graphite and polytetrafluoroethylene as a binder are usually added to this for the purpose of improving strength, and volatile components such as methyl alcohol and water are also added. and knead.
The obtained kneaded product is extruded using an extrusion molding machine, and the volatile components are removed by drying to obtain a carbon porous molded positive electrode.
本発明において、炭素多孔質成形体正極を作製する配合
剤とは、上記のような押出成形に際して使用した揮発性
成分を含む混線物から水、メチルアルコールなどの揮発
性成分を除いた固形分をいい、該配合剤において前記特
定のカーボンブラックの量は通常８５〜９５重量％であ
る。In the present invention, the compounding agent for producing the carbon porous molded positive electrode is the solid content obtained by removing volatile components such as water and methyl alcohol from the mixture containing volatile components used during extrusion molding as described above. Yes, the amount of the specific carbon black in the formulation is usually 85 to 95% by weight.
本発明においては、用いるカーボンブランクの揮発性物
質を０．２重量％以下に特定しているが、これは揮発性
物質量をアセチレンブラックと同程度にして、不純物に
よるオキシハロゲン化物との副反応をできるだけ少なく
するためである。また、用いるカーボンブラックのＣｕ
Ｋα線によるＸ線回折で回折角２６．９°付近の炭素（
００２）の半価幅を４．９°としているのは、このよう
に炭素（００２）の半価幅が小さいものは結晶性が高く
黒鉛化度が大きく、かつ不純物が少な（電子伝導性も良
好であるからである。そして、用いるカーボンブランク
のアブソープションスティフネス値を３３−１５ｇ〜４
０ｃｍ３／５ｇの範囲に特定しているのは、アプソーブ
シロンステイフネス値が３３ａＪ／５ｇより小さいとア
セチレンブラックとの差が少なくなり、このカーボンブ
ラックの特徴を充分に発揮させることができず、一方、
アブソープションスティフネス値が４０ａＪ／５ｇより
大きなものは、表面積が大きく結晶性が小さいので、機
械的強度が小さくなり、初期のアブソーブションスティ
フネス値が大きくても混練による鎮状構造の破壊が生じ
て電子伝導性の高い正極が得られなくなるからである。In the present invention, the volatile substances of the carbon blank used are specified to be 0.2% by weight or less, but this is because the amount of volatile substances is about the same as that of acetylene black, and side reactions with oxyhalides caused by impurities are prevented. The purpose is to minimize this. In addition, Cu of the carbon black used
X-ray diffraction using Kα rays reveals carbon (
The reason why the half-width of carbon (002) is set at 4.9° is because carbon (002) with a small half-width has high crystallinity, a high degree of graphitization, and has few impurities (also has low electronic conductivity). This is because the absorption stiffness value of the carbon blank used is 33-15g to 4.
The reason for specifying the range of 0cm3/5g is that if the Absorbsilon stiffness value is smaller than 33aJ/5g, the difference from acetylene black will be small and the characteristics of this carbon black will not be fully exhibited. on the other hand,
If the absorption stiffness value is larger than 40aJ/5g, the surface area is large and the crystallinity is small, so the mechanical strength is small, and even if the initial absorption stiffness value is large, the quenched structure will be destroyed by kneading. This is because a positive electrode with high electron conductivity cannot be obtained.
つまり、３３ａＪ／ ５ ｇ 〜４０ｃｓｉ／ ５ ｇ
という特定範囲のアブソーブションスティフネス値のも
ののみが電子伝導性の高い正極を得る上において有用な
のである。That is, 33aJ/5g ~40csi/5g
Only those having an absorption stiffness value within a specific range are useful in obtaining a positive electrode with high electron conductivity.
つぎに実施例をあげて本発明をさらに詳細に説明する。 Next, the present invention will be explained in more detail by giving Examples.
第１図は本発明の無機非水電解液電池の一実施例を示す
断面図であり、この実施例の電池は単３形の塩化チオニ
ル−リチウム電池である。FIG. 1 is a sectional view showing an embodiment of the inorganic non-aqueous electrolyte battery of the present invention, and the battery of this embodiment is a AA-sized thionyl chloride-lithium battery.
第１図において、ｌは負極端子を兼ねるステンレス鋼製
の電池ケース、２はリチウム金属からなる負極、３はガ
ラス繊維不織布からなるセパレータ、４は上記負極２に
対してセパレータ３を介して対向させた炭素多孔質成形
体正極である。なお、上記正極４の下部および上部には
セパレータ３と同じガラス繊維不織布からなる底部絶縁
材１）および上部絶縁材１２が配置されている。In FIG. 1, l is a stainless steel battery case that also serves as a negative electrode terminal, 2 is a negative electrode made of lithium metal, 3 is a separator made of glass fiber nonwoven fabric, and 4 is a battery case facing the negative electrode 2 with a separator 3 in between. This is a carbon porous molded positive electrode. Note that a bottom insulating material 1) and an upper insulating material 12 made of the same glass fiber nonwoven fabric as the separator 3 are disposed below and above the positive electrode 4.
上記正極４は、揮発性物質が少な（、黒鉛化度が大きく
、かつ大きな鎖状構造を有するカーボンブランク（セデ
マ社製、商品名：エンサグリ・スーパーＳ、揮発性物質
含有量０．１５重量％、ＣｕＫα線によるＸ線回折で回
折角２６．９°付近の炭素（００２）の半価幅が４．９
°、アブソープションスティフネス値が３５ｃｄ／ ５
ｇ ） ９０重量％と黒鉛１０重量％の混合物１００
重量部に対し、ポリテトラフルオロエチレンの水分散体
（固形分６０重量％）２０重量部、メチルアルコール１
２０Ｍ量部および水２５０重量部を加えて、回転速度３
４０ｒｐｍのリボン式混練機で５分間混練し、その混練
物を油圧式の押出成形機で直径１０１ＩＩ１）の円柱状
に成形し、切断したのち、乾燥して水、メチルアルコー
ルなどの揮発性成分を除去することによって作製したも
のである。The positive electrode 4 is made of a carbon blank (manufactured by Sedema, trade name: Ensagri Super S, volatile substance content: 0.15 wt% , the half width of carbon (002) around the diffraction angle of 26.9° is 4.9 in X-ray diffraction using CuKα rays.
°, absorption stiffness value is 35cd/5
g) Mixture of 90% by weight and 10% by weight of graphite 100
20 parts by weight of an aqueous dispersion of polytetrafluoroethylene (solid content 60% by weight), 1 part by weight of methyl alcohol
Add 20M parts and 250 parts by weight of water, and rotate at a rotation speed of 3.
Knead for 5 minutes with a ribbon kneader at 40 rpm, then form the kneaded product into a cylinder with a diameter of 101II1) with a hydraulic extruder, cut it, and dry it to remove volatile components such as water and methyl alcohol. It was created by removing the
図中の５は電池蓋であり、この電池蓋５はステンレス鋼
で形成され、外周部は前記電池ケース１の開口端部と溶
接によって接合されている。そして電池蓋５の中央部に
はガラスシール６を介して正極端子７が設けられている
。この正極端子７は、電池蓋５にガラスシール６を介し
てあらかじめ取り付けておいたステンレス鋼製のバイブ
８から電池内に電解液を注入したのち、該バイブ８にス
テンレス鋼製の正極集電棒９を挿入し、バイブ８の上端
部と正極１）？ｉ棒９の上端部とを溶接することによっ
て形成されたものである。１０は電解液で、この電解液
１０は塩化チオニルに支持電解質としてリチウムテトラ
クロロアルミネート（ＬｔＡＩＣ１４）を１．２ ｍｏ
ｌ／ ｊ２熔解させたものである。そして、この電池に
おいては、塩化チオニルは上記のように電解液の溶媒で
あると共に、正極活物質でもある。Reference numeral 5 in the figure denotes a battery cover, which is made of stainless steel, and its outer periphery is joined to the open end of the battery case 1 by welding. A positive electrode terminal 7 is provided in the center of the battery lid 5 with a glass seal 6 interposed therebetween. This positive electrode terminal 7 is connected to a stainless steel positive electrode current collector rod 9 after injecting electrolyte into the battery from a stainless steel vibrator 8 that has been previously attached to the battery lid 5 via a glass seal 6. Insert the upper end of the vibrator 8 and the positive electrode 1)? It is formed by welding the upper end of the i-rod 9. 10 is an electrolytic solution, and this electrolytic solution 10 contains 1.2 mo of lithium tetrachloroaluminate (LtAIC14) as a supporting electrolyte in thionyl chloride.
l/j2 was melted. In this battery, thionyl chloride is not only the solvent of the electrolytic solution as described above, but also the positive electrode active material.
上記実施例の電池を電池Ａとし、正極に通常のアセチレ
ンブラックを用いたほかは前記実施例と同様に構成した
ｆｆ１３形の塩化チオニル−リチウム電池を電池Ｂとし
、両電池を６０℃で５０日間貯藏した後、２０℃、３０
０Ωで連続放電させたときの放電特性を調べた。その結
果を第２図に示す。なお、電池Ｂの正極作製に際する混
練物開裂のための混練機、回転速度、混練時間はいずれ
も電池Ａの場合と同じである。The battery of the above example was designated as battery A, and the FF13 type lithium thionyl chloride battery constructed in the same manner as in the above example except that ordinary acetylene black was used for the positive electrode was designated as battery B. Both batteries were stored at 60°C for 50 days. After storage, 20℃, 30
The discharge characteristics when continuously discharged at 0Ω were investigated. The results are shown in FIG. In addition, the kneader, rotation speed, and kneading time for cleaving the kneaded material during the production of the positive electrode of battery B were all the same as in the case of battery A.
第２図に示すように、実施例の電池人は放電時間が従来
電池Ｂに比べて長く、しかも放電電圧が高く、かつ安定
していた。これは実施例の電池Ａの正極作製に用いられ
たエンサグリ・スーパーＳが従来電池Ｂの正極作製に用
いられたアセチレンブラックより大きな鎮状構造を有す
るため、実施例の電池Ａの正極が従来電池Ｂの正極より
電子伝導性が優れていたためであると考えられる。As shown in FIG. 2, the battery of Example had a longer discharge time than conventional battery B, and the discharge voltage was higher and more stable. This is because Ensagri Super S, which was used to fabricate the positive electrode of Battery A in the example, has a larger slag structure than the acetylene black used in the fabrication of the positive electrode in conventional battery B. This is thought to be because the electron conductivity was better than that of the B positive electrode.
なお、上記実施例では正極４に円柱状のものを角いたが
、本発明はこの場合のみに限られるものではなく、前記
特定のカーボンブランクを主成分とする配合剤を金属集
電体に塗布圧着して作製した帯状の炭素多孔質成形体を
渦巻状にして正極に用いる場合にも同様の効果かえられ
る。In the above embodiment, the positive electrode 4 was made of a cylindrical shape, but the present invention is not limited to this case, and a metal current collector may be coated with a compound containing the above-mentioned specific carbon blank as a main component. A similar effect can be obtained when a band-shaped porous carbon body produced by pressure bonding is made into a spiral shape and used as a positive electrode.
マタ・塩化チオニルに代えて塩化スルフリル、塩化ホス
ホリルを用いても同様の効果が得られ、リチウムに代え
てナトリウムを用いても同様の効果が得られる。A similar effect can be obtained by using sulfuryl chloride or phosphoryl chloride in place of thionyl chloride, and a similar effect can be obtained by using sodium in place of lithium.
以上説明したように、本発明では、揮発性物質が０．２
重量％以下で、ＣｕＫα線によるＸ線回折で回折角２６
．９°付近の炭素（００２）の半価幅が４．９゛であり
、かつアブソープションスティフネス値が３３ｃｄ１５
ｇ〜４０ｃｄ１５ｇという、揮発性物質が少なく、黒鉛
化度が大きく、かつ大きな鎖状構造を有するカーボンブ
ラックを主成分とする配合剤で炭素多孔質成形体正極を
作製することによって、正極の電子伝導性を高めて放電
容量を向上させることができた。As explained above, in the present invention, the volatile substance is 0.2
Weight% or less, the diffraction angle is 26 by X-ray diffraction using CuKα rays.
．． The half width of carbon (002) near 9° is 4.9°, and the absorption stiffness value is 33cd15
By producing a carbon porous molded positive electrode with a carbon porous molded positive electrode containing carbon black as a main component, which has a small amount of volatile substances, a high degree of graphitization, and a large chain structure, the electron conductivity of the positive electrode is improved. It was possible to improve discharge capacity by increasing performance.
第１図は本発明の無機非水電解液電池の一実施例を示す
断面図であり、第２図は本発明の電池Ａと従来電池Ｂの
放電特性図である。第３図は本発明で用いるカーボンブ
ラックとアセチレンブラックをボールミルで粉砕したと
きの粉砕時間とアブソーブションスティフネス値との関
係を示す図である。
２・・・負極、 ３・・・セパレータ、 ４・・・炭素
多孔質成形体正極、 １０・・・電解液
放電特開（ｈ）FIG. 1 is a sectional view showing an embodiment of an inorganic non-aqueous electrolyte battery of the present invention, and FIG. 2 is a discharge characteristic diagram of a battery A of the present invention and a conventional battery B. FIG. 3 is a diagram showing the relationship between the pulverization time and absorption stiffness value when carbon black and acetylene black used in the present invention are pulverized using a ball mill. 2... Negative electrode, 3... Separator, 4... Carbon porous molded body positive electrode, 10... Electrolyte discharge patent publication (h)
Claims (1)
物質とし、アルカリ金属からなる負極に対してセパレー
タを介して対向させた炭素多孔質成形体正極を備えた無
機非水電解液電池において、上記炭素多孔質成形体正極
を、揮発性物質が０．２重量％以下で、ＣｕＫα線によ
るＸ線回折で回折角２６．９°付近の炭素（００２）の
半価幅が４．９°であり、アブソープションスティフネ
ス（Ａｂｓｏｒｐｔｉｏｎ Ｓｔｉｆｆｉｎｅｓｓ）値
が３３ｃｍ＾３／５ｇ〜４０ｃｍ＾３／５ｇの鎖状構造
を有するカーボンブラックを主成分とする配合剤で作製
したことを特徴とする無機非水電解液電池。(1) In an inorganic non-aqueous electrolyte battery equipped with a carbon porous molded positive electrode in which an oxyhalide is used as an electrolyte solvent and a positive electrode active material and is opposed to a negative electrode made of an alkali metal with a separator interposed therebetween, the above-mentioned The carbon porous molded positive electrode has a volatile substance content of 0.2% by weight or less, and the half width of carbon (002) at a diffraction angle of around 26.9° is 4.9° in X-ray diffraction using CuKα rays. , an inorganic non-aqueous electrolyte prepared from a compound mainly composed of carbon black having a chain structure with an absorption stiffness value of 33cm^3/5g to 40cm^3/5g. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61091026A JPS62249355A (en) | 1986-04-19 | 1986-04-19 | Inorganic nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61091026A JPS62249355A (en) | 1986-04-19 | 1986-04-19 | Inorganic nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62249355A true JPS62249355A (en) | 1987-10-30 |
Family
ID=14015013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61091026A Pending JPS62249355A (en) | 1986-04-19 | 1986-04-19 | Inorganic nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62249355A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59128773A (en) * | 1983-01-14 | 1984-07-24 | Toshiba Corp | Nonaqueous solvent battery |
-
1986
- 1986-04-19 JP JP61091026A patent/JPS62249355A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59128773A (en) * | 1983-01-14 | 1984-07-24 | Toshiba Corp | Nonaqueous solvent battery |
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