JPS62216170A - Manufacture of positive pole of nonaqueous solvent battery - Google Patents
Manufacture of positive pole of nonaqueous solvent batteryInfo
- Publication number
- JPS62216170A JPS62216170A JP61058064A JP5806486A JPS62216170A JP S62216170 A JPS62216170 A JP S62216170A JP 61058064 A JP61058064 A JP 61058064A JP 5806486 A JP5806486 A JP 5806486A JP S62216170 A JPS62216170 A JP S62216170A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- battery
- positive electrode
- positive pole
- lithium hydroxide
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 title abstract description 7
- 239000006229 carbon black Substances 0.000 claims abstract description 35
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 241000872198 Serjania polyphylla Species 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910006124 SOCl2 Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 208000028659 discharge Diseases 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 101150114085 soc-2 gene Proteins 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GURLNXRFQUUOMW-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[AlH3] Chemical compound [Al](Cl)(Cl)Cl.[AlH3] GURLNXRFQUUOMW-UHFFFAOYSA-K 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
-
- 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
-
- 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］
本発明は非水溶媒電池用正極の製造方法に関し、さらに
詳しくは、とくに、正極活物質とじて１１！化チオニル
を使用した非水溶媒電池用正極であって、該電池の放電
特性を向上させうる正極を製造する方法に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for manufacturing a positive electrode for a non-aqueous battery, and more particularly, to 11! The present invention relates to a method for producing a positive electrode for a non-aqueous battery using thionyl chloride, which can improve the discharge characteristics of the battery.
［従来技術］
負極活物質としてリチウム（Ｌｉ）、ナトリウム（Ｎ
ａ）などを用いた非水溶媒電池は、エネルギー密度が高
く、貯蔵特性に優れ、しかも作動温度範囲が広いという
利点を有するため１例えば、電卓、時計、あるいは各種
メモリーのバックアップ′尼源として重用されている。[Prior art] Lithium (Li) and sodium (N) are used as negative electrode active materials.
Nonaqueous solvent batteries using a) have the advantages of high energy density, excellent storage characteristics, and a wide operating temperature range, so they are used as backup sources for calculators, watches, and various types of memory, for example. has been done.
このような非水溶媒電池のなかでも、負極としてＬｉを
、正極活物質として塩化チオニル（ＳＯＣｕｚ）をそれ
ぞれ用いた、いわゆるＬｉ−５ＯＣ文２系電池は、とく
に高いエネルギー密度を有するため注目され“ている、
かかるＬｔ−５ＯＣ１２系電池は、一般に、カーボンブ
ラックを原料とする多孔質炭素体および金属集電体から
なる正極を具備し、例えば塩化リチウム（Ｌ ｉ ＣＪ
Ｉ）およびＪｉ１化アルアルミニウムｇＬＣ１３）を溶
解したＳ ＯＣｌ ２が内填されてなるものである。Among such nonaqueous solvent batteries, the so-called Li-5OC type 2 battery, which uses Li as the negative electrode and thionyl chloride (SOCuz) as the positive electrode active material, is attracting attention because it has a particularly high energy density. ing,
Such Lt-5OC12-based batteries generally include a positive electrode made of a porous carbon body made of carbon black and a metal current collector, and include, for example, lithium chloride (L i CJ
I) and aluminum aluminum chloride gLC13) are dissolved therein.
［発明が解決しようとする問題点］
ところで、上記のような非水溶媒電池用正極の構成部材
である多孔質炭素体の原料として使用されるカーボンブ
ラック中には、その製造段階で発生したカルボキシル基
、カルボニル基、水酸基などの含酸素官能基が不可避的
に含有されている。[Problems to be Solved by the Invention] By the way, carbon black used as a raw material for the porous carbon material that is a component of the positive electrode for non-aqueous batteries as described above contains carboxyl compounds generated during the manufacturing process. Oxygen-containing functional groups such as carbonyl groups, carbonyl groups, and hydroxyl groups are inevitably contained.
いま、カルボキシル基を例にとると、カルボキシル基は
正極活物質である塩化チオニルと式（１）のように反応
して塩化チオニルを分解する。Taking the carboxyl group as an example, the carboxyl group reacts with thionyl chloride, which is a positive electrode active material, as shown in formula (1) to decompose thionyl chloride.
ＲＣ０ＯＨ＋５ＯＣｕ２−
Ｒ−ｃｏｃｘ ＋ｓｏ２＋Ｈｃｌ−・・−・−（１）こ
のような分解反応により生ずるＳ０２やＨＣｌは電池内
圧を上昇させて電池のフクレや、破損等の原因となり、
さらにＮ０文はＬｉ負極表面で式（２）のように反応し
て、Ｌｉ負極表面を不動態化させる。RC0OH+5OCu2- R-cocx +so2+Hcl-...-(1) S02 and HCl generated by such decomposition reactions increase the internal pressure of the battery, causing blistering and damage to the battery.
Furthermore, the N0 statement reacts on the surface of the Li negative electrode as shown in equation (2) to passivate the surface of the Li negative electrode.
Ｌ’ｉ＋ＨＣｇ、→ＬｉＣ文＋ｙ２Ｈ２↑・・・・・・
（２）この反応により、電池貯蔵後の放電初期の電圧の
落込みおよび電池の放電容量の低下などが発生するとい
う問題があった。L'i+HCg, →LiC sentence+y2H2↑・・・・・・
(2) This reaction causes problems such as a drop in voltage at the initial stage of discharge after storage of the battery and a decrease in the discharge capacity of the battery.
本発明は、従来のかかる問題を解消し。The present invention solves this conventional problem.
５００文２を正極活物質とする非水溶媒電池用正極を製
造する方法であって、正極を構成する多孔質炭素体と５
ＯＣＩ２との反応に起因する電池の特性劣化を防止しう
る正極の製造方法の提供を目的とする。A method for manufacturing a positive electrode for a non-aqueous battery using 500 Bun 2 as a positive electrode active material, the porous carbon body constituting the positive electrode and 5
The purpose of the present invention is to provide a method for manufacturing a positive electrode that can prevent deterioration of battery characteristics due to reaction with OCI2.
［問題点を解決するための手段］
本発明者らは、非水溶媒電池用正極の製造工程のうち、
該正極の構成要素の１つである多孔質炭素質材料の製造
工程に着目し、原料となるカーボンブラックを所定条件
で加熱処理する工程を挿入することにより、含酸素官能
基の含右率が低く。[Means for Solving the Problems] The present inventors have discovered that, in the manufacturing process of a positive electrode for a non-aqueous battery,
By focusing on the manufacturing process of the porous carbonaceous material, which is one of the components of the positive electrode, and inserting a step of heat-treating the raw material carbon black under predetermined conditions, the content of oxygen-containing functional groups can be reduced. Low.
また、極めて高い導電性および大きな比表面積を有する
カーボンブラックが得られることを見出し、このような
カーボンブラックから製造された多孔質炭素質材料より
構成された正極を組込んだＳ ＯＣ４１２系電池が良好
な特性を有することを確認して本発明を完成するに到っ
た。We also discovered that carbon black with extremely high conductivity and a large specific surface area can be obtained, and SOC412-based batteries incorporating a positive electrode made of a porous carbonaceous material made from such carbon black have been found to be good. The present invention was completed after confirming that the present invention has excellent characteristics.
すなわち１本発明は、カーボンブラックを原料とする多
孔質炭素質材料と全屈集電体とからなる非水溶媒電池用
正極の製造方法であって、カーボンブラックを不活性雰
囲気中、４００〜ｇ ｏ ｏ ’ｃで減圧加熱処理する
工程を含むことを特徴とする。That is, 1. the present invention is a method for producing a positive electrode for a non-aqueous solvent battery comprising a porous carbonaceous material made of carbon black as a raw material and a total bending current collector, the method comprising: The method is characterized in that it includes a step of performing a heat treatment under reduced pressure at o o'c.
さらに、上記の製造工程において、該減圧加熱処理工程
終了後に、該カーボンブラックを水酸化リチウムで中和
処理する工程を追加することは、上記工程において、カ
ーボンブラック中に未だ微量残存している含酸素官能基
のＳＯＣ交２に対する反応性を低下せしめることができ
るためさらに効果的である。Furthermore, in the above manufacturing process, adding a step of neutralizing the carbon black with lithium hydroxide after the end of the reduced-pressure heat treatment step means that in the above step, a trace amount of the carbon black still remaining in the carbon black can be removed. This is even more effective because it can reduce the reactivity of oxygen functional groups to SOC 2.
［具体的説明］
本発明の非水溶媒電池用正極の製造方法は、前述したよ
うに、正極の構成要素の１つである多孔質炭素質材料の
原料であるカーボンブラックのいわば処理工程に特徴を
有するものであり、その他の工程あるいは、正極の形状
などはとくに限定されるものではない。[Specific Description] As described above, the method for producing a positive electrode for a non-aqueous solvent battery of the present invention is characterized by the so-called treatment step of carbon black, which is a raw material for the porous carbonaceous material that is one of the constituent elements of the positive electrode. Other steps or the shape of the positive electrode are not particularly limited.
以下に、本発明方法の骨子となるカーボンブラックの処
理工程について説明する。The carbon black treatment step, which is the gist of the method of the present invention, will be explained below.
使用する原料カーボンブラックとしては、とくに限定さ
れるものではないが、例えば、アセチレンブラック、フ
ァネスブラック、チャンネルブラックなどを使用するこ
とが好ましい。The raw material carbon black to be used is not particularly limited, but it is preferable to use, for example, acetylene black, furnace black, channel black, or the like.
まず、上記のカーボンブラックを不活性雰囲気中、４０
０〜８００’０で減圧加熱処理する。不活性雰囲気とし
ては、例えば、アルゴン（Ａｒ）、窒素（Ｎ２）などを
あげることができる、また、圧力は、例えば０．０５〜
０ 、１Ｔｏｒｒに設定することが好ましい。この工程
において加熱温度が４００℃未満であると、カーボンブ
ラック中の含酸素官能基を充分に除去することができず
、得られた正極を組込んだ非水溶媒電池は貯蔵後に放電
初期電圧の落ち込みが発生する場合が多い。一方、加熱
温度が１，０００℃を超えると、カーボンブラック自体
の分解が生じるため好ましくない。なお、この工程にお
ける加熱処理時間は、上述した加熱温度等に応じて適宜
設定することが望ましく、通常は、８〜３０時間程度で
ある。First, the above carbon black was heated at 40°C in an inert atmosphere.
Heat treatment under reduced pressure at 0 to 800'0. Examples of the inert atmosphere include argon (Ar) and nitrogen (N2), and the pressure is, for example, 0.05~
It is preferable to set it to 0.1 Torr. If the heating temperature in this step is less than 400°C, the oxygen-containing functional groups in the carbon black cannot be sufficiently removed, and the non-aqueous solvent battery incorporating the obtained positive electrode will have a lower initial discharge voltage after storage. Depression often occurs. On the other hand, if the heating temperature exceeds 1,000°C, the carbon black itself will decompose, which is not preferable. Note that the heat treatment time in this step is desirably set appropriately depending on the above-mentioned heating temperature, etc., and is usually about 8 to 30 hours.
このようにして得られた熱処理カーボンブラックは、カ
ルボキシル基を始めとする含酸素官能基の含有量が極め
て少なくなっており、かかるカーボンブラックから製造
された炭素多孔質体は、正極活物質であるＳ ＯＣｌ
２どの反応性が極めて低いものである。The heat-treated carbon black thus obtained has an extremely low content of oxygen-containing functional groups including carboxyl groups, and a porous carbon material produced from such carbon black can be used as a positive electrode active material. SOCl
2. Which reactivity is extremely low.
さらに、本発明方法においては、上述したカーボンブラ
ックの加熱処理工程の後に、所望により、この熱処理カ
ーボンブラックを水酸化リチウム（Ｌ ｉ ＯＨ）で中
和処理する工程を設けることができる。このような中和
処理を施すと、上熱加熱処理カーボンブラック中に極微
量残留している含酸素官能基のＳ ＯＣｌ ２に対する
反応性を低下せしめることができるためさらに有利であ
る。Furthermore, in the method of the present invention, after the carbon black heat treatment step described above, a step of neutralizing the heat treated carbon black with lithium hydroxide (L i OH) can be provided, if desired. Such a neutralization treatment is further advantageous because it can reduce the reactivity of the oxygen-containing functional groups remaining in extremely small amounts in the upper heat-treated carbon black with respect to SOCl 2 .
なお、この中和処理工程において、使用するＬｊＯＨ水
溶液の濃度は０．００５〜２モル／見、処理温度は２０
〜１００℃とすることが好ましい。In addition, in this neutralization treatment step, the concentration of the LjOH aqueous solution used is 0.005 to 2 mol/min, and the treatment temperature is 20
It is preferable to set it as -100 degreeC.
そして、この中和処理工程終了後、カーボンブラックを
乾燥するために、減圧下、４０〜１００℃において、１
〜８時間加熱処理することが好ましい。After completing this neutralization process, in order to dry the carbon black, it is heated at 40 to 100°C under reduced pressure for 1 hour.
Preferably, the heat treatment is performed for ~8 hours.
しかるのち、このカーボンブラックとポリマー結着剤と
を混合、混練したのち、例えば集電体金網に圧着するこ
とにより正極を得る。前述したように、この正極の形状
はとくに限定されるものではなく、例えば４円筒形の集
電体金網の外周面に多孔質炭素体が圧着されてなる正極
あるいは、多孔質炭素体を圧着した帯状の集電体金網を
巻回してなる渦巻状の正極などとすることができる。Thereafter, this carbon black and a polymer binder are mixed and kneaded, and then pressed onto, for example, a current collector wire gauze to obtain a positive electrode. As mentioned above, the shape of this positive electrode is not particularly limited, and for example, a positive electrode formed by pressing a porous carbon material onto the outer peripheral surface of a four-cylindrical current collector wire mesh, or a positive electrode formed by pressing a porous carbon material onto the outer circumferential surface of a four-cylindrical current collector metal mesh. A spiral positive electrode formed by winding a band-shaped current collector wire mesh can be used.
［実施例］
実施例１
（１） 非水溶媒電池用正極の製造
カーボンブラック（アセチレンブラック、商品名：デン
カブラック、電気化学工業■製）Ｚｏ。[Examples] Example 1 (1) Production of positive electrode for nonaqueous solvent batteries Carbon black (acetylene black, trade name: Denka Black, manufactured by Denki Kagaku Kogyo ■) Zo.
ｇを内径７０ｍｍ、長さ５００’ｍｓの管状炉に入れ、
Ａｒガスを流速１０ｃｃ／分で流しながら、６００°Ｃ
で２４時間加熱処理した。ついで、得られたカーボンブ
ラック９９１量部に、ポリマー結着材としてポリテトラ
フルオロエチレンｔｏ重３１部を添加混合し、さらにエ
チルアルコールを添加して充分に攪拌、混練したのち、
この混練物を円筒状の金属集電体に圧着し、１５０’Ｏ
で１２時間減圧乾燥して正極を得た。g into a tube furnace with an inner diameter of 70 mm and a length of 500'ms,
600°C while flowing Ar gas at a flow rate of 10cc/min.
The mixture was heat-treated for 24 hours. Next, 31 parts by weight of polytetrafluoroethylene as a polymer binder was added and mixed to 991 parts by weight of the obtained carbon black, and after further adding ethyl alcohol and sufficiently stirring and kneading,
This kneaded material was crimped onto a cylindrical metal current collector, and
A positive electrode was obtained by drying under reduced pressure for 12 hours.
（２） 非水溶媒電池の製造およびその評価試験上記
により得られた正極を使用して第１図に示したようなＬ
ｉ−３ＯＣ１２電池を製造した。(2) Manufacture of nonaqueous solvent battery and its evaluation test Using the positive electrode obtained above, L
An i-3OC12 battery was manufactured.
すなわち、第１図において、負極端子を兼ねるステンレ
ス製負極缶１の内周面に金属Ｌｉからなる筒状の負極２
が圧着されており、この負極２の内部に上記により得ら
れた正極３がガラス繊維の不織布からなるセパレータ４
を介して装入されている。ここで、正極３は上述したよ
うに円筒状ステンレス金網よりなる集電体６と該金網６
に圧着された多孔質炭素体７とから構成されている。な
お、正極３と負極毎１底面との間には絶縁紙５が介装さ
れ、正極３の上部には、セパレータ４に支持された絶縁
紙８が配設されている。負極毎１の上部開口端にはメタ
ルトップ９が例えばレーザ溶接により封着されており、
このメタルトップ９の中心には開口部１０が設けられ、
該１３Ｆ４日部１０から、負極毎１内へ電解液、すなわ
ち、ＬｉＡＪＬＣＪ１４を１．８モル濃度となるように
溶解した５ＯＣｆＬ２溶液が注入されている。また。That is, in FIG. 1, a cylindrical negative electrode 2 made of metal Li is placed on the inner peripheral surface of a stainless steel negative electrode can 1 which also serves as a negative electrode terminal.
The positive electrode 3 obtained above is placed inside the negative electrode 2, and a separator 4 made of a nonwoven glass fiber fabric is placed inside the negative electrode 2.
It is charged through. Here, as described above, the positive electrode 3 includes a current collector 6 made of a cylindrical stainless wire mesh and the wire mesh 6.
The porous carbon body 7 is crimped onto the porous carbon body 7. Note that an insulating paper 5 is interposed between the positive electrode 3 and the bottom surface of each negative electrode, and an insulating paper 8 supported by a separator 4 is disposed above the positive electrode 3. A metal top 9 is sealed to the upper open end of each negative electrode by, for example, laser welding.
An opening 10 is provided in the center of this metal top 9,
An electrolytic solution, that is, a 5OCfL2 solution in which LiAJLCJ14 was dissolved to have a 1.8 molar concentration, was injected into each negative electrode from the 13F4 part 10. Also.
メタルトップ９の開口部１ｏには正極端子１１がメタル
−ガラスシール材１２により電気的に絶縁されて固定さ
れており、この正極端子１１はその下端に取付けられた
リード線１３を介して正極３の金属集電体に接続されて
いる。A positive electrode terminal 11 is electrically insulated and fixed in the opening 1o of the metal top 9 by a metal-glass sealing material 12, and this positive electrode terminal 11 is connected to the positive electrode 3 via a lead wire 13 attached to its lower end. is connected to a metal current collector.
かかるＬｉ−５ＯＣｕ２電池について以下に述べる各評
価試験を行なった。The following evaluation tests were conducted on this Li-5OCu2 battery.
（イ） 放電特性評価試験
電池製造直後に、常温下、外部抵抗１５０Ωで負荷放電
を行なわせ、その結果を第２図に実線工で示した。(a) Discharge characteristic evaluation test Immediately after the battery was manufactured, a load discharge was performed at room temperature with an external resistance of 150Ω, and the results are shown in solid lines in FIG.
（ロ） 貯蔵特性評価試験
電池製造後、得られた電池を８０℃において６０日間貯
蔵したのち、上記（イ）と同様の放電試験を行なって、
結果を第３図に実線工で示した。(b) Storage characteristics evaluation test After battery production, the resulting battery was stored at 80°C for 60 days, and then a discharge test similar to (a) above was conducted.
The results are shown in Figure 3 as solid lines.
実施例２
カーボンブラック（ファネスブラック、商品名：ケッチ
ェンブラック、アクゾ社製）ｌｏｏｇを内径７０ｒａｔ
ａ、長さ５００ａ＋ｍの管状炉に入れ、Ａｒガスを流速
１０ｃｃ／分で流しながら４００°Ｃで１２時間加熱処
理した。これとは別に、Ｌｉ０Ｈ−Ｈ２Ｏを０．０１モ
ル／文の濃度となるように溶解したアルカリ溶液５００
ｍ１を用意し、この溶液中に上記のカーボンブラックを
分散して５０”０に加熱し３０分間攪拌して中和処理し
た。しかるのち、カーボンブラックをろ過して減圧下で
１００’（！に加熱し、６時間乾燥した。そして、以下
の工程は上記実施例１と全く同様にして正極を得た。Example 2 Carbon black (Furness black, product name: Ketjen black, manufactured by Akzo) loog with an inner diameter of 70 rat
a. It was placed in a tube furnace with a length of 500 a+m, and heat-treated at 400°C for 12 hours while flowing Ar gas at a flow rate of 10 cc/min. Separately, 500 g of an alkaline solution containing Li0H-H2O dissolved at a concentration of 0.01 mol/state
m1 was prepared, the above carbon black was dispersed in this solution, heated to 50'0, stirred for 30 minutes, and neutralized.Then, the carbon black was filtered and dissolved under reduced pressure at 100' (! It was heated and dried for 6 hours.Then, the following steps were carried out in exactly the same manner as in Example 1 above to obtain a positive electrode.
この正極を上記したＬｉ−５ＯＣ１２電池に組み込み、
上記実施例と同様の評価試験を行ない、その結果を第２
図および第３図に実線ＩＩで示した。This positive electrode was incorporated into the Li-5OC12 battery described above,
An evaluation test similar to that of the above example was conducted, and the results were used as a second
It is shown by the solid line II in the figure and FIG.
比較例１および２
カーボンブラックの熱処理温度を２００℃（比較例１）
オ、Ｉ−び１，０００°Ｃ（比較例２）とじたことを除
いては、上記実施例１と全く同様にして正極およびＬｉ
５ＯＣ１ｔ電池を製造し、同様の評価試験を行なっ
て結果を第２図、第３図にそれぞれ実線■および■で示
した。Comparative Examples 1 and 2 Heat treatment temperature of carbon black was 200°C (Comparative Example 1)
The positive electrode and Li
A 5OC1t battery was manufactured, and a similar evaluation test was conducted, and the results are shown in FIGS. 2 and 3 with solid lines ■ and ■, respectively.
［発明の効果］
以上の説明から明らかなように１本発明方法を適用して
製造された非水溶媒電池用正極は、特定の条件で加熱処
理されたカーボンブラックを原料とする多孔質炭素質材
料をその構成要素として含有するため、非水溶媒電池、
とくにＬＩ−８ＯＣｆＬ２系電池に組込んだ際に正極活
物質であるＳｏＣ交２と多孔質炭素質材料中の含酸素官
能基との反応が充分抑制され、電池の放電特性が良好な
ものとなる。さらに、上記加熱処理後に。[Effects of the Invention] As is clear from the above description, the positive electrode for nonaqueous solvent batteries manufactured by applying the method of the present invention is a porous carbonaceous material made from carbon black that has been heat-treated under specific conditions. Because it contains materials as its constituent elements, non-aqueous solvent batteries,
In particular, when incorporated into a LI-8OCfL2 battery, the reaction between the positive electrode active material SoC2 and the oxygen-containing functional groups in the porous carbonaceous material is sufficiently suppressed, resulting in good discharge characteristics of the battery. . Furthermore, after the above heat treatment.
ＬｉＯＨによる中和処理を実施すれば、電池の貯蔵特性
が一層向上するため、その工業的価値は極めて大である
。If neutralization treatment with LiOH is carried out, the storage characteristics of the battery will be further improved, so its industrial value is extremely large.
第１図は本発明方法を適用して得られた非水溶媒電池用
正極が組み込まれたＬｉ−５ＯＣＬ；Ｌ２電池の構造の
一例を示す縦断面図、第２図および第３図はＬ １−５
ＯＣ１２７１！池の製造直後および貯蔵後の放電特性曲
線を示す図である。
１・・・負極毎 ２００．負極３・・・正極
４・・・セパレータ６・・・金属集電体
７・・・多孔質炭素体第１図
ゑ
（翫
式宅綺関（ｈｒｓ）
第２図Figure 1 is a Li-5OCL incorporating a positive electrode for a non-aqueous solvent battery obtained by applying the method of the present invention; a longitudinal cross-sectional view showing an example of the structure of an L2 battery, and Figures 2 and 3 are L1 -5
OC1271! FIG. 3 is a diagram showing discharge characteristic curves of the battery immediately after manufacture and after storage. 1...each negative electrode 200. Negative electrode 3...positive electrode
4... Separator 6... Metal current collector
7...Porous carbon body Fig. 1 (HRS) Fig. 2
Claims (1)
金属集電体とからなる非水溶媒電池用正極の製造方法で
あつて、 カーボンブラックを不活性雰囲気中、４００〜８００℃
で減圧加熱処理する工程を含むことを特徴とする非水溶
媒電池用正極の製造方法。 ２、該減圧加熱処理工程終了後に、該カーボンブラック
を水酸化リチウムで中和処理する工程を含む特許請求の
範囲第１項記載の製造方法。 ３、該非水溶媒電池の正極活物質が、塩化チオニルであ
る特許請求の範囲第１項記載の製造方法。[Scope of Claims] 1. A method for producing a positive electrode for a non-aqueous battery comprising a porous carbonaceous material made of carbon black as a raw material and a metal current collector, the method comprising: 800℃
1. A method for producing a positive electrode for a non-aqueous battery, comprising the step of heat treatment under reduced pressure. 2. The manufacturing method according to claim 1, which comprises a step of neutralizing the carbon black with lithium hydroxide after the reduced pressure heat treatment step. 3. The manufacturing method according to claim 1, wherein the positive electrode active material of the non-aqueous solvent battery is thionyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61058064A JPS62216170A (en) | 1986-03-18 | 1986-03-18 | Manufacture of positive pole of nonaqueous solvent battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61058064A JPS62216170A (en) | 1986-03-18 | 1986-03-18 | Manufacture of positive pole of nonaqueous solvent battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62216170A true JPS62216170A (en) | 1987-09-22 |
Family
ID=13073478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61058064A Pending JPS62216170A (en) | 1986-03-18 | 1986-03-18 | Manufacture of positive pole of nonaqueous solvent battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62216170A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146259A (en) * | 1987-12-01 | 1989-06-08 | Hitachi Maxell Ltd | Inorganic nonaqueous electrolyte battery |
-
1986
- 1986-03-18 JP JP61058064A patent/JPS62216170A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146259A (en) * | 1987-12-01 | 1989-06-08 | Hitachi Maxell Ltd | Inorganic nonaqueous electrolyte battery |
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