JPH0738304B2 - Method for manufacturing sheet electrode - Google Patents
Method for manufacturing sheet electrodeInfo
- Publication number
- JPH0738304B2 JPH0738304B2 JP11293189A JP11293189A JPH0738304B2 JP H0738304 B2 JPH0738304 B2 JP H0738304B2 JP 11293189 A JP11293189 A JP 11293189A JP 11293189 A JP11293189 A JP 11293189A JP H0738304 B2 JPH0738304 B2 JP H0738304B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- mixture
- current collector
- polyvinyl butyral
- alcohol
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims description 80
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 18
- 239000004809 Teflon Substances 0.000 claims description 14
- 229920006362 Teflon® Polymers 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 この発明は、スパイラル形リチウム電池などの正極に使
用される、シート状電極の製造方法に関するものであ
る。Description: <Industrial field of application> The present invention relates to a method for producing a sheet-like electrode used for a positive electrode of a spiral lithium battery or the like.
〈従来の技術〉 非水電解液電池、例えばリチウム−マンガン電池では、
それぞれシート状の正極と負極とを、セパレータを介し
て重ね合わせ、更にこれらを一緒に渦巻状に巻回して構
成される発電要素を電池缶に収納する構成を用いてい
る。<Prior Art> In a non-aqueous electrolyte battery, for example, a lithium-manganese battery,
A sheet-shaped positive electrode and a negative electrode are stacked on each other with a separator interposed therebetween, and a power generating element configured by spirally winding these together is housed in a battery can.
上記正極を作製する場合、通常は例えば、二酸化マンガ
ンを主成分としこれに導電剤として黒鉛やアセチレンブ
ラックなどを混合してなる活物質に、バインダーとして
のテフロン水性ディスパージョンと適当量の水を加え一
定時間混練してスラリー状の正極合剤を作り、このスラ
リー状合剤を集電体に塗布した後、熱風乾燥炉などで水
分除去して乾燥させ、爾後圧延ロールなどで所定の厚さ
に圧延するといった手順が採られている。In the case of producing the above positive electrode, usually, for example, an active material obtained by mixing manganese dioxide as a main component with graphite or acetylene black as a conductive agent, a Teflon aqueous dispersion as a binder and an appropriate amount of water are added. After kneading for a certain period of time to make a slurry-like positive electrode mixture, apply this slurry-like mixture to a current collector, remove water by a hot air drying oven etc. and dry, and then roll to a prescribed thickness with a rolling roll or the like. The procedure of rolling is adopted.
〈発明が解決しようとする課題〉 しかしながら、上記従来技術においてバインダーに使用
されているテフロン水性ディスパージョンはその結着力
が弱いことから、上記手順の製造方法には次のような問
題がある。<Problems to be Solved by the Invention> However, since the Teflon aqueous dispersion used as a binder in the above-mentioned conventional technique has a weak binding force, the production method of the above procedure has the following problems.
テフロン水性ディスパージョンをバインダーとする
上記スラリー状合剤と集電体との結着力が弱く、合剤が
集電体より剥離し易い。The binding force between the above-mentioned slurry-like mixture containing Teflon aqueous dispersion as a binder and the current collector is weak, and the mixture is easily separated from the current collector.
上記スラリー状合剤は延展性が悪く、従ってこの合
剤を集電体上に均一に塗布することが困難で、塗布厚の
バラツキが大きく、また例えば電極面積を広げるために
合剤の塗布厚を薄くすることが難しい。The above-mentioned slurry-like mixture has poor spreadability, and therefore it is difficult to apply this mixture uniformly on the current collector, there is a large variation in coating thickness, and for example, the coating thickness of the mixture for expanding the electrode area. Is difficult to thin.
このように集電体からの合剤剥離や集電体への合剤
塗布厚のバラツキなどによる不良が発生し易いので歩留
りが低い。As described above, a defect is apt to occur due to peeling of the material mixture from the current collector or variation in the thickness of the material mixture applied to the current collector, so that the yield is low.
スラリー状合剤の粘度調整が難しい。 It is difficult to adjust the viscosity of the slurry mixture.
圧延ロールなどによる圧延時の圧力を高くすると集
電体と合剤が剥離するため、この圧力を高くできず、合
剤塗布膜の密度を高めて放電性能の向上を図ることがで
きない。If the pressure at the time of rolling by a rolling roll or the like is increased, the current collector and the mixture are separated, so this pressure cannot be increased, and the density of the mixture coating film cannot be increased to improve the discharge performance.
この発明は、このような問題なしに、合剤と集電体との
結着力が強固であり、厚さが均一で且つ合剤密度の大き
なシート状正極を容易に作製することができる、シート
状電極の製造方法提供することを目的とする。According to the present invention, a sheet-like positive electrode having a strong binding force between the mixture and the current collector, having a uniform thickness and a large mixture density can be easily produced without such a problem. An object of the present invention is to provide a method for manufacturing a strip electrode.
〈課題を解決するための手段〉 この発明においては、二酸化マンガンを主成分とする活
物質に、バインダーとしてポリビニルブチラールを、可
塑剤としてフタル酸ジブチルを、また溶剤としてアルコ
ールをそれぞれ加え混練してなる合剤を用い、またこの
合剤を押出成形によりシート状に成形して使用するよう
にした。<Means for Solving the Problems> In the present invention, an active material containing manganese dioxide as a main component is kneaded by adding polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, and alcohol as a solvent. A mixture was used, and this mixture was formed into a sheet by extrusion and used.
即ち、この発明のシート状電極の製造方法は、上記組成
の合剤を押出成形により多孔性集電体とともにシート状
の電極構成材に一体成形し、またこの電極構成材を300
℃以下の温度において段階的に熱処理した後、圧延やプ
レスなどにより加圧して所定の厚さ及び密度にすること
を要旨とする。That is, the method for producing a sheet-like electrode of the present invention is a mixture of the above composition is integrally molded into a sheet-like electrode constituent material by extrusion molding together with a porous current collector, and the electrode constituent material is
The gist is to perform heat treatment stepwise at a temperature of ℃ or less, and then pressurize by rolling or pressing to obtain a predetermined thickness and density.
上記の方法において、一体成形された電極構成材を熱処
理前に圧延やプレスなどを施し、成形厚さのバラツキを
調整するようにしても良い。その場合、圧延やプレスの
際の圧力が高すぎると流動性を帯びた合剤自身が延ばさ
れて多孔性集電体からはみだしてしまう虞があるので、
合剤がはみださない程度の圧力で圧延やプレスを行う必
要がある。具体的には最大圧力が押出成形後の厚さの40
％程度の厚さになるような圧力で行えば良い。このこと
は、以下に述べる他の製造方法においても同様であ。
尚、このような圧力の調整は、例えばロールによる圧延
を用いた場合にはロール間の間隙を適宜調整することで
容易に行える。In the above method, the integrally formed electrode component material may be rolled or pressed before heat treatment to adjust the variation in the forming thickness. In that case, if the pressure at the time of rolling or pressing is too high, the mixture itself having fluidity may be stretched and protrude from the porous current collector,
It is necessary to carry out rolling and pressing with a pressure that does not cause the mixture to overflow. Specifically, the maximum pressure is 40% of the thickness after extrusion.
The pressure may be such that the thickness becomes about%. This also applies to other manufacturing methods described below.
Note that such pressure adjustment can be easily performed by appropriately adjusting the gap between the rolls, for example, when rolling with rolls is used.
また本発明の他の製造方法として、上記組成の合剤を押
出成形して得た２枚のシート状合剤の間に集電体を挿入
し、圧延あるいはプレスによりこれらを連続して積層一
体化し、次いで300℃以下の温度において段階的に熱処
理した後、圧延やプレスなどにより加圧して所定の厚さ
及び密度にするようにしても良い。As another manufacturing method of the present invention, a current collector is inserted between two sheet-shaped mixture obtained by extrusion-molding the mixture having the above composition, and these are continuously laminated and integrated by rolling or pressing. Then, after heat treatment is performed stepwise at a temperature of 300 ° C. or less, pressure may be applied by rolling, pressing or the like to obtain a predetermined thickness and density.
更に本発明の別の製造方法として、上記組成の合剤をシ
ート状に押出成形した後に所定寸法に裁断し、こうして
得たシート状合剤片を集電体の両面にそれぞれ位置さ
せ、圧延あるいはプレスによりこれらシート状合剤片と
多孔性集電体とを積層一体化し、次いで300℃以下の温
度において段階的に熱処理した後、圧延やプレスなどに
より加圧して所定の厚さ及び密度にする構成としても良
い。Furthermore, as another production method of the present invention, the mixture of the above composition is extruded into a sheet and then cut into a predetermined size, and the sheet-like mixture pieces thus obtained are respectively positioned on both sides of the current collector and rolled or These sheet-shaped mixture pieces and the porous current collector are laminated and integrated by pressing, and then heat-treated stepwise at a temperature of 300 ° C. or less, and then pressed by rolling or pressing to have a predetermined thickness and density. It may be configured.
上記合剤において、ポリビニルブチラールの添加量は活
物質に対して２〜15重量％が好ましい。この範囲より少
なければ合剤をシート状とするのに必要なゴム性状が得
られなくなる。また、ポリビニルブチラールの添加量が
15重量％より多い場合、後述する理由により電池の内部
抵抗増大を招く。In the above mixture, the addition amount of polyvinyl butyral is preferably 2 to 15% by weight based on the active material. If the amount is less than this range, the rubber properties necessary for forming the mixture into a sheet cannot be obtained. Also, the amount of polyvinyl butyral added is
If the amount is more than 15% by weight, the internal resistance of the battery increases due to the reason described below.
また前記フタル酸ジブチルの添加量はポリビニルブチラ
ールに対して30〜70重量％であることが好適である。30
重量％より少ない場合は合剤に十分な可塑性を持たせる
ことができず、また70重量％より多い場合には可塑性が
ありすぎるようになり、いずれの場合にも合剤を表面平
滑に押出成形することができなくなる。The addition amount of dibutyl phthalate is preferably 30 to 70% by weight based on polyvinyl butyral. 30
If it is less than wt%, the mixture cannot have sufficient plasticity, and if it is more than 70 wt%, it becomes too plastic. In any case, the mixture is extruded with a smooth surface. Can not do.
更に、上記アルコールとしては、エチルアルコール及び
その他のアルコール類を用いることができる。また、こ
のアルコールの添加量は、後述するように混練後に合剤
にゴム性状を持たせるための必要量とすればよい。Further, ethyl alcohol and other alcohols can be used as the alcohol. Further, the amount of the alcohol added may be a necessary amount for giving the mixture a rubbery property after kneading as described later.
一方、合剤に使用する上記バインダーとして、ポリビニ
ルブチラールに、テフロン水性ディスパーションにエタ
ノールなどのアルコールを添加・攪拌して乳化させたも
のを加えたものを使用してもよく、バインダー効果を更
に向上させることができる。尚、この乳化物を添加した
ものをバインダーとする場合、電極における内部抵抗増
大を招く虞があるため、ポリビニルブチラールの使用量
を調整する必要がある。On the other hand, as the above-mentioned binder used in the mixture, polyvinyl butyral may be used in which Teflon aqueous dispersion added with alcohol such as ethanol and stirred and emulsified is added to further improve the binder effect. Can be made. In addition, when the one to which this emulsion is added is used as the binder, the internal resistance of the electrode may be increased, so that it is necessary to adjust the amount of polyvinyl butyral used.
このようにテフロン水性ディスパージョンにアルコール
を添加して乳化させる際、テフロン水性ディスパージョ
ンを20℃以上になるように温度コントロールをする必要
がある。温度が極端に低い場合は乳化に時間がかかった
り、あるいは乳化しない場合があるからである。In this way, when alcohol is added to the Teflon aqueous dispersion to emulsify it, it is necessary to control the temperature so that the Teflon aqueous dispersion becomes 20 ° C. or higher. This is because when the temperature is extremely low, the emulsification may take a long time or may not be emulsified.
またアルコールの使用量はテフロン水性ディスパージョ
ンの30重量％程度が好ましい。アルコール量が少ない場
合（例えば10重量％以下）は乳化しないし、多すぎる場
合（例えば80重量％以上）には余剰のアルコールが離漿
する。The amount of alcohol used is preferably about 30% by weight of the Teflon aqueous dispersion. When the amount of alcohol is small (for example, 10% by weight or less), it does not emulsify, and when it is too large (for example, 80% by weight or more), excess alcohol is synergic.
更に、上記集電体として、導電性粉末にバインダーとし
てポリビニルブチラールを、可塑剤としてフタル酸ジブ
チルを、溶剤としてアルコールをそれぞれ加えスラリー
状とした導電塗料を塗布・乾燥処理したものを用いても
良い。この処理を施した集電体を用いれば、上記押出成
形時において合剤に含まれているアルコールにより接着
力が発揮されるようになり、この結果集電体と合剤との
接着性が更に向上する。Further, as the above-mentioned current collector, it is possible to use a conductive powder coated with polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, alcohol as a solvent, and a conductive paint applied in a slurry form and dried. . When the current collector subjected to this treatment is used, the adhesive force is exerted by the alcohol contained in the mixture during the above-mentioned extrusion molding, and as a result, the adhesiveness between the current collector and the mixture is further improved. improves.
上記の導電性粉末としては、例えば、黒鉛やアセチレン
ブラックを単独ないし混合したものを用いれば良い。そ
して、上記導電塗料としては、例えば、導電性粉末92重
量％（黒鉛46重量％＋アセチレンブラック46重量％），
ポリビニルブチラール5.5重量％，フタル酸ジブチル2.5
重量％を混合したものに溶剤としてのアルコールを適当
量加えスラリー状にしたものを用いれば良い。As the conductive powder, for example, graphite or acetylene black may be used alone or in a mixture. And as the above-mentioned conductive paint, for example, conductive powder 92% by weight (graphite 46% by weight + acetylene black 46% by weight),
Polyvinyl butyral 5.5% by weight, dibutyl phthalate 2.5
An appropriate amount of alcohol as a solvent may be added to a mixture of wt% to form a slurry.
また、上記熱処理により、合剤中などに添加されたポリ
ビニルブチラールやフタル酸ジブチルなどが熱分解さ
れ、合剤の流動性が消失するようになる。この熱処理
は、上記の通り、300℃以下の温度において段階的に昇
温して行う必要がある。つまり、この熱処理を300℃ま
で直線的に昇温して行った場合、熱分解で発生したｎ−
ブチラール、ブチルアルデヒド、CO、CO2、H2Oなどの酸
化反応熱により合剤が燃焼する虞があるからである。Further, the heat treatment causes the polyvinyl butyral, dibutyl phthalate, and the like added in the mixture to be thermally decomposed and the fluidity of the mixture to disappear. As described above, this heat treatment needs to be performed stepwise at a temperature of 300 ° C. or lower. That is, when this heat treatment is performed by linearly raising the temperature to 300 ° C, n-
This is because the mixture may be burned by the heat of oxidation reaction of butyral, butyraldehyde, CO, CO 2 , H 2 O and the like.
そして、150〜180℃付近でフタル酸ジブチルがまず分解
し、次いで170〜200℃でポリビニルブチラールの一次分
解（側鎖部分の分解）がまた250℃付近でその二次分解
（直鎖部分の分解）がそれぞれ起きるため、上記のよう
に段階的に昇温することで、これらの分解が同時に起こ
らないように上記の熱分解反応をコントロールすること
ができ、従って合剤の燃焼が防止される。Then, dibutyl phthalate first decomposes at around 150 to 180 ° C, then primary decomposition of polyvinyl butyral (decomposition of side chain part) at 170 to 200 ° C and its secondary decomposition (decomposition of straight chain part) at around 250 ° C. ) Respectively, the above-mentioned thermal decomposition reaction can be controlled so that these decompositions do not occur at the same time by raising the temperature stepwise as described above, and thus the combustion of the mixture is prevented.
上記熱処理において、フタル酸ジブチルは熱分解により
ほぼ100％分解するが、ポリビニルブチラールは300℃ま
での熱分解では約90％が分解し、残りの10％は低分子化
し残渣として合剤中に残存する。この残渣量が多いと電
池内部抵抗増大の要因となるため、ポリビニルブチラー
ルの使用量は前記した通り15％以内が好ましい。In the above heat treatment, dibutyl phthalate decomposes almost 100% by thermal decomposition, but polyvinyl butyral decomposes about 90% by thermal decomposition up to 300 ° C, and the remaining 10% becomes low molecular weight and remains in the mixture as a residue. To do. Since a large amount of this residue causes an increase in internal resistance of the battery, the amount of polyvinyl butyral used is preferably within 15% as described above.
尚、この熱分解量を大きくするために上記熱処理を300
℃より高温で行うことも考えられるが、高温すぎれば二
酸化マンガンの変態や集電体（通常ステンレス鋼などで
作られる）の表面に絶縁性の酸化被膜が発生する虞があ
る。従って熱処理温度は300℃以下に制限する必要があ
る。In addition, in order to increase the amount of this thermal decomposition, the above heat treatment
It may be possible to carry out the treatment at a temperature higher than 0 ° C, but if the temperature is too high, there is a risk of transformation of manganese dioxide and formation of an insulating oxide film on the surface of the current collector (generally made of stainless steel). Therefore, it is necessary to limit the heat treatment temperature to 300 ° C or lower.
また、熱処理時間は、処理槽の大きさやシート状合剤の
厚さや容量などを考慮して適当な時間に定められ、具体
的には例えば48時間程度行えば良い。熱処理時間を例え
ば８時間にして昇温を急激に行って熱分解サイクルを短
くした場合には合剤が燃焼する虞がある。また、熱処理
時間を例えば16時間として合剤が燃焼しない程度の熱分
解サイクルで行った場合でも、所定量の熱分解（例えば
90％分解）を確保することができない。更に熱処理時間
を例えば96時間と長くしても、熱分解される量は一定量
であり、長くしすぎても意味がない。Further, the heat treatment time is set to an appropriate time in consideration of the size of the treatment tank, the thickness and capacity of the sheet-like mixture, and specifically, it may be performed for about 48 hours. When the heat treatment time is set to, for example, 8 hours and the temperature is rapidly raised to shorten the thermal decomposition cycle, the mixture may burn. Further, even when the heat treatment time is set to, for example, 16 hours in a thermal decomposition cycle such that the mixture does not burn, a predetermined amount of thermal decomposition (for example,
90% decomposition) cannot be secured. Further, even if the heat treatment time is increased to, for example, 96 hours, the amount of thermal decomposition is a constant amount, and it is meaningless to make it too long.
ところで、上記の集電体としてはパンチングメタルやエ
クスパンデットメタルなどの多孔性集電体を使用するこ
とができるが、発電要素巻回時における集電体のバリに
よる内部短絡を防ぐ観点から、このようなバリの少ない
パンチングメタルを用いることが良い。また、パンチン
グメタルの幅方向の両側に基材部分（無孔部分）を設け
たものが好ましい。このような基材部分を設けることに
より、パンチングメタル自身の引張り強度が向上し、ま
た発電要素巻回時などにおけるパンチングメタルの変形
に起因する電池の内部短絡が有効に防止され、電池の安
全性が向上する。By the way, it is possible to use a porous current collector such as punching metal or expanded metal as the current collector, but from the viewpoint of preventing an internal short circuit due to a burr of the current collector when the power generating element is wound, It is preferable to use punching metal with less burr. Further, it is preferable to provide a base material portion (non-perforated portion) on both sides of the punching metal in the width direction. By providing such a base material portion, the tensile strength of the punching metal itself is improved, and the internal short circuit of the battery due to the deformation of the punching metal at the time of winding the power generating element is effectively prevented, and the safety of the battery is improved. Is improved.
更に、パンチングメタルにエンボス加工を施すことによ
り、多孔性集電体と合剤との接触が良好となり、取出し
得る電流値も大きくなるので好ましい。Further, by embossing the punched metal, the contact between the porous current collector and the mixture is improved and the current value that can be taken out is increased, which is preferable.
また、多孔性集電体に一定間隔で所定寸法の基材部分を
設けることにより、集電体への連絡板の溶接、及びその
ための合剤の掻き取りが容易かつ正確に行えるようにな
る。Further, by providing the porous current collector with base material portions having a predetermined size at regular intervals, welding of the connecting plate to the current collector and scraping of the mixture for that can be performed easily and accurately.
〈作用〉 上記のようにポリビニルブチラールを添加し、またこれ
をアルコールとともに混練することで、合剤にゴム性状
が付加され、押出成形などによって容易にシート状に成
形することが可能になる。<Operation> By adding polyvinyl butyral as described above and kneading it with alcohol, a rubbery property is added to the mixture, and it becomes possible to easily form a sheet by extrusion molding or the like.
また、フタル酸ジブチルを添加することで、合剤に可塑
性を持たせることができ、成形性の安定化を図ることが
できる。Moreover, by adding dibutyl phthalate, the mixture can be made to have plasticity, and the moldability can be stabilized.
更に、熱処理後に上記のように加圧を施すことで、熱処
理の際ポリビニルブチラールなどの分解により生じた合
剤中の空隙がなくなり、また合剤の厚さ調整や合剤密度
の増大などを容易に行うことができる。Furthermore, by applying pressure as described above after the heat treatment, voids in the mixture caused by decomposition of polyvinyl butyral etc. during the heat treatment are eliminated, and it is easy to adjust the thickness of the mixture and increase the mixture density. Can be done.
〈実施例〉 二酸化マンガン80重量％，導電剤７重量％，テフロン水
性ディスパージョンの乳化物（比重1.5、固形分60重量
％）３重量％，ポリビニルブチラール6.5重量％，フタ
ル酸ジブチル3.5重量％に適当量のアルコールを混合
し、これを１時間混練してゴム性状を有した合剤を得
た。尚、上記乳化物は、30℃に加温したテフロン水性デ
ィスパージョン100gに対してアルコールを全体で40mlに
なる割合で投入し攪拌を繰返すことにより得たものを用
いた。<Example> Manganese dioxide 80% by weight, conductive agent 7% by weight, Teflon aqueous dispersion emulsion (specific gravity 1.5, solid content 60% by weight) 3% by weight, polyvinyl butyral 6.5% by weight, dibutyl phthalate 3.5% by weight. An appropriate amount of alcohol was mixed and kneaded for 1 hour to obtain a mixture having a rubber property. The emulsion used was obtained by adding alcohol to 100 g of the Teflon aqueous dispersion heated at 30 ° C. at a ratio of 40 ml in total and repeating stirring.
次いで第１図のように、上記の合剤１を45°クロスヘッ
ドを取付けた押出成形機２に投入し、このクロスヘッド
内で合剤１とステンレス製パンチングメタルからなる多
孔性集電体３とを一体成形して、多孔性集電体３の両面
にそれぞれ合剤１を圧着してなるシート状の電極構成４
を得た。この電極構成材を、10〜20％の圧縮比で圧延ロ
ールにより圧延して成形厚のバラツキを調整した後、テ
フロン樹脂シートを介在させて巻取機により巻き取る。
尚、押出成形機としては加圧型ダイやチューブ型ダイな
どを有したものを適宜使用することができる。Then, as shown in FIG. 1, the mixture 1 is put into an extruder 2 equipped with a 45 ° crosshead, and the mixture 1 and the porous current collector 3 made of punching metal made of stainless steel are placed in the crosshead. And sheet-shaped electrode structure 4 in which the mixture 1 is pressure-bonded to both surfaces of the porous current collector 3 by integrally molding
Got This electrode constituent material is rolled by a rolling roll at a compression ratio of 10 to 20% to adjust the variation of the molding thickness, and then wound by a winder with a Teflon resin sheet interposed.
An extruder having a pressure die, a tube die, or the like can be appropriately used as the extruder.
こうして巻き取った電極構成材を乾燥炉に投入し、第２
図に示した温度サイクルで、50〜300℃まで48時間かけ
て段階的に昇温して、合剤中のポリビニルブチラールや
フタル酸ジブチルなどの熱分解を行う。その後、圧延ロ
ールやプレスにて圧縮比20〜50％（圧縮前の厚さにバラ
ツキがあるので圧縮比は変動する）で圧延して、所定厚
さ及び密度のシート状電極を得る。The electrode constituent material thus wound up is put into a drying furnace, and the second
In the temperature cycle shown in the figure, the temperature is raised stepwise from 50 to 300 ° C. over 48 hours to thermally decompose polyvinyl butyral and dibutyl phthalate in the mixture. Then, it is rolled with a rolling roll or a press at a compression ratio of 20 to 50% (the compression ratio varies because the thickness before compression varies) to obtain a sheet electrode having a predetermined thickness and density.
このようにして作ったシート状電極を所定寸法に裁断し
たものを正極とした。尚、シート状の電極構成材を所定
寸法に裁断するのは上記一体成型後なら何時行なっても
良い。The sheet-like electrode thus produced was cut into a predetermined size to be used as a positive electrode. The sheet-shaped electrode constituent material may be cut into a predetermined size at any time after the integral molding.
そして、この正極と、リチウムシートからなる負極とを
用い、これら正極と負極とをセパレータを介して積重し
且つ渦巻状に巻回して発電要素とし、この発電要素を電
池缶に収納するなどして、第３図に示したような、本発
明に係わる直径17mm,高さ33.5mmのリチウム−マンガン
電池（本発明品）を作った。第３図において、５〜７は
それぞれ正極，セパレータ，負極、８〜11はそれぞれ電
池缶，絶縁ガスケット，端子板，封口板、12,13は連絡
板である。Then, using this positive electrode and a negative electrode made of a lithium sheet, these positive electrode and negative electrode are stacked via a separator and spirally wound into a power generating element, and this power generating element is housed in a battery can. Then, a lithium-manganese battery (invention product) having a diameter of 17 mm and a height of 33.5 mm according to the present invention as shown in FIG. 3 was produced. In FIG. 3, 5 to 7 are positive electrodes, separators, negative electrodes, 8 to 11 are battery cans, insulating gaskets, terminal plates, sealing plates, and 12 and 13 are connecting plates.
一方、テフロン水性ディスパージョンの乳化物，ポリビ
ニルブチラール，フタル酸ジブチル，並びにアルコール
に代えて、テフロン水性ディスパージョンと水を用いた
他は同様な組成物からなるスラリー状の合剤を作り、こ
れを多孔性集電体に塗布・乾燥させた後、圧延ロールで
所定厚さに圧延・圧着してシート状電極を作製した。そ
して、このシート状電極を正極として用いた他は本発明
品と同じリチウム−マンガン電池（従来品）を作製し
た。On the other hand, instead of the emulsion of Teflon aqueous dispersion, polyvinyl butyral, dibutyl phthalate, and alcohol, Teflon aqueous dispersion and water were used to prepare a slurry-like mixture of the same composition, and this was prepared. After coating and drying on the porous current collector, it was rolled and pressure-bonded with a rolling roll to a predetermined thickness to produce a sheet electrode. Then, the same lithium-manganese battery (conventional product) as the product of the present invention was produced except that this sheet electrode was used as a positive electrode.
これらの電池における正極の歩留り（％）を第１表に示
した。従来品の場合、多孔性集電体からの合剤剥離や多
孔性集電体への合剤塗布厚のバラツキなどによる不良が
大きく、歩留りが低い。The yield (%) of the positive electrode in these batteries is shown in Table 1. In the case of the conventional product, the defect is large due to peeling of the mixture from the porous current collector and variation in the thickness of the mixture applied to the porous current collector, and the yield is low.
またこれらの電池を、製造後に温度20℃、並びに温度−
20℃において、750Ωの抵抗で終止電圧2.0Vまで連続放
電させたときの各電池の放電時間をそれぞれ測定した。
結果は第２表の通りである。尚、この結果は、従来品の
放電時間を100とした値で示した。 After manufacturing these batteries, the temperature was 20 ° C and the temperature
At 20 ° C., the discharge time of each battery when continuously discharged to a final voltage of 2.0 V with a resistance of 750 Ω was measured.
The results are shown in Table 2. The results are shown as values with the discharge time of the conventional product as 100.
また、これらの電池を製造後に温度60℃で40〜120日保
存し、また40日,80日並びに120日経過時点において、そ
れぞれ温度20℃、並びに温度−20℃で750Ωの抵抗で終
止電圧2.0Vまで連続放電させたときの各電池の放電時間
を測定した。結果は第３表に、従来品の初度の放電時間
を100とした値で示した。 Further, these batteries were stored at a temperature of 60 ° C for 40 to 120 days after production, and after 40 days, 80 days, and 120 days had elapsed, a temperature of 20 ° C and a termination voltage of 750Ω at a temperature of -20 ° C and a termination voltage of 2.0. The discharge time of each battery when continuously discharged to V was measured. The results are shown in Table 3 as a value with the initial discharge time of the conventional product as 100.
また、第４図は、本発明におけるシート状電極の他の製
造方法を説明したもので、二酸化マンガン，導電剤，テ
フロン水性ディスパージョンないしその乳化物，並びに
ポリビニルブチラール，フタル酸ジブチルに適当量のア
ルコールを混合し、混練した合剤は第４図のように２つ
の押出成形機14,15にそれぞれ投入され、これらの押出
成形機14,15からそれぞれシート状合剤16,17となって押
出される。 FIG. 4 illustrates another method for producing a sheet electrode according to the present invention. Manganese dioxide, a conductive agent, a Teflon aqueous dispersion or its emulsion, and polyvinyl butyral and dibutyl phthalate are added in appropriate amounts. The mixture mixed with alcohol and kneaded is fed into two extruders 14 and 15 as shown in Fig. 4, and extruded into sheet-like mixture 16 and 17 from these extruders 14 and 15, respectively. To be done.
その後、シート状合剤16,17の間に、送出しロールから
送出されたシート状の多孔性集電体18を挿入し、また圧
延ロール19によりこれらシート状合剤16,17並びに多孔
性集電体18を一体で連続して圧延し、積層一体化してシ
ート状の電極構成材20を作製する。Thereafter, between the sheet-shaped mixture 16, 17, the sheet-shaped porous current collector 18 delivered from the delivery roll is inserted, and the sheet-shaped mixture 16, 16 and the porous collector are provided by the rolling roll 19. The electric body 18 is continuously rolled as one body and laminated to form a sheet-shaped electrode constituent material 20.
こうして得た電極構成材を巻取後に乾燥炉などにより上
記と同様に段階的に昇温して熱処理した後、圧延ロール
やプレスにて加圧して所定厚さ及び密度のシート状電極
を得、爾後これを所定寸法に裁断したものを正極として
用いる訳である。尚、シート状の電極構成材を所定寸法
に裁断するのは上記積層一体化後なら何時行なっても良
い。After winding the electrode constituent material thus obtained and heat-treating it stepwise by a drying furnace or the like in the same manner as above, it is pressed with a rolling roll or a press to obtain a sheet-like electrode having a predetermined thickness and density, After that, it is cut into a predetermined size and used as a positive electrode. The sheet-shaped electrode constituent material may be cut into a predetermined size at any time after the above-mentioned lamination and integration.
更に、上記合剤を押出成形機により合剤のみのシート状
に成形した後に所定寸法に裁断し、こうして作った２枚
のシート状合剤片の間に所定寸法に裁断した集電体を介
在させ、圧延ロールもしくはプレスにて圧着成形を行
い、その他は上記と同様な工程によりシート状電極を作
製するようにしても良い。Further, the mixture is molded into a sheet of the mixture only by an extruder and then cut into a predetermined size, and a current collector cut into a predetermined size is interposed between the two sheet-shaped mixture pieces thus formed. Then, the sheet-shaped electrode may be produced by performing the pressure-bonding molding with a rolling roll or a press, and otherwise by the same steps as described above.
また、以上説明した押出成形において、押出成形機とク
ロスヘッドの間に公知のブレーカプレート、及び／また
はスクリーンメッシュなどを設けることにより、合剤に
おける粒径調整が行なえ、また合剤中のバインダー塊を
除去することなどができる結果、成形性が安定化し、ま
たクロスヘッド出口における合剤詰まりによるシート状
合剤でのスジや亀裂を防止することができる。In addition, in the above-described extrusion molding, by providing a known breaker plate, and / or a screen mesh between the extruder and the crosshead, the particle size of the mixture can be adjusted, and the binder mass in the mixture can be adjusted. As a result, it is possible to stabilize the moldability and prevent streaks and cracks in the sheet-shaped mixture due to the mixture mixture clogging at the crosshead outlet.
〈発明の効果〉 以上のように、この発明によれば、合剤と集電体との結
着力が強固で、また厚さが均一で且つ合剤密度の大きな
シート状電極を容易に製造することができる。<Effects of the Invention> As described above, according to the present invention, a sheet-like electrode having a strong binding force between the mixture and the current collector and having a uniform thickness and a large mixture density can be easily produced. be able to.
第１図は実施例の製造方法における押出成形時の説明
図、第２図はこの製造方法における熱処理の一例を示し
たグラフ、第３図は実施例の電池の断面図、第４図は他
の製造方法の説明図である。 １……合剤、2,14,15……押出成形機、3,18……多孔性
集電体、５……正極、６……セパレータ、７……負極、
８……電池缶。FIG. 1 is an explanatory view at the time of extrusion molding in the manufacturing method of the embodiment, FIG. 2 is a graph showing an example of heat treatment in this manufacturing method, FIG. 3 is a sectional view of a battery of the embodiment, and FIG. FIG. 6 is an explanatory diagram of a manufacturing method of. 1 ... mixture, 2,14,15 ... extruder, 3,18 ... porous current collector, 5 ... positive electrode, 6 ... separator, 7 ... negative electrode,
8 ... Battery can.
Claims (6)
バインダーとしてポリビニルブチラールを、可塑剤とし
てフタル酸ジブチルを、また溶剤としてアルコールをそ
れぞれ加え混練してなる合剤を、押出成形により集電体
とともにシート状の電極構成材に一体成形し、またこの
電極構成材を300℃以下の温度において段階的に昇温し
て熱処理した後、加圧して所定の厚さ及び密度にするこ
とを特徴とするシート状電極の製造方法。1. An active material containing manganese dioxide as a main component,
Polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, and alcohol as a solvent were kneaded and kneaded together to form a sheet-like electrode component together with a current collector by extrusion molding. A method for producing a sheet-shaped electrode, which comprises stepwise heating a constituent material at a temperature of 300 ° C. or lower to heat-treat it, and then applying pressure to a predetermined thickness and density.
バインダーとしてポリビニルブチラールを、可塑剤とし
てフタル酸ジブチルを、また溶剤としてアルコールをそ
れぞれ加え混練してなる合剤を押出成形して得た２枚の
シート状合剤の間に集電体を挿入し、圧延あるいはプレ
スによりこれらを連続して積層一体化し、次いで300℃
以下の温度において段階的に昇温して熱処理した後、加
圧して所定の厚さ及び密度にすることを特徴とするシー
ト状電極の製造方法。2. An active material containing manganese dioxide as a main component,
Polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, and alcohol as a solvent were added and kneaded, and a current collector was inserted between two sheet-like mixture obtained by extrusion molding. These are continuously laminated and integrated by rolling, pressing or pressing, then at 300 ℃
A method for producing a sheet electrode, comprising stepwise heating at the following temperatures, heat treatment, and pressurization to a predetermined thickness and density.
バインダーとしてポリビニルブチラールを、可塑剤とし
てフタル酸ジブチルを、また溶剤としてアルコールをそ
れぞれ加え混練してなる合剤をシート状に押出成形した
後に所定寸法に裁断し、こうして得たシート状合剤片を
集電体の両面にそれぞれ位置させ、圧延あるいはプレス
によりこれらシート状合剤片と集電体とを積層一体化
し、次いで300℃以下の温度において段階的に昇温して
熱処理した後、加圧して所定の厚さ及び密度にすること
を特徴とするシート状電極の製造方法。3. An active material containing manganese dioxide as a main component,
Polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, and alcohol as a solvent are added and kneaded, and the mixture is extruded into a sheet and then cut into a predetermined size, and the sheet-shaped mixture piece thus obtained is cut. Positioned on both sides of the current collector, the sheet-shaped mixture pieces and the current collector are laminated and integrated by rolling or pressing, and then heat-treated by stepwise heating at a temperature of 300 ° C. or less and then pressed. A method for manufacturing a sheet-shaped electrode, wherein the sheet-shaped electrode has a predetermined thickness and density.
ンガンを主成分とする活物質に対して２〜15重量％であ
り、またフタル酸ジブチルの添加量が前記ポリビニルブ
チラールに対して30〜70重量％であることを特徴とする
請求項1,2または３記載のシート状電極の製造方法。4. The addition amount of polyvinyl butyral is 2 to 15% by weight based on the active material containing manganese dioxide as a main component, and the addition amount of dibutyl phthalate is 30 to 70% by weight based on the polyvinyl butyral. The method for producing a sheet-like electrode according to claim 1, 2 or 3, wherein
に、テフロン水性ディスパージョンにアルコールを添加
し攪拌してなる乳化物を加えたものを用いることを特徴
とする請求項1,2または３記載のシート状電極の製造方
法。5. The sheet-shaped electrode according to claim 1, 2 or 3, wherein the binder is polyvinyl butyral to which an emulsion prepared by adding alcohol to Teflon aqueous dispersion and stirring is added. Manufacturing method.
してポリビニルブチラールを、可塑剤としてフタル酸ジ
ブチルを、溶剤としてアルコールをそれぞれ加えスラリ
ー状とした導電塗料を塗布・乾燥させたものを用いるこ
とを特徴とする請求項1,2または３記載のシート状電極
の製造方法。6. As a current collector, use is made of conductive powder, polyvinyl butyral as a binder, dibutyl phthalate as a plasticizer, alcohol as a solvent, and a slurry-like conductive paint applied and dried. The method for producing a sheet-shaped electrode according to claim 1, 2, or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11293189A JPH0738304B2 (en) | 1989-05-02 | 1989-05-02 | Method for manufacturing sheet electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11293189A JPH0738304B2 (en) | 1989-05-02 | 1989-05-02 | Method for manufacturing sheet electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02291664A JPH02291664A (en) | 1990-12-03 |
| JPH0738304B2 true JPH0738304B2 (en) | 1995-04-26 |
Family
ID=14599072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11293189A Expired - Fee Related JPH0738304B2 (en) | 1989-05-02 | 1989-05-02 | Method for manufacturing sheet electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0738304B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002175950A (en) * | 2000-09-26 | 2002-06-21 | Asahi Glass Co Ltd | Method for manufacturing electrode body for electric double layer capacitor |
| US11276846B2 (en) | 2017-09-25 | 2022-03-15 | Lg Energy Solution, Ltd. | Method for manufacturing electrode for secondary battery and electrode manufactured thereby |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06163034A (en) * | 1992-11-24 | 1994-06-10 | Fuji Elelctrochem Co Ltd | Manufacture of positive electrode for nonaqueous electrolyte battery |
| FR2738396B1 (en) * | 1995-09-05 | 1997-09-26 | Accumulateurs Fixes | LITHIUM RECHARGEABLE ELECTROCHEMICAL GENERATOR ANODE AND MANUFACTURING METHOD THEREOF |
| WO2009139397A1 (en) * | 2008-05-01 | 2009-11-19 | 日本碍子株式会社 | Plate-like crystal grain and production method thereof, and secondary lithium battery |
| WO2019124263A1 (en) * | 2017-12-19 | 2019-06-27 | 株式会社クラレ | Binder solution for non-aqueous electrolyte battery electrode |
| JP7168813B1 (en) * | 2022-07-01 | 2022-11-09 | 株式会社日本製鋼所 | Battery material manufacturing apparatus, battery material manufacturing system, and battery material manufacturing method |
| EP4549128A1 (en) * | 2022-07-01 | 2025-05-07 | The Japan Steel Works, Ltd. | Battery material production device, battery material production system, and battery material production method |
| CN115101721B (en) * | 2022-07-29 | 2023-06-02 | 广东利元亨智能装备股份有限公司 | A method and device for forming an electrode film, and a method and device for manufacturing a pole piece |
-
1989
- 1989-05-02 JP JP11293189A patent/JPH0738304B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002175950A (en) * | 2000-09-26 | 2002-06-21 | Asahi Glass Co Ltd | Method for manufacturing electrode body for electric double layer capacitor |
| US11276846B2 (en) | 2017-09-25 | 2022-03-15 | Lg Energy Solution, Ltd. | Method for manufacturing electrode for secondary battery and electrode manufactured thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02291664A (en) | 1990-12-03 |
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