JPS62243249A - Positive mix sheet for lithium battery and its manufacture - Google Patents
Positive mix sheet for lithium battery and its manufactureInfo
- Publication number
- JPS62243249A JPS62243249A JP8515886A JP8515886A JPS62243249A JP S62243249 A JPS62243249 A JP S62243249A JP 8515886 A JP8515886 A JP 8515886A JP 8515886 A JP8515886 A JP 8515886A JP S62243249 A JPS62243249 A JP S62243249A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- rubber
- positive electrode
- electrode mixture
- powder
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 13
- 239000010935 stainless steel Substances 0.000 abstract description 13
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013470 LiC1 Inorganic materials 0.000 description 1
- -1 LiCl24 Chemical class 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-M Pentobarbital sodium Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)[N-]C1=O QGMRQYFBGABWDR-UHFFFAOYSA-M 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000007965 rubber solvent Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
Abstract
Description
【発明の詳細な説明】
〔発明の技術的分野〕
本発明はリチウム電池用正極合剤シートおよびその製造
方法、さらに詳細には可撓性があり、しかも広い厚さ範
囲で製造可能なリチウム電池用正極合剤シートおよびそ
の製造方法に関するものである。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a positive electrode mixture sheet for lithium batteries and a method for producing the same, and more particularly to a lithium battery that is flexible and can be produced in a wide range of thickness. The present invention relates to a positive electrode mixture sheet and a method for manufacturing the same.
リチウム電池は、リチウムを負極活物質とし、二酸化マ
ンガンなどを正極活物質とするとともに前記負極活物質
および正極活物質に対し化学的に安定で、かつリチウム
イオンが正極活物質と電気化学的に反応をするための移
動を行うことが可能な電解質を用いた構造の電池である
。このようなリチウム電池は、小型で高°エネルギ密度
の電池として、現在広く使用されている。Lithium batteries use lithium as a negative electrode active material and manganese dioxide as a positive electrode active material, are chemically stable with respect to the negative electrode active material and positive electrode active material, and lithium ions electrochemically react with the positive electrode active material. This is a battery with a structure that uses an electrolyte that can be moved to Such lithium batteries are currently widely used as small, high energy density batteries.
前述のような二酸化マンガンを正極活物質として用いる
リチウム電池の正極合剤は、シート状に形成され、たと
えば第１図に示すような構造のリチウム電池に組み込ま
れる。すなわち、Ｎｉなどの負極板１上にリチウムを負
極活物質とする負極合剤あるいは金属リチウム層２を形
成し、電解賃を含むセパレータ３を介して正極合剤シー
ト４を積層し、この正極合剤シート４にさらにＮｉなど
の正極板５を積層した構造を有している。The positive electrode mixture for a lithium battery using manganese dioxide as a positive electrode active material as described above is formed into a sheet shape and incorporated into a lithium battery having a structure as shown in FIG. 1, for example. That is, a negative electrode mixture containing lithium as a negative electrode active material or a metal lithium layer 2 is formed on a negative electrode plate 1 made of Ni or the like, and a positive electrode mixture sheet 4 is laminated via a separator 3 containing an electrolyte. It has a structure in which a positive electrode plate 5 made of Ni or the like is further laminated on the agent sheet 4.
このような構造のリチウム電池において、正極活物質合
剤シート４は、第２図に示すように、細いステンレス繊
維を編んで製造したステンレスネット４０を二酸化マン
ガンを正極活物質とする正極合剤層４１で覆ってシート
状にした構造を有している。このような正極合剤シート
４は、粘度をｖＡ１１シた正極合剤液中に前記帯状のス
テンレスネット４０を連続して浸漬する、いわゆるディ
ッピングにより製造される。In a lithium battery having such a structure, as shown in FIG. 2, the positive electrode active material mixture sheet 4 is a positive electrode mixture layer in which a stainless steel net 40 made by knitting thin stainless steel fibers is made of manganese dioxide as the positive electrode active material. It has a sheet-like structure covered with 41. Such a positive electrode mixture sheet 4 is manufactured by so-called dipping, in which the belt-shaped stainless steel net 40 is continuously immersed in a positive electrode mixture liquid having a viscosity of vA11.
このような正極合剤シート４を製造するための正極合剤
液に添加されるバインダとしては、水系の樹脂が用いら
れている。このため前記正極合剤液における溶媒として
は、水が使用されるのが一般的であった。このためステ
ンレスネット４０に正極合剤層４１を形成するにあたっ
ては、前記正極合剤層４１をステンレスネット４０に設
けたのち、水を充分に乾燥除去する必要がある。。しか
しながら、このような溶媒である水の乾燥除去には多大
な時間と、エネルギを要するという欠点があった。A water-based resin is used as a binder added to the positive electrode mixture liquid for manufacturing such a positive electrode mixture sheet 4. For this reason, water has generally been used as a solvent in the positive electrode mixture liquid. Therefore, in forming the positive electrode mixture layer 41 on the stainless steel net 40, it is necessary to provide the positive electrode mixture layer 41 on the stainless steel net 40 and then thoroughly dry and remove water. . However, there is a drawback that drying and removing water, which is a solvent, requires a large amount of time and energy.
また、上記の水系樹脂バインダは可撓性に欠けるという
欠点があるため、０．４ｎ＋ｓ＋以上の正極合剤シート
４を製造しようとすると、乾燥時間が長くなり、このた
めに乾燥温度を上げると、乾燥時の収縮で亀裂を生じ、
実質的に連続した厚い正極合剤シート４を製造すること
はできないという欠点もあった。In addition, since the water-based resin binder described above has the disadvantage of lacking flexibility, when attempting to manufacture a positive electrode mixture sheet 4 of 0.4n+s+ or more, the drying time becomes long, and for this reason, if the drying temperature is increased, Cracks occur due to shrinkage during drying,
There was also a drawback that it was impossible to manufacture a substantially continuous thick positive electrode mixture sheet 4.
また、反対に０．１ｍｓ＋以下の厚さの正極合剤シート
４は、ステンレスネット４０を支持体として使用できな
いことになり、強度に欠け、実用とはならなかった。On the other hand, if the positive electrode mixture sheet 4 had a thickness of 0.1 ms+ or less, the stainless steel net 40 could not be used as a support, and the sheet lacked strength and was not put to practical use.
すなわち、このような従来の正極合剤シート４は上述の
ように可撓性に欠けるため、支持体としてのステンレス
ネット４０を必要とし、このステンレス繊維）４０がな
い場合には、曲げによって簡単に破壊されるという欠点
もある。That is, since such a conventional positive electrode mixture sheet 4 lacks flexibility as described above, it requires a stainless steel net 40 as a support, and if this stainless steel fiber 40 is not available, it can be easily bent by bending. It also has the disadvantage of being destroyed.
本発明は上述の点に鑑みなされたものであり、乾燥工程
に多大のエネルギと時間を消費せず、しかも充分な可撓
性を有する、したがってステンレスネットなどの支持体
を必要としない正極合剤シートおよびその製造方法を提
供することを目的とするものである。The present invention has been made in view of the above points, and provides a positive electrode mixture that does not consume a large amount of energy and time in the drying process, has sufficient flexibility, and does not require a support such as a stainless steel net. The object of the present invention is to provide a sheet and a method for manufacturing the same.
したがって、本発明によるリチウム電池用正極合剤シー
トは、二酸化マンガンおよびカーボンを主成分とし、上
記粉末の結合剤として耐熱性ゴムを３〜１０ｆｆｌ量％
添加したことを特徴とするものである。Therefore, the positive electrode mixture sheet for lithium batteries according to the present invention contains manganese dioxide and carbon as main components, and contains 3 to 10 ffl of heat-resistant rubber as a binder for the powder.
It is characterized by the addition of
また、本発明によるリチウム電池用正極合剤シートの製
造方法は、二酸化マンガン、カーボンおよび耐熱性ゴム
分が３〜１０重量％になるような量の耐熱性ゴム溶液を
混合し、次いで乾燥して溶媒を蒸発させ、えられた固形
分を粉砕して混合粉体を形成するとともに、圧縮してシ
ート状にすることを特徴とするものである。In addition, the method for manufacturing a positive electrode mixture sheet for lithium batteries according to the present invention includes mixing manganese dioxide, carbon, and a heat-resistant rubber solution in an amount such that the heat-resistant rubber content is 3 to 10% by weight, and then drying. The method is characterized by evaporating the solvent, pulverizing the resulting solid content to form a mixed powder, and compressing it into a sheet.
本発明によるリチウム電池用正極合剤シートによれば、
シートを形成するための結合剤として、３〜１０重量％
のゴムを添加したため、可撓性のあるシートとすること
ができ、このため、ステンレスなどの基体を必要とする
ことのない正極合剤シートとすることができるという利
点がある。According to the positive electrode mixture sheet for lithium batteries according to the present invention,
3-10% by weight as a binder to form a sheet
Because of the addition of rubber, the sheet can be made flexible, which has the advantage that it can be made into a positive electrode mixture sheet that does not require a substrate such as stainless steel.
また、本発明によるリチウム電池用正極合剤シートの製
造方法によれば、水系樹脂を使用しておらず、蒸発しや
すい溶媒を使用するため、乾燥工程においても多大のエ
ネルギと時間を消費することがないという利点がある。In addition, according to the method for manufacturing a positive electrode mixture sheet for lithium batteries according to the present invention, a water-based resin is not used, and a solvent that easily evaporates is used, so a large amount of energy and time is consumed in the drying process. The advantage is that there is no
また、ステンレスネットなどの基体を使用しないととも
に、可撓性があるために、広い厚さ範囲で正極合剤シー
トを製造可能であるという利点もある。Another advantage is that it does not use a substrate such as stainless steel net, and because it is flexible, positive electrode mixture sheets can be manufactured in a wide range of thicknesses.
本発明をさらに詳しく説明する。 The present invention will be explained in more detail.
本発明によるリチウム電池用正極合剤シートは前述のよ
うに、二酸化マンガンとカーボンより基本的になる正極
合剤を使用したものである。このような正極合剤におい
て、二酸化マンガンの含有量は７６〜８９％であるのが
好ましい。７６％未満であると、リチウムの放電効率が
低下する虞を生じ、一方８９％を超えると、前記正極合
剤をシート状にするのが困難になるからである。As described above, the positive electrode mixture sheet for a lithium battery according to the present invention uses a positive electrode mixture consisting basically of manganese dioxide and carbon. In such a positive electrode mixture, the content of manganese dioxide is preferably 76 to 89%. If it is less than 76%, there is a risk that the lithium discharge efficiency will decrease, while if it exceeds 89%, it will be difficult to form the positive electrode mixture into a sheet shape.
前述の正極合剤シートは、上述のように耐熱性ゴム分を
３〜１０重量％含んでいる。このゴム分は二酸化マンガ
ンおよびカーボン粉末の結合剤となるものであり、乾燥
処理などが行われることから耐熱性があり、良好な接着
性を有していることが必要になる。さらに、シート状に
する必要があるために物性が良好でシート化が容易であ
り、またリチウムの放電効率を上昇させるためには、不
純物が少ないゴムであることが好ましい。このようなゴ
ム分としては、たとえば、アクリル系ゴム、ＥＰＤＭ、
Ｎｌ３Ｒなどの一種以上を例として挙げることができる
。The above-mentioned positive electrode mixture sheet contains 3 to 10% by weight of heat-resistant rubber as described above. This rubber component serves as a binder for manganese dioxide and carbon powder, and since it is subjected to drying treatment, it must be heat resistant and have good adhesive properties. Further, since it is necessary to form the rubber into a sheet, it is preferable to use a rubber that has good physical properties and is easy to form into a sheet, and has few impurities in order to improve the lithium discharge efficiency. Examples of such rubber components include acrylic rubber, EPDM,
Examples include one or more of Nl3R and the like.
このようなゴム分の添加量は３〜１０重量％であるが、
このゴム分の添加量が３重量％未満であると可撓性が不
足してシート状にすることが困難になり、また１０Ｍ量
％を超えると、正極合剤シートの導電性が不足し、良好
な放電効率かえられない虞があるからである。The amount of such rubber added is 3 to 10% by weight,
If the amount of this rubber added is less than 3% by weight, flexibility will be insufficient and it will be difficult to form a sheet, and if it exceeds 10M%, the conductivity of the positive electrode mixture sheet will be insufficient. This is because there is a possibility that good discharge efficiency may not be achieved.
このような正極合剤シートは、０．１〜５１ＩＩ１１の
広い厚さ範囲で製造可能である。Such a positive electrode mixture sheet can be manufactured in a wide thickness range of 0.1 to 51II11.
つぎに本発明によるリチウム電池用正極合剤シートの製
造方法を説明する。Next, a method for manufacturing a positive electrode mixture sheet for lithium batteries according to the present invention will be explained.
本発明による製造方法によれば、まず二酸化マンガンお
よびカーボン粉末に対し、３〜１０重量％のゴム分が添
加可能なゴム溶液を添加し、これを乾燥してゴム分の溶
媒を蒸発させて固体状態にする。According to the production method of the present invention, first, a rubber solution to which 3 to 10% by weight of rubber can be added is added to manganese dioxide and carbon powder, and this is dried to evaporate the rubber solvent and solidify. state.
上述のゴム溶液の溶媒としては、乾燥効率を上げるため
に、前記ゴム分を熔解可能で、かつ良好に蒸発するよう
な溶媒であるのが好ましい。たとえば、トルエン、メチ
ルエチルケトン、アセトン、酢酸エチルエステルなど。As the solvent for the above-mentioned rubber solution, in order to increase the drying efficiency, it is preferable to use a solvent that can dissolve the rubber component and evaporate it well. For example, toluene, methyl ethyl ketone, acetone, acetic acid ethyl ester, etc.
このゴム溶液のゴム分の濃度は、好ましくは１０〜２０
重量％であるのが好ましい。ゴム分の濃度が１０重量％
未満であると、乾燥に時間およびエネルギを多大に消費
する虞があり、一方２０重量％を超えると、二酸化マン
ガンおよびカーボン粉末との混合がむずかしくなる。The rubber concentration of this rubber solution is preferably 10 to 20
Preferably, it is % by weight. Rubber concentration is 10% by weight
If it is less than 20% by weight, it may be difficult to mix with manganese dioxide and carbon powder.
上述のような混合物を乾燥し、溶媒を除去して固体化す
るものであるが、この乾燥は、二酸化マンガン、カーボ
ン、ゴム分を劣化せしめないような温度で行うのが好ま
しい。一般に、５０〜１００℃の温度で、０．５〜ＩＯ
時間乾燥するのがよい。The above-mentioned mixture is dried to remove the solvent and solidify, and this drying is preferably carried out at a temperature that does not deteriorate the manganese dioxide, carbon, and rubber components. Generally, at a temperature of 50 to 100 °C, 0.5 to IO
It is best to let it dry for a while.
１００℃を超えると、ゴム分などが劣化する虞を生じ、
５０℃未満であると、乾燥時間がながくなって効率的で
はなくなるからである。また、乾燥時間が０６５時間未
満であると、均一な乾燥粉粒体にするのがむずかしい。If the temperature exceeds 100℃, there is a risk that the rubber content will deteriorate.
This is because if the temperature is less than 50°C, the drying time becomes long and becomes inefficient. Moreover, if the drying time is less than 0.65 hours, it is difficult to form a uniform dry powder.
一方、乾燥時間が１０時間を超えると、効率が悪化して
好ましくないからである。On the other hand, if the drying time exceeds 10 hours, the efficiency deteriorates, which is not preferable.
このようにして製造された固形分を粉砕して粉末状にす
る。この粉砕方法は、本発明において基本的に限定され
るものではなく、たとえばハンマーなどで粉砕すること
ができる。このような粉末の粒径は、好ましくは、０．
５ ｎｕｎ以下であるのがよい。０．５ ｍ＋ｗを超え
ると、均一な密度の高いシートが得られない。The solid content thus produced is ground into powder. This pulverization method is basically not limited in the present invention, and for example, pulverization can be performed using a hammer or the like. The particle size of such powder is preferably 0.
It is preferable that it is 5 nun or less. If it exceeds 0.5 m+w, a uniform, high-density sheet cannot be obtained.
このように製造した粉末を圧縮してシート状にする。こ
のシート状にする方法は、本発明においては基本的に限
定されるものではなく、たとえばゴム練用オープンロー
ルあるいは圧延機で圧縮シート化することができる。The powder thus produced is compressed into a sheet. The method of forming the material into a sheet is basically not limited in the present invention, and for example, it may be compressed into a sheet using an open roll for rubber kneading or a rolling mill.
この圧縮化の圧力は、好ましくは２０００〜５０００Ｋ
ｇ／ｃｄであるのがよい。２０００Ｋｇ／−未満であ°
るとシート化がむずかしい。The pressure of this compression is preferably 2000 to 5000K.
It is preferable that it be g/cd. Less than 2000Kg/-
This makes it difficult to make sheets.
このようにシート化するに際し、前記粉末混合物に加湿
剤を添加し、加湿することができる。When forming the powder into a sheet in this way, a humidifier can be added to the powder mixture to humidify it.
このような加湿剤としては、たとえば上記ゴム分を溶解
させた溶媒などの有機化合物、可塑剤および水の一種以
上であることができる。すなわち、若干の湿り気をあた
えてシート化が容易になるようにするためである。Such a humidifier may be one or more of, for example, an organic compound such as a solvent in which the rubber component is dissolved, a plasticizer, and water. That is, this is to make it easier to form a sheet by adding some moisture.
このようなシート化する際に使用される加湿剤はの具体
例としては、たとえば前記ゴム分を溶解したものと同一
の溶媒、また異なる溶媒であるような通常有機溶媒とし
て使用される、トルエン、メチルエチルケトン、アセト
ン、１Ｂ１エチルエステル、エチルアルコール、メチル
イソブチルケトン、酢酸ブチルエステルなどの一種以上
、リチウム電池の電気的特性を低下させないような不活
性のたとえばフロンなどの弗素系樹脂の一種以上の可塑
剤および水よりなる群より選択された一種以上であるこ
とができる。このような加湿剤は、好ましくは、８重量
％以下添加するのが好ましい。Specific examples of the humidifying agent used when forming such a sheet include toluene, which is usually used as an organic solvent, such as the same solvent in which the rubber component is dissolved, or a different solvent. One or more plasticizers such as methyl ethyl ketone, acetone, 1B1 ethyl ester, ethyl alcohol, methyl isobutyl ketone, butyl acetate, and one or more inert fluorine-based resins such as fluorocarbons that do not deteriorate the electrical characteristics of lithium batteries. and water. It is preferable to add such a humidifying agent in an amount of 8% by weight or less.
８Ｍ量％を超えると、湿り気が多くなり、粉体の流動性
が悪く、シート化の際途切れたりロールに付着して均一
な連続シートが出来ない。If it exceeds 8M%, the powder will become too wet and have poor fluidity, resulting in breakage or adhesion to rolls when forming into a sheet, making it impossible to form a uniform continuous sheet.
このように製造したリチウム電池用正極合剤シートは、
第１図に示すようなリチウム電池に組みこまれるが、こ
のときの電解質としては、従来この種のリチウム゛電池
に用いられている非水電解液を使用することができる。The positive electrode mixture sheet for lithium batteries manufactured in this way is
The electrolyte is incorporated into a lithium battery as shown in FIG. 1, and a non-aqueous electrolyte conventionally used in this type of lithium battery can be used as the electrolyte.
たとえばＬｉＣｌ２４、ＬｉＣ１、Ｌｉ＾ＩＣ１４など
の無機リチウム塩をプロピレンカーボネート、メチルテ
トラヒドロフランなどの有機溶媒に溶解した電解質をセ
パレータなどの支持体に含浸させたものであることがで
きる。For example, a support such as a separator may be impregnated with an electrolyte in which an inorganic lithium salt such as LiCl24, LiC1, or Li^IC14 is dissolved in an organic solvent such as propylene carbonate or methyltetrahydrofuran.
さらに負極としては、負極活物質としてリチウムを含む
合剤あるいはリチウム金属板などを用いることができる
。Further, as the negative electrode, a mixture containing lithium as a negative electrode active material, a lithium metal plate, or the like can be used.
つぎに本発明の実施例について説明する。Next, embodiments of the present invention will be described.
実施例に
酸化マンガン ３６０ ｇカーボン
４８ ｇ１０％ ゴム溶液
３６０ｇよりなる混合物をボールミルで
１週間混合したのち、乾燥機中で、９０℃、５時間加熱
して溶媒を揮散させた。えられた固形分をハンマーで粉
砕したのち、５０メソシユのふるいにかけ、前記ふるい
を通過した粉体（粒径０．３＋ｎ以下）をゴム練用オー
プンロールで潰し、約１．０ ｍｎ＋のシート状とした
。Example: manganese oxide 360 g carbon
A mixture of 48 g and 360 g of 10% rubber solution was mixed in a ball mill for one week, and then heated in a dryer at 90° C. for 5 hours to volatilize the solvent. After crushing the obtained solid content with a hammer, it is passed through a 50 msieve sieve, and the powder that passes through the sieve (particle size of 0.3+n or less) is crushed with an open roll for rubber kneading to form a sheet of about 1.0 mm+. And so.
さらに、圧延機で３０００にｇ／ｃｒＡの圧力で３回圧
延し、０．３１１ｍの連続シートにした。Furthermore, it was rolled three times in a rolling mill at a pressure of 3000 g/crA to form a continuous sheet of 0.311 m.
このシートは可撓性があり、また導電性は １０Ω／
ｃｄであった。This sheet is flexible and has an electrical conductivity of 10Ω/
It was a CD.
このように製造された正極合剤シートを用い、第１図に
示すような構造のリチウム電池を製造した。電解質とし
ては、ＩＭのＬｉＣ１０ａをプロピレンカーボネートに
溶解させた電解質を用い、負極として金属リチウムを用
いた場合の放電容量は、５６ｍＡ・ｈｒであり、従来の
水系バインダを用いた場合の５０ｍＡ−ｈｒより優れた
値を示した。Using the positive electrode mixture sheet thus produced, a lithium battery having the structure shown in FIG. 1 was produced. When using IM's LiC10a dissolved in propylene carbonate as the electrolyte and using metallic lithium as the negative electrode, the discharge capacity is 56 mA-hr, which is higher than 50 mA-hr when using a conventional water-based binder. It showed excellent value.
実施例２
二酸化マンガン ３８０ ｇカーボン
４８ ｇ１０％ ゴム溶
液 ２４０ ｇよりなる混合物をボールミ
ルで１週間混合したのち、乾燥機中で、９０℃、４時間
加熱して溶媒を揮散させた。えられた固形分をハンマー
で粉砕したのち、５０メツシユのふるいにかけ、前記ふ
るいを通過した粉体（粒径０．３ ｗ以下）に、６％の
トルエンを添加し加湿した。ついで、ゴム練用オープン
ロールで潰し、約１．Ｏｎ’ｓのシート状とした。Example 2 A mixture consisting of 380 g of manganese dioxide, 48 g of carbon, and 240 g of 10% rubber solution was mixed in a ball mill for one week, and then heated in a dryer at 90° C. for 4 hours to volatilize the solvent. The obtained solid content was crushed with a hammer, then passed through a 50-mesh sieve, and the powder (particle size: 0.3 W or less) that passed through the sieve was humidified by adding 6% toluene. Then, crush it with an open roll for rubber kneading to about 1. It was made into a sheet from On's.
さらに、圧延機で３回圧延し、０．３ ｍｓの連続シー
トにした。Furthermore, it was rolled three times using a rolling mill to form a continuous sheet of 0.3 ms.
このシートは可撓性があり、また導電性は ９Ω／ｄで
あった。This sheet was flexible and had an electrical conductivity of 9Ω/d.
このように製造された正極合剤シートを用い、第１図に
示すような構造のリチウム電池を製造した。電解質とし
ては、ＬＭのＬｉＣ１０ａをプロピレンカーボネートに
溶解させた電解質を用い、負極として金属リチウムを用
いた場合の放電容量は、６０−＾・ｈｒであった。Using the positive electrode mixture sheet thus produced, a lithium battery having the structure shown in FIG. 1 was produced. As the electrolyte, an electrolyte in which LM LiC10a was dissolved in propylene carbonate was used, and when metallic lithium was used as the negative electrode, the discharge capacity was 60-^·hr.
第１図はリチウム電池の構造を示す断面図、第２図は従
来の正極合剤シートの断面図である。
１・・・負極板、２・・・リチウム負極、３・・・セパ
レータ、４・・・正極合剤シート、５・・・正極板、６
・・・封止材、４０・・・ステンレスネット、４１・・
・正極合剤層。FIG. 1 is a sectional view showing the structure of a lithium battery, and FIG. 2 is a sectional view of a conventional positive electrode mixture sheet. DESCRIPTION OF SYMBOLS 1... Negative electrode plate, 2... Lithium negative electrode, 3... Separator, 4... Positive electrode mixture sheet, 5... Positive electrode plate, 6
...Sealing material, 40...Stainless steel net, 41...
・Positive electrode mixture layer.
Claims (2)
記粉末の結合剤として耐熱性ゴムを３〜１０重量％添加
したことを特徴とするリチウム電池用正極合剤シート。(1) A positive electrode mixture sheet for lithium batteries, characterized in that the main components are manganese dioxide and carbon, and 3 to 10% by weight of heat-resistant rubber is added as a binder for the powder.
３〜１０重量％になるような量の耐熱性ゴム溶液を混合
し、次いで乾燥して溶媒を蒸発させ、えられた固形分を
粉砕して混合粉体を形成するとともに、圧縮してシート
状にすることを特徴とするリチウム電池用合剤シートの
製造方法。(2) Mix manganese dioxide, carbon, and a heat-resistant rubber solution in an amount such that the heat-resistant rubber content is 3 to 10% by weight, then dry to evaporate the solvent, and crush the resulting solid content. A method for producing a mixture sheet for lithium batteries, which comprises forming a mixed powder and compressing it into a sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085158A JPH0746604B2 (en) | 1986-04-15 | 1986-04-15 | Method for producing positive electrode mixture sheet for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085158A JPH0746604B2 (en) | 1986-04-15 | 1986-04-15 | Method for producing positive electrode mixture sheet for lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243249A true JPS62243249A (en) | 1987-10-23 |
| JPH0746604B2 JPH0746604B2 (en) | 1995-05-17 |
Family
ID=13850861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61085158A Expired - Lifetime JPH0746604B2 (en) | 1986-04-15 | 1986-04-15 | Method for producing positive electrode mixture sheet for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0746604B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399246B1 (en) | 2000-05-05 | 2002-06-04 | Eveready Battery Company, Inc. | Latex binder for non-aqueous battery electrodes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5334823A (en) * | 1976-09-14 | 1978-03-31 | Hodogaya Chem Co Ltd | Solubilization of dye into hydrocarbon solvent |
| JPS5848360A (en) * | 1981-09-17 | 1983-03-22 | Matsushita Electric Ind Co Ltd | Battery |
-
1986
- 1986-04-15 JP JP61085158A patent/JPH0746604B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5334823A (en) * | 1976-09-14 | 1978-03-31 | Hodogaya Chem Co Ltd | Solubilization of dye into hydrocarbon solvent |
| JPS5848360A (en) * | 1981-09-17 | 1983-03-22 | Matsushita Electric Ind Co Ltd | Battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399246B1 (en) | 2000-05-05 | 2002-06-04 | Eveready Battery Company, Inc. | Latex binder for non-aqueous battery electrodes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0746604B2 (en) | 1995-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017024720A1 (en) | Preparation method for high capacity lithium-ion battery negative electrode material | |
| JPS60133656A (en) | Battery electrode and method of producing same | |
| CN108270004B (en) | Lithium iron phosphate anode material and preparation method thereof | |
| CN108807842B (en) | Silicon @ carbon-graphene-based flexible composite material, preparation method thereof and lithium battery | |
| WO2021238600A1 (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method therefor | |
| CN114447325A (en) | Porous carbon material, preparation method thereof, negative electrode and lithium metal battery | |
| CN110098374A (en) | A kind of flexible electrode film and the preparation method and application thereof | |
| US20240105941A1 (en) | Negative Electrode Material, Negative Electrode Plate, and Sodium Ion Battery | |
| EP4210140A1 (en) | All-solid-state secondary cell mixture, all-solid-state secondary cell mixture sheet, method for manufacturing same, and all-solid-state secondary cell | |
| JP3341693B2 (en) | Active material powder for electrode of silver oxide battery, electrode material and production method thereof | |
| CN111477859A (en) | Composite positive electrode material, preparation method thereof and water-based secondary battery | |
| JPS62243249A (en) | Positive mix sheet for lithium battery and its manufacture | |
| US5441833A (en) | Paste nickel electrode plate and a storage battery including an electroconductive material | |
| CN115036462A (en) | Pure dry method sodium ion battery cathode, preparation method and battery thereof | |
| US5514497A (en) | Paste nickel electrode plate and a storage battery including an electroconductive material | |
| CN115425210A (en) | Binary high-nickel sodium-ion battery positive electrode material, preparation method and application | |
| US4205432A (en) | Method of manufacturing plastic bonded battery plates having controlled porosity | |
| CN111146401A (en) | Preparation method of battery pole piece and battery | |
| JPS6146948B2 (en) | ||
| CN114665056B (en) | High-compaction-density lithium iron phosphate positive electrode plate and preparation method thereof | |
| JP3107242B2 (en) | Lead storage battery | |
| JP2871058B2 (en) | Electrodes for alkaline storage batteries | |
| CN117133879A (en) | Negative electrode for lithium battery and manufacturing method thereof | |
| CN117497706A (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| TW202347853A (en) | Secondary battery binder, secondary battery binder sheet, production method therefor, and solid-state secondary battery |