JPH11120991A - Manufacture of battery positive electrode sheet - Google Patents
Manufacture of battery positive electrode sheetInfo
- Publication number
- JPH11120991A JPH11120991A JP9280350A JP28035097A JPH11120991A JP H11120991 A JPH11120991 A JP H11120991A JP 9280350 A JP9280350 A JP 9280350A JP 28035097 A JP28035097 A JP 28035097A JP H11120991 A JPH11120991 A JP H11120991A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- material paste
- kneading
- electrode material
- electrode sheet
- 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
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電池用正極シート
の製造方法に関する。The present invention relates to a method for producing a positive electrode sheet for a battery.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池など、正極シー
トおよび負極シートをセパレータを介して巻き回し、ス
パイラル状に巻込む構造の電極体を形成し、円筒型ある
いは角型の電池缶に収納した電池が使用されている。2. Description of the Related Art A battery, such as a lithium ion secondary battery, in which a positive electrode sheet and a negative electrode sheet are wound through a separator to form an electrode body having a structure wound in a spiral shape and accommodated in a cylindrical or square battery can Is used.
【０００３】リチウムイオン二次電池など、スパイラル
状に巻込む構造の電池の製造において、正極活材が少な
くともＮｉ系正極活材を含む正極材ペーストである場合
に、該正極活剤、導電剤、結着剤等と溶剤とを混練・攪
拌して正極材ペーストを作製する際に、該正極材ペース
トがゲル化したり、あるいは、正極材ペースト製造後、
塗工するまでの間の保管時に粘度が増大する場合があ
る。[0003] In the manufacture of a battery having a spirally wound structure such as a lithium ion secondary battery, if the positive electrode active material is a positive electrode material paste containing at least a Ni-based positive electrode active material, the positive electrode active material, the conductive agent, When preparing a positive electrode material paste by kneading and stirring a binder and a solvent, the positive electrode material paste gels, or, after the positive electrode material paste production,
Viscosity may increase during storage before coating.
【０００４】このように正極材ペーストがゲル化あるい
は、高粘度化すると集電体への正極材ペーストの塗工が
困難となったり、あるいは塗工可能としても塗工後の膜
厚にむらが生じてしまうなどの問題があり、製造時の歩
留まりを低下させる問題となる。As described above, when the positive electrode material paste gels or becomes highly viscous, it becomes difficult to apply the positive electrode material paste to the current collector, or even if the positive electrode material paste can be applied, the film thickness after application becomes uneven. There is a problem such as occurrence of such a problem, which causes a problem of lowering the production yield.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記従来技
術の欠点を解決せんとするものであり、正極ペーストの
ゲル化や、粘度上昇を防止して正極シート作製時の歩留
まりを向上させる電池用正極シートの製造方法を提供せ
んとするものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to improve the yield in producing a positive electrode sheet by preventing the gelation of the positive electrode paste and the increase in viscosity. It is intended to provide a method for producing a positive electrode sheet for use.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するために以下の構成を有するものである。すなわ
ち、正極シートおよび負極シートを、セパレータを介し
てスパイラル状に巻込む構造の電池用の正極シートの製
造において、正極材ペーストが少なくともＮｉ系正極活
材を含む正極材ペーストであって、該正極材ペーストの
混練時、送液時、保管時の温度を低温度に保持すること
を特徴とする電池用正極シートの製造方法である。SUMMARY OF THE INVENTION The present invention has the following arrangement to solve the above-mentioned problems. That is, in manufacturing a positive electrode sheet for a battery having a structure in which a positive electrode sheet and a negative electrode sheet are spirally wound with a separator interposed therebetween, the positive electrode material paste is a positive electrode material paste containing at least a Ni-based positive electrode active material. A method for producing a positive electrode sheet for a battery, wherein the temperature during kneading, feeding, and storing the material paste is maintained at a low temperature.
【０００７】[0007]
【発明の実施の形態】本発明の電池用正極シートに使用
できる集電体としては、金属箔、金属織物、金属メッシ
ュ等が使用可能であるが、電気抵抗の小さいものが好ま
しい。リチウムイオン二次電池用集電体としては金属箔
が最も好ましく、具体的にはアルミニウム箔、銅箔、ス
テンレス箔等が使用できる。BEST MODE FOR CARRYING OUT THE INVENTION As a current collector which can be used in the positive electrode sheet for a battery of the present invention, a metal foil, a metal fabric, a metal mesh or the like can be used, but those having a small electric resistance are preferable. As the current collector for the lithium ion secondary battery, a metal foil is most preferable, and specifically, an aluminum foil, a copper foil, a stainless steel foil or the like can be used.
【０００８】本発明における電池用正極シートとは、集
電体の片面または両面に正極剤を積層した構成のもので
ある。The positive electrode sheet for a battery according to the present invention has a structure in which a positive electrode agent is laminated on one side or both sides of a current collector.
【０００９】すなわち、正極シートは、正極活剤と結着
剤とを混練し、溶剤にてペースト状にした正極材（以
下、正極材ペーストという）を集電体の片面もしくは両
面に塗工し、乾燥、プレスして形成した構成のものであ
る。該正極材ペーストには正極シートの導電性を高める
ために導電材を適量混合した方が好ましい。That is, the positive electrode sheet is prepared by kneading a positive electrode active agent and a binder and forming a paste into a paste with a solvent (hereinafter referred to as a positive electrode paste) on one or both surfaces of the current collector. , Dried and pressed. It is preferable to mix an appropriate amount of a conductive material with the positive electrode material paste in order to increase the conductivity of the positive electrode sheet.
【００１０】本発明の正極材ペーストの製造方法の一例
について、以下に述べる。An example of the method for producing the cathode material paste of the present invention will be described below.
【００１１】正極材ペーストの混練・攪拌装置として
は、市販の混練・攪拌機を用いることができる。混練・
攪拌機の容器内に正極活材として例えばＬｉＮｉＣｏＯ
2 、結着剤としてポリフッ化ビニリデン、導電剤として
カーボンブラックを所定の重量比としたものに、溶剤で
あるＮ−メチルピロリドンを加え混練・攪拌して正極材
ペーストを製造する。As the kneading / stirring device for the positive electrode material paste, a commercially available kneading / stirring device can be used. Kneading
In the container of the stirrer, for example, LiNiCoO
2. N-methylpyrrolidone as a solvent is added to a mixture of polyvinylidene fluoride as a binder and carbon black as a conductive agent in a predetermined weight ratio, and the mixture is kneaded and stirred to produce a cathode material paste.
【００１２】かかる際に該混練・攪拌機の容器を低温度
に保持することが、本発明の重要な要件となる。なお、
容器を低温度に保持するために、容器に、例えば冷却管
等の冷却手段を設け、冷却水など冷却用の冷媒を流し、
積極的に冷却するものである。In this case, it is an important requirement of the present invention to keep the temperature of the container of the kneading / stirring machine low. In addition,
In order to maintain the container at a low temperature, the container is provided with a cooling means such as a cooling pipe, for example, and a cooling medium such as cooling water is allowed to flow,
Active cooling.
【００１３】本発明に述べる低温度とは、５０℃以下１
０℃以上の範囲が好ましく、さらに好ましくは４５℃以
下１５℃以上の範囲である。なお、混練・攪拌は脱泡の
ため減圧下で行うことが好ましい。The low temperature described in the present invention is 50 ° C. or less.
The range is preferably 0 ° C. or higher, more preferably 45 ° C. or lower and 15 ° C. or higher. The kneading and stirring are preferably performed under reduced pressure for defoaming.
【００１４】なお、所定時間混練・攪拌後の正極材ペー
ストをコーター近傍の貯槽タンクに送液するが、かかる
ペーストの送液時にも低温度を維持することが好まし
い。従って送液管等を使用する場合は、この送液管につ
いても低温度に冷却することが好ましい。The positive electrode material paste after kneading and stirring for a predetermined time is sent to a storage tank near the coater, and it is preferable to maintain a low temperature even when the paste is sent. Therefore, when a liquid sending pipe is used, it is preferable that this liquid sending pipe is also cooled to a low temperature.
【００１５】さらに、正極ペースト保管用の該貯槽タン
クも同様に低温度に維持し、かつ攪拌しておくことが好
ましい。Further, it is preferable that the storage tank for storing the positive electrode paste is similarly maintained at a low temperature and stirred.
【００１６】また、正極材ペーストのゲル化、高粘度化
をさらに防止するためには、水分等の影響を抑制するこ
とが効果的であり、正極材ペーストの混練時、送液時、
保管時の雰囲気を低湿度雰囲気とすることが好ましい。
具体的には、減圧雰囲気、あるいは窒素ガス等の不活性
ガス雰囲気あるいはドライエアー雰囲気等とすることが
好ましい。In order to further prevent the positive electrode material paste from gelling and increasing the viscosity, it is effective to suppress the influence of moisture and the like.
It is preferable that the atmosphere during storage be a low humidity atmosphere.
Specifically, it is preferable to use a reduced pressure atmosphere, an inert gas atmosphere such as a nitrogen gas atmosphere, a dry air atmosphere, or the like.
【００１７】上述の製造方法で作製した正極材ペースト
を、乾燥ゾーン、ロールプレスなどを有する市販のロー
ルコーター装置を使用して、例えばアルミ箔の片面ある
いは両面に塗工し、所定の温度にて乾燥する。ロールプ
レスによって所定圧力でプレスし、さらに所定幅にスリ
ットして正極シートを得る。The cathode material paste produced by the above-described production method is applied to one or both sides of, for example, an aluminum foil using a commercially available roll coater having a drying zone, a roll press, etc. dry. Pressing is performed at a predetermined pressure by a roll press, and further slit into a predetermined width to obtain a positive electrode sheet.
【００１８】なお、本発明の製造方法はＮｉ系正極活材
を含む正極ペーストの製造方法に関するものであるが、
負極ペーストやあるいは、Ｎｉ系正極を含まない正極ペ
ーストに適用しても一向に差し支えない。The production method of the present invention relates to a method for producing a positive electrode paste containing a Ni-based positive electrode active material.
Even if it is applied to a negative electrode paste or a positive electrode paste containing no Ni-based positive electrode, there is no problem.
【００１９】本発明に使用される、Ｎｉ系正極活剤とし
ては、ＬｉＮｉＯ2 、ＬｉＮｉＣｏＯ2 やあるいは次式
で示されるリチウム複合酸化物や、リチウム層間化合物
等である。Examples of the Ni-based positive electrode active agent used in the present invention include LiNiO 2 , LiNiCoO 2 , a lithium composite oxide represented by the following formula, and a lithium intercalation compound.
【００２０】Ｌｉy Ｎｉ1-x Ｍｅx Ｏ2 （Ｍｅ：Ｔｉ，
Ｖ，Ｍｎ，Ｆｅのいずれかから選ばれる）、Ｌｉ1-x-a
Ａx Ｎｉ1-y-b Ｂy Ｏ2 （ただし、Ａは少なくとも１種
類のアルカリまたはアルカリ土類金属元素、Ｂは少なく
とも１種類の遷移金属元素）は、電圧が高く、エネルギ
ー密度も大きいために好ましく使用できる。特に、Ｌｉ
1-x-a Ａx Ｎｉ1-y-b Ｂy Ｏ2 においては、０＜ｘ≦
０．１，０≦ｙ≦０．３，−０．１≦ａ≦０．１，−
０．１５≦ｂ≦０．１５（ただし、Ａ，Ｂが２種類以上
の元素からなる場合は、ｘはＬｉを除くアルカリまたは
アルカリ土類金属元素、ｙはＮｉを除く全遷移金属元素
の総モル数、ｙ＝０の場合、Ａは少なくとも１種類以上
のアルカリ土類金属を含む。）とすることによって、優
れた特性の正極活剤を得ることができる。また、この場
合、Ａ，Ｂの種類、数、組成を変えたり、あるいはｘ，
ｙ，ａ，ｂを変えた正極活剤を用いることはいっこうに
差支えない。Li y Ni 1-x Me x O 2 (Me: Ti,
V, Mn, or Fe), Li 1-xa
A x Ni 1-yb B y O 2 ( however, A is at least one alkali or alkaline earth metal element, B is at least one transition metal element) is preferred for high voltage, energy density greater Can be used. In particular, Li
In 1-xa A x Ni 1-yb B y O 2 , 0 <x ≦
0.1, 0 ≦ y ≦ 0.3, −0.1 ≦ a ≦ 0.1, −
0.15 ≦ b ≦ 0.15 (However, when A and B are composed of two or more elements, x is an alkali or alkaline earth metal element excluding Li, and y is the total of all transition metal elements excluding Ni. When the number of moles and y = 0, A contains at least one or more kinds of alkaline earth metals), whereby a positive electrode active material having excellent characteristics can be obtained. In this case, the type, number and composition of A and B are changed, or x and B are changed.
The use of a positive electrode active material having different y, a, and b can be used.
【００２１】本発明の正極シートの結着剤は、特に限定
するものではなく種々のものが使用可能である。熱可塑
性樹脂が好ましく用いられ、具体的には、ポリフッ化ビ
ニリデン、ポリテトラフルオロエチレン、ポリフルオロ
エチレン、ポリビニルアルコール、カルボキシメチルセ
ルロース、ポリビニルピロリドン等が使用可能である。
なかでも弗素系樹脂が結着力、化学的安定性、塗工性な
どの点で優れるため好ましい。The binder for the positive electrode sheet of the present invention is not particularly limited, and various binders can be used. Thermoplastic resins are preferably used, and specifically, polyvinylidene fluoride, polytetrafluoroethylene, polyfluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, and the like can be used.
Among them, a fluorine-based resin is preferred because it is excellent in binding power, chemical stability, coatability and the like.
【００２２】また、導電性を向上するために使用するこ
とが望ましい正極シート用の導電剤としては、特に限定
するものではないが、種々の炭素質材料を使用すること
ができる。導電性が良好で、かつ活剤的な特性はなるべ
く有しない材料であることが望ましい。具体的には人工
黒鉛、アセチレンブラック、ケッチェンブラックなどの
熱分解炭素、気相生長炭素、メソフェーズ炭素、コーク
ス、有機物焼成体などが使用できる。The conductive agent for the positive electrode sheet which is desirably used to improve the conductivity is not particularly limited, but various carbonaceous materials can be used. It is desirable that the material has good conductivity and does not have active agent properties as much as possible. Specifically, pyrolytic carbon such as artificial graphite, acetylene black, and Ketjen black, vapor-grown carbon, mesophase carbon, coke, and a fired organic material can be used.
【００２３】[0023]
【実施例】市販の混練・攪拌機を用いた実施例および比
較例について以下に述べる。EXAMPLES Examples and comparative examples using a commercially available kneading / stirring machine will be described below.
【００２４】（実施例１〜４）正極の活剤としてＬｉＣ
ｏＮｉＯ2 と、導電剤として電気化学工業製のアセチレ
ンブラックである“デンカブラック”、および結着剤と
して呉羽化学工業製ポリフッ化ビニリデンを重量比８
５：５：１０としたものに、溶媒としてＮ−メチルピロ
リドンを加えたものを、市販混練・攪拌機を用い、16時
間連続して混練・攪拌した。なお、かかる際に混練容器
の温度を１５℃、２５℃、４５℃、５５℃となるように
水冷し、正極ペーストを作製したものを実施例１〜４と
する。(Examples 1 to 4) LiC was used as an active material for the positive electrode.
oNiO 2 , "Denka Black" which is acetylene black manufactured by Denki Kagaku Kogyo as a conductive agent, and polyvinylidene fluoride manufactured by Kureha Kagaku Kogyo as a binder 8
A mixture of 5: 5: 10 and N-methylpyrrolidone as a solvent was kneaded and stirred continuously for 16 hours using a commercially available kneading and stirring machine. At this time, the kneading vessel was cooled with water so that the temperature of the kneading vessel was 15 ° C., 25 ° C., 45 ° C., and 55 ° C., and the positive electrode paste was prepared.
【００２５】実施例１〜４の結果を表１に示す。実施例
１〜３についてはゲル化および粘度の上昇は観察されな
かった。なお実施例４については、混練・攪拌時間１２
時間経過後に、やや粘度上昇が観察されたが、集電体へ
の塗工は可能なレベルであった。Table 1 shows the results of Examples 1 to 4. No gelation and no increase in viscosity were observed for Examples 1 to 3. In Example 4, the kneading and stirring time was 12 hours.
After the lapse of time, a slight increase in viscosity was observed, but application to the current collector was at a possible level.
【００２６】（比較例１）正極の活剤、導電剤、結着剤
としては実施例に記載のものを用い、混練容器を冷却せ
ずに１６時間連続して混練・攪拌したものを比較例１と
する。実施の結果を表１に示すが、比較例１の正極ペー
ストはゲル化したため、塗工困難となった。なおこの比
較例１において、混練・攪拌時間１６時間後に容器温度
が６４℃にまで上昇していた。(Comparative Example 1) The positive electrode active agent, conductive agent, and binder used in the Examples were mixed and stirred for 16 hours without cooling the kneading vessel. Let it be 1. The results of the implementation are shown in Table 1. The coating of the positive electrode paste of Comparative Example 1 became difficult because of gelation. In Comparative Example 1, the container temperature had risen to 64 ° C. after 16 hours of kneading and stirring.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明の電池用正極シートの製造方法に
よれば、正極ペーストのゲル化や、あるいは粘度上昇が
生じないので、以降の工程である塗工工程等に悪影響が
無く、従って製造時の歩留まりを改善することができ
る。According to the method for producing a positive electrode sheet for a battery according to the present invention, no gelation or an increase in viscosity of the positive electrode paste occurs, so that there is no adverse effect on the subsequent coating step and the like, and therefore the production is not affected. Time yield can be improved.
Claims (3)
タを介してスパイラル状に巻込む構造の電池用の正極シ
ートの製造方法において、正極材ペーストが少なくとも
Ｎｉ系正極活材を含む正極材ペーストであって、該正極
材ペーストの混練時、送液時、保管時の温度を低温度に
保持することを特徴とする電池用正極シートの製造方
法。1. A method for manufacturing a positive electrode sheet for a battery having a structure in which a positive electrode sheet and a negative electrode sheet are spirally wound with a separator interposed therebetween, wherein the positive electrode material paste contains at least a Ni-based positive electrode active material. A method for producing a positive electrode sheet for a battery, wherein the temperature during kneading, feeding, and storing the positive electrode material paste is kept low.
温度が１０℃〜５０℃である請求項１記載の電池用正極
シートの製造方法。2. The method for producing a positive electrode sheet for a battery according to claim 1, wherein the temperature during kneading, feeding, and storing the positive electrode material paste is 10 ° C. to 50 ° C.
の雰囲気が低湿度雰囲気であることを特徴とする請求項
１または２に記載の電池用正極シートの製造方法。3. The method for producing a positive electrode sheet for a battery according to claim 1, wherein the atmosphere during kneading, feeding, and storing the positive electrode material paste is a low humidity atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9280350A JPH11120991A (en) | 1997-10-14 | 1997-10-14 | Manufacture of battery positive electrode sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9280350A JPH11120991A (en) | 1997-10-14 | 1997-10-14 | Manufacture of battery positive electrode sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11120991A true JPH11120991A (en) | 1999-04-30 |
Family
ID=17623786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9280350A Pending JPH11120991A (en) | 1997-10-14 | 1997-10-14 | Manufacture of battery positive electrode sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11120991A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005022666A2 (en) * | 2003-05-20 | 2005-03-10 | Phoenix Innovation, Inc. | A novel carbon nanotube lithium battery |
| CN102683644A (en) * | 2012-05-23 | 2012-09-19 | 东莞新能源科技有限公司 | Preparation method of anode slurry of lithium ion battery |
| JP2013037955A (en) * | 2011-08-09 | 2013-02-21 | Toyota Motor Corp | Method for manufacturing positive electrode plate |
| JP2017147188A (en) * | 2016-02-19 | 2017-08-24 | エリーパワー株式会社 | Method of producing battery electrode slurry |
-
1997
- 1997-10-14 JP JP9280350A patent/JPH11120991A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005022666A2 (en) * | 2003-05-20 | 2005-03-10 | Phoenix Innovation, Inc. | A novel carbon nanotube lithium battery |
| WO2005022666A3 (en) * | 2003-05-20 | 2007-02-22 | Phoenix Innovation Inc | A novel carbon nanotube lithium battery |
| JP2013037955A (en) * | 2011-08-09 | 2013-02-21 | Toyota Motor Corp | Method for manufacturing positive electrode plate |
| CN102683644A (en) * | 2012-05-23 | 2012-09-19 | 东莞新能源科技有限公司 | Preparation method of anode slurry of lithium ion battery |
| CN102683644B (en) * | 2012-05-23 | 2014-11-12 | 东莞新能源科技有限公司 | Preparation method of anode slurry of lithium ion battery |
| JP2017147188A (en) * | 2016-02-19 | 2017-08-24 | エリーパワー株式会社 | Method of producing battery electrode slurry |
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