JPH1167193A - Negative electrode for nonaqueous electrolyte lithium secondary battery and manufacture thereof - Google Patents
Negative electrode for nonaqueous electrolyte lithium secondary battery and manufacture thereofInfo
- Publication number
- JPH1167193A JPH1167193A JP9231288A JP23128897A JPH1167193A JP H1167193 A JPH1167193 A JP H1167193A JP 9231288 A JP9231288 A JP 9231288A JP 23128897 A JP23128897 A JP 23128897A JP H1167193 A JPH1167193 A JP H1167193A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- flake
- graphite material
- secondary battery
- paste
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液リチウ
ム二次電池用正極および負極、その製造方法並びにリチ
ウム二次電池に関する。The present invention relates to a positive electrode and a negative electrode for a non-aqueous electrolyte lithium secondary battery, a method for producing the same, and a lithium secondary battery.
【０００２】[0002]
【従来の技術】近年オーディオテープレコーダー、カメ
ラ一体型ビデオテープレコーダー、パーソナルコンピュ
ーター、携帯電話等小型で携帯に適した精密電気・電子
機器の需要が益々増大している。これに伴って、これら
の駆動用電源を担う小型、軽量で且つ高エネルギー密度
を有する、充電可能ないわゆる二次電池が求められるよ
うになり、従来の鉛蓄電池やニッケル−カドミウム二次
電池以外に、ニッケル−水素系や、リチウム系等の新し
い高性能の二次電池が次々と商品化されている。2. Description of the Related Art In recent years, there has been an increasing demand for small and portable precision electric and electronic devices such as audio tape recorders, camera-integrated video tape recorders, personal computers, and portable telephones. Along with this, there has been a demand for a so-called rechargeable secondary battery having a small size, a light weight and a high energy density, which is responsible for these driving power supplies, in addition to a conventional lead storage battery and a nickel-cadmium secondary battery. New high-performance secondary batteries such as nickel-hydrogen batteries and lithium batteries have been commercialized one after another.
【０００３】これらの新しい二次電池の中でも、特に負
極にリチウム等のアルカリ金属やその合金あるいはアル
カリ金属イオンを吸蔵・放出できる化合物を備えた、い
わゆる非水電解液二次電池はそのエネルギー密度の高さ
から大きな期待を寄せられている。Among these new secondary batteries, a so-called non-aqueous electrolyte secondary battery having a negative electrode containing an alkali metal such as lithium, an alloy thereof, or a compound capable of occluding and releasing alkali metal ions, has a high energy density. High expectations are placed on the height.
【０００４】これら非水電解液二次電池の製造方法とし
て、例えば特開平４−２４９８６０号公報には炭素材料
を、Ｎ−メチルピロリドン（ＮＭＰ）等の有機溶媒を用
いてペースト化し、金属箔に塗布してシート状の負極を
作製し、正極・セパレーターとともに巻回して円筒型電
池を作製する方法が提案されている。また、特開平６−
２１５７６１号には、溶媒として水を用いて同様にシー
ト状負極を作製する方法が提案されている。[0004] As a method of manufacturing these non-aqueous electrolyte secondary batteries, for example, Japanese Patent Application Laid-Open No. Hei 4-249860 discloses a method in which a carbon material is pasted using an organic solvent such as N-methylpyrrolidone (NMP), and is then formed into a metal foil. A method has been proposed in which a sheet-shaped negative electrode is formed by coating and wound together with a positive electrode and a separator to form a cylindrical battery. In addition, Japanese Unexamined Patent Publication No.
No. 2,157,761 proposes a method for similarly producing a sheet-shaped negative electrode using water as a solvent.
【０００５】さらに、特開平２−１５８０５５号公報に
は、正極活物質と共に、導電剤として炭素材料を用いて
シート状正極を作製する方法が提案されている。Further, Japanese Patent Application Laid-Open No. 2-158055 proposes a method for producing a sheet-shaped positive electrode using a carbon material as a conductive agent together with a positive electrode active material.
【０００６】これら従来の製造方法においては、ペース
トを金属箔上に塗布した後に乾燥させるため、水やＮＭ
Ｐ等の溶媒はできるだけ少ない方が生産性が高く好まし
い。例えば、特開平７−１６１３５０号公報には、ペー
スト作製時に溶媒を徐々に仕込むことにより溶媒使用量
を低減する方法が記載されている。In these conventional production methods, since the paste is applied to a metal foil and then dried, water or NM is used.
It is preferable that the amount of the solvent such as P is as small as possible because the productivity is high. For example, Japanese Patent Application Laid-Open No. 7-161350 describes a method of reducing the amount of solvent used by gradually charging a solvent during paste production.
【０００７】従来用いられてきた炭素材料のなかでも鱗
片状の形態を有する天然黒鉛や人造黒鉛は、一般的に結
晶性が高いことが特徴である。これを負極材料として用
いた場合には、高い放電容量と安定した放電電圧を有す
る電池が期待できる。また、導電剤として正極に用いた
場合にも高い電気伝導性が期待できる。さらには、他の
炭素材料に比べて安価であることから、工業的にも有利
である。しかしながら、鱗片状の天然黒鉛や人造黒鉛
は、その形状異方性のために塗料中で粒子同士の相互作
用が大きく、ペーストの粘度が高くなるため、均一な混
合が困難であり、ひいてはこのペーストを塗工して作成
した電極が不均質になるため電池性能が悪化する原因と
なっていた。[0007] Among the carbon materials conventionally used, natural graphite and artificial graphite having a flaky morphology are generally characterized by high crystallinity. When this is used as a negative electrode material, a battery having a high discharge capacity and a stable discharge voltage can be expected. Also, when used as a conductive agent for a positive electrode, high electric conductivity can be expected. Furthermore, since it is cheaper than other carbon materials, it is industrially advantageous. However, flake-like natural graphite and artificial graphite have a large interaction between particles in the coating due to their shape anisotropy, and the viscosity of the paste is high, so that uniform mixing is difficult, and thus this paste The electrode formed by coating with Pb becomes inhomogeneous, which causes deterioration of battery performance.
【０００８】[0008]
【発明が解決しようとする課題】本発明者らは、前記課
題を解決するために鱗片状黒鉛材料を用いたペーストの
粘度を下げることにより、混練を容易にし、均質なペー
ストを得るため、検討を行った。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present inventors have studied to reduce the viscosity of a paste using flaky graphite material to facilitate kneading and obtain a homogeneous paste. Was done.
【０００９】その結果驚くべきことに、フッ素で処理し
た鱗片状黒鉛材料は溶媒とのなじみが改善されて混練が
容易になり、従来よりも少量の溶媒で均質なペーストを
得ることが可能であることを見出し、本発明に至った。[0009] As a result, surprisingly, the flake graphite material treated with fluorine has improved compatibility with the solvent and can be easily kneaded, and a homogeneous paste can be obtained with a smaller amount of solvent than before. This led to the present invention.
【００１０】本発明は、下記の項１から項５を提供する
ものである。[0010] The present invention provides the following items 1 to 5.
【００１１】項１． フッ素化処理した鱗片状黒鉛材料
を、バインダーポリマー及び溶媒とともに混練する工
程、及び得られたペーストを金属箔上に塗布、乾燥する
工程を含むことを特徴とするリチウム二次電池用負極の
製造方法。Item 1. A method for producing a negative electrode for a lithium secondary battery, comprising: a step of kneading a fluorinated flake graphite material together with a binder polymer and a solvent; and a step of applying and drying the obtained paste on a metal foil. .
【００１２】項２． フッ素化処理した鱗片状黒鉛材料
及びバインダーポリマーを含むリチウム二次電池用負
極。Item 2. A negative electrode for a lithium secondary battery comprising a fluorinated flake graphite material and a binder polymer.
【００１３】項３． 項２に記載の負極を有するリチウ
ム二次電池。Item 3. Item 3. A lithium secondary battery having the negative electrode according to Item 2.
【００１４】項４． フッ素化処理した鱗片状黒鉛材
料、バインダーポリマー及び正極活物質（リチウム含有
複合酸化物）を含むリチウム二次電池用正極。Item 4. A positive electrode for a lithium secondary battery containing a fluorinated flake graphite material, a binder polymer, and a positive electrode active material (lithium-containing composite oxide).
【００１５】項５． 項４に記載の正極を有するリチウ
ム二次電池。Item 5. Item 6. A lithium secondary battery having the positive electrode according to item 4.
【００１６】[0016]
【発明の実施の形態】本発明において、鱗片状黒鉛材料
としては、鱗片状の形状を有する天然黒鉛および人造黒
鉛が挙げられる。人造黒鉛としては、鱗片状であれば、
原料（石油コークス、石炭コークス、石油ピッチ、石炭
ピッチなど）および製造法は限定されない。好ましい鱗
片状黒鉛材料は、天然黒鉛である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the flaky graphite material include scaly natural graphite and artificial graphite. As artificial graphite, if it is scaly,
Raw materials (petroleum coke, coal coke, petroleum pitch, coal pitch, etc.) and production methods are not limited. A preferred flaky graphite material is natural graphite.
【００１７】なお、通常「鱗片状」と称されるのは、ｃ
軸方向の厚みに対するａｂ軸方向の直径の比の平均が３
以上であり、ｃ軸方向の面間隔が３．３５〜３．４０Å
の高結晶性を有するものである。Incidentally, what is usually referred to as "scaly" is c
The average of the ratio of the diameter in the ab-axis direction to the thickness in the axial direction is 3
That is, the surface interval in the c-axis direction is 3.35 to 3.40 °.
It has high crystallinity.
【００１８】フッ素化処理した鱗片状黒鉛材料のフッ素
の割合は、通常０．１〜５重量％程度、好ましくは０．
３〜３重量％程度である。The proportion of fluorine in the fluorinated flake graphite material is usually about 0.1 to 5% by weight, preferably 0.1 to 5% by weight.
It is about 3 to 3% by weight.
【００１９】鱗片状黒鉛材料のフッ素化方法について
は、特に限定するものではないが、気体状のフッ素と直
接反応する方法、テトラフルオロメタン等のフッ素化剤
と反応する方法、無水フッ酸中に鱗片状黒鉛材料を分散
させ、フッ素を吹き込んで反応する方法、ＫＦ−ＨＦ電
解浴中で電気化学的にフッ素化する方法などがある。The method of fluorinating the flaky graphite material is not particularly limited, but includes a method of directly reacting with gaseous fluorine, a method of reacting with a fluorinating agent such as tetrafluoromethane, and a method of fluorinating anhydrous hydrofluoric acid. There are a method in which flaky graphite material is dispersed and a reaction is performed by blowing fluorine, and a method in which electrochemical fluorination is performed in a KF-HF electrolytic bath.
【００２０】工業的には、気体状のフッ素と直接反応す
る方法が最も簡便であり好ましい。Industrially, the method of directly reacting with gaseous fluorine is the simplest and preferred.
【００２１】フッ素化の温度は、１００℃〜５００℃程
度、好ましくは１５０℃〜４００℃程度である。フッ素
化の時間は、１分〜２時間程度である。The fluorination temperature is about 100 ° C. to 500 ° C., preferably about 150 ° C. to 400 ° C. The fluorination time is about 1 minute to 2 hours.
【００２２】未反応のフッ素は、電池内で自己放電の原
因になることがあるため、未反応フッ素を取り除くため
に、フッ素化処理した鱗片状黒鉛材料を空気中や減圧下
または不活性ガス中で４００℃以下で加熱することも可
能である。Since unreacted fluorine may cause self-discharge in the battery, in order to remove unreacted fluorine, the fluorinated flake graphite material is placed in air, under reduced pressure, or in inert gas. At 400 ° C. or less.
【００２３】バインダーポリマーとしては、特に限定さ
れないが、ＰＴＦＥ、ＰＦＡ、ＦＥＰ、ＰＶＤＦ、ＰＣ
ＴＦＥ及びそれらの変性ポリマー等のフッ素樹脂や、フ
ッ素ゴム、ポリエチレン、ポリプロピレン等のポリオレ
フィン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリ
（メタ）アクリル酸樹脂、スチレン−ブタジエンゴム
（ＳＢＲ）等のブタジエン系のゴムなどが用いられる。
好ましいバインダーポリマーは、ＰＴＦＥ、ＰＶＤＦ等
のフッ素樹脂、ＳＢＲ等のブタジエン系のゴムなどであ
る。The binder polymer is not particularly limited, but PTFE, PFA, FEP, PVDF, PC
Fluororesins such as TFE and modified polymers thereof, fluoro rubbers, polyolefin resins such as polyethylene and polypropylene, butadiene rubbers such as polyester resins, polyamide resins, poly (meth) acrylate resins, and styrene-butadiene rubber (SBR) Are used.
Preferred binder polymers include fluororesins such as PTFE and PVDF, and butadiene rubbers such as SBR.
【００２４】正極ないし負極製造時の溶媒としては、特
に限定されず、水、増粘剤を溶解した水溶液及び任意の
有機溶媒が挙げられるが、好ましくはカルボキシメチル
セルロースなどのセルロース誘導体、ポリアクリル酸、
ポリビニルアルコールなどの増粘剤を溶解した水溶液、
Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミ
ド、Ｎ，Ｎ−ジメチルアセトアミド、アセトニトリルな
どの含窒素有機溶媒、酢酸エチルなどのエステル系有機
溶媒、ＭＥＫ、ＭＩＢＫ、シクロヘキサノンなどのケト
ン系有機溶媒が用いられる。有機溶媒については、２種
以上の有機溶媒を混合して用いることもできる。The solvent for producing the positive electrode or the negative electrode is not particularly limited, and includes water, an aqueous solution in which a thickener is dissolved, and any organic solvent. Preferably, a cellulose derivative such as carboxymethyl cellulose, polyacrylic acid,
An aqueous solution in which a thickener such as polyvinyl alcohol is dissolved,
Nitrogen-containing organic solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and acetonitrile; ester organic solvents such as ethyl acetate; and ketone organic solvents such as MEK, MIBK, and cyclohexanone are used. . As for the organic solvent, a mixture of two or more kinds of organic solvents can be used.
【００２５】溶媒の使用量は、混練を可能にする量であ
ればよく、当業者であれば容易に決定できる。The amount of the solvent to be used may be any amount that allows kneading, and can be easily determined by those skilled in the art.
【００２６】ペーストは、フッ素化処理した鱗片状黒鉛
材料を、バインダーポリマー及び溶媒を混合して混練す
ることにより、容易に得ることができる。The paste can be easily obtained by mixing the fluorinated flake graphite material with a binder polymer and a solvent and kneading the mixture.
【００２７】集電体の材質としては、銅、アルミ、ステ
ンレススチール、チタン、ニッケル、タングステン鋼、
炭素材料などが用いられ、その形状も箔、網、不織布、
パンチドメタル等があるが、負極には銅箔、正極にはア
ルミ箔が好ましく用いられる。As the material of the current collector, copper, aluminum, stainless steel, titanium, nickel, tungsten steel,
Carbon materials and the like are used, and the shape is also foil, net, non-woven fabric,
Although there are punched metals and the like, copper foil is preferably used for the negative electrode and aluminum foil is preferably used for the positive electrode.
【００２８】本発明の負極は、フッ素化処理した鱗片状
黒鉛材料を用いて混練することにより、鱗片状黒鉛材料
の均一性が非常に高い負極が得られる。The negative electrode of the present invention can be obtained by kneading the fluorinated flaky graphite material and kneading the same, whereby the flake graphite material has extremely high uniformity.
【００２９】本発明のフッ素化鱗片状黒鉛材料は、リチ
ウムイオンの吸蔵、放出を行うホスト材料として、負極
に用いてもよく、または導電剤として正極に添加するこ
とができる。The fluorinated flaky graphite material of the present invention may be used for a negative electrode as a host material for absorbing and releasing lithium ions, or may be added to a positive electrode as a conductive agent.
【００３０】リチウム二次電池の形態としては、特に限
定するものではないが、活物質や導電剤、バインダーポ
リマー等の電極材料を水や有機溶媒を分散媒としてペー
スト化し、これを金属箔上に塗布することによって得ら
れるシート上の正極及び負極をセパレーターを介して巻
回して作製する構造が好ましく用いられる。The form of the lithium secondary battery is not particularly limited, but an electrode material such as an active material, a conductive agent, and a binder polymer is made into a paste using water or an organic solvent as a dispersion medium, and this is put on a metal foil. A structure in which a positive electrode and a negative electrode on a sheet obtained by coating are wound around a separator is preferably used.
【００３１】負極用ペーストの作製方法としては、ポリ
ビニルアルコール等の増粘剤水溶液に、ＳＢＲ等のラテ
ックスバインダーを分散させた溶液に、本発明の黒鉛材
料を分散する方法、ＰＶＤＦ等のフッ素系バインダーを
ＮＭＰ等に溶解した溶液に、本発明の黒鉛材料を分散す
る方法などがある。The method for preparing the paste for the negative electrode includes a method in which the graphite material of the present invention is dispersed in a solution in which a latex binder such as SBR is dispersed in an aqueous solution of a thickener such as polyvinyl alcohol, and a fluorine-based binder such as PVDF. For example, a method of dispersing the graphite material of the present invention in a solution in which is dissolved in NMP or the like.
【００３２】また、正極用としては活物質であるＬｉＣ
ｏＯ2などのリチウム含有複合酸化物と導電剤として本
発明の鱗片性黒鉛材料を用い、溶媒を用いて負極と同様
にペーストを作製することができる。ここで、活物質は
概ね絶縁性であるため、電極に電子導電性を付与する導
電剤が必要になる。For the positive electrode, LiC which is an active material is used.
A paste can be prepared using the scaly graphite material of the present invention as a conductive agent using a lithium-containing composite oxide such as oO 2 and a solvent in the same manner as the negative electrode. Here, since the active material is generally insulative, a conductive agent for imparting electronic conductivity to the electrode is required.
【００３３】本発明の黒鉛材料は、負極または正極のい
ずれか一方に使用してもよいし、両極に使用することも
できる。The graphite material of the present invention may be used for either the negative electrode or the positive electrode, or may be used for both electrodes.
【００３４】正極活物質としてはＬｉＣｏＯ2、ＬｉＮ
ｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＭｎＯ2、ＬｉＦｅＯ2、さ
らにこれらにＶ、Ａｌ、Ｔｉなどを添加した材料などの
リチウム含有複合酸化物が例示される。As the positive electrode active material, LiCoO 2 , LiN
iO 2, LiMn 2 O 4, LiMnO 2, LiFeO 2, further lithium-containing composite oxide such as material obtained by adding V, Al, Ti, etc. These are exemplified.
【００３５】電解質としては、リチウムイオン伝導性を
有する非水溶液状電解質、およびこれをポリマーマトリ
ックスで固定したゲル電解質、リチウムイオン伝導性を
有するポリマー電解質などが挙げられる。Examples of the electrolyte include a non-aqueous electrolyte having lithium ion conductivity, a gel electrolyte in which this is fixed with a polymer matrix, and a polymer electrolyte having lithium ion conductivity.
【００３６】非水溶液状の電解質は、非水溶媒とその溶
媒に溶解するリチウム塩から構成される。非水溶媒とし
ては、プロピレンカーボネート、エチレンカーボネー
ト、ブチレンカーボネート等の環状カーボネート、ジエ
チルカーボネート、ジメチルカーボネート、メチルエチ
ルカーボネート等の鎖状カーボネート、γ−ブチロラク
トン、テトラヒドロフラン、ジメトキシエタン、ジエト
キシエタン、ジメチルスルホキシド、アセトニトリルな
どが例示できる。The non-aqueous electrolyte comprises a non-aqueous solvent and a lithium salt dissolved in the solvent. As the non-aqueous solvent, propylene carbonate, ethylene carbonate, cyclic carbonate such as butylene carbonate, diethyl carbonate, dimethyl carbonate, chain carbonate such as methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dimethoxyethane, diethoxyethane, dimethyl sulfoxide, Acetonitrile and the like can be exemplified.
【００３７】リチウム塩としては、ＬｉＰＦ6、ＬｉＡ
ｓＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＣ4Ｆ9Ｓ
Ｏ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3
等が挙げられる。As the lithium salt, LiPF 6 , LiA
sF 6 , LiBF 4 , LiCF 3 SO 3 , LiC 4 F 9 S
O 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3
And the like.
【００３８】[0038]
【実施例】以下、本発明について具体的に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.
【００３９】なお、粘度は、Ｂ型粘度計、Ｎｏ．４ロー
ター、６ｒｐｍの条件で測定した。The viscosity was measured using a B-type viscometer, No. The measurement was performed under the conditions of 4 rotors and 6 rpm.
【００４０】調製例１ 市販のマダガスカル産天然黒鉛をニッケル製反応容器に
１００ｇ仕込み、ニッケル製反応容器内、窒素流通下で
２５０℃に昇温した。ここに窒素で１０％に希釈したフ
ッ素ガスを流通し、１０分間処理した。その後窒素を流
通しながら室温まで冷却し、サンプルＡを得た。Preparation Example 1 A commercially available natural graphite produced in Madagascar was charged in an amount of 100 g into a nickel-made reaction vessel, and the temperature was raised to 250 ° C. in a nickel-made reaction vessel under a flow of nitrogen. Fluorine gas diluted to 10% with nitrogen was circulated and treated for 10 minutes. Thereafter, the mixture was cooled to room temperature while flowing nitrogen to obtain Sample A.
【００４１】調製例２ 市販の鱗片状人造黒鉛（ＬＯＮＺＡ製）を用い、反応温
度を４００℃とした以外は調製例１と同様にして、サン
プルＢを得た。Preparation Example 2 A sample B was obtained in the same manner as in Preparation Example 1, except that commercially available flaky artificial graphite (manufactured by LONZA) was used and the reaction temperature was changed to 400 ° C.
【００４２】実施例１（ペースト粘度） サンプルＡ（４７ｇ）とフッ化ビニリデン樹脂３ｇをＮ
ＭＰ３０ｇに分散してペーストを得た。ペーストの粘度
は１３０ポイズであった。Example 1 (viscosity of paste) Sample A (47 g) and 3 g of vinylidene fluoride resin were mixed with N
The paste was dispersed in 30 g of MP to obtain a paste. The viscosity of the paste was 130 poise.
【００４３】比較例１ 未処理のマダガスカル産天然黒鉛（４７ｇ）とフッ化ビ
ニリデン樹脂３ｇをＮＭＰ５０ｇに分散してペーストを
得た。ペーストの粘度は１３０ポイズであった。Comparative Example 1 Untreated natural graphite (47 g) from Madagascar and 3 g of vinylidene fluoride resin were dispersed in 50 g of NMP to obtain a paste. The viscosity of the paste was 130 poise.
【００４４】比較例２ 未処理のマダガスカル産天然黒鉛４７ｇとフッ化ビニリ
デン樹脂３ｇをＮＭＰ３０ｇに分散したところ、粘度が
高すぎて均質な混合ができなかった。Comparative Example 2 When 47 g of untreated natural graphite from Madagascar and 3 g of vinylidene fluoride resin were dispersed in 30 g of NMP, the viscosity was too high to achieve homogeneous mixing.
【００４５】実施例２ 市販のＰＴＦＥディスパージョン（ポリクロンＴＦＥデ
ィスパージョンＤ−１；ダイキン工業製）５ｇとカルボ
キシメチルセルロース０．５ｇを水３５ｇに分散させ
た。この溶液に市販のコバルト酸リチウム（ＬｉＣｏＯ
2）４４ｇとサンプルＢ（３ｇ）を添加し、混合してペ
ーストを得た。このペーストの粘度は１００ポイズであ
った。Example 2 5 g of a commercially available PTFE dispersion (Polyclone TFE dispersion D-1; manufactured by Daikin Industries) and 0.5 g of carboxymethyl cellulose were dispersed in 35 g of water. This solution was added to a commercially available lithium cobaltate (LiCoO
2 ) 44 g and sample B (3 g) were added and mixed to obtain a paste. The viscosity of this paste was 100 poise.
【００４６】比較例３ サンプルＢの代わりに未処理の鱗片状人造黒鉛を用いた
以外は実施例２と同様にしてペーストを得た。このペー
ストの粘度は１１０ポイズであった。Comparative Example 3 A paste was obtained in the same manner as in Example 2 except that untreated flake artificial graphite was used instead of Sample B. The viscosity of this paste was 110 poise.
【００４７】実施例３（塗膜密度） 厚さ２０μｍの銅箔表面に、アプリケーターを用いて実
施例１で得たペーストを乾燥後の厚みが１５０μｍにな
るように塗布し、１００℃の赤外乾燥機中で１時間乾燥
させて負極シートを得た。この塗膜の密度を測定したと
ころ0.82g・cm-3であった。Example 3 (Coating Density) The paste obtained in Example 1 was applied to the surface of a copper foil having a thickness of 20 μm using an applicator so that the thickness after drying became 150 μm. After drying in a dryer for 1 hour, a negative electrode sheet was obtained. When the density of this coating film was measured, it was 0.82 g · cm −3 .
【００４８】比較例４ 比較例１で得たペーストを実施例３と同様に銅箔上に塗
布して負極シートを得た。この塗膜の密度を測定したと
ころ、0.51g・cm-3であった。Comparative Example 4 The paste obtained in Comparative Example 1 was applied on a copper foil in the same manner as in Example 3 to obtain a negative electrode sheet. When the density of this coating film was measured, it was 0.51 g · cm −3 .
【００４９】以上のように、本発明によりペーストの粘
度を大幅に低減でき、使用する溶媒量を削減することが
できる。また、本発明により作製した電極（正極、負
極）シートは密度が大きく、活物質が高密度で均質に充
填されているため、電池に加工した場合にも良好な性能
が期待できる。As described above, according to the present invention, the viscosity of the paste can be significantly reduced, and the amount of the solvent used can be reduced. Further, since the electrode (positive electrode, negative electrode) sheet produced according to the present invention has a high density and the active material is densely and uniformly filled, good performance can be expected even when processed into a battery.
Claims (5)
ンダーポリマー及び溶媒とともに混練する工程、及び得
られたペーストを金属箔上に塗布、乾燥する工程を含む
ことを特徴とするリチウム二次電池用負極の製造方法。1. A lithium secondary battery comprising: a step of kneading a fluorinated flake graphite material together with a binder polymer and a solvent; and a step of applying and drying the obtained paste on a metal foil. Of producing a negative electrode.
ンダーポリマーを含むリチウム二次電池用負極。2. A negative electrode for a lithium secondary battery comprising a fluorinated flake graphite material and a binder polymer.
次電池。3. A lithium secondary battery having the negative electrode according to claim 2.
ダーポリマー及び正極活物質（リチウム含有複合酸化
物）を含むリチウム二次電池用正極。4. A positive electrode for a lithium secondary battery comprising a fluorinated flake graphite material, a binder polymer and a positive electrode active material (lithium-containing composite oxide).
次電池。5. A lithium secondary battery having the positive electrode according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9231288A JPH1167193A (en) | 1997-08-27 | 1997-08-27 | Negative electrode for nonaqueous electrolyte lithium secondary battery and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9231288A JPH1167193A (en) | 1997-08-27 | 1997-08-27 | Negative electrode for nonaqueous electrolyte lithium secondary battery and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1167193A true JPH1167193A (en) | 1999-03-09 |
Family
ID=16921264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9231288A Pending JPH1167193A (en) | 1997-08-27 | 1997-08-27 | Negative electrode for nonaqueous electrolyte lithium secondary battery and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1167193A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322606C (en) * | 2003-11-17 | 2007-06-20 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery and rechargeable lithium battery comprising same |
| CN101875457A (en) * | 2009-04-28 | 2010-11-03 | 株式会社日立制作所 | Elevator control gear and lift facility with this elevator control gear |
| JP2018113218A (en) * | 2017-01-13 | 2018-07-19 | トヨタ自動車株式会社 | Method for manufacturing lithium ion secondary battery |
| US10944098B2 (en) | 2017-04-28 | 2021-03-09 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material particle, negative electrode, lithium-ion secondary battery, and production method of negative electrode active material particle |
-
1997
- 1997-08-27 JP JP9231288A patent/JPH1167193A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322606C (en) * | 2003-11-17 | 2007-06-20 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery and rechargeable lithium battery comprising same |
| CN101875457A (en) * | 2009-04-28 | 2010-11-03 | 株式会社日立制作所 | Elevator control gear and lift facility with this elevator control gear |
| JP2018113218A (en) * | 2017-01-13 | 2018-07-19 | トヨタ自動車株式会社 | Method for manufacturing lithium ion secondary battery |
| US10944098B2 (en) | 2017-04-28 | 2021-03-09 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material particle, negative electrode, lithium-ion secondary battery, and production method of negative electrode active material particle |
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