JP2001250558A - Active substance slurry for negative electrode of nonaqueous electrolyte secondary cell and the nonaqueous electrolyte secondary cell using the same - Google Patents

Active substance slurry for negative electrode of nonaqueous electrolyte secondary cell and the nonaqueous electrolyte secondary cell using the same

Info

Publication number
JP2001250558A
JP2001250558A JP2000063483A JP2000063483A JP2001250558A JP 2001250558 A JP2001250558 A JP 2001250558A JP 2000063483 A JP2000063483 A JP 2000063483A JP 2000063483 A JP2000063483 A JP 2000063483A JP 2001250558 A JP2001250558 A JP 2001250558A
Authority
JP
Japan
Prior art keywords
negative electrode
electrolyte secondary
active material
electrode active
aqueous electrolyte
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
Application number
JP2000063483A
Other languages
Japanese (ja)
Inventor
Takashi Egawa
崇 江川
Tomohito Okamoto
朋仁 岡本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Storage Battery Co Ltd
Sanyo GS Soft Energy Co Ltd
Original Assignee
Japan Storage Battery Co Ltd
GS Melcotec Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Storage Battery Co Ltd, GS Melcotec Co Ltd filed Critical Japan Storage Battery Co Ltd
Priority to JP2000063483A priority Critical patent/JP2001250558A/en
Publication of JP2001250558A publication Critical patent/JP2001250558A/en
Pending legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To provide an active substance slurry for a negative electrode of nonaqueous electrolyte secondary cell capable of being coated evenly on a metal foil collector. SOLUTION: A carbon material capable of absorbing and liberating lithium, a binder containing water as a dispersing solvent, a viscosity-enhancing agent and a fluorinated detergent or the like are combined. It is desirable that the fluorinated detergent have a perfluoro-alkyl radical in its chemical structure.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、リチウムを吸蔵・
放出することが可能な炭素材料を負極活物質とする非水
電解質二次電池用負極活物質スラリーおよびこのスラリ
ーを用いて作製される非水電解質二次電池に関する。
TECHNICAL FIELD The present invention relates to a method for storing lithium.
The present invention relates to a negative electrode active material slurry for a non-aqueous electrolyte secondary battery using a carbon material that can be released as a negative electrode active material, and a non-aqueous electrolyte secondary battery manufactured using the slurry.

【0002】[0002]

【従来の技術】近年、ポータブル電子機器の小型軽量化
は目覚しく、それに伴い電源となる電池に対しても小型
軽量化の要望が非常に大きい。このような要求を満足す
るために種々の二次電池が開発され、現在、主にリチウ
ムイオン電池が実用化されている。この二次電池の電極
形成方法としては、電極活物質と結着剤である有機重合
体とを混合し圧縮形成する方法、あるいは有機重合体の
溶液に電極活物質を分散してスラリーとした後、集電体
である金属箔上に塗工乾燥することにより電極を形成す
る方法などが知られている。
2. Description of the Related Art In recent years, the size and weight of portable electronic devices has been remarkably reduced, and accordingly, there has been a great demand for a battery as a power supply to be reduced in size and weight. Various secondary batteries have been developed to satisfy such demands, and at present, lithium ion batteries are mainly put to practical use. As a method of forming an electrode of this secondary battery, a method of mixing and compressing an electrode active material and an organic polymer as a binder, or a method of dispersing the electrode active material in a solution of the organic polymer to form a slurry. A method of forming an electrode by coating and drying on a metal foil as a current collector is known.

【0003】後者の方法において、水を分散媒とする結
着剤を用いた場合、集電体である金属箔が前記スラリー
をはじいてしまい、均一に塗工ができなく、そのため実
際に電池を製造するうえにおいて、不良率が高くなり、
コストが増大するというデメリットがあった。
[0003] In the latter method, when a binder containing water as a dispersion medium is used, the metal foil as a current collector repels the slurry and cannot be uniformly applied. In manufacturing, the defect rate increases,
There was a disadvantage that the cost increased.

【0004】[0004]

【発明が解決しようとする課題】そこで、本発明の課題
は、集電体金属箔に均一に塗工することができる非水電
解質二次電池用負極活物質スラリーを提供することにあ
る。
Accordingly, an object of the present invention is to provide a negative electrode active material slurry for a non-aqueous electrolyte secondary battery which can be uniformly applied to a current collector metal foil.

【0005】[0005]

【課題を解決するための手段】本発明の非水電解質二次
電池用負極活物質スラリーは、リチウムを吸蔵・放出す
る炭素材料と、水を分散媒とする結着剤と、水溶性増粘
剤と、フッ素系界面活性剤類を含有することを特徴とす
る。
SUMMARY OF THE INVENTION A negative electrode active material slurry for a non-aqueous electrolyte secondary battery according to the present invention comprises a carbon material that stores and releases lithium, a binder that uses water as a dispersion medium, and a water-soluble thickener. And a fluorine-containing surfactant.

【0006】前記フッ素系界面活性剤類が、パーフルオ
ロアルキルスルホン酸塩、パーフルオロアルキルカルボ
ン酸塩、パーフルオロアルキルエチレンオキシド付加
物、パーフルオロアルキルトリメチルアンモニウム塩、
パーフルオロアルキルアミノスルホン酸塩、パーフルオ
ロアルキル燐酸エステルからなる群より1種類以上を選
択することが好ましい。
The above-mentioned fluorine-containing surfactants include perfluoroalkylsulfonic acid salts, perfluoroalkylcarboxylate salts, perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts,
It is preferable to select one or more types from the group consisting of perfluoroalkylaminosulfonic acid salts and perfluoroalkyl phosphates.

【0007】前記フッ素系界面活性剤類の添加量として
は、炭素材料100重量部あたり0.01重量部以上
0.5重量部以下であるのが好ましい。
[0007] The amount of the fluorine-based surfactants to be added is preferably 0.01 to 0.5 parts by weight per 100 parts by weight of the carbon material.

【0008】前記フッ素系界面活性剤類が、パーフルオ
ロアルキルスルホン酸塩、パーフルオロアルキルカルボ
ン酸塩、パーフルオロアルキルエチレンオキシド付加
物、パーフルオロアルキルトリメチルアンモニウム塩、
パーフルオロアルキルアミノスルホン酸塩、パーフルオ
ロアルキル燐酸エステルからなる群より選択される1種
類以上のフッ素系界面活性剤からなり、添加量が、炭素
材料100重量部あたり0.01重量部以上0.1重量
部以下であるのが、より好ましい。
The above-mentioned fluorine-based surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylate salts, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts,
It is composed of one or more fluorine-based surfactants selected from the group consisting of perfluoroalkylaminosulfonates and perfluoroalkylphosphates, and is added in an amount of 0.01 to 0.3 parts by weight per 100 parts by weight of the carbon material. It is more preferable that the amount be 1 part by weight or less.

【0009】本発明の非水電解質二次電池は、前記非水
電解質二次電池負極活物質スラリーを用いて作製した負
極を備えたことを特徴とする。
A non-aqueous electrolyte secondary battery according to the present invention is characterized in that the non-aqueous electrolyte secondary battery is provided with a negative electrode manufactured using the negative electrode active material slurry.

【0010】[0010]

【発明の実施の形態】本発明で用いる炭素材料として
は、導電性を有したものであり、リチウムイオンを吸蔵
・放出することができる難黒鉛化炭素、コークスや天然
黒鉛、人造黒鉛などが使用可能である。これらの炭素材
料の粒子径は特に限定されるものではない。
BEST MODE FOR CARRYING OUT THE INVENTION As the carbon material used in the present invention, non-graphitizable carbon, coke, natural graphite, artificial graphite and the like, which have conductivity and can absorb and release lithium ions, are used. It is possible. The particle size of these carbon materials is not particularly limited.

【0011】本発明で用いる水を分散媒とする結着剤と
しては、ブタジエン基を有する共重合体を用いることが
好ましい。ブタジエン基を有する共重合体としては、ス
チレンブタジエン共重合ラテックス(SBR)、カルボ
キシ変性SBR、アクリロニトリルブタジエン共重合ラ
テックス(NBR)、アクリレートブタジエン共重合ラ
テックスなどであり、好ましくはスチレンブタジエン共
重合ラテックスである。また、これらの共重合体を混合
して使用することも可能である。
It is preferable to use a copolymer having butadiene groups as the binder containing water as a dispersion medium used in the present invention. Examples of the copolymer having a butadiene group include styrene butadiene copolymer latex (SBR), carboxy-modified SBR, acrylonitrile butadiene copolymer latex (NBR), and acrylate butadiene copolymer latex, and preferably styrene butadiene copolymer latex. . It is also possible to use a mixture of these copolymers.

【0012】本発明で用いる水溶性増粘剤としては、カ
ルボキシメチルセルロース、メチルセルロース、ヒドロ
キシプロピルセルロースなどを用いることができる。好
ましくは、カルボキシメチルセルロースを用いる。
As the water-soluble thickener used in the present invention, carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose and the like can be used. Preferably, carboxymethyl cellulose is used.

【0013】本発明で用いるフッ素系界面活性剤類とし
ては、直鎖状界面活性剤が好ましい。さらに、その化学
構造中にパーフルオロアルキル基(一般式CF3(C
2n―:nは1以上の整数)を含有したものがよく、
特に、パーフルオロアルキルスルホン酸塩(RfSO
3M)(M:アルカリ金属、Rf―:パーフルオロアルキ
ル基)、パーフルオロアルキルカルボン酸塩(Rf―CO
OM)、パーフルオロアルキルエチレンオキシド付加物
(Rf―(CH2CH2O)mH:mは1以上の整数)、パ
ーフルオロアルキルトリメチルアンモニウム塩、パーフ
ルオロアルキルアミノスルホン酸塩(Rf―NH―SO3
M)、パーフルオロアルキル燐酸エステル(Rf―OP
(O)(OH)2)が好適に用いられる。
As the fluorinated surfactants used in the present invention, linear surfactants are preferred. Further, a perfluoroalkyl group (general formula CF 3 (C
F 2 ) n- : n is preferably an integer of 1 or more).
In particular, perfluoroalkyl sulfonates (RfSO
3 M) (M: an alkali metal, Rf-: perfluoroalkyl groups), perfluoroalkyl carboxylate (Rf-CO
OM), perfluoroalkylethylene oxide adduct (Rf- (CH 2 CH 2 O) m H: m is an integer of 1 or more), perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate (Rf-NH-SO Three
M), perfluoroalkyl phosphate (Rf-OP
(O) (OH) 2 ) is preferably used.

【0014】本発明の負極活物質スラリーは、炭素材料
と、スチレンブタジエン共重合体ラテックスなどの水を
分散媒とする結着剤と、水溶性増粘剤と、フッ素系界面
活性剤類とを、必要に応じて水を加えて高剪断力の混合
装置でよく混合することによって製作できる。
The negative electrode active material slurry of the present invention comprises a carbon material, a binder such as styrene-butadiene copolymer latex using water as a dispersion medium, a water-soluble thickener, and a fluorine-based surfactant. It can be manufactured by adding water as needed and mixing well with a high shear mixing device.

【0015】スチレンブタジエン共重合ラテックスなど
の水を分散媒とする結着剤は、炭素材料100重量部あ
たり、固形分を見積もって0.1〜10重量部使用する
ことができるが、これは0.1重量部未満では結着性能
が低くなり、10重量部を超えると導電性が低くなるか
らである。好ましくは1〜5重量部である。
The binder containing water as a dispersion medium, such as styrene-butadiene copolymer latex, can be used in an amount of 0.1 to 10 parts by weight, assuming a solid content, per 100 parts by weight of the carbon material. If the amount is less than 0.1 part by weight, the binding performance is low, and if it exceeds 10 parts by weight, the conductivity is low. Preferably it is 1 to 5 parts by weight.

【0016】水溶性増粘剤は、炭素材料100重量部あ
たり、固形分を見積もって0.1〜10重量部使用でき
る。0.1重量部未満ではスラリーの粘度が大きく低下
してしまい、10重量部を超えると導電性が低くなるか
らである。好ましくは、1〜5重量部である。
The water-soluble thickener can be used in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the carbon material, assuming a solid content. If the amount is less than 0.1 part by weight, the viscosity of the slurry is greatly reduced, and if it exceeds 10 parts by weight, the conductivity is lowered. Preferably, it is 1 to 5 parts by weight.

【0017】フッ素系界面活性剤類は、炭素材料100
重量部あたり、0.01〜0.5重量部使用することが
できる。0.01重量部未満では集電体金属箔にスラリ
ーがはじかれてしまし、0.5重量部を超えると金属集
電体への結着性が悪くなるからである。より好ましくは
0.1〜0.3重量部を使用するのがよい。
Fluorosurfactants include carbon material 100
0.01 to 0.5 part by weight can be used per part by weight. If the amount is less than 0.01 part by weight, the slurry is repelled to the current collector metal foil, and if the amount exceeds 0.5 part by weight, the binding property to the metal current collector deteriorates. It is more preferable to use 0.1 to 0.3 parts by weight.

【0018】本発明の負極活物質スラリーの固形分濃度
は特に限定するものではないが、通常20〜70重量
%、好ましくは25〜60重量%である。
The solid content of the negative electrode active material slurry of the present invention is not particularly limited, but is usually 20 to 70% by weight, preferably 25 to 60% by weight.

【0019】上述した要領で調整した負極活物質スラリ
ーを用いて非水電解質二次電池を製作することができ
る。該スラリーは、塗工液として集電体金属箔に塗布
し、乾燥させる。塗布方法としてリバースロール法、コ
ンマバー法、グラビヤ法、エアーナイフ法などの任意の
コーターヘッドを用いることができる。乾燥方法として
は、放置乾燥のほか、送風乾燥機、温風乾燥機、赤外線
加熱機、遠赤外線加熱機などが使用できるが、特に限定
されるものではない。
A non-aqueous electrolyte secondary battery can be manufactured using the negative electrode active material slurry prepared as described above. The slurry is applied as a coating liquid to a current collector metal foil and dried. As a coating method, any coater head such as a reverse roll method, a comma bar method, a gravure method, and an air knife method can be used. As the drying method, besides standing drying, a blow dryer, a warm air dryer, an infrared heater, a far infrared heater, or the like can be used, but is not particularly limited.

【0020】本発明の非水電解質二次電池に用いる電解
液の有機溶媒には、特に制限はなく、例えばエーテル
類、ケトン類、ラクトン類、ニトリル類、アミン類、ア
ミド類、硫黄化合物、ハロゲン化炭化水素類、エステル
類、カーボネート類、ニトロ化合物、リン酸エステル系
化合物、スルホラン系炭化水素類等を用いることができ
るが、これらのうちでもエーテル類、ケトン類、エステ
ル類、ラクトン類、ハロゲン化炭化水素類、カーボネー
ト類、スルホラン系化合物が好ましい。これらの例とし
ては、テトラヒドロフラン、2−メチルテトラヒドロフ
ラン、1,4−ジオキサン、アニソール、モノグライ
ム、4−メチル−2−ペンタノン、酢酸エチル、酢酸メ
チル、プロピオン酸メチル、プロピオン酸エチル、1,
2−ジクロロエタン、γ−ブチロラクトン、ジメトキシ
エタン、メチルフォルメイト、ジメチルカーボネート、
メチルエチルカーボネート、ジエチルカーボネート、プ
ロピレンカーボネート、エチレンカーボネート、ビニレ
ンカーボネート、ジメチルホルムアミド、ジメチルスル
ホキシド、ジメチルチオホルムアミド、スルホラン、3
−メチル−スルホラン、リン酸トリメチル、リン酸トリ
エチル及びこれらの混合溶媒等を挙げることができる
が、必ずしもこれらに限定されるものではない。好まし
くは環状カーボネート類及び環状エステル類である。も
っとも好ましくは、エチレンカーボネート、プロピレン
カーボネート、メチルエチルカーボネート、及びジエチ
ルカーボネートのうち、1種又は2種以上した混合物の
有機溶媒である。
The organic solvent of the electrolytic solution used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and examples thereof include ethers, ketones, lactones, nitriles, amines, amides, sulfur compounds, halogen compounds and the like. Hydrocarbons, esters, carbonates, nitro compounds, phosphate ester compounds, sulfolane hydrocarbons, etc., among which ethers, ketones, esters, lactones, halogens Hydrocarbons, carbonates and sulfolane compounds are preferred. Examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, anisole, monoglyme, 4-methyl-2-pentanone, ethyl acetate, methyl acetate, methyl propionate, ethyl propionate,
2-dichloroethane, γ-butyrolactone, dimethoxyethane, methylformate, dimethyl carbonate,
Methyl ethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, vinylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, sulfolane,
Examples include -methyl-sulfolane, trimethyl phosphate, triethyl phosphate, and a mixed solvent thereof, but are not necessarily limited thereto. Preferred are cyclic carbonates and cyclic esters. Most preferably, it is an organic solvent of a mixture of one or more of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and diethyl carbonate.

【0021】また、本発明の非水電解質二次電池に用い
る電解質塩としてはに特に制限はないが、LiCl
4、LiBF4、LiAsF6、CF3SO3Li、Li
PF6、LiI、LiAlCl4等及びそれらの混合物が
挙げられる。好ましくは、LiBF4、LiPF6のう
ち、1種又は2種を混合物したリチウム塩がよい。
The electrolyte salt used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited.
O 4 , LiBF 4 , LiAsF 6 , CF 3 SO 3 Li, Li
PF 6 , LiI, LiAlCl 4 and the like and mixtures thereof. Preferably, a lithium salt obtained by mixing one or two of LiBF 4 and LiPF 6 is preferable.

【0022】また、上記電解質には補助的に固体のイオ
ン導伝性ポリマー電解質を用いることもできる。この場
合、非水電解質二次電池の構成としては、正極、負極お
よびセパレータと有機又は無機の固体電解質と上記非水
電解液との組み合わせ、又は正極、負極およびセパレー
タとしての有機又は無機の固体電解質膜と上記非水電解
液との組み合わせがあげられる。ポリマー電解質膜がポ
リエチレンオキシド、ポリアクリロニトリル又はポリエ
チレングリコールおよびこれらの変成体などの場合に
は、軽量で柔軟性があり、巻回極板に使用する場合に有
利である。さらに、ポリマー電解質以外にも、無機固体
電解質あるいは有機ポリマー電解質と無機固体電解質と
の混合材料などを使用することができる。
In addition, a solid ion-conductive polymer electrolyte can be used as an auxiliary for the above-mentioned electrolyte. In this case, as a configuration of the non-aqueous electrolyte secondary battery, a combination of a positive electrode, a negative electrode and a separator with an organic or inorganic solid electrolyte and the above non-aqueous electrolyte, or a positive electrode, an organic or inorganic solid electrolyte as a negative electrode and a separator A combination of the membrane and the above-mentioned non-aqueous electrolyte may be used. When the polymer electrolyte membrane is made of polyethylene oxide, polyacrylonitrile, polyethylene glycol, or a modified product thereof, the polymer electrolyte membrane is lightweight and flexible, which is advantageous when used for a wound electrode plate. Further, in addition to the polymer electrolyte, an inorganic solid electrolyte or a mixed material of an organic polymer electrolyte and an inorganic solid electrolyte can be used.

【0023】本発明の負極と組み合わされる正極の活物
質としては、リチウムを吸蔵・放出可能な化合物であれ
ば、特に制限がなく使用することができ、特にリチウム
含有複合酸化物は、組成式LixMO2またはLiy2
4(ただし、Mは遷移元素、0≦x≦1、0≦y≦2)
で表され、具体的にはLiCoO2、LiMnO2、Li
NiO2、LiMn24等が挙げられる。
The active material of the positive electrode combined with the negative electrode of the present invention can be used without any particular limitation as long as it is a compound capable of inserting and extracting lithium. In particular, the lithium-containing composite oxide has the composition formula Li x MO 2 or Li y M 2 O
4 (where M is a transition element, 0 ≦ x ≦ 1, 0 ≦ y ≦ 2)
Specifically, LiCoO 2 , LiMnO 2 , Li
NiO 2 , LiMn 2 O 4 and the like can be mentioned.

【0024】電池の構成要素として、要すればセパレー
ター、端子、絶縁板等の部品が用いられる。
If necessary, components such as a separator, a terminal, and an insulating plate are used as components of the battery.

【0025】[0025]

【実施例】以下に、本発明の実施例を、比較例とあわせ
て、説明する。
EXAMPLES Examples of the present invention will be described below together with comparative examples.

【0026】(実施例1)高速攪拌混合容器に人造黒鉛
100重量部に対し、水溶性増粘剤としてカルボキシメ
チルセルロース(アンモニウム塩)1.6重量部、フッ
素系界面活性剤類としてパーフルオロアルキルスルホン
酸塩(上記n(炭素数)=8)を0.05重量部、水を
分散媒とする結着剤としてスチレンブタジエン共重合体
ラテックス(固形分50%)4重量部、水を加え、攪拌
して、負極活物質スラリーを得た。
Example 1 1.6 parts by weight of carboxymethylcellulose (ammonium salt) as a water-soluble thickener and 100 parts by weight of a perfluoroalkyl sulfone as a fluorine-based surfactant per 100 parts by weight of artificial graphite in a high-speed stirring mixing vessel 0.05 parts by weight of the acid salt (n (carbon number) = 8), 4 parts by weight of a styrene-butadiene copolymer latex (solid content: 50%) as a binder using water as a dispersion medium, and water are added, followed by stirring. Thus, a negative electrode active material slurry was obtained.

【0027】(実施例2)フッ素系界面活性剤類のパー
フルオロアルキルスルホン酸塩の量を0.1重量部に変
える以外は実施例1と同様にして負極活物質スラリーを
得た。
(Example 2) A negative electrode active material slurry was obtained in the same manner as in Example 1, except that the amount of the perfluoroalkyl sulfonate of the fluorinated surfactant was changed to 0.1 part by weight.

【0028】(実施例3)水溶性増粘剤をカルボキシメ
チルセルロース(ナトリウム塩)に変える以外は実施例
1と同様にして負極活物質スラリーを得た。
Example 3 A negative electrode active material slurry was obtained in the same manner as in Example 1, except that the water-soluble thickener was changed to carboxymethyl cellulose (sodium salt).

【0029】(実施例4)フッ素系界面活性剤類をパー
フルオロアルキルカルボン酸塩に変える以外は実施例1
と同様にして負極活物質スラリーを得た。
Example 4 Example 1 except that the fluorosurfactants were changed to perfluoroalkylcarboxylates.
In the same manner as in the above, a negative electrode active material slurry was obtained.

【0030】(実施例5)フッ素系界面活性剤類のパー
フルオロアルキルエチレンオキシド付加物に変える以外
は実施例1と同様にして負極活物質スラリーを得た。
Example 5 A negative electrode active material slurry was obtained in the same manner as in Example 1 except that the fluorosurfactants were changed to perfluoroalkylethylene oxide adducts.

【0031】(実施例6)フッ素系界面活性剤類のパー
フルオロアルキルトリメチルアンモニウム塩に変える以
外は実施例1と同様にして負極活物質スラリーを得た。
(Example 6) A negative electrode active material slurry was obtained in the same manner as in Example 1 except that perfluoroalkyltrimethylammonium salts of fluorine-based surfactants were used.

【0032】(実施例7)フッ素系界面活性剤類のパー
フルオロアルキルアミノスルホン酸塩に変える以外は実
施例1と同様にして負極活物質スラリーを得た。
Example 7 A negative electrode active material slurry was obtained in the same manner as in Example 1 except that perfluoroalkylaminosulfonic acid salts of fluorine-based surfactants were used.

【0033】(実施例8)フッ素系界面活性剤類のパー
フルオロアルキル燐酸エステルに変える以外は実施例1
と同様にして負極活物質スラリーを得た。
(Example 8) Example 1 except that fluorosurfactants were changed to perfluoroalkyl phosphates.
In the same manner as in the above, a negative electrode active material slurry was obtained.

【0034】(実施例9)フッ素系界面活性剤類のパー
フルオロアルキルスルホン酸塩の量を0.5重量部に変
える以外は実施例1と同様にして負極活物質スラリーを
得た。
Example 9 A negative electrode active material slurry was obtained in the same manner as in Example 1, except that the amount of the perfluoroalkyl sulfonate of the fluorosurfactants was changed to 0.5 part by weight.

【0035】(比較例1)フッ素系界面活性剤類を用い
ない以外、実施例1と全く同様にして、比較例1の負極
活物質スラリーを得た。
Comparative Example 1 A negative electrode active material slurry of Comparative Example 1 was obtained in exactly the same manner as in Example 1 except that no fluorine-based surfactants were used.

【0036】(比較例2)フッ素系界面活性剤類を用い
ない以外、実施例3と全く同様にして、比較例2の負極
活物質スラリーを得た。
Comparative Example 2 A negative electrode active material slurry of Comparative Example 2 was obtained in exactly the same manner as in Example 3 except that no fluorine-based surfactant was used.

【0037】上記、実施例及び比較例の評価は、次のよ
うにして行った。
The above Examples and Comparative Examples were evaluated as follows.

【0038】集電体金属箔への塗工性:厚さ15μmの
銅箔を集電体に選択し、これにロールコーターを用い
て、送り速度0.50m/min、乾燥温度125℃、
送風量10.0m/sの条件で、上記実施例1〜3およ
び比較例1〜4によって得られた負極活物質スラリーを
塗布し、膜厚100〜120μmの塗工膜を得た。その
塗工膜の表面状態を肉眼で観察した評価結果を表1に示
す。評価内容としては、スラリー塗工時に集電体箔上で
のスラリーのはじけによって生じる塗工面に銅箔が見え
ている箇所、を数えた。
Coating property on current collector metal foil: A copper foil having a thickness of 15 μm was selected as a current collector, and was fed using a roll coater at a feed rate of 0.50 m / min and a drying temperature of 125 ° C.
The negative electrode active material slurries obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were applied under the conditions of a blowing rate of 10.0 m / s to obtain a coating film having a thickness of 100 to 120 µm. Table 1 shows the evaluation results obtained by observing the surface state of the coating film with the naked eye. As the content of the evaluation, the places where the copper foil was visible on the coating surface caused by the splashing of the slurry on the current collector foil during the slurry coating were counted.

【0039】集電体金属箔への結着性:次に上記の塗工
膜を5cm×5cmの大きさに切り出し、その中央部に
10mm×10mmの切り込み領域を設定し、鋭利なカ
ッターナイフで縦横に1mm間隔に切り込みを入れ、縦
横10個ずつ、合計100個の立方片からなる碁盤目を
作った。この切り込み領域全面に文房具用接着テープを
貼り付け、指先で良く押さえつけた後、テープを剥がし
た。そして、活物質層が剥離しなかった碁盤目の数を数
えた。評価結果を表1に示す。
Bonding property to current collector metal foil: Next, the above-mentioned coating film was cut into a size of 5 cm × 5 cm, a 10 mm × 10 mm cutting area was set in the center, and a sharp cutter knife was used. Cuts were made at 1 mm intervals in the vertical and horizontal directions to make a grid of 100 cubic pieces, 10 in each of vertical and horizontal directions. An adhesive tape for stationery was stuck on the entire cut area, pressed well with fingertips, and then peeled off. Then, the number of grids in which the active material layer did not peel was counted. Table 1 shows the evaluation results.

【0040】[0040]

【表1】 表1中に示している塗工面に銅箔が見えている箇所は、
当然電極として用いることができず、この箇所が少なけ
れば少ないほど、電池を製造する場合における歩留まり
が大きく向上する事が容易に理解される。この表から明
らかなごとく、フッ素系界面活性剤類を添加した実施例
の負極活物質スラリーは、集電体金属箔にはじかれるこ
となく均一に結着していることがわかる。この結果か
ら、本発明にかかる負極活物質スラリー(実施例1〜
9)は比較負極活物質スラリー(比較例1、2)に比べ
て、格段に均一に塗布されていることがわかる。
[Table 1] The places where the copper foil is visible on the coated surface shown in Table 1
Naturally, it cannot be used as an electrode, and it is easily understood that the smaller the number of the portions, the greater the yield in the case of manufacturing a battery. As is apparent from this table, the negative electrode active material slurries of Examples to which the fluorine-based surfactants were added were uniformly bound without being repelled by the current collector metal foil. From these results, the negative electrode active material slurry according to the present invention (Examples 1 to 5)
It can be seen that 9) was applied much more uniformly than the comparative negative electrode active material slurry (Comparative Examples 1 and 2).

【0041】[0041]

【発明の効果】以上から明らかなように本発明の二次電
池用負極活物質スラリーは、集電体である金属箔に均一
に結着する。また、実際に電池を製造するときの歩留ま
りを向上し、コスト削減に好適である。
As apparent from the above, the negative electrode active material slurry for a secondary battery of the present invention is uniformly bound to a metal foil as a current collector. In addition, the yield when actually manufacturing a battery is improved, which is suitable for cost reduction.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 5H029 AJ14 AK03 AL06 AM03 AM04 AM05 AM07 DJ08 EJ12 HJ01 5H050 AA19 BA17 CA07 CB07 DA09 DA11 DA14 EA24 HA01  ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H029 AJ14 AK03 AL06 AM03 AM04 AM05 AM07 DJ08 EJ12 HJ01 5H050 AA19 BA17 CA07 CB07 DA09 DA11 DA14 EA24 HA01

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】リチウムを吸蔵・放出することができる炭
素材料と、水を分散媒とする結着剤と、水溶性増粘剤
と、フッ素系界面活性剤類を含有することを特徴とする
非水電解質二次電池用負極活物質スラリー。
1. It comprises a carbon material capable of inserting and extracting lithium, a binder using water as a dispersion medium, a water-soluble thickener, and fluorine-based surfactants. Negative electrode active material slurry for non-aqueous electrolyte secondary batteries.
【請求項2】前記フッ素系界面活性剤類が、その化学構
造中にパーフルオロアルキル基を含有することを特徴と
する請求項1に記載の非水電解質二次電池用負極活物質
スラリー。
2. The negative electrode active material slurry for a non-aqueous electrolyte secondary battery according to claim 1, wherein the fluorine-based surfactants contain a perfluoroalkyl group in a chemical structure thereof.
【請求項3】前記フッ素系界面活性剤類が、パーフルオ
ロアルキルスルホン酸塩、パーフルオロアルキルカルボ
ン酸塩、パーフルオロアルキルエチレンオキシド付加
物、パーフルオロアルキルトリメチルアンモニウム塩、
パーフルオロアルキルアミノスルホン酸塩、パーフルオ
ロアルキル燐酸エステルからなる群より選択される1種
類以上の物質を有するフッ素系界面活性剤であることを
特徴とする請求項1または2に記載の非水電解質二次電
池用負極活物質スラリー。
3. The fluorosurfactants include a perfluoroalkyl sulfonate, a perfluoroalkyl carboxylate, a perfluoroalkyl ethylene oxide adduct, a perfluoroalkyl trimethyl ammonium salt,
The non-aqueous electrolyte according to claim 1 or 2, wherein the non-aqueous electrolyte is a fluorine-based surfactant having at least one substance selected from the group consisting of perfluoroalkylaminosulfonate and perfluoroalkylphosphate. Negative electrode active material slurry for secondary batteries.
【請求項4】前記フッ素系界面活性剤類の添加量が、炭
素材料100重量部あたり0.01重量部以上0.5重
量部以下であることを特徴とする請求項1、2または3
に記載の非水電解質二次電池用負極活物質スラリー。
4. The method according to claim 1, wherein the amount of the fluorine-based surfactant is 0.01 to 0.5 parts by weight per 100 parts by weight of the carbon material.
4. The negative electrode active material slurry for a non-aqueous electrolyte secondary battery according to 1.
【請求項5】請求項1、2、3または4に記載の非水電
解質二次電池用負極活物質スラリーを用いて作製した負
極を備えたことを特徴とする非水電解質二次電池。
5. A non-aqueous electrolyte secondary battery comprising a negative electrode produced using the negative electrode active material slurry for a non-aqueous electrolyte secondary battery according to claim 1.
JP2000063483A 2000-03-08 2000-03-08 Active substance slurry for negative electrode of nonaqueous electrolyte secondary cell and the nonaqueous electrolyte secondary cell using the same Pending JP2001250558A (en)

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Publication number Priority date Publication date Assignee Title
WO2008099873A1 (en) * 2007-02-15 2008-08-21 Daikin Industries, Ltd. Composition for electrode coating using fluoroether surfactant
WO2008126968A1 (en) * 2007-04-16 2008-10-23 Ls Mtron, Ltd. Anode material for secondary battery, method for preparing the same, and secondary battery containing the same for anode
KR101116551B1 (en) 2005-02-28 2012-02-24 삼성에스디아이 주식회사 Negative electrode for lithium secondary battery and lithium secondary battery comprising same
EP2913869A1 (en) 2014-02-26 2015-09-02 Jtekt Corporation Apparatus and process for producing electricity storage material
JP2016225135A (en) * 2015-05-29 2016-12-28 三菱化学株式会社 Active material for nonaqueous secondary battery negative electrode and negative electrode using the same, and nonaqueous secondary battery
CN108281615A (en) * 2017-12-30 2018-07-13 宁夏科捷锂电池股份有限公司 A kind of negative electrode slurry performance improvement method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101116551B1 (en) 2005-02-28 2012-02-24 삼성에스디아이 주식회사 Negative electrode for lithium secondary battery and lithium secondary battery comprising same
WO2008099873A1 (en) * 2007-02-15 2008-08-21 Daikin Industries, Ltd. Composition for electrode coating using fluoroether surfactant
JP5218066B2 (en) * 2007-02-15 2013-06-26 ダイキン工業株式会社 Electrode coating composition using fluoroether surfactant
WO2008126968A1 (en) * 2007-04-16 2008-10-23 Ls Mtron, Ltd. Anode material for secondary battery, method for preparing the same, and secondary battery containing the same for anode
EP2913869A1 (en) 2014-02-26 2015-09-02 Jtekt Corporation Apparatus and process for producing electricity storage material
US10374217B2 (en) 2014-02-26 2019-08-06 Jtekt Corporation Apparatus and process for producing electricity storage material
JP2016225135A (en) * 2015-05-29 2016-12-28 三菱化学株式会社 Active material for nonaqueous secondary battery negative electrode and negative electrode using the same, and nonaqueous secondary battery
CN108281615A (en) * 2017-12-30 2018-07-13 宁夏科捷锂电池股份有限公司 A kind of negative electrode slurry performance improvement method

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