JP2000082472A - Nonaqueous battery electrode - Google Patents
Nonaqueous battery electrodeInfo
- Publication number
- JP2000082472A JP2000082472A JP10249733A JP24973398A JP2000082472A JP 2000082472 A JP2000082472 A JP 2000082472A JP 10249733 A JP10249733 A JP 10249733A JP 24973398 A JP24973398 A JP 24973398A JP 2000082472 A JP2000082472 A JP 2000082472A
- Authority
- JP
- Japan
- Prior art keywords
- cmc
- electrode
- binder
- active material
- electrode active
- 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
- 239000007772 electrode material Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 8
- 239000002033 PVDF binder Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 6
- 238000006266 etherification reaction Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polypropylene propylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- OFHQVNFSKOBBGG-UHFFFAOYSA-N 1,2-difluoropropane Chemical compound CC(F)CF OFHQVNFSKOBBGG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電池に用いら
れる電極に関するものであり、特にシート状の電極に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode used for a non-aqueous battery, and more particularly to a sheet-like electrode.
【０００２】[0002]
【従来の技術】非水電池用電極としては、電極活物質と
バインダーと溶剤とからなるスラリーを、金属箔の表面
に塗布し乾燥させることにより、金属箔の表面に電極活
物質層を形成したシート状電極が従来より用いられてい
る。2. Description of the Related Art As an electrode for a non-aqueous battery, a slurry comprising an electrode active material, a binder and a solvent is applied to the surface of a metal foil and dried to form an electrode active material layer on the surface of the metal foil. Sheet electrodes have been used in the past.
【０００３】このようなシート状電極に用いられるバイ
ンダーとしては、数多くのものが提案されてきたが、中
でもポリフッ化ビニルやポリフッ化ビニリデン、ポリフ
ッ化プロピレン等のフッ素系高分子が好適に利用できる
とされている。[0003] Many binders have been proposed as the binder used for such a sheet-like electrode. Among them, a fluorine-based polymer such as polyvinyl fluoride, polyvinylidene fluoride, and polypropylene propylene is preferably used. Have been.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記フ
ッ素系高分子であるポリフッ化エチレンやポリフッ化ビ
ニリデン、ポリフッ化プロピレン等は、Ｎ−メチルピロ
リドン、ジメチルアセトアミド、ヘキサメチルホスホア
ミド、ジメチルスルホキシド、テトラメチル尿素等の特
殊な溶媒にしか溶解せず、しかもこれらの溶剤には毒性
のあるものも含まれているという問題を有している。However, the fluoropolymers such as poly (ethylene fluoride), poly (vinylidene fluoride), and poly (propylene fluoride) are not limited to N-methylpyrrolidone, dimethylacetamide, hexamethylphosphamide, dimethylsulfoxide, tetramethyl. They have the problem that they are soluble only in special solvents such as urea, and that these solvents also contain toxic substances.
【０００５】かかる問題を解決するために、上記のよう
なシート状電極において、溶剤として無害な水が使用可
能で、かつ安価なカルボキシメチルセルロース（以下Ｃ
ＭＣと称す）をバインダーとして用いることが検討され
ている。In order to solve such a problem, harmless water can be used as a solvent and an inexpensive carboxymethylcellulose (hereinafter referred to as C) is used in the above-mentioned sheet electrode.
MC) is being studied as a binder.
【０００６】ところが、ＣＭＣをバインダーに用いた場
合、得られる電極活物質層が硬くなり、その結果損傷し
やすくなるという問題がある。However, when CMC is used as a binder, there is a problem that the obtained electrode active material layer becomes hard and, as a result, is easily damaged.
【０００７】特開平９−２２３５０１号公報では、この
問題を解決するために、ＣＭＣを用いて形成してなる電
極活物質層にシラン系カップリング剤を添加することが
提案されている。Japanese Patent Application Laid-Open No. 9-223501 proposes, in order to solve this problem, to add a silane coupling agent to an electrode active material layer formed using CMC.
【０００８】しかしながら、シラン系カップリング剤
は、電気化学的に分解するおそれがあり、充放電に伴う
電極活物質層劣化の懸念があった。However, the silane coupling agent may be electrochemically decomposed, and there is a concern that the electrode active material layer may be deteriorated due to charge and discharge.
【０００９】さらにリチウムイオンを輸送することで成
立しているリチウム電池系において、その存在が許され
るイオンはリチウムイオンのみであり、その他のイオ
ン、例えばナトリウムイオン等のアルカリ金属イオンの
混入は、電池性能の低下を引き起こすばかりでなく、安
全性の低下をも引き起こす。Further, in a lithium battery system which is established by transporting lithium ions, the only ion that is allowed to exist is lithium ions, and other ions, for example, alkali metal ions such as sodium ions are mixed in the battery. Not only does it cause a decrease in performance, it also causes a decrease in safety.
【００１０】以上のことから、リチウムイオン以外のイ
オンが多量に存在しているであろうＣＭＣをリチウム電
池用電極バインダーに使用することは好ましくないと言
える。From the above, it can be said that it is not preferable to use CMC in which a large amount of ions other than lithium ions will be present as an electrode binder for lithium batteries.
【００１１】本発明は上記に鑑みてなされたもので、安
全性が高く、金属箔表面と電極活物質層間の密着性が高
く、かつ副反応による電池性能の低下のない非水電池用
電極を提供することを課題とする。The present invention has been made in view of the above, and is intended to provide an electrode for a non-aqueous battery having high safety, high adhesion between a metal foil surface and an electrode active material layer, and having no reduction in battery performance due to side reactions. The task is to provide.
【００１２】[0012]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討した結果、金属箔の表面に電極活物
質層を形成するシート状電極において、バインダーにカ
ルボキシメチルセルロースリチウム（以下ＣＭＣ−Ｌｉ
と称す）を用いたとき、溶剤として水が使用可能である
ことから安全面や環境面でも好ましく、またＣＭＣをリ
チウムイオン化処理することで、リチウム電池に適用し
た場合に前記したような好ましくない副反応が抑制さ
れ、従って充放電サイクルライフに影響が少なく、かつ
前記フッ素系高分子と比較して、金属箔表面と電極活物
質層間の密着性の非常に高い非水電池用シート状電極を
得ることが可能であることを見出し、本発明を完成する
に至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that, in a sheet-like electrode having an electrode active material layer formed on the surface of a metal foil, lithium carboxymethylcellulose (hereinafter referred to as CMC) −Li
When water is used as a solvent, water and water can be used as a solvent, which is also preferable in terms of safety and environment. In addition, when CMC is subjected to lithium ionization treatment, the above-mentioned undesired side effect when applied to a lithium battery is obtained. The reaction is suppressed, so that the charge / discharge cycle life is less affected, and a sheet-like electrode for a non-aqueous battery is obtained which has a very high adhesion between the metal foil surface and the electrode active material layer as compared with the fluoropolymer. The inventors have found that it is possible to accomplish the present invention.
【００１３】すなわち、請求項１の非水電池用電極は、
電極活物質とバインダーと溶剤からなるスラリーを、金
属箔の表面に塗布して乾燥させることにより、前記金属
箔の表面に電極活物質層を形成した電極であって、前記
バインダーがカルボキシメチルセルロースリチウムを含
有するものとする。That is, the electrode for a non-aqueous battery according to claim 1 is
An electrode having an electrode active material layer formed on the surface of the metal foil by applying a slurry comprising an electrode active material, a binder, and a solvent to the surface of the metal foil and drying the slurry, wherein the binder comprises lithium carboxymethylcellulose. Shall be included.
【００１４】前記溶剤としては、水が好適に用いられる
（請求項２）。As the solvent, water is preferably used (claim 2).
【００１５】[0015]
【発明の実施の形態】本発明でバインダーとして用いら
れるＣＭＣ−Ｌｉは、市販品等では入手しにくいもので
あるが、ＣＭＣ−Ｎａを酸と反応させてＣＭＣ−Ｈと
し、これをＬｉＯＨと反応させてＣＭＣ−Ｌｉとするこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION CMC-Li used as a binder in the present invention is difficult to obtain as a commercial product or the like, but CMC-Na is reacted with an acid to form CMC-H, which is reacted with LiOH. Thus, CMC-Li can be obtained.
【００１６】ＣＭＣ−Ｌｉのエーテル化度は、通常０．
４〜２．５の範囲であり、好ましくは０．６〜１．０、
より好ましくは０．６５〜０．８の範囲である。また、
ＣＭＣ−Ｌｉの1％水溶液粘度（濃度は無水物基準）は
５〜１００００ｍＰａ・ｓの範囲であり、好ましくは５
０〜１０００ｍＰａ・ｓの範囲である。The degree of etherification of CMC-Li is usually 0.1.
4 to 2.5, preferably 0.6 to 1.0,
More preferably, it is in the range of 0.65 to 0.8. Also,
The viscosity of a 1% aqueous solution of CMC-Li (concentration is based on anhydride) is in the range of 5 to 10,000 mPa · s, preferably
The range is from 0 to 1000 mPa · s.
【００１７】ＣＭＣ−Ｌｉは単独で用いることができる
が、ポリフッ化ビニリデン、ポリブタジエン等の他のバ
インダーを併用することも可能である。他のバインダー
を併用する場合は、バインダー総量中のＣＭＣ−Ｌｉの
割合を２０％以上とするのが好ましい。Although CMC-Li can be used alone, other binders such as polyvinylidene fluoride and polybutadiene can be used in combination. When another binder is used in combination, it is preferable that the proportion of CMC-Li in the total amount of the binder is 20% or more.
【００１８】バインダーの使用量は特に限定されるもの
ではないが、通常は得られる電極活物質層（すなわち電
極活物質とバインダーの総量）１００重量部に対して、
０．１〜２０重量部、好ましくは０．５〜１０重量部、
より好ましくは１〜５重量部の範囲とする。Although the amount of the binder used is not particularly limited, it is usually based on 100 parts by weight of the obtained electrode active material layer (that is, the total amount of the electrode active material and the binder).
0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight,
It is more preferably in the range of 1 to 5 parts by weight.
【００１９】上記ＣＭＣ−Ｌｉを溶解させる溶剤として
は、水、Ｎ−メチルピロリドン、ジメチルスルホキシド
（ＤＭＳＯ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭ
Ｆ）等が用いられるが、安全面や環境面から水が特に好
ましい。As the solvent for dissolving the CMC-Li, water, N-methylpyrrolidone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DM
F) and the like are used, and water is particularly preferable from the viewpoint of safety and environment.
【００２０】溶剤の使用量は特に限定されず、ＣＭＣ−
Ｌｉを溶解させるのに十分であって、所望の溶液粘度が
得られる量を適宜選択すればよい。The amount of the solvent used is not particularly limited.
An amount sufficient to dissolve Li and obtain a desired solution viscosity may be appropriately selected.
【００２１】本発明で用いられる電極活物質は、特に限
定されるものではないが、一例としては、Ｌｉ(1-x)Ｃ
ｏＯ2（但し０＜ｘ＜１、以下同様）、Ｌｉ(1-x)ＮｉＯ
2 、Ｌｉ(1-x)Ｍｎ2Ｏ4 、ＭｎＯ2、ＭｏＯ3、Ｍｏ
Ｓ2、Ｖ2Ｏ5、Ｖ6Ｏ13、ＴｉＳ2や、フッ化カーボン、
グラファイト、易黒鉛化炭素、難黒鉛化炭素、低温焼成
炭素等のカーボン材料が挙げられる。Although the electrode active material used in the present invention is not particularly limited, for example, Li (1-x) C
oO 2 (where 0 <x <1, the same applies hereinafter), Li (1-x) NiO
2 , Li (1-x) Mn 2 O 4 , MnO 2 , MoO 3 , Mo
S 2 , V 2 O 5 , V 6 O 13 , TiS 2 , carbon fluoride,
Examples include carbon materials such as graphite, graphitizable carbon, non-graphitizable carbon, and low-temperature calcined carbon.
【００２２】電極活物質の使用量は、総重量の４５％以
上、好ましくは６０％以上、さらに好ましくは８０％以
上である。The amount of the electrode active material used is at least 45%, preferably at least 60%, more preferably at least 80% of the total weight.
【００２３】上記ＣＭＣ−Ｌｉをバインダーとして用い
る方法としては、ＣＭＣ−Ｌｉを水に溶解せしめたバイ
ンダー溶液を調整し、これに電極活物質の粉末を分散せ
しめてペースト状にし、これを塗工液として用いる方法
が一例として挙げられる。As a method of using CMC-Li as a binder, a binder solution prepared by dissolving CMC-Li in water is prepared, and a powder of an electrode active material is dispersed in the binder solution to form a paste. Is used as an example.
【００２４】シート状電極の作製方法は特に限定されな
いが、上記ペースト状物を、アルミ箔、銅箔等の集電体
に塗布し、乾燥・圧着する方法を採ることができる。The method for producing the sheet-like electrode is not particularly limited, but a method in which the above-mentioned paste is applied to a current collector such as an aluminum foil or a copper foil, followed by drying and pressing may be employed.
【００２５】本発明の非水電池用電極は、用いる電極活
物質によって、正極として用いることも負極として用い
ることもできる。The nonaqueous battery electrode of the present invention can be used as a positive electrode or a negative electrode depending on the electrode active material used.
【００２６】本発明の非水電池用電極を用いて電池を作
製する場合の非水電解液の電解質塩は特に限定されない
が、一例としては、ＬｉＣｌＯ4、 ＬｉＰＦ6、ＬｉＢ
Ｆ4、ＬｉＡｓＦ6、ＣＦ3ＳＯ3Ｌｉ、（ＣＦ3ＳＯ2）2
ＮＬｉ、（Ｃ2Ｆ5ＳＯ2）2ＮＬｉ等が挙げられる。The electrolyte salt of the non-aqueous electrolyte when a battery is manufactured using the non-aqueous battery electrode of the present invention is not particularly limited. Examples thereof include LiClO 4 , LiPF 6 and LiB.
F 4 , LiAsF 6 , CF 3 SO 3 Li, (CF 3 SO 2 ) 2
NLi, (C 2 F 5 SO 2 ) 2 NLi, and the like.
【００２７】また、非水電解液の有機溶媒の例として
は、エチレンカーボネート、プロピレンカーボネート、
γ−ブチロラクトン、２−メチルテトラヒドロフラン、
ジメチルカーボネート、ジエチルカーボネート、エチル
メチルカーボネート、ジメトキシエタン及びこれらの混
合溶媒等が挙げられるが、必ずしもこれらに限定される
ものではない。Examples of the organic solvent of the non-aqueous electrolyte include ethylene carbonate, propylene carbonate,
γ-butyrolactone, 2-methyltetrahydrofuran,
Examples thereof include, but are not limited to, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethoxyethane, and a mixed solvent thereof.
【００２８】また、非水電池に用いられる電解質として
は、上記非水電解液のほかに、例えば有機高分子化合物
を上記非水電解液で膨潤させたイオン伝導性高分子組成
物や、上記電解質塩を有機高分子化合物に溶解させて架
橋させた高分子固体電解質を使用することも可能であ
る。上記有機高分子化合物の種類は特に限定されない
が、一例として、ポリアクリロニトリル、ポリアルキレ
ンオキサイド、ポリフッ化ビニリデン、ポリメタクリル
酸メチル等が挙げられる。Examples of the electrolyte used in the non-aqueous battery include, in addition to the above-mentioned non-aqueous electrolyte, an ion-conductive polymer composition obtained by swelling an organic polymer compound with the above-mentioned non-aqueous electrolyte, and the above-mentioned electrolyte. It is also possible to use a polymer solid electrolyte in which a salt is dissolved in an organic polymer compound and crosslinked. The type of the organic polymer compound is not particularly limited, but examples include polyacrylonitrile, polyalkylene oxide, polyvinylidene fluoride, polymethyl methacrylate, and the like.
【００２９】[0029]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれらの実施例によって限定されるもので
はない。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
【００３０】（1）ＣＭＣ−Ｌｉの製造製造例1 エーテル化度０．６のＣＭＣ−Ｎａ１００ｇを、１０%
Ｈ2ＳＯ4水溶液５００ｇに添加し、５０℃で３０分間攪
拌後、遠心分離機で液体を分離した。ケーキ状になった
ＣＭＣ−Ｎａを取り出し、５０℃の純水１０００ｍｌで
３０分間攪拌し、その後遠心分離機で液体を分離した。
この操作を３回繰り返し、残酸分を除去した。(1) Production of CMC-Li Production Example 1 100 g of CMC-Na having a degree of etherification of 0.6 was added to 10%
The solution was added to 500 g of an H 2 SO 4 aqueous solution, stirred at 50 ° C. for 30 minutes, and then separated by a centrifuge. The caked CMC-Na was taken out, stirred with 1000 ml of pure water at 50 ° C. for 30 minutes, and then the liquid was separated by a centrifuge.
This operation was repeated three times to remove residual acid.
【００３１】分離したケーキ状のＣＭＣ−Ｈを取り出
し、リボン型ブレンダー（3Ｌ容）に投入し、４０〜５
０℃で攪拌した後、ＬｉＯＨ粉末を１０ｇ添加して６０
分間攪拌した。The separated cake-like CMC-H is taken out and put into a ribbon-type blender (3 L capacity).
After stirring at 0 ° C., 10 g of LiOH powder was added and
Stirred for minutes.
【００３２】得られた混合物を取り出し、８０ｗｔ%メ
タノール２０００ｍｌ中に添加し、室温で３０分間攪拌
後、遠心分離機によってメタノールを除去した。得られ
たケーキ状物を取り出し、同じ操作を５回繰り返すこと
により、過剰のＬｉＯＨを除去した。The obtained mixture was taken out, added to 2000 ml of 80 wt% methanol, stirred at room temperature for 30 minutes, and then methanol was removed by a centrifuge. The obtained cake was taken out and the same operation was repeated five times to remove excess LiOH.
【００３３】ケーキ状のＣＭＣ−Ｌｉを８０℃で３時間
乾燥し粉砕することで、水分５％以下のＣＭＣ−Ｌｉを
白色粉末として得た（化合物（１））。The cake-like CMC-Li was dried at 80 ° C. for 3 hours and pulverized to obtain CMC-Li having a water content of 5% or less as a white powder (compound (1)).
【００３４】製造例2 エーテル化度０．７５のＣＭＣ−Ｎａを用いた以外は、
製造例1と同様の操作を行い、水分５％以下のＣＭＣ−
Ｌｉを白色粉末として得た（化合物（２））。 Production Example 2 Except that CMC-Na having a degree of etherification of 0.75 was used,
The same operation as in Production Example 1 was performed, and CMC-
Li was obtained as a white powder (compound (2)).
【００３５】製造例3 エーテル化度１．０のＣＭＣ−Ｎａを用いた以外は、製
造例1と同様の操作を行い、水分５％以下のＣＭＣ−Ｌ
ｉを白色粉末として得た（化合物（３））。 Production Example 3 The same operation as in Production Example 1 was carried out except that CMC-Na having a degree of etherification of 1.0 was used.
i was obtained as a white powder (compound (3)).
【００３６】上記製造例１〜３により得られたＣＭＣ−
Ｌｉ（化合物（１）〜（３））を用いた試験電極の作成
例を以下に示す。CMC obtained by the above Preparation Examples 1 to 3
An example of preparing a test electrode using Li (compounds (1) to (3)) is shown below.
【００３７】（2）試験電極の作成実施例1 化合物（１）０．０５ｇを水３．３３ｇに溶解させ、電
極活物質としてカーボン０．９５ｇを添加し、ペースト
状にした後、厚さ２０μｍ、４ｃｍ×５ｃｍの銅箔上に
塗布し、２００℃で真空乾燥した後、１ｔｏｎ／ｃｍ2
で圧着して、厚さ１００μｍの試験電極を得た。(2) Preparation of Test Electrode Example 1 0.05 g of the compound (1) was dissolved in 3.33 g of water, 0.95 g of carbon was added as an electrode active material to form a paste, and the thickness was 20 μm. , Applied on a 4 cm × 5 cm copper foil and vacuum dried at 200 ° C., then 1 ton / cm 2
To obtain a test electrode having a thickness of 100 μm.
【００３８】実施例2 化合物（１）に代えて、化合物（２）を用いた以外は実
施例1と同様にして試験電極を作成した。 Example 2 A test electrode was prepared in the same manner as in Example 1 except that Compound (2) was used instead of Compound (1).
【００３９】実施例3 化合物（１）に代えて、化合物（３）を用いた以外は実
施例1と同様にして試験電極を作成した。 Example 3 A test electrode was prepared in the same manner as in Example 1 except that Compound (3) was used instead of Compound (1).
【００４０】実施例４ 化合物（１）０．０５ｇを水３．３３ｇに溶解し、ポリ
フッ化ビニリデン（ＰＶＤＦ）０．０１ｇをＮ−メチル
ピロリドン１．００ｇに溶解し、両液を混合し、これに
電極活物質としてカーボン０．８０ｇを添加してペース
ト状とした後、実施例1と同様にして試験電極を作成し
た。 Example 4 0.05 g of compound (1) was dissolved in 3.33 g of water, 0.01 g of polyvinylidene fluoride (PVDF) was dissolved in 1.00 g of N-methylpyrrolidone, and the two solutions were mixed. After adding 0.80 g of carbon as an electrode active material to form a paste, a test electrode was prepared in the same manner as in Example 1.
【００４１】比較例1 ポリビニリデンフルオリド（ＰＶＤＦ）０．０５ｇをＮ
−メチルピロリドン（ＮＭＰ）１．６７ｇに溶解させ、
電極活物質としてカーボン０．９５ｇを添加し、ペース
ト状にした後、厚さ２０μm、４ｃｍ×５ｃｍの銅箔上
に塗布し、２００℃で真空乾燥した後、１ｔｏｎ／ｃｍ
2で圧着して、厚さ１００μｍの試験電極を得た。 Comparative Example 1 0.05 g of polyvinylidene fluoride (PVDF)
-Dissolved in 1.67 g of methylpyrrolidone (NMP)
After adding 0.95 g of carbon as an electrode active material to form a paste, it was applied on a copper foil having a thickness of 20 μm and 4 cm × 5 cm, dried at 200 ° C. under vacuum, and then 1 ton / cm
2 was pressed to obtain a test electrode having a thickness of 100 μm.
【００４２】（３）密着性の評価 上記により得られた試験電極各１０枚に、それぞれ２ｃ
ｍ×４ｃｍの粘着テープを貼った後、粘着テープを剥離
して、銅箔からの電極活物質層の剥離の有無を観察し
た。得られた結果を表1に示す。(3) Evaluation of Adhesion Each of the 10 test electrodes obtained above was subjected to 2c
After adhering an mx 4 cm adhesive tape, the adhesive tape was peeled off, and the presence or absence of peeling of the electrode active material layer from the copper foil was observed. Table 1 shows the obtained results.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】本発明の非水電池用電極は、従来用いら
れてきたフッ素系高分子と比較して、金属箔表面と電極
活物質層との間の密着性が非常に高い。また、溶剤とし
て水が使用可能であることから安全面や環境面でも好ま
しく、副反応による電池性能の低下も引き起こさない。
従って、これを用いることにより、性能と安全性の両面
で信頼性の非常に高い非水電池が得られる。The electrode for a non-aqueous battery according to the present invention has an extremely high adhesion between the surface of the metal foil and the electrode active material layer as compared with the conventionally used fluoropolymer. In addition, since water can be used as a solvent, it is preferable in terms of safety and environment, and does not cause deterioration of battery performance due to side reactions.
Therefore, by using this, a highly reliable nonaqueous battery can be obtained in both performance and safety.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H003 AA08 AA10 BA00 BA01 BA03 BB11 BC05 5H014 AA02 BB01 BB06 BB08 CC01 EE01 5H029 AJ12 AJ14 AK02 AK03 AK05 AL06 AM02 AM07 BJ04 CJ02 CJ08 CJ22 DJ06 EJ11 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H003 AA08 AA10 BA00 BA01 BA03 BB11 BC05 5H014 AA02 BB01 BB06 BB08 CC01 EE01 5H029 AJ12 AJ14 AK02 AK03 AK05 AL06 AM02 AM07 BJ04 CJ02 CJ08 CJ22 DJ06 EJ11
Claims (2)
ラリーを、金属箔の表面に塗布して乾燥させることによ
り、前記金属箔の表面に電極活物質層を形成した電極で
あって、 前記バインダーがカルボキシメチルセルロースリチウム
を含有することを特徴とする非水電池用電極。An electrode in which a slurry comprising an electrode active material, a binder and a solvent is applied to the surface of a metal foil and dried to form an electrode active material layer on the surface of the metal foil. Contains lithium carboxymethylcellulose.
ことを特徴とする、請求項１に記載の非水電池用電極。2. The electrode for a non-aqueous battery according to claim 1, wherein the solvent contained in the slurry is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10249733A JP2000082472A (en) | 1998-09-03 | 1998-09-03 | Nonaqueous battery electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10249733A JP2000082472A (en) | 1998-09-03 | 1998-09-03 | Nonaqueous battery electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000082472A true JP2000082472A (en) | 2000-03-21 |
Family
ID=17197405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10249733A Pending JP2000082472A (en) | 1998-09-03 | 1998-09-03 | Nonaqueous battery electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000082472A (en) |
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| JP2009043641A (en) * | 2007-08-10 | 2009-02-26 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery and negative electrode used for the same |
| JP2014022039A (en) * | 2012-07-12 | 2014-02-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Negative electrode binder for lithium secondary battery |
| WO2014197242A1 (en) * | 2013-06-04 | 2014-12-11 | Dow Global Technologies Llc | Process for manufacturing lithium carboxymethyl cellulose |
| WO2016031449A1 (en) * | 2014-08-28 | 2016-03-03 | 第一工業製薬株式会社 | Method for producing carboxymethyl cellulose salt for electrodes of nonaqueous electrolyte secondary batteries, electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
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| JP2022141404A (en) * | 2021-03-15 | 2022-09-29 | プライムプラネットエナジー＆ソリューションズ株式会社 | Nonaqueous electrolyte secondary battery |
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-
1998
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| JP2014022039A (en) * | 2012-07-12 | 2014-02-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Negative electrode binder for lithium secondary battery |
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