JPH03225750A - Positive electrode sheet for lithium battery - Google Patents
Positive electrode sheet for lithium batteryInfo
- Publication number
- JPH03225750A JPH03225750A JP2021139A JP2113990A JPH03225750A JP H03225750 A JPH03225750 A JP H03225750A JP 2021139 A JP2021139 A JP 2021139A JP 2113990 A JP2113990 A JP 2113990A JP H03225750 A JPH03225750 A JP H03225750A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- sheet
- lithium battery
- conductive agent
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000000853 adhesive Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000008096 xylene Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006230 acetylene black Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910012970 LiV3O8 Inorganic materials 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 229920002125 Sokalan® Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- -1 acyclic carbonates Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 102100031416 Gastric triacylglycerol lipase Human genes 0.000 description 1
- 101000941284 Homo sapiens Gastric triacylglycerol lipase Proteins 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012219 LiPFa Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
-
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はリチウムイオンを吸蔵、放出可能なリチウム電
池用正極シートに関し、更に詳述すると安定で性能のバ
ラツキの少ないリチウム電池を製造するために２００℃
以上で熱処理可能なリチウム電池用正極シートに関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a positive electrode sheet for a lithium battery that is capable of intercalating and deintercalating lithium ions, and more specifically, for producing a stable lithium battery with less variation in performance. 200℃
The above relates to a heat-processable positive electrode sheet for lithium batteries.
〔従来の技術及び発明が解決しようとする課題〕従来か
ら、筒形リチウム電池、特に−次電池においては、正極
シートはパンチング・メタルやエキスバンド・メタルに
活物質を含む正極合剤ペーストを塗布し、乾燥する方法
により製造されている。また、筒形リチウム二次電池（
モーリー社等）においても金属箔にペースト状正極活物
質をコーティングする方法が採られている。しかし、こ
れらは単に金属箔上に活物質が物理的にコーティングさ
れているだけであるため電池の組み立て工程の途中で剥
れたり、部分的に脱落する恐れがある。[Prior art and problems to be solved by the invention] Conventionally, in cylindrical lithium batteries, especially secondary batteries, the positive electrode sheet is formed by coating punched metal or expanded metal with a positive electrode mixture paste containing an active material. It is manufactured by a method of drying. In addition, cylindrical lithium secondary batteries (
Morley Co., Ltd., etc.) also employ a method of coating metal foil with a paste-like positive electrode active material. However, since these are merely physical coatings of active material on metal foil, there is a risk that they may peel off or partially fall off during the battery assembly process.
そこで、あらかじめ活物質を含む正極合剤シートを作っ
ておきこれを導電性接着剤で金属箔集電体に接着させる
方法が行われるようになってきており、この場合、導電
性接着剤のベースポリマーとしては、ポリアクリル酸を
用いることが提案されている（特開昭６２−１６０６５
６号公報）。Therefore, a method has begun to be used in which a positive electrode mixture sheet containing an active material is made in advance and then adhered to a metal foil current collector using a conductive adhesive. It has been proposed to use polyacrylic acid as the polymer (Japanese Unexamined Patent Publication No. 16065/1986).
Publication No. 6).
ここで電池製造工程において、正極合剤シート又は集電
体が一体化された正極シートは次工程に進むまでにある
期間放置又は保管される場合が多いが、このような場合
この期間に吸湿や吸湿による構造変化が起きる場合があ
るため、次工程へ進む前に加熱脱水して、元の状態へも
どすことがよく行われる。即ち、一般に正極活物質はＬ
ｉ゛を吸蔵する「穴」を持っており、この「穴」は水分
子に対しても鋭敏で、これを取り込む場合が多く見受け
られる。この「穴ｊに取り込まれた水分子は２００℃以
下の温度ではながなか取り除くことができず、従って２
００℃以上の温度で正極シートを加熱する必要が生じる
ものである。In the battery manufacturing process, the positive electrode mixture sheet or the positive electrode sheet with an integrated current collector is often left or stored for a certain period of time before proceeding to the next process, but in such cases, moisture absorption and Because structural changes may occur due to moisture absorption, it is often heated and dehydrated to return to its original state before proceeding to the next step. That is, generally the positive electrode active material is L
It has ``holes'' that absorb i, and these ``holes'' are also sensitive to water molecules, and are often seen taking in water molecules. The water molecules taken into this "hole j" cannot be removed for a long time at temperatures below 200℃, so
It is necessary to heat the positive electrode sheet at a temperature of 00°C or higher.
しかしながら、このような正極シートに対して、２００
℃以上の高温で熱処理を施すと、耐熱温度が低いポリア
クリル酸などの接着剤が使われている場合、剥離が生じ
るという欠点を持っている。However, for such a positive electrode sheet, 200
If heat treatment is performed at a high temperature of ℃ or higher, peeling may occur if an adhesive such as polyacrylic acid, which has a low heat resistance, is used.
本発明は、上記事情に鑑みなされたもので、２００℃以
上の温度で熱処理を施しても剥離や脱落といった不都合
を生じることなく、良好に熱処理を行なうことができ、
高性能のリチウム電池を構成することができる正極シー
トを提供することを目的とする。The present invention has been made in view of the above circumstances, and allows heat treatment to be performed satisfactorily without causing inconveniences such as peeling or falling off even when heat treatment is performed at a temperature of 200°C or higher.
The purpose of the present invention is to provide a positive electrode sheet that can constitute a high-performance lithium battery.
〔課題を解決するための手段及び作用〕本発明者は、上
記目的を達成するため、鋭意検討を行った結果、接着剤
のベース・ポリマーとしてボロシロキサン樹脂、ポリエ
ステルスルホン、アクリルシリコン樹脂などの耐熱性ポ
リマーを用い、カーボンやグラファイトなどの導電剤を
加えて、溶剤で塗料化したものを接着剤として集電体に
塗り、合剤シートを接着一体化させたものが、後工程で
の加熱にも耐え、接着はがれを起こさないことを知見し
、本発明を完成するに至ったものである。[Means and effects for solving the problem] In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that heat-resistant materials such as borosiloxane resin, polyester sulfone, and acrylic silicone resin are used as base polymers for adhesives. Using a conductive polymer such as carbon or graphite, the paint is made with a solvent and applied to the current collector as an adhesive, and the mixture sheet is integrated with the adhesive. The present invention was completed based on the finding that the adhesive can withstand the heat and does not cause adhesive peeling.
従って、本発明は、正極活物質に導電剤及びバインダー
を添加して形成された正極合剤シートと金属箔集電体と
を導電性接着剤で接着して一体化させたリチウム電池用
正極シートにおいて、上記導電性接着剤として、２００
℃以上の耐熱性を有する高分子物質と導電剤とを含有す
る組成物を用いたことを特徴とするリチウム電池用正極
シートを提供するものである。Therefore, the present invention provides a positive electrode sheet for lithium batteries in which a positive electrode mixture sheet formed by adding a conductive agent and a binder to a positive electrode active material and a metal foil current collector are bonded and integrated with a conductive adhesive. In, as the conductive adhesive, 200
The present invention provides a positive electrode sheet for a lithium battery, characterized in that it uses a composition containing a polymer substance having heat resistance of 0.degree. C. or higher and a conductive agent.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明の正極シートは、２００℃以上の耐熱性を有する
高分子物質と導電剤とを含有する組成物で活物質を含む
正極合剤シートと金属箔集電体とを接着一体化したもの
であり、リチウム電池、特にリチウム二次電池用の正極
として好適に用いられる。The positive electrode sheet of the present invention is made of a composition containing a polymer substance having heat resistance of 200° C. or higher and a conductive agent, and is made by bonding and integrating a positive electrode mixture sheet containing an active material and a metal foil current collector. It is suitable for use as a positive electrode for lithium batteries, especially lithium secondary batteries.
ここで、上記高分子物質としては、前述したボロシロキ
サン、ポリエステルスルホン、アクリルシリコン樹脂の
王者に限らず、２００℃以上の耐熱性と、適当な溶剤に
可溶であれば特に制限されるものではない。また、導電
剤に関しても特に制限はないが、導電性カーボンやグラ
ファイトが好適に用いられる。Here, the above-mentioned polymeric substance is not limited to the above-mentioned kings of borosiloxane, polyester sulfone, and acrylic silicone resin, but is not particularly limited as long as it has heat resistance of 200°C or more and is soluble in an appropriate solvent. do not have. Further, there are no particular restrictions on the conductive agent, but conductive carbon and graphite are preferably used.
上記高分子物質と導電剤とを混合し、溶剤に溶解するこ
とにより、正極合剤シートと金属箔集電体とを接着する
接着剤組成物を調整するが、この場合溶剤としてはトル
エン、キシレンなどの芳香族溶剤、酢酸エチルなどのエ
ステル類、メチルエチルケトンなどのケトン類、ジクロ
ロエタンなどのハロゲン化炭化水素類、エタノールなど
のアルコール類、ヘキサン、シクロヘキサンなどの炭化
水素類又はこれらの混合溶剤が挙げられるが、これらに
制限されるものではない、また、高分子物質と導電剤と
の混合比は、特に制限されないが、導電剤として、導電
性カーボンやグラファイトを用いた場合は２：８〜４：
６（バインダー：高分子物質、重量比）の範囲が好適で
ある。An adhesive composition for bonding the positive electrode mixture sheet and the metal foil current collector is prepared by mixing the above-mentioned polymeric substance and a conductive agent and dissolving it in a solvent. In this case, the solvent may be toluene or xylene. Examples include aromatic solvents such as esters such as ethyl acetate, ketones such as methyl ethyl ketone, halogenated hydrocarbons such as dichloroethane, alcohols such as ethanol, hydrocarbons such as hexane and cyclohexane, or mixed solvents thereof. However, the mixing ratio of the polymer substance and the conductive agent is not particularly limited, but when conductive carbon or graphite is used as the conductive agent, it is 2:8 to 4:
A range of 6 (binder: polymeric substance, weight ratio) is suitable.
次に、正極合剤シートは、正極活物質に導電剤及びバイ
ンダーを添加して有機溶剤で混練し、ロール等でシート
状に圧延し、乾燥させるなどの方法により製造されたも
のである。Next, the positive electrode mixture sheet is produced by adding a conductive agent and a binder to the positive electrode active material, kneading the mixture with an organic solvent, rolling it into a sheet shape with a roll, and drying it.
ここで、上記正極活物質に特に制限はないが、し１ｔ＋
ｘＶｓＯｅ＋ｙ（０≦Ｘ≦０．６．−０．５ ≦ｙ≦
０．３）や非晶質ｖ２０．などの吸湿性の比較的強い活
物質の場合に本発明の効果が特に顕著である。なお、導
電剤の配合量は活物質１００部（重量部、以下同様）に
対して１０〜３０部とすることが好ましく、またバイン
ダーの配合量は３〜２０部とすることが好ましい。Here, the positive electrode active material is not particularly limited, but
xVsOe+y(0≦X≦0.6.-0.5 ≦y≦
0.3) and amorphous v20. The effects of the present invention are particularly remarkable in the case of active materials with relatively strong hygroscopicity such as. The amount of the conductive agent to be blended is preferably 10 to 30 parts per 100 parts (by weight, hereinafter the same) of the active material, and the amount of the binder to be blended is preferably 3 to 20 parts.
本発明の正極シートは、この正極合剤シートと金属箔集
電体とを上記接着塗料で接着一体化したものであるが、
この場合集電体と正極合剤シートの接合方法としては、
集電体に接着塗料を塗付し、合剤シートを圧着した後に
乾燥（脱溶剤）する方法や、塗付後乾燥させたものに合
剤シートを熱圧着する方法があるが、特にこの二つに制
限されるものではない。なお、金属箔集電体としてはア
ルミニウム箔、ニッケル箔、ステンレススチール箔等が
好適に使用される。The positive electrode sheet of the present invention is obtained by bonding this positive electrode mixture sheet and a metal foil current collector together with the above-mentioned adhesive paint.
In this case, the method for joining the current collector and positive electrode mixture sheet is as follows:
There are two methods: applying adhesive paint to the current collector, pressing the mixture sheet on it, and then drying it (removing the solvent), and applying heat and pressing the mixture sheet onto the dried material. It is not limited to. Note that aluminum foil, nickel foil, stainless steel foil, etc. are preferably used as the metal foil current collector.
また、単に正極合剤シートと金属箔集電体とを互いに接
合してもよいが、特に上記集電体の両側に一枚づつ正極
合剤シートを接合し、２枚の正極合剤シートで集電体を
挟み込んだ構造の正極シートとすることが好ましい。Alternatively, the positive electrode mixture sheet and the metal foil current collector may be simply bonded to each other, but in particular, one positive electrode mixture sheet may be bonded to each side of the current collector, and two positive electrode mixture sheets may be bonded together. It is preferable that the positive electrode sheet has a structure in which a current collector is sandwiched between the positive electrode sheets.
本発明の正極シートは、リチウム電池、特にリチウム二
次電池の正極として好適に使用される。The positive electrode sheet of the present invention is suitably used as a positive electrode for lithium batteries, especially lithium secondary batteries.
この場合、本発明正極シートは、２００℃以上の高温で
良好に熱処理を施すことができ、従って高性能なリチウ
ム電池を安定的に製造することができる。In this case, the positive electrode sheet of the present invention can be favorably heat-treated at a high temperature of 200° C. or higher, and therefore a high-performance lithium battery can be stably manufactured.
なお、本発明の正極シートを用いてリチウム二次電池を
構成する場合、負極及び電解質としては、特に制限はな
く、通常のリチウム電池に用いられるものを好適に使用
し得るが、特に二次電池を構成する場合には、負極とし
てリチウム金属又はリチウムとＡ ｌ 、Ｉｎ、 Ｓｎ
、 ｐｂ、 Ｌ ＋ Ｃｄ＋ Ｚｎなどとの合金が好適
に用いられ、また電解質としてはＬＩＰＦ＆１ＬｉＡｓ
Ｆ、、、 ＬｉＳｂＦ６． ＬｉＢＦｍｌＬｉＣＪ０４
＋ ＬｉＩ、 ＬｉＢｒ。In addition, when constructing a lithium secondary battery using the positive electrode sheet of the present invention, there are no particular restrictions on the negative electrode and electrolyte, and those used in ordinary lithium batteries can be suitably used. lithium metal or lithium and Al, In, Sn as a negative electrode.
, pb, L + Cd + Zn, etc., and as an electrolyte, LIPF & 1LiAs are preferably used.
F., LiSbF6. LiBFmlLiCJ04
+ LiI, LiBr.
ＬｉＣｊ！＋ １ｉＡＩＣｊ！、、’Ｌｉｔ（Ｆｚ、
Ｌｉ５ＣＮ＋ Ｌｉ５ＯｓＣＦ３などが好ましく、これ
らの中でも特にＬｉＰＦ６． ＬＩＡＳＦ６１ＬｉＣｉ
！ Ｏａが好適である。なお、これら電解質は、通常溶
媒によって溶解され、電解液として用いられるが、この
場合溶媒としては、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
ート類、ジエチルカーボネート、ジブチルカーボネート
などの非環状カーボネート類、テトラヒドロフラン、２
−メチルテトラヒドロフラン、ジオキソラン、ジオキサ
ン、ジメトキシエタン、ジエチレングリコールジメチル
エーテル等のグライム類、γ−ブチロラクトン、等のラ
クトン類、トリエチルフォスフェート等のリン酸エステ
ル類、ホウ酸トリエチル等のホウ酸エステル類、スルホ
ラン、ジメチルスルホキシド等の硫黄化合物、アセトニ
トリル等のニトリル類、ジメチルホルムアミド、ジメチ
ルアセトアミド等のアミド類、硫酸ジメチル、ニトロメ
タン、ニトロベンゼン、ジクロロエタン等の１種または
２種以上の混合物を挙げることができる。これらのうち
では、特にエチレンカーボネート、プロピレンカーボネ
ートなどの環状カーボネート類、ジエチルカーボネート
などの非環状カーボネート類から選ばれた１種または２
種以上の混合溶媒が好適である。LiCj! + 1iAICj! ,,'Lit(Fz,
Li5CN+ Li5OsCF3 etc. are preferable, and among these, LiPF6. LIASF61LiCi
! Oa is preferred. These electrolytes are usually dissolved in a solvent and used as an electrolytic solution. In this case, the solvent may be cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, or acyclic carbonates such as diethyl carbonate or dibutyl carbonate. , tetrahydrofuran, 2
- Glymes such as methyltetrahydrofuran, dioxolane, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, lactones such as γ-butyrolactone, phosphoric acid esters such as triethyl phosphate, boric acid esters such as triethyl borate, sulfolane, dimethyl Examples include one or a mixture of two or more of sulfur compounds such as sulfoxide, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, dimethyl sulfate, nitromethane, nitrobenzene, and dichloroethane. Among these, one or two selected from cyclic carbonates such as ethylene carbonate and propylene carbonate, and acyclic carbonates such as diethyl carbonate.
A mixed solvent of more than one species is suitable.
以上説明したように、本発明のリチウム電池用正極シー
トは、２００℃以上の高温で正極合剤シートの剥離や脱
落といった不都合を生じることなく良好に熱処理するこ
とができ、このため効率的に加熱脱水工程を行なうこと
ができ、残留水分も極度に少なくすることができるので
、高性能のリチウム電池を安定的に製造することができ
る。特に、リチウム二次電池を構成する場合には、充放
電サイクル耐久性を大巾に向上させることができ、本発
明の効果が特に顕著である。As explained above, the positive electrode sheet for lithium batteries of the present invention can be well heat-treated at high temperatures of 200°C or higher without causing any inconveniences such as peeling or falling off of the positive electrode mixture sheet, and therefore can be heated efficiently. Since a dehydration process can be performed and residual moisture can be extremely reduced, high-performance lithium batteries can be stably manufactured. In particular, when constructing a lithium secondary battery, the charge/discharge cycle durability can be greatly improved, and the effects of the present invention are particularly remarkable.
以下、実施例及び比較例を示し、本発明を具体的に説明
するが、本発明は下記の実施例に制限されるものではな
い。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below.
また、実施例及び比較例で作成した正極シートを用いて
リチウム二次電池を構成し、電池性能を評価した。これ
を参考例に示す。In addition, a lithium secondary battery was constructed using the positive electrode sheets prepared in Examples and Comparative Examples, and battery performance was evaluated. This is shown as a reference example.
Ｌｉ＋、ｏｚＶ＋Ｏａ＜Ｄ粉末１００部（重１部、以下
間ｍ）に導電剤としてアセチレンブラック１５部及び結
着剤としてフッ素樹脂粉末１５部を加え、十分混合した
後、有機溶剤で混練りし、ロールで約１００μｍに圧延
し、１５０℃で真空乾燥し、正極合剤シートを作成した
。Add 15 parts of acetylene black as a conductive agent and 15 parts of fluororesin powder as a binder to 100 parts of Li +, ozV + Oa<D powder (1 part by weight, hereinafter m), mix thoroughly, and then knead with an organic solvent, It was rolled to about 100 μm with a roll and vacuum dried at 150° C. to prepare a positive electrode mixture sheet.
一方、トルエンとキシレンの混合物にＮ−メチルピロリ
ドンを１０％添加した溶剤にボロシロキサン樹脂３部に
対してグラファイト７部の割合で混合し、これを添加し
て溶解分散させ、接着塗料を調製した。この塗料を２０
０℃、減圧下で溶剤を揮発させた後の重量分率は５２％
であった。On the other hand, a mixture of toluene and xylene containing 10% N-methylpyrrolidone was mixed with 3 parts of borosiloxane resin and 7 parts of graphite, and this was added to dissolve and disperse to prepare an adhesive paint. . 20% of this paint
The weight fraction after evaporating the solvent at 0°C and under reduced pressure is 52%.
Met.
この塗料を２０μｍ厚みのアルミ箔に塗付し、乾燥後正
極合剤を重ねて１５０℃でプレスし、５分間熱圧着し、
集電体と一体化した正極シートを作成した。This paint was applied to aluminum foil with a thickness of 20 μm, and after drying, the positive electrode mixture was layered and pressed at 150°C for 5 minutes.
A positive electrode sheet integrated with a current collector was created.
このシートのＸ線回折を測定（第１図参照）した後、■
日間大気中に放置し、再度Ｘ線回折を測定したところ、
第２図のようにパターンが変化した。これを２５０℃で
１０分間加熱したが剥離は起きなかった。これを再びＸ
線回折測定したところ、第１図のパターンにもどってい
た。After measuring the X-ray diffraction of this sheet (see Figure 1),
When it was left in the air for several days and X-ray diffraction was measured again,
The pattern changed as shown in Figure 2. This was heated at 250° C. for 10 minutes, but no peeling occurred. X this again
Line diffraction measurements revealed that the pattern had returned to that shown in Figure 1.
〔実施例２〕
トルエンとキシレンとメチルエチルケトンとの混合溶剤
を用い、ポリマーをポリエーテルスルホンに代えて接着
塗料を調製し、正極合剤シートを塗料が乾燥する前に接
着させ、１５０℃のプレスで圧着した以外は実施例１と
全く同様にして正極シートを作成し、同様な加熱処理を
行ったところ、剥離は起きなかった。[Example 2] Using a mixed solvent of toluene, xylene, and methyl ethyl ketone, an adhesive paint was prepared by replacing the polymer with polyether sulfone, and a positive electrode mixture sheet was adhered before the paint dried, and was pressed at 150°C. A positive electrode sheet was prepared in exactly the same manner as in Example 1 except that it was crimped, and when the same heat treatment was performed, no peeling occurred.
溶剤として水を用い、ポリマーをポリアクリル酸樹脂に
代えた以外は実施例１と全く同様に正極シートを作成し
、同様の熱処理を行ったところ、集電体と正極合剤シー
トが剥離してしまった。そこで加熱脱水温度を２５０℃
から１５０℃に下げて、２０分間熱処理・し、Ｘ線回折
を測定したところ、第３図のＸ線回折パターンを示した
。A positive electrode sheet was prepared in exactly the same manner as in Example 1, except that water was used as the solvent and polyacrylic acid resin was used as the polymer. When the same heat treatment was performed, the current collector and the positive electrode mixture sheet were separated. Oops. Therefore, the heating dehydration temperature was set to 250℃.
When the temperature was lowered to 150° C., heat treatment was performed for 20 minutes, and X-ray diffraction was measured, the X-ray diffraction pattern shown in FIG. 3 was obtained.
実施例１において、２５０℃、１０分加熱脱水して、第
１図のＸ線回折パターンにもどった試料を所定の径に打
抜いて電池正極を作成した。In Example 1, a battery positive electrode was prepared by heating and dehydrating the sample at 250° C. for 10 minutes and punching the sample, which returned to the X-ray diffraction pattern shown in FIG. 1, into a predetermined diameter.
上記電池正極を用い、所定寸法に打抜いたリチウム箔を
負極とし、プロピレンカーボネートとエチレンカーボネ
ートとの混合溶媒（容量比１：１）にリチウム・六フッ
化リン（ＬｉＰＦａ ）を１モル／ｌで溶解したものを
電解液として使用して第４図に示す電池を組み立てた。Using the above battery positive electrode, a lithium foil punched to a specified size was used as the negative electrode, and lithium/phosphorus hexafluoride (LiPFa) was added at 1 mol/l in a mixed solvent of propylene carbonate and ethylene carbonate (volume ratio 1:1). Using the dissolved solution as an electrolyte, a battery shown in FIG. 4 was assembled.
ここで、第４図において、１は正極、２はステンレスス
チール製の正極集電体で正極１と集電体２とは一体化さ
れており、集電体２は金属板からなるスペーサー３にス
ポット溶接されており、またこのスペーサー３は正極缶
４の内面にスポット溶接されている。５は負極、６は負
極集電体で、負極５は負極缶７の内底面に固着した負極
集電体６にスポット溶接されている。更に８は双六質プ
ロピレンよりなるセパレーターであり、これに前記電解
液が含浸されている。なお、９は絶縁バッキングである
。また、電池寸法は直径２０．０ｍ。Here, in FIG. 4, 1 is a positive electrode, 2 is a positive electrode current collector made of stainless steel, and the positive electrode 1 and current collector 2 are integrated, and the current collector 2 is attached to a spacer 3 made of a metal plate. This spacer 3 is spot welded to the inner surface of the positive electrode can 4. 5 is a negative electrode, 6 is a negative electrode current collector, and the negative electrode 5 is spot-welded to the negative electrode current collector 6 fixed to the inner bottom surface of the negative electrode can 7. Furthermore, 8 is a separator made of staghorn propylene, which is impregnated with the electrolytic solution. Note that 9 is an insulating backing. In addition, the battery dimensions are 20.0m in diameter.
厚さ１．６鶴である◎
この電池を充放電電流１ｍＡにおいて放電終止電圧２．
ＯＶ、充電終止電圧３．５ｖで充放電を繰り返した。こ
の時のサイクル特性を第５図に示す。The thickness of this battery is 1.6 mm. This battery has a discharge end voltage of 2.6 mm at a charging/discharging current of 1 mA.
Charging and discharging were repeated at OV and a charge end voltage of 3.5V. The cycle characteristics at this time are shown in FIG.
また、比較のため、上記比較例で作成した正極シートを
電池正極として用い、上記と同様の電池を組み立て同様
にサイクル特性を調べた。結果を第５図に併記する。For comparison, a battery similar to that described above was assembled using the positive electrode sheet prepared in the above comparative example as a battery positive electrode, and its cycle characteristics were examined in the same manner. The results are also shown in Figure 5.
第５図に示した結果から、本発明の正極シートを正極に
用いたリチウム二次電池は、優れたサイクル特性を示す
ことが確認された。From the results shown in FIG. 5, it was confirmed that a lithium secondary battery using the positive electrode sheet of the present invention as a positive electrode exhibited excellent cycle characteristics.
第１図は実施例１の正極シートの作成直後のＸ線回折チ
ャート、第２図は同正極シートを２４時間放置した後の
Ｘ線回折チャート、第３図は比較例の正極シートのＸ線
回折チャート、第４図は参考例で組み立てた電池を示す
断面図。第５図は参考例で組み立てた電池のサイクル特
性を示すグラフである。
１・・・正極、２・・・正極集電体、３・・・スペーサ
ー４・・・正極缶、５・・・負極、６・・・負極集電体
、７・・・負極缶、８・・・セパレーター、９・・・絶
縁バッキング。Figure 1 is an X-ray diffraction chart of the positive electrode sheet of Example 1 immediately after its creation, Figure 2 is an X-ray diffraction chart of the same positive electrode sheet after it has been left for 24 hours, and Figure 3 is an X-ray diffraction chart of the positive electrode sheet of Comparative Example. Diffraction chart, FIG. 4 is a sectional view showing a battery assembled in a reference example. FIG. 5 is a graph showing the cycle characteristics of the battery assembled in the reference example. DESCRIPTION OF SYMBOLS 1... Positive electrode, 2... Positive electrode current collector, 3... Spacer 4... Positive electrode can, 5... Negative electrode, 6... Negative electrode current collector, 7... Negative electrode can, 8 ...Separator, 9...Insulating backing.
Claims (1)
された正極合剤シートと金属箔集電体とを導電性接着剤
で接着して一体化させた正極シートにおいて、上記導電
性接着剤として、２００℃以上の耐熱性を有する高分子
物質と導電剤とを含有する組成物を使用したことを特徴
とするリチウム電池用正極シート。1. In a positive electrode sheet in which a positive electrode mixture sheet formed by adding a conductive agent and a binder to a positive electrode active material and a metal foil current collector are bonded and integrated with a conductive adhesive, the above-mentioned conductive adhesive is used. A positive electrode sheet for a lithium battery, characterized in that a composition containing a polymer substance having heat resistance of 200° C. or higher and a conductive agent is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021139A JPH03225750A (en) | 1990-01-30 | 1990-01-30 | Positive electrode sheet for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021139A JPH03225750A (en) | 1990-01-30 | 1990-01-30 | Positive electrode sheet for lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03225750A true JPH03225750A (en) | 1991-10-04 |
Family
ID=12046567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021139A Pending JPH03225750A (en) | 1990-01-30 | 1990-01-30 | Positive electrode sheet for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03225750A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692833A1 (en) * | 1994-07-08 | 1996-01-17 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| US5693307A (en) * | 1995-06-07 | 1997-12-02 | Duracell, Inc. | Process for making a lithiated lithium manganese oxide spinel |
| KR19980059084A (en) * | 1996-12-30 | 1998-10-07 | 손욱 | Pretreatment method of the electrode plate for lithium battery |
| JP2000011991A (en) * | 1998-06-25 | 2000-01-14 | Shin Kobe Electric Mach Co Ltd | Organic electrolyte secondary battery |
| KR100362281B1 (en) * | 2000-04-12 | 2002-11-23 | 삼성에스디아이 주식회사 | Lithium ion polymer battery using cathod current collector coated electron-conductive polymer |
-
1990
- 1990-01-30 JP JP2021139A patent/JPH03225750A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692833A1 (en) * | 1994-07-08 | 1996-01-17 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| US5693307A (en) * | 1995-06-07 | 1997-12-02 | Duracell, Inc. | Process for making a lithiated lithium manganese oxide spinel |
| KR19980059084A (en) * | 1996-12-30 | 1998-10-07 | 손욱 | Pretreatment method of the electrode plate for lithium battery |
| JP2000011991A (en) * | 1998-06-25 | 2000-01-14 | Shin Kobe Electric Mach Co Ltd | Organic electrolyte secondary battery |
| KR100362281B1 (en) * | 2000-04-12 | 2002-11-23 | 삼성에스디아이 주식회사 | Lithium ion polymer battery using cathod current collector coated electron-conductive polymer |
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