JPH0765862A - Nonaqueous solvent secondary battery - Google Patents
Nonaqueous solvent secondary batteryInfo
- Publication number
- JPH0765862A JPH0765862A JP5209388A JP20938893A JPH0765862A JP H0765862 A JPH0765862 A JP H0765862A JP 5209388 A JP5209388 A JP 5209388A JP 20938893 A JP20938893 A JP 20938893A JP H0765862 A JPH0765862 A JP H0765862A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- electrode body
- secondary battery
- positive electrode
- 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
- 239000002904 solvent Substances 0.000 title claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000004804 winding Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Inert Electrodes (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、負極体の集電体が炭素
繊維シートである非水溶媒二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous solvent secondary battery in which the negative electrode current collector is a carbon fiber sheet.
【０００２】[0002]
【従来の技術】近年、電子機器の発達に伴い、小型で軽
量かつエネルギー密度が高く、さらに繰り返して使用可
能な二次電池の開発が要望されている。この種の二次電
池としては、負極にリチウムを吸蔵・放出可能な炭素質
材料を、正極にコバルト、ニッケル又はマンガンなどを
含むリチウム含有複合酸化物を用いたものが知られてい
る。2. Description of the Related Art In recent years, with the development of electronic equipment, there has been a demand for the development of a secondary battery that is small, lightweight, has a high energy density, and can be used repeatedly. Known secondary batteries of this type include a carbonaceous material capable of inserting and extracting lithium in the negative electrode and a lithium-containing composite oxide containing cobalt, nickel, manganese, or the like in the positive electrode.
【０００３】これらの電池の負極体は、図１に縦断面図
を示すように、リチウムを吸蔵・放出可能な炭素質材料
を負極活物質層（１）として、これに水溶媒系結着剤又
は非水溶媒系結着剤を加えてスラリー状にし、厚さ１０
〜５０μm の銅、ニッケルなどからなる金属製薄板の負
極集電体（２）の片面又は両面に塗布し、これを圧延、
乾燥したものが用いられている。The negative electrode body of these batteries has a carbonaceous material capable of occluding / releasing lithium as a negative electrode active material layer (1) as shown in a vertical sectional view in FIG. Alternatively, a non-aqueous solvent binder is added to form a slurry, and the thickness is 10
Apply to one or both sides of the negative electrode current collector (2), which is a thin metal plate made of copper, nickel or the like having a thickness of up to 50 μm, and roll it.
The dried one is used.
【０００４】しかしながら、従来の非水溶媒二次電池で
は、負極の集電体に銅（比重８．９）、ニッケル（比重
８．８）など比重の大きい金属を使用しているので、リ
チウムを吸蔵した炭素材料を負極に用いているにもかか
わらず、電池の単位重量当りのエネルギー密度が大きく
ないという問題があった。However, in a conventional non-aqueous solvent secondary battery, a metal having a large specific gravity such as copper (specific gravity 8.9) and nickel (specific gravity 8.8) is used as a current collector of the negative electrode, so that lithium is not used. Despite the use of the occluded carbon material for the negative electrode, there is a problem that the energy density per unit weight of the battery is not large.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上述
した問題を解決するために、軽量な負極集電体を用いる
ことによって、高い単位重量当りのエネルギー密度を有
する非水溶媒二次電池を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems by using a light-weight negative electrode current collector, thereby providing a non-aqueous solvent secondary battery having a high energy density per unit weight. Is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明はリチウムを吸蔵
及び放出可能な炭素質材料からなる負極体、セパレータ
ならびにリチウム含有複合酸化物を正極活物質とする正
極体を、この順序で一体的に積層又は巻回してなる電池
要素を具備する非水溶媒二次電池において、該負極体の
集電体が炭素繊維シートである非水溶媒二次電池に関す
る。Means for Solving the Problems The present invention integrally forms a negative electrode body made of a carbonaceous material capable of occluding and releasing lithium, a separator, and a positive electrode body having a lithium-containing composite oxide as a positive electrode active material in this order. A non-aqueous solvent secondary battery comprising a laminated or wound battery element, wherein the negative electrode current collector is a carbon fiber sheet.
【０００７】負極体は、次のようにして作製する。すな
わち、有機化合物の焼成体である炭素質材料に、カルボ
キシメチルセルロース等の水溶媒系結着剤又はエチレン
・プロピレン・ジエン三元共重合体等の非水溶媒系結着
剤を加えてスラリー状に調製する。次いで、１０〜２０
μm の厚さで、比重２．０以下の軽量な炭素繊維シート
を集電体とし、その両面または片面に上記スラリーを塗
布し、圧延、乾燥する。The negative electrode body is manufactured as follows. That is, to a carbonaceous material which is a fired body of an organic compound, an aqueous solvent-based binder such as carboxymethyl cellulose or a non-aqueous solvent-based binder such as an ethylene / propylene / diene terpolymer is added to form a slurry. Prepare. Then 10-20
A lightweight carbon fiber sheet having a thickness of μm and a specific gravity of 2.0 or less is used as a current collector, and the slurry is applied to both sides or one side of the current collector, rolled and dried.
【０００８】本発明で用いる炭素繊維には、石油ピッチ
を紡糸した繊維を、例えば窒素雰囲気中で１，２００℃
で２時間熱処理したものや、ポリアクリロニトリル、レ
ーヨンなどの有機繊維を、例えば窒素雰囲気中で１，４
００℃で５時間熱処理したものを用いることができる。
このようにして得られる炭素繊維は従来用いられていた
金属製集電体に比べて軽量であり、また熱処理条件によ
っては、リチウムを吸蔵させ負極容量を増大させるとい
う利点もある。また、このようにして得られる炭素繊維
は、シート状にして使用することができるが、ペーパー
状として用いるのが好ましい。The carbon fiber used in the present invention is a fiber obtained by spinning petroleum pitch, for example, in a nitrogen atmosphere at 1,200 ° C.
Heat treated for 2 hours at room temperature or organic fibers such as polyacrylonitrile and rayon in a nitrogen atmosphere for 1,4
What was heat-processed at 00 degreeC for 5 hours can be used.
The carbon fiber thus obtained is lighter in weight than the conventionally used metal current collector, and has an advantage that lithium is occluded and the negative electrode capacity is increased depending on heat treatment conditions. The carbon fiber thus obtained can be used in the form of a sheet, but is preferably used in the form of paper.
【０００９】図３は、このようにして作製した負極の断
面図を示したものであり、３１はリチウムを吸蔵・放出
可能な炭素質材料層からなる負極活物質層、３２は負極
集電体の炭素繊維シートである。FIG. 3 is a cross-sectional view of the negative electrode thus manufactured, in which 31 is a negative electrode active material layer made of a carbonaceous material layer capable of absorbing and releasing lithium, and 32 is a negative electrode current collector. Is a carbon fiber sheet.
【００１０】正極体には、コバルト、ニッケル又はマン
ガンなどを含むリチウム含有複合酸化物に導電剤、結着
剤を混合したものを、チタン又はアルミニウムのシート
状集電体に塗布し、これを圧延、乾燥したものを用い
る。As the positive electrode body, a mixture of a lithium-containing composite oxide containing cobalt, nickel, manganese, etc., with a conductive agent and a binder is applied to a titanium or aluminum sheet current collector and rolled. , Use dried ones.
【００１１】またセパレータには、ポリプロピレンもし
くはポリエチレンの多孔質シートを用いる。As the separator, a polypropylene or polyethylene porous sheet is used.
【００１２】非水電解液には、例えば、リチウム塩を電
解質として、これを有機溶媒に溶解したものを用いる。As the non-aqueous electrolyte, for example, a lithium salt as an electrolyte, which is dissolved in an organic solvent, is used.
【００１３】ここで、上記有機溶媒にはプロピレンカー
ボネート、エチレンカーボネート、１，２−ジメトキシ
エタン、１，２−ジエトキシエタン、γ−ブチロラクト
ン、テトラヒドロフラン、１，３−ジオキソラン、４−
メチル−１，３−ジオキソラン、ジエチルエーテル、ス
ルホラン、メチルスルホラン、アセトニトリル、プロピ
オニトリルなどの単独もしくは複数の混合溶媒を用いる
ことができる。上記電解質には、公知のものを用いるこ
とが可能であって、具体的には、ＬｉＣｌＯ4、ＬｉＡ
ｓＦ6 、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＢ（Ｃ6 Ｈ5)
4 、ＬｉＣｌ、ＬｉＢｒ、ＣＨ3 ＳＯなどを用いること
ができる。Here, as the organic solvent, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, 4-
A single solvent or a plurality of mixed solvents such as methyl-1,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile and propionitrile can be used. Known electrolytes may be used as the electrolyte, and specifically, LiClO 4 , LiA
sF 6 , LiPF 6 , LiBF 4 , LiB (C 6 H 5 ).
4 , LiCl, LiBr, CH 3 SO and the like can be used.
【００１４】次に本発明の電池構成について述べる。図
２は本発明の非水溶媒二次電池の断面図であり、積層電
極体（３）は、リチウム含有複合酸化物、導電剤、結着
剤などからなる帯状正極４と炭素質材料からなる帯状負
極（５）との間に、帯状セパレータ（６）を介在させて
渦巻状に巻回することにより構成される。帯状セパレー
タ（６）は、帯状正極（４）及び帯状負極（５）より少
なくとも電極の上端又は下端において幅広になってい
る。したがって、セパレータ（６）の上端及び下端は、
積層電極体（３）の上端面および下端面において、帯状
正極（４）及び帯状負極（５）より幅広に突出する突出
部（７）を形成している。帯状正極（４）にはアルミニ
ウム、チタン等の板状正極リード（８）が、また帯状負
極（５）にはニッケル、チタン製等の板状負極リード
（９）が、それぞれの電極への集電のために取り付けら
れている。これらの電池要素は、積層電極体（３）の上
下端面にそれぞれ配置される円盤状の隔離板（１０）及
び（１１）とともに、ステンレス製又はニッケルめっき
を施した鉄製などの電池外装缶（１２）内に収納されて
いる。隔離板（１０）及び（１１）は合成樹脂などの絶
縁材料で作られていて、その中心に中心孔をそれぞれ備
えている。また、上端面の隔離板（１０）は閉蓋用蓋体
（１３）、安全弁（１４）及び中蓋（１５）を、また下
端面の隔離板（１１）は電池外装缶（１２）を、それぞ
れ積層電極体（３）に対して隔離し、電気的に絶縁して
いる。Next, the battery structure of the present invention will be described. FIG. 2 is a cross-sectional view of the non-aqueous solvent secondary battery of the present invention. The laminated electrode body (3) is composed of a strip-shaped positive electrode 4 including a lithium-containing composite oxide, a conductive agent, a binder and the like, and a carbonaceous material. It is formed by spirally winding a strip separator (6) between the strip negative electrode (5) and the strip negative electrode (5). The strip separator (6) is wider than the strip positive electrode (4) and the strip negative electrode (5) at least at the upper or lower ends of the electrodes. Therefore, the upper and lower ends of the separator (6) are
On the upper end surface and the lower end surface of the laminated electrode body (3), there are formed protrusions (7) which protrude wider than the strip-shaped positive electrode (4) and the strip-shaped negative electrode (5). A strip-shaped positive electrode (4) is provided with a plate-shaped positive electrode lead (8) made of aluminum, titanium or the like, and a strip-shaped negative electrode (5) is provided with a plate-shaped negative electrode lead (9) made of nickel, titanium, etc. It is installed for electricity. These battery elements include disc-shaped separators (10) and (11) arranged on the upper and lower end surfaces of the laminated electrode body (3), as well as a battery outer can (12) made of stainless steel or nickel-plated iron. ) Is stored inside. The separators (10) and (11) are made of an insulating material such as synthetic resin and have a central hole in the center thereof. Further, the separator (10) on the upper end surface is the lid (13) for closing the lid, the safety valve (14) and the inner lid (15), and the separator (11) on the lower end surface is the battery outer can (12). Each is isolated from the laminated electrode body (3) and electrically insulated.
【００１５】電池外装缶（１２）の上端面は開放されて
おり、上端部（１６）に上方開口が設けられている。封
口板を構成する閉蓋用蓋体（１３）、安全弁（１４）及
び中蓋（１５）が、上方開口を閉塞するために電池外装
缶（１２）の上端部（１６）に取り付けられている。す
なわち、閉蓋用蓋体（１３）、安全弁（１４）及び中蓋
（１５）のそれぞれの外周面は互いに重ね合わされ、こ
の重ね合わせ部の外側に封口ガスケット（１７）が嵌め
込まれている。そして、この重ね合わせ部が、封口ガス
ケット（１７）を介して電池外装缶（１２）の上端部
（１６）にかしめ止めされることにより、積層電極体
（３）等の電池要素は電池外装缶（１２）内に密封され
る。The upper end surface of the battery outer can (12) is open and the upper end (16) is provided with an upper opening. A lid (13) for closing the lid, a safety valve (14), and an inner lid (15) that form a sealing plate are attached to the upper end (16) of the battery outer can (12) to close the upper opening. . That is, the outer peripheral surfaces of the lid body (13) for closing the lid, the safety valve (14) and the inner lid (15) are overlapped with each other, and the sealing gasket (17) is fitted on the outer side of the overlapping portion. Then, the overlapped portion is caulked to the upper end portion (16) of the battery outer can (12) through the sealing gasket (17), so that the battery element such as the laminated electrode body (3) can be attached to the battery outer can. It is sealed in (12).
【００１６】また、閉蓋用蓋体（１３）には、電池内に
ガスなどが発生して電池内圧が所定値以上に上昇した場
合に、安全弁（１４）を開裂するための突起が備えられ
ている。さらに、閉蓋用蓋体（１３）と中蓋（１５）に
は、ガスを逃すためのガス抜き穴も設けられている。板
状正極リード（８）は上端面の隔離板（１０）の中心孔
を通って中蓋（１５）まで延び、板状負極リード（９）
は下端面の隔離板（１１）の中心孔を通って電池外装缶
（１２）の底面まで延び、それぞれそこで溶接されてい
る。The lid (13) for closing the lid is provided with a protrusion for opening the safety valve (14) when gas or the like is generated in the battery and the internal pressure of the battery rises above a predetermined value. ing. Further, the lid body (13) for closing the lid and the inner lid (15) are also provided with gas vent holes for letting out gas. The plate-shaped positive electrode lead (8) extends through the center hole of the separator plate (10) on the upper end surface to the inner lid (15), and the plate-shaped negative electrode lead (9).
Extends through the center hole of the separator plate (11) at the lower end surface to the bottom surface of the battery outer can (12) and is welded there.
【００１７】[0017]
【実施例】以下に、本発明を実施例及び比較例によって
詳細に説明する。The present invention will be described in detail below with reference to examples and comparative examples.
【００１８】実施例１ （１）負極体の作製 ノボラック樹脂を窒素雰囲気中で９５０℃の温度で１時
間焼成した。次いで、これを同じく窒素雰囲気中で１，
５００℃の温度で２時間処理することによって炭素化し
た。このようにして得られた炭素化物を破砕して、平均
径が１０μm の粉末とした。次に、この粉末にカルボキ
シメチルセルロースとスチレンブタジエンゴムの混合物
（重量比１：２）である水溶媒系結着剤を加えてスラリ
ーを調製した。このスラリーを、厚さ２０μm のペーパ
ー状炭素繊維からなる集電体の両面に塗布し、圧延、乾
燥して負極体（５）とした。このようにして作製した負
極体は、幅４０mm、長さ３５０mm、厚さ０．２５mmの形
状に裁断して用いた。Example 1 (1) Preparation of Negative Electrode Body A novolak resin was fired in a nitrogen atmosphere at a temperature of 950 ° C. for 1 hour. Then, in the same nitrogen atmosphere,
It was carbonized by treatment at a temperature of 500 ° C. for 2 hours. The carbonized material thus obtained was crushed to obtain a powder having an average diameter of 10 μm. Next, a slurry was prepared by adding an aqueous solvent-based binder, which is a mixture of carboxymethyl cellulose and styrene-butadiene rubber (weight ratio 1: 2), to this powder. This slurry was applied to both sides of a current collector made of paper-like carbon fiber having a thickness of 20 μm, rolled and dried to obtain a negative electrode body (5). The negative electrode body thus produced was cut into a shape having a width of 40 mm, a length of 350 mm and a thickness of 0.25 mm and used.
【００１９】（２）積層電極体の作製 図２に従って説明する。上記の方法により作製した帯
状負極（５）；ＬｉＣｏＯ2 を活物質として用いた帯
状正極（４）；及びエチレンカーボネートとプロピレ
ンカーボネート１：１（容量比）の混合溶媒に、ＬｉＢ
Ｆ4 を１モル/Lの濃度で溶解した電解液を含浸させたポ
リプロピレン多孔質シートからなるセパレータ（６）
を、この順序で帯状に積層して帯状負極（５）が外側に
なるように巻回して積層電極体（３）を作製した。(2) Fabrication of laminated electrode body A description will be given with reference to FIG. A strip negative electrode (5) produced by the above method; a strip positive electrode (4) using LiCoO 2 as an active material; and a mixed solvent of ethylene carbonate and propylene carbonate 1: 1 (volume ratio), LiB
Separator (6) consisting of a polypropylene porous sheet impregnated with an electrolytic solution in which F 4 is dissolved at a concentration of 1 mol / L
Was laminated in this order in a strip shape and wound so that the strip negative electrode (5) was on the outer side to prepare a laminated electrode body (3).
【００２０】（３）電池の組立て 図２に従って説明する。上記のようにして作製した巻回
した円筒形の積層電極体（３）を、底部に隔離板（１
１）を着設し負極端子を兼ねる有底電池外装缶（１２）
内に収納し、中蓋（１５）、安全弁（１４）、及び閉蓋
用蓋体（１３）によって封口して、Ａサイズ（外径１７
mm、高さ５０mm）電池を組立てた。(3) Assembling the Battery A battery will be described with reference to FIG. The wound cylindrical laminated electrode body (3) produced as described above is provided with a separator (1
Bottomed battery outer can (12) that is also equipped with 1) and doubles as a negative electrode terminal
It is housed inside and sealed by the inner lid (15), the safety valve (14), and the lid body (13) for closing the lid, and the A size (outer diameter 17
mm, height 50 mm) A battery was assembled.
【００２１】（４）充放電サイクル試験 このようにして組立てた電池を、０．５Ａの電流で４．
２Ｖになるまで充電し、次に０．５Ａの電流で２．７Ｖ
まで放電して、この充放電を１０サイクル繰り返した。
このときの放電容量を測定し、電池の単位重量当りのエ
ネルギー密度を算出したところ、９３．６Wh/kg であっ
た。(4) Charge / Discharge Cycle Test The battery thus assembled was tested at a current of 0.5 A for 4.
Charge to 2V, then 2.7V with 0.5A current
And the charging and discharging were repeated 10 cycles.
The discharge capacity at this time was measured, and the energy density per unit weight of the battery was calculated to be 93.6 Wh / kg.
【００２２】比較例１ 集電体としてペーパー状の炭素繊維の代わりに厚さ２０
μm の銅板を用いた以外は、実施例１と同様にして積層
電極体（３）を作製し、電池を組み立て充放電サイクル
試験を行った。このときの電池単位重量当りのエネルギ
ー密度は、８６．４Wh/kg であった。Comparative Example 1 Instead of paper-like carbon fiber as a current collector, a thickness of 20 was used.
A laminated electrode body (3) was prepared in the same manner as in Example 1 except that a copper plate of μm was used, a battery was assembled, and a charge / discharge cycle test was conducted. The energy density per unit weight of the battery at this time was 86.4 Wh / kg.
【００２３】実施例２ 角形に巻回した積層電極を収納した縦３４mm、横８mm、
高さ４８mmの角形電池とした以外は、実施例１と同様に
して負極を作製し、積層電極を作製し、電池を組立て充
放電サイクル試験を行った。このときの電池単位重量当
りのエネルギー密度は９２Wh/kg であった。Example 2 34 mm in length, 8 mm in width, accommodating laminated electrodes wound in a square shape,
A negative electrode was prepared in the same manner as in Example 1 except that the prismatic battery had a height of 48 mm, a laminated electrode was prepared, and the battery was assembled and subjected to a charge / discharge cycle test. The energy density per unit weight of the battery at this time was 92 Wh / kg.
【００２４】比較例２ 角形に巻回した積層電極を収納した縦３４mm、横８mm、
高さ４８mmの角形電池とした以外は、比較例１と同様に
して負極を作製し、積層電極を作製し、電池を組立て充
放電サイクル試験を行った。このときの電池単位重量当
りのエネルギー密度は８３Wh/kg であった。Comparative Example 2 34 mm in length, 8 mm in width, containing a laminated electrode wound in a rectangular shape,
A negative electrode was prepared in the same manner as in Comparative Example 1 except that a prismatic battery having a height of 48 mm was prepared, a laminated electrode was prepared, and the battery was assembled and subjected to a charge / discharge cycle test. The energy density per unit weight of the battery at this time was 83 Wh / kg.
【００２５】実施例３ 負極体の長さを３８０mmとして電極面積を大きくした以
外は、実施例１と同様にして負極を作製し、積層電極を
作製し、電池を組立て充放電サイクル試験を行った。こ
のときの電池単位重量当りのエネルギー密度は９５Wh/k
g であった。Example 3 A negative electrode was prepared in the same manner as in Example 1 except that the length of the negative electrode was 380 mm to increase the electrode area, a laminated electrode was prepared, a battery was assembled, and a charge / discharge cycle test was conducted. . Energy density per unit weight of the battery at this time is 95Wh / k
It was g.
【００２６】比較例３ 負極体の長さを３８０mmとして電極面積を大きくした以
外は、比較例１と同様にして負極を作製し、積層電極を
作製し、電池を組立て、充放電サイクル試験を行った。
このときの電池単位重量当りのエネルギー密度は８８Wh
/kg であった。Comparative Example 3 A negative electrode was prepared in the same manner as in Comparative Example 1 except that the length of the negative electrode was 380 mm to increase the electrode area, a laminated electrode was prepared, a battery was assembled, and a charge / discharge cycle test was conducted. It was
The energy density per unit weight of the battery at this time is 88Wh.
It was / kg.
【００２７】[0027]
【発明の効果】負極体の集電体に炭素繊維シートを用い
ることにより、電池の単位重量当たりのエネルギー密度
の大きな非水溶媒二次電池を提供できる。By using a carbon fiber sheet for the current collector of the negative electrode, a non-aqueous solvent secondary battery having a large energy density per unit weight of the battery can be provided.
【図１】従来のリチウム二次電池の負極体の縦断面図で
ある。FIG. 1 is a vertical sectional view of a negative electrode body of a conventional lithium secondary battery.
【図２】本発明にかかる円筒形リチウム二次電池の縦断
面図である。FIG. 2 is a vertical sectional view of a cylindrical lithium secondary battery according to the present invention.
【図３】本発明の一実施例である負極体の縦断面図であ
る。FIG. 3 is a vertical cross-sectional view of a negative electrode body that is an example of the present invention.
１…負極活物質層 ２…負極集電体 ３…積層電極体 ４…帯状正極 ５…帯状負極 ６…セパレータ ７…突出部 ８…板状正極リード ９…板状負極リード １０，１１…隔離板 １２…電池外装缶 １３…閉蓋用蓋体 １４…安全弁 １５…中蓋 １６…上端部（上方開口） １７…封口ガスケット ３１…負極活物質層 ３２…負極集電体 DESCRIPTION OF SYMBOLS 1 ... Negative electrode active material layer 2 ... Negative electrode collector 3 ... Laminated electrode body 4 ... Strip positive electrode 5 ... Strip negative electrode 6 ... Separator 7 ... Projection part 8 ... Plate positive electrode lead 9 ... Plate negative electrode lead 10, 11 ... Separator plate 12 ... Battery outer can 13 ... Closing lid 14 ... Safety valve 15 ... Inner lid 16 ... Upper end (upper opening) 17 ... Sealing gasket 31 ... Negative electrode active material layer 32 ... Negative electrode current collector
Claims (1)
料からなる負極体、セパレータならびにリチウム含有複
合酸化物を正極活物質とする正極体を、この順序で一体
的に積層又は巻回してなる電池要素を具備する非水溶媒
二次電池において、該負極体が、炭素繊維シートからな
る集電体の両面又は片面に炭素質材料からなるスラリー
を塗布、乾燥したものであることを特徴とする非水溶媒
二次電池。1. A battery in which a negative electrode body made of a carbonaceous material capable of inserting and extracting lithium, a separator, and a positive electrode body having a lithium-containing composite oxide as a positive electrode active material are integrally laminated or wound in this order. In a non-aqueous solvent secondary battery including an element, the negative electrode body is obtained by applying a slurry made of a carbonaceous material on both sides or one side of a current collector made of a carbon fiber sheet and then drying it. Water solvent secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5209388A JPH0765862A (en) | 1993-08-24 | 1993-08-24 | Nonaqueous solvent secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5209388A JPH0765862A (en) | 1993-08-24 | 1993-08-24 | Nonaqueous solvent secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0765862A true JPH0765862A (en) | 1995-03-10 |
Family
ID=16572085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5209388A Pending JPH0765862A (en) | 1993-08-24 | 1993-08-24 | Nonaqueous solvent secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0765862A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413486B2 (en) | 1998-06-05 | 2002-07-02 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous secondary battery, constituent elements of battery, and materials thereof |
| JP2008108740A (en) * | 2007-12-03 | 2008-05-08 | Showa Denko Kk | Electrode material for battery and secondary battery |
-
1993
- 1993-08-24 JP JP5209388A patent/JPH0765862A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413486B2 (en) | 1998-06-05 | 2002-07-02 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous secondary battery, constituent elements of battery, and materials thereof |
| JP2008108740A (en) * | 2007-12-03 | 2008-05-08 | Showa Denko Kk | Electrode material for battery and secondary battery |
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