JP2006120401A - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary battery Download PDFInfo
- Publication number
- JP2006120401A JP2006120401A JP2004305509A JP2004305509A JP2006120401A JP 2006120401 A JP2006120401 A JP 2006120401A JP 2004305509 A JP2004305509 A JP 2004305509A JP 2004305509 A JP2004305509 A JP 2004305509A JP 2006120401 A JP2006120401 A JP 2006120401A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- aluminum
- current collector
- secondary battery
- electrolyte secondary
- 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
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、有機電解液二次電池に関するものである。 The present invention relates to an organic electrolyte secondary battery.
近年においては、高出力、高エネルギー密度の電池として、非水電解液を用いた電池であるリチウム電池やリチウム二次電池が多くの電子機器などの電源として用いられている。これらの非水電解液電池は、電解液が水溶液である電池に比べて、放電電圧が高く、低温特性や長期保存特性が優れている特徴があり、様々な形状のものが販売されている。それらの中で、コイン形形状を有したものは、小型かつ軽量であり、またその構成部品が少なく製造が容易であることから大量生産されている。最近では、充放電が可能であるコイン形リチウム二次電池が多く開発されており、例えば、エネルギー密度の向上から正極活物質としてコバルト酸リチウム、外装ケースにアルミニウムを用いたコイン形有機電解液二次電池があり、腕時計などの主電源用途のほかに、電子機器のバックアップ用途などで広く用いられている。 In recent years, lithium batteries and lithium secondary batteries, which are batteries using a non-aqueous electrolyte, have been used as power sources for many electronic devices as batteries with high output and high energy density. These non-aqueous electrolyte batteries are characterized by high discharge voltage, excellent low-temperature characteristics and long-term storage characteristics as compared with batteries in which the electrolyte solution is an aqueous solution, and are available in various shapes. Among them, those having a coin-shaped shape are mass-produced because they are small and light and have few components and are easy to manufacture. Recently, many coin-type lithium secondary batteries that can be charged and discharged have been developed. For example, a coin-type organic electrolyte solution that uses lithium cobaltate as a positive electrode active material and aluminum as an outer case for improving energy density. There is a secondary battery, and it is widely used for backup of electronic devices in addition to the main power supply for watches and the like.
このコイン形有機電解液二次電池は、通常、以下のような構造をしている。 This coin-type organic electrolyte secondary battery usually has the following structure.
上部が開口する負極側の外装缶の中に、負極ペレットとセパレータと正極ペレットとが積層され、更に所定の非水電解液が収容されていて、負極側の外装缶の開口は、電気絶縁性のガスケットを介して正極側の外装ケースにより密閉されている。また電極からの集電方式は、電極と外装缶とを集電体を介して接触する方式が一般である。そして集電体としては、導電性を向上させるためにカーボンペーストを塗布したことにより形成されるカーボン薄膜層を用いた方式や、特許文献１に示されるような網目構造が用いられるものがある。
しかしながら、外装ケースにアルミニウムを用い、正極集電体にカーボンペーストを塗布した事より形成されるカーボン薄膜層を有した電池系で、正極電位が４Ｖ（リチウム基準電位）以上となる状態では、カーボン薄膜層とアルミニウム面との間でアルミニウムの溶解反応が起こり、同時に酸化皮膜を生成する反応も起こっている。その結果、酸化皮膜生成のための酸素濃度が低下し、その反応が律速になった時アルミニウム面が表面に露出する。そして、電解液中に水分が多い環境では、電解液中に酸を生じ、表面に露出しているアルミニウム面を腐蝕し、長期信頼性を損なってしまうため、アルミニウムの腐食を防止する対策を講じる必要性があった。 However, in a battery system having a carbon thin film layer formed by applying aluminum paste to the positive electrode current collector and applying a carbon paste to the positive electrode current collector, in a state where the positive electrode potential is 4 V (lithium reference potential) or more, carbon A dissolution reaction of aluminum occurs between the thin film layer and the aluminum surface, and at the same time, a reaction that forms an oxide film also occurs. As a result, the oxygen concentration for forming the oxide film decreases, and when the reaction becomes rate-limiting, the aluminum surface is exposed on the surface. And in an environment where there is a lot of moisture in the electrolytic solution, acid is generated in the electrolytic solution, and the aluminum surface exposed on the surface is corroded and the long-term reliability is impaired. Therefore, measures are taken to prevent corrosion of aluminum. There was a need.
上記課題を解決するために、本発明の有機電解液二次電池は、正極、負極、電解液およびセパレータを備え、前記正極が、正極活物質と正極外装缶と正極集電体を有し、前記正極活物質が、軽金属を吸蔵および離脱することが可能で正極電位が４Ｖ（リチウム基準）
以上である化合物からなる群より選ばれる少なくとも１種の化合物であり、前記正極外装缶が、アルミニウムあるいは正極と接する面にアルミニウム層を有したステンレスからなり、前記正極集電体が、アルミニウムあるいはアルミニウム合金からなるとともに網目突起形状を有することを特徴とする。
In order to solve the above problems, an organic electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and the positive electrode includes a positive electrode active material, a positive electrode outer can, and a positive electrode current collector, The positive electrode active material can occlude and release light metals, and the positive electrode potential is 4 V (lithium reference).
It is at least one compound selected from the group consisting of the above compounds, and the positive electrode outer can is made of aluminum or stainless steel having an aluminum layer on the surface in contact with the positive electrode, and the positive electrode current collector is aluminum or aluminum. It is made of an alloy and has a mesh projection shape.
以下、本発明の実施の形態を、図面を参照しながら説明をする。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は本発明の一実施形態に係る二次電池の断面構造を表すものである。この二次電池はいわゆるコイン型といわれるものであり、外装缶１１内に収容された円板状の負極ペレット１２と外装ケース１３に収容された円板状の正極ペレット１４とがセパレータ１５を介して対向に配置されている。外装缶１１および外装ケース１３の内部は電解液（図示せず）により満たされており、外装缶１１および外装ケース１３の周縁部は絶縁ガスケット１７を介してかしめられることにより密閉されている。外装缶１１および外装ケース１３は、アルミニウムあるいはステンレスなどの金属によりそれぞれ構成されている。 FIG. 1 shows a cross-sectional structure of a secondary battery according to an embodiment of the present invention. This secondary battery is a so-called coin-type battery, and a disk-shaped negative electrode pellet 12 accommodated in an outer can 11 and a disk-shaped positive electrode pellet 14 accommodated in an outer case 13 are interposed via a separator 15. Are arranged opposite to each other. The interiors of the outer can 11 and the outer case 13 are filled with an electrolytic solution (not shown), and the peripheral portions of the outer can 11 and the outer case 13 are sealed by caulking through an insulating gasket 17. The outer can 11 and the outer case 13 are each made of a metal such as aluminum or stainless steel.
また負極集電体１８は、負極ペレット１２と外装缶１１の間に外装缶１１に接して配置されており、負極集電体１８は、カーボンペーストを塗布した事より形成されるカーボン薄膜層により構成されている。 The negative electrode current collector 18 is disposed between the negative electrode pellet 12 and the outer can 11 in contact with the outer can 11, and the negative electrode current collector 18 is formed of a carbon thin film layer formed by applying a carbon paste. It is configured.
一方正極集電体１９は、正極ペレット１４と外装ケース１３の間に外装ケース１３に接して配置されており、正極集電体１９は、カーボンペーストを塗布した事より形成されるカーボン薄膜層により構成されている。 On the other hand, the positive electrode current collector 19 is disposed in contact with the outer case 13 between the positive electrode pellet 14 and the outer case 13, and the positive electrode current collector 19 is formed by a carbon thin film layer formed by applying a carbon paste. It is configured.
負極ペレット１２は、例えば、負極活物質として軽金属であるリチウムを吸蔵および離脱することが可能な負極材料のいずれか１種または２種以上を含んでおり、必要に応じて黒鉛などの導電剤およびポリフッ化ビニリデンなどの結着剤を含んでいてもよく、リチウムを吸蔵および離脱することが可能な負極材料としては、例えば、黒鉛、チタン酸リチウムなどが挙げられる。 The negative electrode pellet 12 includes, for example, any one or two or more negative electrode materials capable of inserting and extracting lithium, which is a light metal, as a negative electrode active material. Examples of the negative electrode material that may contain a binder such as polyvinylidene fluoride and can occlude and release lithium include graphite and lithium titanate.
正極ペレット１４は、例えば、正極活物質として軽金属であるリチウムを吸蔵および離脱することが可能な正極材料のいずれか１種または２種以上を含んでおり、必要に応じて黒鉛などの導電剤およびポリフッ化ビニリデンなどの結着剤を含んでいてもよく、正極活物質としては、一般式ＬｉxＭＯ2で表されるリチウム複合酸化物あるいはリチウムを含んだ層間化合物が好ましい。なお、Ｍは１種類以上の遷移金属であり、例えば、コバルト、ニッケル、マンガンのうち少なくとも１種類が好ましい。ｘは電池の充放電状態によって異なり、通常０．０５≦ｘ≦１．００の範囲内の値である。このようなリチウム複合酸化物の具体例としては、ＬｉＣｏＯ2，ＬｉＮｉＯ2あるいはスピネル型構造を有するＬｉＭｎ2Ｏ4などが挙げられる。 The positive electrode pellet 14 includes, for example, any one or more of positive electrode materials capable of inserting and extracting lithium, which is a light metal, as a positive electrode active material, and a conductive agent such as graphite and the like, if necessary. A binder such as polyvinylidene fluoride may be included, and the positive electrode active material is preferably a lithium composite oxide represented by the general formula Li x MO 2 or an intercalation compound containing lithium. M is one or more transition metals, and for example, at least one of cobalt, nickel, and manganese is preferable. x varies depending on the charge / discharge state of the battery, and is usually a value in the range of 0.05 ≦ x ≦ 1.00. Specific examples of such a lithium composite oxide include LiCoO 2 , LiNiO 2 or LiMn 2 O 4 having a spinel structure.
セパレータ１５は、負極ペレット１２と正極ペレット１４とを隔離し、両極の接触による短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータ１５は、例えば、ポリエチレン、ポリプロピレンなどによる合成樹脂製の多孔質膜、不織布、またはセラミック製の無機材料よりなる多孔質膜により構成されており、これら２種類以上の多孔質膜を積層した構造とされていてもよい。 The separator 15 separates the negative electrode pellet 12 and the positive electrode pellet 14 and allows lithium ions to pass through while preventing a short circuit due to contact between both electrodes. The separator 15 is made of, for example, a porous film made of a synthetic resin made of polyethylene, polypropylene, or the like, a non-woven fabric, or a porous film made of a ceramic inorganic material, and these two or more kinds of porous films are laminated. It may be a structure.
電解液は、溶媒に電解質塩としてリチウム塩を溶解させたものであり、リチウム塩が電離することによりイオン伝導性を示すようになっている。リチウム塩としては、ＬｉＰＦ6が好ましく電解質の塩濃度は良好なイオン伝導度が得られるように０．１〜２．０ｍｏｌ／ｌとすることが好ましい。また、溶媒としては、エチレンカーボネート、プロピレンカーボネート、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、１・２−ジメトキシエタン、ガンマーブチルラクトンなどの非水溶媒が好ましく、これらのうちいずれか１種または２種以上が混合して用いられる。 The electrolytic solution is obtained by dissolving a lithium salt as an electrolyte salt in a solvent, and exhibits ion conductivity when the lithium salt is ionized. As the lithium salt, LiPF 6 is preferable, and the salt concentration of the electrolyte is preferably 0.1 to 2.0 mol / l so that good ionic conductivity is obtained. The solvent is preferably a non-aqueous solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, gamma-butyl lactone, and any one or two of them. The above is mixed and used.
この二次電池は、例えば、次のようにして製造することができる。 For example, the secondary battery can be manufactured as follows.
まず、正極活物質と導電剤と結着剤とを混合して正極合剤を調整した後、この正極合剤を圧縮成型してペレット形状とすることにより正極ペレット１４を作製する。 First, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and then the positive electrode mixture is compression-molded into a pellet shape to produce a positive electrode pellet 14.
続いて、負極活物質と導電剤と結着剤とを混合して負極合剤を調整した後、この負極合剤を圧縮成型してペレット形状とすることにより負極ペレット１２を作製する。 Subsequently, a negative electrode active material, a conductive agent, and a binder are mixed to prepare a negative electrode mixture, and then the negative electrode mixture is compression-molded to form a pellet, thereby preparing the negative electrode pellet 12.
その後に、外装缶１１の中に、負極ペレット１２、セパレータ１５および正極ペレット１４を積層させ、電解液を注入した後、ガスケット１７を介して外装缶１１と外装ケース１３とをかしめる。これにより、図１に示されるような二次電池が形成される。 Thereafter, the negative electrode pellet 12, the separator 15, and the positive electrode pellet 14 are laminated in the outer can 11, and after the electrolyte is injected, the outer can 11 and the outer case 13 are caulked through the gasket 17. Thereby, a secondary battery as shown in FIG. 1 is formed.
本発明のより具体的な実施の形態について、以下に説明する。正極活物質としてリチウム・コバルト複合酸化物（ＬｉＣｏＯ2）９０質量部と、導電剤であるグラファイト５質量部と、結着剤であるポリフッ化ビニリデン５質量部とを混合して正極合剤を調整した。 More specific embodiments of the present invention will be described below. A positive electrode mixture is prepared by mixing 90 parts by mass of lithium-cobalt composite oxide (LiCoO 2 ) as a positive electrode active material, 5 parts by mass of graphite as a conductive agent, and 5 parts by mass of polyvinylidene fluoride as a binder. did.
また、正極集電体１９は、図２に示されるような網目厚み（ｔ１）０．１５ｍｍ、網目幅（ｗ１）０．１５ｍｍ、各交点での集電体高さ（ｈ１）０．３０μｍ、交点間の幅（ｄ１）２ｍｍ、直径（φ１）７ｍｍである網目状突起を有したものを用いる。なお、この集電体の作製方法は、網目状突起形状と同様の構造を有する鋳型に、加熱し融解した金属アルミニウムを流し込んで冷却した後に、直径７ｍｍの打抜きで抜くことにより作製を行った。 The positive electrode current collector 19 has a mesh thickness (t1) of 0.15 mm, a mesh width (w1) of 0.15 mm, and a current collector height (h1) of 0.30 μm at each intersection as shown in FIG. One having a mesh-like projection having a width (d1) of 2 mm and a diameter (φ1) of 7 mm is used. The current collector was manufactured by pouring metal aluminum that had been heated and melted into a mold having the same structure as that of the mesh-like protrusions, cooling, and then punching out by punching with a diameter of 7 mm.
正極集電体１９と正極合剤を同時に圧縮成型することで直径１０ｍｍ、厚み０．５ｍｍの正極ペレット１４を作製した。 A positive electrode pellet 14 having a diameter of 10 mm and a thickness of 0.5 mm was produced by simultaneously compression-molding the positive electrode current collector 19 and the positive electrode mixture.
また、負極活物質として黒鉛９０質量部と、導電剤であるグラファイト５質量部と、結着剤であるポリフッ化ビニリデン５質量部とを混合して負極合剤を調整した。この負極合剤を圧縮成型して直径１０ｍｍの負極ペレット１２を作製した。 Further, 90 parts by mass of graphite as a negative electrode active material, 5 parts by mass of graphite as a conductive agent, and 5 parts by mass of polyvinylidene fluoride as a binder were mixed to prepare a negative electrode mixture. This negative electrode mixture was compression molded to prepare a negative electrode pellet 12 having a diameter of 10 mm.
厚さ２５μｍのポリプロピレン不織布からなるセパレータ１５を用意し、外装缶１１内に挿入した後、負極ペレット１２、セパレータ１５および正極ペレット１４を順に積層し、電解液を注入した。電解液には、エチレンカーボネートとエチルメチルカーボネートを１：３の質量比で混合した溶媒に電解質塩としてＬｉＰＦ6を１．２５ｍｏｌ／ｌの含有量で溶解させたものを用いた。 A separator 15 made of a polypropylene nonwoven fabric having a thickness of 25 μm was prepared and inserted into the outer can 11. Then, the negative electrode pellet 12, the separator 15, and the positive electrode pellet 14 were sequentially laminated, and an electrolyte solution was injected. As the electrolytic solution, a solution obtained by dissolving LiPF 6 as an electrolyte salt at a content of 1.25 mol / l in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a mass ratio of 1: 3 was used.
また、外装ケース１３には、内面に５０μｍのアルミニウム層を有したステンレス材を用いた。 For the outer case 13, a stainless material having an aluminum layer of 50 μm on the inner surface was used.
負極集電体１８は、カーボンペーストを塗布した事より形成されるカーボン薄膜層を外装缶１１の負極ペレット１２と接触する面に作製し、外装缶１１ａとした。
その後、ガスケット１７を介して外装缶１１ａと外装ケース１３とをかしめて封止し図１に示されるような直径１６ｍｍ、高さ１．６ｍｍのコイン形有機電解液二次電池を作製した。
As the negative electrode current collector 18, a carbon thin film layer formed by applying a carbon paste was prepared on the surface of the outer can 11 in contact with the negative electrode pellet 12 to obtain an outer can 11 a.
Thereafter, the outer can 11a and the outer case 13 were caulked through a gasket 17 and sealed to produce a coin-shaped organic electrolyte secondary battery having a diameter of 16 mm and a height of 1.6 mm as shown in FIG.
比較例１の電池として、正極集電体にカーボンペーストを塗布したことにより形成されるカーボン薄膜層を外装ケース１３と正極ペレット１４と接触する面に作製した以外は本実施例の電池と同様にしてコイン形有機電解液二次電池を作製した。 The battery of Comparative Example 1 was the same as the battery of this example, except that a carbon thin film layer formed by applying a carbon paste to the positive electrode current collector was formed on the surface in contact with the outer case 13 and the positive electrode pellet 14. Thus, a coin-type organic electrolyte secondary battery was produced.
比較例２の電池として、正極集電体を取り除いた以外は本実施例の電池と同様にしてコイン形有機電解液二次電池を作製した。 As a battery of Comparative Example 2, a coin-type organic electrolyte secondary battery was produced in the same manner as the battery of this example except that the positive electrode current collector was removed.
比較例３の電池として、正極集電体に網目状突起を有したステンレスを用いたこと以外は本実施例の電池と同様にしてコイン形有機電解液二次電池を作製した。 As the battery of Comparative Example 3, a coin-type organic electrolyte secondary battery was produced in the same manner as the battery of this example, except that stainless steel having a net-like protrusion was used for the positive electrode current collector.
比較例４の電池として、正極集電体に図３に示されるような円板状アルミニウムを用いたこと以外は、本実施例の電池と同様にしてコイン形有機電解液二次電池を作製した。 As the battery of Comparative Example 4, a coin-shaped organic electrolyte secondary battery was produced in the same manner as the battery of this Example, except that a disc-shaped aluminum as shown in FIG. 3 was used for the positive electrode current collector. .
得られた実施例および比較例１〜４の電池について、２．６Ｖの定電圧で充電を行った後、多湿（湿度９０％）、高温（６０℃）下で保存試験を行った。保存日数が２０・３０・４０日目である時に、それぞれの電池の内部抵抗および外装ケース１３のアルミニウム面での腐食の発生を調べた。得られた結果を表１に示す。 About the battery of the obtained Example and Comparative Examples 1-4, after charging with the constant voltage of 2.6V, the storage test was performed under high humidity (90% of humidity) and high temperature (60 degreeC). When the storage days were 20, 30, and 40 days, the internal resistance of each battery and the occurrence of corrosion on the aluminum surface of the outer case 13 were examined. The obtained results are shown in Table 1.
表１から明らかなように、本実施例の電池ではアルミニウム面での腐食は発生せず、電池の内部抵抗も安定していた。しかしながら、カーボン薄膜層を正極集電体とした比較例１の電池では、アルミニウム面での腐食が発生し電池の内部抵抗の上昇が確認された。また、正極集電体を取り除いた比較例２の電池では、アルミニウム面での腐食は確認されなかったものの、集電性の低下から初期において電池の内部抵抗が高かった。さらに比較例３の電池では、正極集電体とした網目状突起ステンレスが腐食し、電池の内部抵抗の上昇も確認された。また比較例４の電池では、アルミニウム面での腐食は確認されなかったが、初期において電池の内部抵抗が高かった。 As is apparent from Table 1, the battery of this example did not corrode on the aluminum surface, and the internal resistance of the battery was stable. However, in the battery of Comparative Example 1 using the carbon thin film layer as the positive electrode current collector, corrosion on the aluminum surface occurred, and an increase in the internal resistance of the battery was confirmed. Further, in the battery of Comparative Example 2 from which the positive electrode current collector was removed, although corrosion on the aluminum surface was not confirmed, the internal resistance of the battery was high in the initial stage due to the decrease in current collecting performance. Furthermore, in the battery of Comparative Example 3, the mesh protrusion stainless steel used as the positive electrode current collector was corroded, and an increase in the internal resistance of the battery was also confirmed. In the battery of Comparative Example 4, corrosion on the aluminum surface was not confirmed, but the internal resistance of the battery was high in the initial stage.
本発明の有機電解液二次電池は、アルミニウムの腐食を防止し長期信頼性を向上させることができるため、多湿環境化における有機電解液二次電池として有用である。 Since the organic electrolyte secondary battery of the present invention can prevent corrosion of aluminum and improve long-term reliability, it is useful as an organic electrolyte secondary battery in a humid environment.
１１ 外装缶
１２ 負極ペレット
１３ 外装ケース
１４ 正極ペレット
１５ セパレータ
１７ ガスケット
１８ 負極集電体
１９ 正極集電体
DESCRIPTION OF SYMBOLS 11 Exterior can 12 Negative electrode pellet 13 Exterior case 14 Positive electrode pellet 15 Separator 17 Gasket 18 Negative electrode current collector 19 Positive electrode current collector
Claims (1)
前記正極が、正極活物質と正極外装缶と正極集電体を有し、
前記正極活物質が、軽金属を吸蔵および離脱することが可能で正極電位が４Ｖ以上である
化合物からなる群より選ばれる少なくとも１種の化合物であり、
前記正極外装缶が、アルミニウムあるいは正極と接する面にアルミニウム層を有したステンレスからなり、
前記正極集電体が、アルミニウムあるいはアルミニウム合金からなるとともに網目突起形状を有することを特徴とする有機電解液二次電池。 An organic electrolyte secondary battery comprising a positive electrode, a negative electrode, an electrolyte and a separator,
The positive electrode has a positive electrode active material, a positive electrode outer can and a positive electrode current collector,
The positive electrode active material is at least one compound selected from the group consisting of compounds capable of inserting and extracting light metals and having a positive electrode potential of 4 V or more;
The positive electrode outer can is made of aluminum or stainless steel having an aluminum layer on the surface in contact with the positive electrode,
An organic electrolyte secondary battery, wherein the positive electrode current collector is made of aluminum or an aluminum alloy and has a mesh protrusion shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004305509A JP2006120401A (en) | 2004-10-20 | 2004-10-20 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004305509A JP2006120401A (en) | 2004-10-20 | 2004-10-20 | Organic electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006120401A true JP2006120401A (en) | 2006-05-11 |
Family
ID=36538107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004305509A Pending JP2006120401A (en) | 2004-10-20 | 2004-10-20 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006120401A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745525A (en) * | 2021-06-16 | 2021-12-03 | 浙江柔震科技有限公司 | Flexible composite plastic film and preparation and test method thereof |
-
2004
- 2004-10-20 JP JP2004305509A patent/JP2006120401A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745525A (en) * | 2021-06-16 | 2021-12-03 | 浙江柔震科技有限公司 | Flexible composite plastic film and preparation and test method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4961654B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP2001325988A (en) | Charging method of non-aqueous electrolyte secondary battery | |
| JP2002203553A (en) | Positive-electrode active material and non-aqueous electrolyte secondary battery | |
| JP2007179765A (en) | Negative electrode and battery | |
| JP2004220819A (en) | Electrolyte, anode, and battery | |
| JP2005071678A (en) | Battery | |
| JP3140977B2 (en) | Lithium secondary battery | |
| JP3819663B2 (en) | Lithium secondary battery charge / discharge method and lithium secondary battery | |
| JP2004303597A (en) | Lithium secondary battery and manufacturing method of the same | |
| JP2006134758A (en) | Secondary battery | |
| JP2005347222A (en) | Electrolyte liquid and battery | |
| JP2005293960A (en) | Anode for lithium ion secondary battery, and lithium ion secondary battery | |
| JPH11120993A (en) | Nonaqueous electrolyte secondary battery | |
| JP2008243704A (en) | Cylindrical type nonaqueous electrolyte battery | |
| JP2005093371A (en) | Nonaqueous electrolyte secondary battery | |
| JPH07272762A (en) | Nonaqueous electrolytic secondary battery | |
| JPH11185822A (en) | Nonaqueous electrolyte secondary battery | |
| JP2006086060A (en) | Manufacturing method of secondary battery | |
| JP2006120401A (en) | Organic electrolyte secondary battery | |
| JPH11214042A (en) | Nonaqueous electrolyte secondary battery | |
| JP2010080226A (en) | Nonaqueous electrolyte secondary battery | |
| JP2001297762A (en) | Secondary cell with nonaqueous electrolyte | |
| JP2002093463A (en) | Nonaqueous electrolyte battery | |
| JP2004022239A (en) | Positive electrode active material and nonaqueous electrolyte secondary battery | |
| JP2001023615A (en) | Flat nonaqueous electrolyte secondary battery |