JPH02192655A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH02192655A JPH02192655A JP1009865A JP986589A JPH02192655A JP H02192655 A JPH02192655 A JP H02192655A JP 1009865 A JP1009865 A JP 1009865A JP 986589 A JP986589 A JP 986589A JP H02192655 A JPH02192655 A JP H02192655A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- lithium
- film
- discharge
- plasma
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 10
- 239000000057 synthetic resin Substances 0.000 claims abstract description 10
- 238000000992 sputter etching Methods 0.000 claims abstract description 9
- 238000001020 plasma etching Methods 0.000 claims abstract description 6
- 239000012982 microporous membrane Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 11
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 abstract 4
- 238000010276 construction Methods 0.000 abstract 2
- 239000011365 complex material Substances 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 18
- 238000012545 processing Methods 0.000 description 15
- -1 polypropylene Polymers 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 239000004745 nonwoven fabric Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000012528 membrane Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000009832 plasma treatment Methods 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 239000011230 binding agent Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013888 LiPF5 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229920000547 conjugated polymer Chemical class 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015028 LiAsF5 Inorganic materials 0.000 description 1
- 229910020050 NbSe3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は非水電解質二次電池に関するものであり、さら
に詳細には、体積効率が高く、強負荷充放電特性に優れ
、製造も容易である非水電解質二次電池に関するもので
ある。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a non-aqueous electrolyte secondary battery, and more specifically, the present invention relates to a non-aqueous electrolyte secondary battery, which has high volumetric efficiency, excellent high-load charge/discharge characteristics, and is easy to manufacture. This relates to a certain non-aqueous electrolyte secondary battery.
〔従来の技術、発明が解決しようとする問題点〕一般に
負極活物質として金属リチウムを用いた電池は高エネル
ギー密度、軽量小型、そして長期保存性などの利点を有
し、すでに多くの一次電池が実用化されている。しかし
ながら、この負極活物質を使用した二次電池において、
−次電池には無い新しい問題点がある。すなわち、金属
リチウムを負極とした二次電池は充放電サイクル寿命が
短く、また、充放電Ｉこ際し、この充放電効率が低いこ
とである。これは負極に析出する金属リチウムがデンド
ライト状（樹枝状）であることによるリチウム負極の劣
化に起因する。[Prior art and problems to be solved by the invention] In general, batteries using metallic lithium as the negative electrode active material have advantages such as high energy density, light weight and small size, and long shelf life, and many primary batteries have already been used. It has been put into practical use. However, in a secondary battery using this negative electrode active material,
-There are new problems not found in next-generation batteries. That is, a secondary battery using metallic lithium as a negative electrode has a short charge/discharge cycle life, and also has a low charge/discharge efficiency during charge/discharge. This is due to the deterioration of the lithium negative electrode due to the dendrite-like (dendritic) metal lithium deposited on the negative electrode.
本発明者らは、負極として金属リチウムを使用すること
の欠点を解消する手段をして、ある特定の格子面間隔を
有する炭素横維成型体に予めリチウムを吸蔵させた複合
体を二次電池用負極とする発明を完成した（特開昭６２
−２６８０５８号）。この負極を用いた二次電池はデン
ドライトの発生もなく充放電サイクル寿命が長く、信頼
性が高く、シかも、軽量である等の優れた性質を有して
いる。The present inventors have taken a method to eliminate the drawbacks of using metallic lithium as a negative electrode, and have developed a secondary battery using a composite in which lithium is occluded in advance in a carbon fiber molded body having a specific lattice spacing. completed the invention as a negative electrode for
-268058). A secondary battery using this negative electrode has excellent properties such as no dendrite generation, long charge/discharge cycle life, high reliability, durability, and light weight.
一方、非水電解質系電池のセパレーターとしては、たと
えばポリプロピレン製不織布、ビニロン−レーヨン混紡
製不織布、ビニロン製不織布、ポリエステル製不織布、
およびガラス線維製不織布などの不織布ならびに、たと
えばポリエチレン製微細孔膜およびポリプロピレン製微
細孔膜などの合成樹脂製微細孔膜がある。特に電解液に
対する安定性、機械的強度などからポリプロピレン製不
織布またはポリプロピレン製微細孔膜が一般に使用され
ている。On the other hand, as a separator for a non-aqueous electrolyte battery, examples include polypropylene nonwoven fabric, vinylon-rayon blend nonwoven fabric, vinylon nonwoven fabric, polyester nonwoven fabric,
and nonwoven fabrics such as glass fiber nonwoven fabrics, and synthetic resin microporous membranes such as polyethylene microporous membranes and polypropylene microporous membranes. In particular, polypropylene nonwoven fabrics or polypropylene microporous membranes are generally used because of their stability against electrolytes and mechanical strength.
しかしながら、炭素繊維または炭素粉末の成型体に予め
リチウムを吸蔵させた複合体は、金属リチウムなどに比
べて体積効率が劣る。従って、二次電池を製造する際に
、前記の様な不織布などをセパレーターとして使用した
場合には、セパレーターの厚さが極端に厚くなり体積効
率が低いことから実用に供し得ないことがわかった。However, a composite in which lithium is occluded in advance in a molded body of carbon fiber or carbon powder has a volumetric efficiency inferior to that of metallic lithium or the like. Therefore, when manufacturing secondary batteries, it was found that if a nonwoven fabric such as the one described above is used as a separator, the thickness of the separator becomes extremely thick and the volumetric efficiency is low, making it impractical. .
一方、合成樹脂製微細孔膜をセパレーターとして使用し
た場合には、電解液に対する濡れおよび保液性が非常に
悪く、そのために、製造時における操作性や強負荷時に
おける充放電特性に問題があることがわかった。On the other hand, when a synthetic resin microporous membrane is used as a separator, its wettability and liquid retention properties for the electrolyte are very poor, resulting in problems with operability during manufacturing and charge/discharge characteristics under heavy loads. I understand.
しかして、合成樹脂製微細孔膜をセパレーターとして使
用する際のこれらの欠点を解決するためには、不織布と
の多層構造にするぢよび／または電解液含浸材をさらに
使用するとかの方法などがあり得る。しかしながら、こ
れらの方法では、不織布を使用した場合と同様に、依然
として体積効率が低く、これまた実用に供し得ない。Therefore, in order to solve these drawbacks when using a synthetic resin microporous membrane as a separator, methods such as creating a multilayer structure with non-woven fabric and/or further using an electrolyte impregnated material are proposed. could be. However, in these methods, the volumetric efficiency is still low as in the case of using nonwoven fabrics, and these methods cannot be put to practical use.
また、濡れを良くするため、微細孔膜の表面をクロム酸
−硫酸混液などによって化学的に処理したものを使用し
た場合には、濡れが実質的に改善されないか、改善され
るにしても処理に長時間を要したし、さらに水分および
重金属などの混入を防ぐための後処理が必要であるとい
う問題があり、これまた実用に供し得ないことが判明し
た。In addition, when using a microporous membrane whose surface has been chemically treated with a chromic acid-sulfuric acid mixture to improve wetting, wetting may not be substantially improved, or even if it is improved, the treatment may It took a long time to complete the process, and there were also problems in that post-treatment was required to prevent the contamination of moisture, heavy metals, etc., and it was found that this method could not be put to practical use.
炭素線維および炭素粉末のそれぞれを使用した成型体（
以下、両者を一括して 炭素成型体と記することもある
。）に、予めリチウムを吸蔵させた複合体を負極とする
二次電池が有する前記の様な間屑点を解決し、体積効率
が高く、強負荷充放電特性に優れ、しかも製造が容易な
二次電池を開発するために鋭意、研究を重ねた結果、た
とえばポリプロピレンのような合成樹脂製の微細孔膜に
プラズマまたはスパッタエツチングで表面処理を施した
膜をセパレーターとして使用することにより、体積効率
が高く強負荷充放電特性に優れ、しかも製造が容易な二
次電池が得られることを見い出し、本発明に到達するに
至った。Molded bodies using carbon fiber and carbon powder (
Hereinafter, both may be collectively referred to as a carbon molded body. ), we have developed a secondary battery that solves the above-mentioned waste point of a secondary battery whose negative electrode is a composite in which lithium is occluded, has high volumetric efficiency, excellent high-load charge/discharge characteristics, and is easy to manufacture. As a result of intensive research to develop next-generation batteries, we have found that volumetric efficiency can be improved by using a microporous membrane made of synthetic resin such as polypropylene that has been surface-treated by plasma or sputter etching as a separator. The present inventors have discovered that a secondary battery can be obtained that has high high load charge/discharge characteristics and is easy to manufacture, leading to the present invention.
すなわち、本発明は、少なくとも、充放電可能なリチウ
ム系負極、充放電可能な正極および有機電解液を含浸さ
せたセパレーターを有する二次電池において、負極が炭
素繊維または炭素粉末を使用した成型体に予めリチウム
を吸蔵させた複合体であり、セパレーターがプラズマお
よびスパッタエツチングのいずれかによ抄表面処理され
た合成樹脂製微細孔膜であることを特徴とする二次電池
である。That is, the present invention provides a secondary battery having at least a chargeable/dischargeable lithium-based negative electrode, a chargeable/dischargeable positive electrode, and a separator impregnated with an organic electrolyte, in which the negative electrode is formed into a molded body using carbon fiber or carbon powder. This secondary battery is a composite body in which lithium is occluded in advance, and the separator is a microporous synthetic resin membrane whose surface has been subjected to either plasma or sputter etching.
本発明の炭素成型体に使用される炭素繊維および炭素粉
末には特に制限はないが、好ましくは格子面間隔（ｄ０
０２）は、３．３８〜３．５６Ｘ１特に好ましくは３．
４０〜３．５０久の炭素繊維および炭素粉末である。There are no particular restrictions on the carbon fibers and carbon powder used in the carbon molded product of the present invention, but preferably the lattice spacing (d0
02) is 3.38 to 3.56X1, particularly preferably 3.
40 to 3.50 years old carbon fiber and carbon powder.
なお、この炭素繊維および炭素粉末をそれぞれ使用した
成型体は、その格子面間隔（ｄ ｏ ０２）は、使用さ
れた炭素繊維および炭素粉末のそれぞれの格子面間隔に
由来して、好ましくは３゜３８〜３．５６Ａ、特に好ま
しくは３．４０〜３．５０Ａのものである。In addition, the lattice spacing (d o 02) of the molded product using the carbon fiber and carbon powder, respectively, is preferably 3° due to the lattice spacing of the carbon fiber and carbon powder used. 38-3.56A, particularly preferably 3.40-3.50A.
３ 、５６Ａをこえる格子面間隔（ｄｏｏ２）を有する
炭素繊維の成型体または炭素粉末の成型体を使用すると
、電池電圧が低くなり、また放電素繊維の成型体または
炭素粉末の成型体を使用したときには、たとえば３．５
６Ａをこえる格子面間隔（ｄ ｏ Ｏ２）を有する炭素
繊維の成型体または炭素粉末の成型体を使用したときと
同様に電池電圧が低くなる以外に、リチウムの吸蔵時に
炭素成型体が膨潤し、ついにはもとの形状を維持できに
くくなる。3. If a molded carbon fiber or molded carbon powder with a lattice spacing (DOO2) exceeding 56A is used, the battery voltage will be low; Sometimes, for example, 3.5
In addition to lowering the battery voltage as in the case of using a carbon fiber molded body or a carbon powder molded body with a lattice spacing (d o O2) exceeding 6A, the carbon molded body swells when lithium is absorbed. Eventually, it becomes difficult to maintain the original shape.
本発明において、格子面間隔（ｄ ｏ Ｏ２）は、Ｘ線
としてＣｕＫαを用い、標準物質として高純度シリコン
を使用する方法によって測定された値である。なお、こ
の方法は、たとえば「炭素繊維」（大谷杉部著、近代編
集社 昭和６１年３月発行）第７３３〜７４２頁に記載
されている。In the present invention, the lattice spacing (d o O2) is a value measured by a method using CuKα as an X-ray and high-purity silicon as a standard substance. This method is described, for example, in "Carbon Fiber" (written by Sugibe Otani, published by Kindai Editorial Company, March 1986), pages 733-742.
炭素繊維成型体に使用される炭素繊維は、その原料、製
法に何ら制限はないが、実用的な原料の代表例として、
ピッチ、ポリアクリロニトリルおよびレーヨンなどがあ
げられる。炭素繊維の繊維径には特に制限はないが、実
用上０．０１〜１００μｍ１好ましくは０．１〜５０μ
ｍのものが使用される。There are no restrictions on the raw material or manufacturing method for the carbon fiber used in carbon fiber molded bodies, but as a representative example of a practical raw material,
Examples include pitch, polyacrylonitrile, and rayon. There is no particular limit to the fiber diameter of carbon fiber, but in practice it is 0.01 to 100 μm, preferably 0.1 to 50 μm.
m is used.
また、炭素繊維は各種の表面処理を施されたものも使用
する事ができる。Furthermore, carbon fibers that have been subjected to various surface treatments can also be used.
本発明で使用される炭素粉末は、たとえば、前記の格子
面間隔（ｄ ｏ ０２）を有する炭素繊維および炭素ブ
ロックなどを粉砕、分級して得られる。炭素粉末の平均
粒子径は一般に０．１〜３０μｍ１好ましくは０．５〜
２０μｍである。The carbon powder used in the present invention is obtained, for example, by crushing and classifying carbon fibers and carbon blocks having the above-mentioned lattice spacing (d o 02). The average particle size of the carbon powder is generally 0.1 to 30 μm, preferably 0.5 to 30 μm.
It is 20 μm.
本発明において、炭素粉末の平均粒子径は、ストークス
の沈降式による液相沈降法によって、光透過法で測定し
て得られた粒度分布から、累積分布が、５０％に相当す
る粒子径として求められた値である。これには、たとえ
ば、「堀場製作所株製、遠心式自動粒度分布測定装置」
が好適に使用される。In the present invention, the average particle size of the carbon powder is determined as the particle size corresponding to 50% of the cumulative distribution from the particle size distribution measured by the light transmission method using the liquid phase sedimentation method using the Stokes sedimentation method. is the value given. For example, "Centrifugal automatic particle size distribution analyzer manufactured by Horiba, Ltd."
is preferably used.
本発明で使用される炭素繊維の成型体は、炭素繊維を、
バインダーを使用しまたは使用しないで、実用上、たと
えば板、網、織布、不織布および抄紙などの形態に成を
したものであるが必ずしもこれらに限定されるものでは
ない。The carbon fiber molded body used in the present invention is made of carbon fibers,
For practical purposes, the material is formed into, for example, a board, a net, a woven fabric, a non-woven fabric, and a paper-making form, with or without the use of a binder, but is not necessarily limited thereto.
また、炭素粉末の成型体は、通常はバインダーを使用し
、一般的には板状あるいはシート状；こ成型されたもの
である。A molded body of carbon powder is generally formed into a plate or sheet shape using a binder.
〜３０ｗｔ％、特に好ましくは５〜２０ｗｔ％とされる
。~30wt%, particularly preferably 5~20wt%.
炭素成型体の厚さは所望される電池容量および電池の形
状などによって異なり一概に特定し得ないが、実用上、
通常は０．０５〜５０酊、好ましくは０．１〜２０市程
度とされる。また、炭素成型体は一枚でもよいが数枚重
ねて使用することもできる。The thickness of the carbon molded body varies depending on the desired battery capacity and battery shape, and cannot be determined unconditionally, but in practice,
Usually it is 0.05 to 50, preferably about 0.1 to 20. Moreover, although the carbon molded body may be used in one piece, it is also possible to use several pieces stacked together.
本発明における魚種は、前記の炭素成型体にリチウムを
吸蔵させた複合体（以下、複合体と記すこともある）で
ある。前記の炭素成型体そのものを負極とした場合には
、エネルギー密度が低く、充放電サイクル寿命が短いな
どの難点を有する。The fish species in the present invention is a composite (hereinafter sometimes referred to as a composite) in which lithium is occluded in the above-mentioned carbon molded body. When the carbon molded body itself is used as a negative electrode, it has disadvantages such as low energy density and short charge/discharge cycle life.
炭素成形体にリチウムを吸蔵させる方法には特に制限は
ないが、通常は電気化学的方法または物理的方法があげ
られる。すなわち、たとえば、電気化学的方法としては
、炭素成形体および金属リチウムをそれぞれ電極として
、有機電解液中で特開昭６２−２８０５８号公報に記載
されているように両電極間に電流を流す方法や特開昭６
３−１０４６２号公報に記載されている様に両電極間を
導体で短絡させる方法などがある。There are no particular restrictions on the method of occluding lithium in the carbon molded body, but electrochemical methods or physical methods are usually used. That is, for example, as an electrochemical method, a method in which a carbon molded body and metallic lithium are respectively used as electrodes and a current is passed between the two electrodes in an organic electrolyte as described in JP-A No. 62-28058. and Tokukai Showa 6
There is a method of short-circuiting both electrodes with a conductor, as described in Japanese Patent No. 3-10462.
物理的方法としては、たとえば、特開昭６２がある。As a physical method, there is, for example, Japanese Patent Application Laid-Open No. 1986-62.
本発明の二次電池に使用される正極としては、充放電可
能なものであればよく、たとえば遷移金属のカルコゲン
化合物、共役高分子化合物、あるいは活性炭素などがあ
るが、これらに限定されるものではない。The positive electrode used in the secondary battery of the present invention may be any material as long as it can be charged and discharged, and includes, but is not limited to, transition metal chalcogen compounds, conjugated polymer compounds, and activated carbon. isn't it.
遷移金属のカルコゲン化合物としては、Ｔｉ０ｚ、Ｃｒ
３０５、Ｖ２Ｏ５％ Ｖ ３０ ’ 、Ｍｎ Ｏ２およ
びＭｏａ０などの酸化物、ＴｔＳ２． ＶＳ２％ Ｆｅ
Ｓ およびＭｏ５３などの硫化物ならびにＮｂＳｅ３
などのセレン化合物などがあげられる。As transition metal chalcogen compounds, Ti0z, Cr
305, V2O5% V30', oxides such as MnO2 and Moa0, TtS2. VS2% Fe
Sulfides such as S and Mo53 and NbSe3
Examples include selenium compounds such as
また、共役高分子化合物としては、ポリアセチレン、ポ
リバラフェニレン、ポリピロール、ポリチオフェンおよ
びポリアニリンなどを用いることができる。Further, as the conjugated polymer compound, polyacetylene, polyvaraphenylene, polypyrrole, polythiophene, polyaniline, etc. can be used.
これら正極は、一般に常法により膜状乃至板状とされて
使用される。These positive electrodes are generally used in the form of a film or a plate by a conventional method.
二次電池の有ＦＭＴＬ解液に使用されるリチウム塩には
特に制限はないが、代表例としては、ＬｉＣ］ 、Ｌｉ
ＣＩＯ４，ＬｉＢＦ４、ＬｉＰＦ５、ＬｉＡｓＦ５およ
びＬｉ５ｂＦｓ などをあげることができる。これら
ノ中テＬｉＣ］ｏ４、ＬｉＰＦ５およびＬｉＢＦ４が好
ましい。There are no particular restrictions on the lithium salt used in the FMTL solution of secondary batteries, but representative examples include LiC], Li
Examples include CIO4, LiBF4, LiPF5, LiAsF5 and Li5bFs. Among these, LiC]o4, LiPF5 and LiBF4 are preferred.
これらのリチウム塩は、通常、単独で使用されるが、二
種類以上を併用することもできる。These lithium salts are usually used alone, but two or more types can also be used in combination.
これらのリチウム塩を溶媒に溶解した溶液が二次電池の
有機電解液として使用される。A solution prepared by dissolving these lithium salts in a solvent is used as an organic electrolyte of a secondary battery.
この溶媒は、リチウム塩を溶解し得る有機溶媒であれば
よいが、非プロトン性で、かつ、高誘電率の有機溶媒が
好ましく、ニドＩＪル、カーボネート、エーテル、ニト
ロ化合物、アミド、含硫黄化合物、塩素化炭化水素、ケ
トンおよびエステルなどを用いろことができる。This solvent may be any organic solvent that can dissolve the lithium salt, but is preferably an organic solvent that is aprotic and has a high dielectric constant. , chlorinated hydrocarbons, ketones and esters can be used.
こレラの代表例として、アセトニトリル、プロピオニト
リル、プロピレンカーボネート、エチレンカーボネート
、テトラヒドロフラン、ジオキサン、１，３−ジオキソ
ラン、４−メチル−１，３−ジオキソラン、ｌ、２−ジ
メトキシエタン、ニトロメタン、Ｎ、Ｎ−ジメチルホル
ムアミド、ジメチルスルホキシド、スルホランおよびｒ
−ブチロラクトンなどを挙げることができる。Typical examples of cholera include acetonitrile, propionitrile, propylene carbonate, ethylene carbonate, tetrahydrofuran, dioxane, 1,3-dioxolane, 4-methyl-1,3-dioxolane, l,2-dimethoxyethane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and r
-Butyrolactone, etc. may be mentioned.
これらの有機溶媒は、一種類でもよく、または、二種類
以上の混合溶媒として用いてもよい。These organic solvents may be used alone or as a mixed solvent of two or more.
このリチウム塩溶液中のリチウム塩の濃度は、通常 ０
、１〜５ 、Ａｒ ｍａｉｌ／ｌ程度、好ましくは０
、５〜１ 、５ ｍａｔ／ｌ 程度とされる。The concentration of lithium salt in this lithium salt solution is usually 0
, 1 to 5, about Ar mail/l, preferably 0
, 5 to 1.5 mat/l.
本発明の二次電池に使用されるセパレーターは、プラズ
マまたはスパッタエツチングによ抄表面処理された合成
樹脂製微細孔膜（以下 微細孔膜 と記することもある
）である。The separator used in the secondary battery of the present invention is a synthetic resin microporous membrane (hereinafter sometimes referred to as microporous membrane) whose surface has been treated by plasma or sputter etching.
本発明における微細孔膜は多数の微細孔を有する薄膜状
組織の集積構造体である。しかして、これらの微細孔は
互いに重なり合って貫通孔とな９、または薄膜状組織の
孔のない部分に塞がこの微細孔膜は、厚さが１００μｍ
以下、好適には３０〜７０μｍのものが使用される。ま
た、処理前の微細孔膜の微細孔の孔径および空孔率のそ
れぞれには制限はないが、実用面から平均孔径として０
．１〜１μｍの範囲のものが好ましく、また空孔率とし
て２０〜６０％のものが好ましい。The microporous membrane in the present invention is an integrated structure of a thin film-like structure having a large number of micropores. These micropores overlap each other to form through holes 9 or fill the non-porous areas of the thin film-like structure. This microporous membrane has a thickness of 100 μm.
Hereinafter, those having a diameter of 30 to 70 μm are preferably used. In addition, there is no limit to the pore diameter and porosity of the micropores in the microporous membrane before treatment, but from a practical standpoint, the average pore diameter is 0.
．． The porosity is preferably in the range of 1 to 1 μm, and the porosity is preferably in the range of 20 to 60%.
なお、本発明において、平均孔径および空孔４）に分割
されているが、処理後には、この多数の仕切りの一部乃
至は全部が消失せしめられるが、この仕切の消失は微細
孔膜の表層において特に著しい。In the present invention, the pores are divided into average pore diameters and pores 4), but after the treatment, some or all of these partitions disappear; This is particularly noticeable.
本発明の微細孔膜は、合成樹脂製であればよく、特に制
限はないが、実用上、ポリエチレン及びポリプロピレン
などのポリオレフィン製のものが好ましい。The microporous membrane of the present invention may be made of synthetic resin and is not particularly limited, but for practical purposes, it is preferably made of polyolefin such as polyethylene and polypropylene.
の直径として定義され、また、空孔率は表面積に対する
微細孔の部分の面積の割合として定義される。The porosity is defined as the ratio of the area of micropores to the surface area.
この様な微細孔膜として、市販品を使用することが出来
るが、市販品の代表例として、ジュラガード、ＮＦレシ
ートよびセルボア（いずれも商品名）などが挙げられる
。Commercially available products can be used as such microporous membranes, and representative examples of commercially available products include Duraguard, NF Receipt, and Cellboa (all trade names).
プラズマ処理装置には、特に制限はなく、容全結合型お
よびコイル結合型のいずれも使用できる。The plasma processing apparatus is not particularly limited, and either a capacitively coupled type or a coil coupled type can be used.
プラズマ処理に使用される気体は、実用上、空気、窒素
、水素、アルゴンおよびヘリウムなどがそれぞれ使用さ
れるが、特に気体の種類による差は実質的にない。In practice, air, nitrogen, hydrogen, argon, helium, and the like are used as gases used in plasma processing, but there is virtually no difference depending on the type of gas.
プラズマ処理条件は、膜の材質、孔径および空孔率など
によって異なり一概に特定し得ないが、一般には処理時
間を変えることによって容易に好適な処理状態を実現で
きる。ここでいう好適な処理状態とは、微細孔膜に存在
する微細孔の平均孔径および空孔率はそれぞれ処理前に
比べて増加するが、その増加率がそれぞれ通常は、１０
０％を越えず、好ましくは５０％を越えないような状態
である。Plasma treatment conditions vary depending on the membrane material, pore diameter, porosity, etc., and cannot be unconditionally specified, but in general, suitable treatment conditions can be easily achieved by changing the treatment time. The preferred treatment conditions here mean that the average pore diameter and porosity of the micropores present in the microporous membrane each increase compared to before treatment, and the rate of increase is usually 10%.
The condition is such that it does not exceed 0%, and preferably does not exceed 50%.
処理時間は、膜の種類、処理条件などシこよって異り、
−概に特定し得ないが、実用上、片面当り３０秒〜５分
が好ましく、また両面処理を行うことが好ましい。Processing time varies depending on the type of membrane, processing conditions, etc.
-Although it cannot be specified generally, it is practically preferable to treat each side for 30 seconds to 5 minutes, and it is preferable to perform both-side treatment.
スパッタエツチング処理に用いる装置には、特に制限は
ない。There are no particular restrictions on the equipment used for the sputter etching process.
この処理に使用される気体は空気、窒素、酸素、水素、
アルゴンおよびヘリウムなどがそれぞれ使用されるが、
特に気体の種類による差は実質的にない。The gases used in this process are air, nitrogen, oxygen, hydrogen,
Argon and helium are used, respectively.
In particular, there is virtually no difference depending on the type of gas.
処理条件は、膿の材質、孔径および空孔率などによって
異なり一概に特定し得ないが、処理は片面当抄５〜１５
分行うことが好ましく、また、両面処理を行うことが好
ましい。The processing conditions vary depending on the material of the pus, the pore size, the porosity, etc., and cannot be unconditionally specified, but the processing is carried out using single-sided Tosho 5-15.
It is preferable to carry out the treatment for several minutes, and it is also preferable to carry out the treatment on both sides.
このようにして好適な処理状態を実現できる。In this way, a suitable processing state can be achieved.
ここでいう好適な処理状態とけ、プラズマ処理％を越え
ない状態である。The preferred processing state here is one in which the plasma processing percentage is not exceeded.
両方の処理のうち膜の表面処理の均一性からプラズマ処
理が好ましい。Of both treatments, plasma treatment is preferred from the viewpoint of uniformity of surface treatment of the film.
従来の電池と同様に集電体を使用することができ、かつ
、好ましい。集電体は、従来の電池で使用されている集
電体を使用しうる。すなわち、電解液ならびに正極およ
び負極のそれぞれに対し、電気化学的に不活性な導体が
用いられる。たとえば、ニッケル、チタン、ステンレス
鋼などの金属を板、箔および網の形態で使用することが
できる。正極集電体と負極集電体とは互いに異なる材質
でもよく、また同じ材質でもよい。またその厚さは０．
００１〜ｌＱｉｍ程度、好ましくは０．０１〜５■程度
とされる。A current collector can be used, and is preferred, as in conventional batteries. The current collector may be a current collector used in conventional batteries. That is, an electrochemically inert conductor is used for each of the electrolyte and the positive and negative electrodes. For example, metals such as nickel, titanium, stainless steel can be used in the form of plates, foils and meshes. The positive electrode current collector and the negative electrode current collector may be made of different materials or may be made of the same material. Also, its thickness is 0.
It is approximately 0.001 to 1Qim, preferably approximately 0.01 to 5.
以下の実施例により、本発明をさらに具体的に説明する
。本発明は、これらの実施例に限定されるものではない
。The present invention will be explained in more detail with reference to the following examples. The present invention is not limited to these examples.
実施例 １
格子面間隔（ｄｏｏｚ）が３．４４Ａのポリアクリロニ
トリル系炭素繊維成型体（繊維径８μｍ１重量 ２５．
０■、直径 １４龍、厚さ ０．４１）と金属リチウム
円板（直径 １８朋、厚さ１．５ｍ５）とを、ガラス繊
維製不織布を介在させて、互いに対向させて配置し、ス
テンレス板で両面から挟持して圧着した。これにプロピ
レンカーボネートと１．３−ジオキソランとの混合溶媒
（ｌ：１容量比）に、濃度が１．０ｍｏｌ／ｌになるよ
うに過塩素酸リチウムを溶解した溶液を含浸させた。つ
づいて外部直流電源「北斗電工■製、電池充放電装置、
ＨＪ−２０１ＢＪ（以下の実施例、比較例でも同様）の
プラス端子を金属リチウム側のステンレス板に、マイナ
ス端子を炭素繊維成型体側のステンレス板に各々接続し
、電流密度０ 、３２ ｍＡ／−の定電流で９．５ｈｒ
ｓａ電し、１．２’１９のリチウムを吸蔵させた複合体
を得た。Example 1 Molded polyacrylonitrile carbon fiber with a lattice spacing (dooz) of 3.44A (fiber diameter 8 μm 1 weight 25.
A metal lithium disk (diameter 18 mm, thickness 1.5 m5) was placed facing each other with a glass fiber non-woven fabric interposed between them, and a stainless steel plate was placed. It was clamped and crimped from both sides. This was impregnated with a solution in which lithium perchlorate was dissolved at a concentration of 1.0 mol/l in a mixed solvent of propylene carbonate and 1,3-dioxolane (l:1 volume ratio). Next, external DC power supply "Battery charging/discharging device made by Hokuto Denko ■,
The positive terminal of HJ-201BJ (the same applies to the following Examples and Comparative Examples) was connected to the stainless steel plate on the metal lithium side, and the negative terminal was connected to the stainless steel plate on the carbon fiber molded body side, and the current density was 0 and 32 mA/-. 9.5 hours at constant current
Sa electrolysis was performed to obtain a composite in which 1.2'19 lithium was occluded.
このようにして得られた複合体を負極とし、五酸化バナ
ジウム ２０重量部、導電剤としてアセチレンブラック
１０重量部、バインターとしてポリテトラフルオロエ
チレン粉末 １０重量部の混合物を使用した円板状の成
型体（重量 １００ｗ、直径 １４ｍｍ）を正極とし、
プロピレンカーボネートと１．３−ジオキソランの混合
溶媒（１：１容量比）に、濃度が１．０ｍｏｌ／ ｌに
なるように過塩素酸リチウムを溶解させた溶液を電解液
として含浸させたポリプロピレン製微細孔膜をセパレー
タとして二次電池を作製した。こ＼でのセパレータとし
て、厚す５０μｍ１平均孔径 ０．３μｍおよび空孔率
３０％のポリプロピレン製微細孔膜に、株式会社サムコ
インターナショナル研究所製、プラズマ基礎研究装置モ
デルＢＰ−１によ抄プラズマ処理を施したものを使用し
た。The composite thus obtained was used as a negative electrode, and a disc-shaped molded body was used using a mixture of 20 parts by weight of vanadium pentoxide, 10 parts by weight of acetylene black as a conductive agent, and 10 parts by weight of polytetrafluoroethylene powder as a binder. (weight 100W, diameter 14mm) as a positive electrode,
A fine polypropylene product impregnated with a solution of lithium perchlorate dissolved in a mixed solvent of propylene carbonate and 1.3-dioxolane (1:1 volume ratio) to a concentration of 1.0 mol/l as an electrolyte. A secondary battery was produced using the porous membrane as a separator. As a separator in this case, a polypropylene microporous membrane with a thickness of 50 μm, an average pore diameter of 0.3 μm, and a porosity of 30% was subjected to plasma treatment using plasma basic research equipment model BP-1 manufactured by Samco International Laboratories Co., Ltd. I used the one that had been treated with
なお、この処理装置は容量結合型であり、処理条件は発
振周波数１３ 、５６ ＭＨｚであり、処理条件は空気
雰囲気下、圧力２０Ｐａｓ高周波出力２０Ｗ１プレート
電流 ３００ｍＡ、 処理時間は片面当り１分間とし
て、両面処理を行なった。この処理によって、微細孔膜
の平均孔径および空孔率は、それぞれ０．３３Ｊ’ｍお
よび３５％となった。This processing equipment is a capacitively coupled type, and the processing conditions are an oscillation frequency of 13 and 56 MHz, the processing conditions are an air atmosphere, a pressure of 20 Pa, a high frequency output of 20 W, a plate current of 300 mA, and a processing time of 1 minute per side. Processed. As a result of this treatment, the average pore diameter and porosity of the microporous membrane were 0.33 J'm and 35%, respectively.
プラズマ処理された微細孔膜の表面状態を第１図で示す
。すなわち、第１図は、プラズマ処理された微細孔膜の
表面の走査型電子顕微鏡写真である（第２〜４図におい
ても同様）。FIG. 1 shows the surface condition of the plasma-treated microporous membrane. That is, FIG. 1 is a scanning electron micrograph of the surface of a plasma-treated microporous membrane (the same applies to FIGS. 2 to 4).
なお、電子顕微鏡写真の撮影条件などは次のとおりであ
る（以下の実施例でも同様）。すなわち、
電子顕微傭：明石走査電子顕微鏡
（ＡＬＰＨＡ−２５）
加速電圧 ２５’ＫＶ
陰 極 タングステン
撮影倍率 ｓ ｏ ｏ ｏ＠
写真撮影 ：ポラロイド６６５ を使用この様にして、
得られた二次電池を、枚’ＫＷ圧が１．５０Ｖになるま
で５ 、０ ｍＡ／ｎ／Ｉ の定電流放電を行なった
ところ、３．４ｍＡｈ の放電容量が得られ、また体
積効率は４ 、６ Ａｈ／１であった。Note that the conditions for taking electron micrographs are as follows (the same applies to the following examples). Namely, electron microscope: Akashi scanning electron microscope (ALPHA-25) Acceleration voltage: 25'KV Cathode Tungsten Photography magnification: SOOO@ Photography: Polaroid 665
When the obtained secondary battery was subjected to constant current discharge of 5.0 mA/n/I until the KW pressure reached 1.50 V, a discharge capacity of 3.4 mAh was obtained, and the volumetric efficiency was It was 4,6 Ah/1.
次に、５ｍＡ／−の定電流で下限電圧を２．００■、上
限電圧を３．９０Ｖとし、充放電サイクル試験を行なっ
たところ、４０サイクル目および１２０サイクル目の放
電容量はいずれも３．２ｍＡｈ であった。Next, a charge/discharge cycle test was conducted using a constant current of 5 mA/- with a lower limit voltage of 2.00 V and an upper limit voltage of 3.90 V, and the discharge capacities at the 40th and 120th cycles were both 3.0V and 3.90V, respectively. It was 2mAh.
実施例 ２
プラズマ処理時間を片面当り５分間として、両面処理を
おこなった以外は実施例１と同様にして二次電池を作製
した。この処理によって、微細孔膜の平均孔径および空
孔率は、それぞれ０．３５μｍおよび４０％となった。Example 2 A secondary battery was produced in the same manner as in Example 1 except that the plasma treatment time was 5 minutes per side and both sides were treated. As a result of this treatment, the average pore diameter and porosity of the microporous membrane were 0.35 μm and 40%, respectively.
プラズマ処理後の微細孔膜の表面状態を第２図で示す。FIG. 2 shows the surface condition of the microporous membrane after plasma treatment.
この二次電池を放電電圧が１．５０Ｖになるまで５ 、
０ ｍＡ／−の定電池放電をおこなったところ、３．４
ｍＡｈ の放電容量が得られ、また体積効率は４．６
ｋｈ／ｌであった。5 times until the discharge voltage reaches 1.50V,
When a constant battery discharge of 0 mA/- was performed, 3.4
A discharge capacity of mAh is obtained, and the volumetric efficiency is 4.6.
It was kh/l.
次に、５．０ｍＡ／−の定電流で下限電圧を２．００Ｖ
、上限電圧を３ 、９０ＶトＬ、、充放電サイクル試験
を行なったところ、４０サイクル目および１２０サイク
ル目の放電容量はいずれも３ 、２ ｍＡｈ であっ
た。Next, set the lower limit voltage to 2.00V with a constant current of 5.0mA/-.
When a charge/discharge cycle test was conducted with an upper limit voltage of 3 and 90 V to L, the discharge capacities at the 40th cycle and the 120th cycle were both 3.2 mAh.
実施例 ３
アルゴン雰囲気中で、プラズマ処理をおこなった以外は
実施例２と同様にして二次電池を作製した。Example 3 A secondary battery was produced in the same manner as in Example 2 except that plasma treatment was performed in an argon atmosphere.
この処理によって、微細孔膜の平均孔径および空孔率は
、それぞれ０．３５μｍおよび４０％となった。プラズ
マ処理された微細孔膜の表面状態を第３図１こ示す。As a result of this treatment, the average pore diameter and porosity of the microporous membrane were 0.35 μm and 40%, respectively. The surface condition of the plasma-treated microporous membrane is shown in FIG.
この二次電池を放電電圧が１．５０Ｖになるまで５ 、
０ ｍＡ／６Ｉ の定電流放電を行なったところ３．
４ｍＡｈ の放電容量が得られ、また体積効率は４
、６ Ａｈ／ｉｔであった。5 times until the discharge voltage reaches 1.50V,
When a constant current discharge of 0 mA/6I was performed, 3.
A discharge capacity of 4mAh is obtained, and the volumetric efficiency is 4
, 6 Ah/it.
次に、５．０ｍＡ／−の定電流で下限電圧を２゜００ｖ
１上限電圧を３．９０Ｖとし、充放電サイクル試験を行
なったところ、４０サイクル目および１２０サイクル目
の放電容量はいずれも３．２ｍＡｈ であった。Next, set the lower limit voltage to 2°00v with a constant current of 5.0mA/-.
When a charge/discharge cycle test was conducted with the upper limit voltage set at 3.90 V, the discharge capacities at the 40th cycle and the 120th cycle were both 3.2 mAh.
実施例 ４
セパレーターとして、厚さ５０μｍ、平均孔ング社製Ｉ
Ｂ−３型イオンコーターを用いて、スパッタエツチング
処理をおこなった微細孔膜を使用した以外は実施例１と
同様にして二次電池を作製した。Example 4 As a separator, a thickness of 50 μm, I made by Mean Holing Co., Ltd.
A secondary battery was produced in the same manner as in Example 1, except that a microporous membrane subjected to sputter etching using a B-3 type ion coater was used.
なお、スパッタエツチング処理条件は、空気ず囲気下、
圧力Ｑ −２Ｔｏｒｒｓイオン電流 ６ｍＡで処理時間
は片面当り１０分として両面処理をおこなった。In addition, the sputter etching processing conditions were: under an atmosphere without air;
Both sides were processed at a pressure of Q-2 Torrs and an ion current of 6 mA, with a processing time of 10 minutes per side.
この処理（こよって、微細孔膜の平均孔径および空孔率
は、それぞれ０．３５μｍおよび４０％となった。スパ
ッタエツチング処理された微細孔膜の表面状態を第４図
に示す。As a result of this treatment, the average pore diameter and porosity of the microporous membrane were 0.35 μm and 40%, respectively. The surface condition of the sputter-etched microporous membrane is shown in FIG.
この様１こして得られた二次電池を放ＩＥ電圧が１．５
０Ｖになるまで５ 、０ ｍＡ／−の定電流放電をおこ
なったところ、３．３ｍＡｈ の放電容量が得られ、
また、体積効率は４ 、５ Ａｈ／１であった。The discharge IE voltage of the secondary battery obtained in this way is 1.5.
When a constant current discharge of 5.0 mA/- was performed until it reached 0V, a discharge capacity of 3.3mAh was obtained.
Moreover, the volumetric efficiency was 4.5 Ah/1.
比較例 に
次電池のセパレーターとして、未処理の以外は、実施例
１と同様にして二次電池を作製した。この微細孔膜の表
面状態を第５図に示す。Comparative Example As a separator for a secondary battery, a secondary battery was produced in the same manner as in Example 1, except that it was not treated. The surface condition of this microporous membrane is shown in FIG.
この二次電池を放ＩＵ［圧が１．５０Ｖになるまで５
、０ ｍＡ／−の定電流放電をおこなったところ２ 、
８ ｍＡｈの放電容量しか得られなかった。Discharge this secondary battery to IU [5 minutes until the pressure reaches 1.50V]
, when a constant current discharge of 0 mA/- was performed2,
A discharge capacity of only 8 mAh was obtained.
比較例 ２
を使用した以外は、実施例１と同様にして二次電池を作
製した。この二次電池を放電電圧が１．５０Ｖになるま
で５．０ｍＡ／ｉ の定電流放電をおこなったところ
３．６ｍＡｈ の放電容量が得られたが、体積効率は
３．７Ａｈ／ｌにとどまった。A secondary battery was produced in the same manner as in Example 1 except that Comparative Example 2 was used. When this secondary battery was subjected to constant current discharge of 5.0 mA/i until the discharge voltage reached 1.50 V, a discharge capacity of 3.6 mAh was obtained, but the volumetric efficiency remained at 3.7 Ah/l. .
比較例 ３ 二次電池のセパレーターとして、厚さ５０μｍ。Comparative example 3 50μm thick for use as a separator for secondary batteries.
量比 １：１）で６０℃、１時間処理したものを使用し
た以外は実施例１と同様にして二次電池を作製した。こ
の二次電池を放電電圧が１．５０Ｖになるまで５ 、０
ｍＡ／−の定電流放電をおこなったところ、２．８ｍ
Ａｈの放電容量しか得られなかった。A secondary battery was produced in the same manner as in Example 1, except that the battery was treated at 60° C. for 1 hour at a ratio of 1:1. 5,0V until the discharge voltage reaches 1.50V.
When a constant current discharge of mA/- was performed, the distance was 2.8 m.
Only a discharge capacity of Ah was obtained.
実施例 ５
（１：１容量比）に濃度が１ 、０ ｍｏｌ／ｌになる
様に過塩素酸リチウムを溶解させた溶液を使用した以外
は実施例１と同様にして二次電池を作製した。Example 5 A secondary battery was produced in the same manner as in Example 1, except that a solution in which lithium perchlorate was dissolved at a concentration of 1.0 mol/l (1:1 volume ratio) was used. .
この二次電池を放電電圧が１．５０Ｖになるまで５ 、
０ ｍＡ／ｃｌの定電流放電をおこなったところ、３．
３ｍＡｈ の放電容量が得られ、また体積効率は４ 、
５ Ａｈ／ｌであった。5 times until the discharge voltage reaches 1.50V,
When a constant current discharge of 0 mA/cl was performed, 3.
A discharge capacity of 3mAh was obtained, and the volumetric efficiency was 4.
It was 5 Ah/l.
実施例 ６
二次電池のセパレーターとして、実施例１と同じ条件で
プラズマ処理をした、厚さ２６μｍ１と同様にして二次
電池を作製した。この処理によって、微細孔膜の平均孔
径および空孔率は、それぞれ０．５５μｍおよび５５％
となった。Example 6 As a separator for a secondary battery, a secondary battery was produced in the same manner as in Example 1, with a thickness of 26 μm1 and subjected to plasma treatment under the same conditions. Through this treatment, the average pore diameter and porosity of the microporous membrane are 0.55 μm and 55%, respectively.
It became.
この二次電池を放電電圧が１．５０Ｖになるまで５ 、
０ ｍＡ／−の定電流放電をおこなったところ、３．４
ｍＡｈ の放電容量が得られ、また体積効率は４．６
Ａｈ／ｌであった。5 times until the discharge voltage reaches 1.50V,
When a constant current discharge of 0 mA/- was performed, 3.4
A discharge capacity of mAh is obtained, and the volumetric efficiency is 4.6.
It was Ah/l.
実施例 ７
格子面間隔（ｄ ｏ ｏ ２） が３．４１Ａの炭素
ブロック「日本カーボン株製、５ＥＧ−ＲＢＪを粉砕し
て炭素粉末にした。この炭素粉末の平均粒子径を自動粒
度分布測定器「堀場製作所株製、ＣＡＰＡ−５００Ｊで
測定したところ３．５μｍであった。この炭素粉末９０
重量部とポリテトラフルオロエチレン粉末１０重量部と
を混練したのち、加圧成形で重２５０■、直径１５絹、
厚さ０．１８寵の炭素粉末成型体を得た。Example 7 A carbon block with a lattice spacing (d o o 2) of 3.41A, "5EG-RBJ manufactured by Nippon Carbon Co., Ltd., was ground into carbon powder. The average particle diameter of this carbon powder was measured using an automatic particle size distribution analyzer. "It was measured with CAPA-500J, manufactured by Horiba, Ltd., and it was 3.5 μm. This carbon powder 90
After kneading parts by weight and 10 parts by weight of polytetrafluoroethylene powder, the mixture was press-molded into a silk product with a weight of 250 cm and a diameter of 15 mm.
A carbon powder molded body having a thickness of 0.18 cm was obtained.
得られた炭素粉末成型体と金属リチウム円板（直径１８
ｒｌＩ１１厚さ１．５ｍｍ）とを、ガラス繊維製不織布
を介在させて、互いに対向させて配置し、ステンレス板
で両面から挾持して圧着した。これにプロピレンカーボ
ネートと１．３−ジオキソランとの混合溶媒（ｌ：１容
量比）に、濃度が１ 、０ ｍａｔ／ｌ になるように
過塩素酸リチウムを溶解させた溶液を含浸させ、炭素粉
末成型体をマーｆナス極とし、一方の金属リチウムをプ
ラス魚として外部直流電源に接続し、電流密度１ 、３
ｍＡ／−の定電流で７ 、 Ｏｈｒｓ通電し、４．１
１１＆のリチウムを吸蔵させた複合体を得た。The obtained carbon powder molded body and metallic lithium disk (diameter 18
rlI11 (thickness: 1.5 mm) were placed facing each other with a glass fiber nonwoven fabric interposed therebetween, and were sandwiched between stainless steel plates from both sides and crimped. This was impregnated with a solution of lithium perchlorate dissolved in a mixed solvent of propylene carbonate and 1,3-dioxolane (l:1 volume ratio) to a concentration of 1.0 mat/l, and the carbon powder was The molded body is connected to an external DC power supply with one metal lithium as a positive polarity and a current density of 1 and 3.
7 Ohrs with constant current of mA/-, 4.1
A composite in which lithium of 11& was occluded was obtained.
この様にして得られた複合体を負極としたほかは、実施
例１と同様にして二次電池を作製した。A secondary battery was produced in the same manner as in Example 1, except that the composite thus obtained was used as a negative electrode.
この二次電池を、放電電圧が２．００Ｖになるまで５
、０ ｍＡ／−の定電流放電を行なったところ、２．９
ｍＡｈ の放電容量が得られ、また、体積効率は６．
５Ａｈ／ｌであった。This secondary battery was heated for 5 minutes until the discharge voltage reached 2.00V.
, when a constant current discharge of 0 mA/- was performed, 2.9
A discharge capacity of mAh is obtained, and the volumetric efficiency is 6.
It was 5Ah/l.
第１〜４図と第５図とを比較して、本発明で［発明の効
果〕
本発明の二次電池は、体積効率が高く、強負荷放電特性
に優れ、製造も容易な非水電解質二次電池である。Comparing FIGS. 1 to 4 and FIG. 5, it is found that the present invention [Effects of the Invention] It is a secondary battery.
図面は、微細孔膜の表面状態を示すための電子顕微鏡写
真である。
第１〜４図は表面処理された微細孔膜についてのもので
あや、第５図は処理前の微細孔膜についてのものである
。
特許出願人 三菱瓦斯化学株式会社
代表者西川禮二The drawing is an electron micrograph showing the surface condition of the microporous membrane. Figures 1 to 4 show the surface-treated microporous membrane, and Figure 5 shows the microporous membrane before treatment. Patent applicant Reiji Nishikawa, representative of Mitsubishi Gas Chemical Co., Ltd.
Claims (1)
能な正極および有機電解液を含浸させたセパレーターを
有する二次電池において、負極が炭素繊維または炭素粉
末を使用した成型体に予めリチウムを吸蔵させた複合体
であり、セパレーターがプラズマおよびスパッタエッチ
ングのいずれかにより表面処理された合成樹脂製微細孔
膜であることを特徴とする二次電池。At least, in a secondary battery having a chargeable/dischargeable lithium-based negative electrode, a chargeable/dischargeable positive electrode, and a separator impregnated with an organic electrolyte, the negative electrode is a molded body made of carbon fiber or carbon powder in which lithium is occluded in advance. 1. A secondary battery, which is a composite body, and the separator is a synthetic resin microporous membrane whose surface has been treated by either plasma or sputter etching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1009865A JP2665479B2 (en) | 1989-01-20 | 1989-01-20 | Rechargeable battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1009865A JP2665479B2 (en) | 1989-01-20 | 1989-01-20 | Rechargeable battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02192655A true JPH02192655A (en) | 1990-07-30 |
| JP2665479B2 JP2665479B2 (en) | 1997-10-22 |
Family
ID=11732036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1009865A Expired - Lifetime JP2665479B2 (en) | 1989-01-20 | 1989-01-20 | Rechargeable battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2665479B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04308654A (en) * | 1991-04-08 | 1992-10-30 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JPH06176750A (en) * | 1992-12-10 | 1994-06-24 | Tomoegawa Paper Co Ltd | Manufacture of base material sheet battery separator |
| JP2003151635A (en) * | 2001-11-15 | 2003-05-23 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2009510689A (en) * | 2005-09-30 | 2009-03-12 | コンスタンティノビッチ フィリポフ、アレクサンドル | Carbon-containing material and lithium ion storage battery for lithium ion storage battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5894752A (en) * | 1981-11-30 | 1983-06-06 | Toshiba Battery Co Ltd | Manufacture of alkaline cell |
| JPS5895752A (en) * | 1981-12-02 | 1983-06-07 | Hitachi Metals Ltd | Magnetic toner |
| JPS6178053A (en) * | 1984-09-26 | 1986-04-21 | Matsushita Electric Ind Co Ltd | Electric cell |
| JPS62268058A (en) * | 1986-05-13 | 1987-11-20 | Mitsubishi Gas Chem Co Inc | Negative electrode for secondary battery |
-
1989
- 1989-01-20 JP JP1009865A patent/JP2665479B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5894752A (en) * | 1981-11-30 | 1983-06-06 | Toshiba Battery Co Ltd | Manufacture of alkaline cell |
| JPS5895752A (en) * | 1981-12-02 | 1983-06-07 | Hitachi Metals Ltd | Magnetic toner |
| JPS6178053A (en) * | 1984-09-26 | 1986-04-21 | Matsushita Electric Ind Co Ltd | Electric cell |
| JPS62268058A (en) * | 1986-05-13 | 1987-11-20 | Mitsubishi Gas Chem Co Inc | Negative electrode for secondary battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04308654A (en) * | 1991-04-08 | 1992-10-30 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JP2574952B2 (en) * | 1991-04-08 | 1997-01-22 | 富士電気化学株式会社 | Non-aqueous electrolyte secondary battery |
| JPH06176750A (en) * | 1992-12-10 | 1994-06-24 | Tomoegawa Paper Co Ltd | Manufacture of base material sheet battery separator |
| JP2003151635A (en) * | 2001-11-15 | 2003-05-23 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2009510689A (en) * | 2005-09-30 | 2009-03-12 | コンスタンティノビッチ フィリポフ、アレクサンドル | Carbon-containing material and lithium ion storage battery for lithium ion storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2665479B2 (en) | 1997-10-22 |
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