JPH03257767A - Secondary cell - Google Patents
Secondary cellInfo
- Publication number
- JPH03257767A JPH03257767A JP2054904A JP5490490A JPH03257767A JP H03257767 A JPH03257767 A JP H03257767A JP 2054904 A JP2054904 A JP 2054904A JP 5490490 A JP5490490 A JP 5490490A JP H03257767 A JPH03257767 A JP H03257767A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- porous
- membrane
- pores
- film
- 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
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000001741 organic sulfur group Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 17
- 229920000098 polyolefin Polymers 0.000 abstract description 12
- 239000004020 conductor Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229920000515 polycarbonate Polymers 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000006182 cathode active material Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 241001235534 Graphis <ascomycete fungus> Species 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- SZBCPGQROWCIIO-UHFFFAOYSA-N SC1=C(S)SSN1 Chemical compound SC1=C(S)SSN1 SZBCPGQROWCIIO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は二次電池に係り、より詳しく述べると電解質と
して有機硫黄酸化還元化合物を用いた二次電池に関する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a secondary battery, and more specifically to a secondary battery using an organic sulfur redox compound as an electrolyte.
（従来の技術〕
ごく最近、有機硫黄酸化還元化合物を使用する電池に関
する報告がなされた。この電池は陰極としてはＬｉ又は
Ｎａを使用し、陽極としてはＲ５５Ｒの一般形をもつ有
機硫黄化合物を使用する。その陽極の充放電反応は次の
式となる。(Prior Art) Very recently, a report has been made on a battery using an organic sulfur redox compound.This battery uses Li or Na as the cathode and an organic sulfur compound having the general form R55R as the anode. The charge/discharge reaction of the anode is as follows.
２Ｒ３ＳＲ＋２ ｅ−＝２Ｒ３
ＲはＣｌ１ｉ 、 （Ｃｚｌ（ｓ） ＪＣ＝ Ｓ 、
ＣＨ：＋ＣＨｚＯＣＨｚＣＨｚなとである。これら
の有機化合物は、その充放電反応で、電気化学的に酸化
還元されると同時に三量化する。2R3SR+2 e-=2R3 R is Cl1i, (Czl(s) JC=S,
CH: +CHzOCHzCHz. These organic compounds are electrochemically redoxed and trimerized at the same time during the charge/discharge reaction.
この有機硫黄化合物又は有機硫黄ポリマー化合物を使っ
て次のような電池を構成しうまく充放電することが確認
されている。It has been confirmed that the following batteries can be constructed using this organic sulfur compound or organic sulfur polymer compound and can be successfully charged and discharged.
θＬｉ／Ｌｉ／電解式レーター） ／Ｒ５５Ｒ■・・・
（１）θＮａ／電解質（セパレーター） ／ｌ？ｓｓｌ
？■・（２）そして、テトラエチルチウラムジスルフィ
ド（ＴＥＴＤ）とＬｉの組合せでつくった電池は、２０
″Ｃで１６１１ＩＡ／ｃ１１１という高電流で放電可能
であり、３．４ｍＡ／ｃ＋１１で充放電すると２０″Ｃ
で１４０回充放電したあとでも特性が劣化しないと報告
されている。θLi/Li/electrolytic rater) /R55R ■...
(1) θNa/electrolyte (separator)/l? ssl
? ■・(2) Then, a battery made from a combination of tetraethylthiuram disulfide (TETD) and Li is 20
It can be discharged at a high current of 1611IA/c111 at ``C, and 20''C when charged and discharged at 3.4mA/c+11.
It is reported that the characteristics do not deteriorate even after being charged and discharged 140 times.
〔発明が解決しようとする課題］
このようなカソード活物質は、カソードにいかにして固
定するかが問題である。従来は微多孔質の分離膜（Ｃａ
ｌｇａｒｄ ２４００等）に含浸しグラファイトフェル
トなどの集電（３）電極と接触させることによりカソー
ドとして゛いるが、電池ホルダーなどにより液もれかな
い様に封じることが必要である。この封止技術は電解液
が有機溶媒であったり電池の厚さが薄い場合には大変能
しい技術である。[Problems to be Solved by the Invention] The problem with such cathode active materials is how to fix them to the cathode. Conventionally, microporous separation membranes (Ca
It is used as a cathode by impregnating it into a liquid (such as Lgard 2400) and contacting it with a current collecting (3) electrode such as graphite felt, but it is necessary to seal it with a battery holder or the like to prevent leakage. This sealing technology is very effective when the electrolyte is an organic solvent or the battery is thin.
そこで、適当なカソード活物質保持手段が求められる。Therefore, an appropriate cathode active material holding means is required.
［課題を解決するための手段］
本発明は、上記課題を解決するために、カソードに膜厚
が１〜１１０００ｐ、空孔率が３０〜９０％、比導電率
が１０−５Ｓｃｍ−’以上の多孔性導電膜を用いたこと
を特徴とする二次電池を提供する。[Means for Solving the Problems] In order to solve the above problems, the present invention provides a cathode having a film thickness of 1 to 11000p, a porosity of 30 to 90%, and a specific conductivity of 10-5 Scm-' or more. A secondary battery characterized by using a porous conductive film is provided.
この多孔性導電膜は多孔性薄膜でありながら導電性を保
有したものであり、これによりこの多孔膜の空孔中にカ
ソード活物質を充填することが可能になる。活物質を充
填した導電膜は全体として固体であり、かつ導電性を保
有している。Although this porous conductive film is a porous thin film, it retains conductivity, and this makes it possible to fill the pores of this porous film with a cathode active material. The conductive film filled with the active material is solid as a whole and has conductivity.
本発明の多孔性導電膜は、１〜１０００ｎ、好ましくは
５〜５０戸の膜厚を有する。厚さが１−未満では、機械
的強度および取扱い性の観点から実用に供することが難
しい。一方、１０００ｐを超える場合には、実効抵抗が
大きくなり、導電膜としての体積効率も不利となる。The porous conductive film of the present invention has a thickness of 1 to 1000 nm, preferably 5 to 50 nm. If the thickness is less than 1 mm, it is difficult to put it into practical use from the viewpoints of mechanical strength and handleability. On the other hand, if it exceeds 1000p, the effective resistance becomes large and the volumetric efficiency as a conductive film becomes disadvantageous.
また、膜の空孔率は、３０〜９０％、好ましくは４０〜
９０％である。空孔率が４０％未満では、比導電率は向
上するが、電極材料として用いる場合の電解質溶液との
界面が少なくなり、電池やエレクトロクロミック素子と
しての応用が実用性の面から制約される。一方空孔率が
９０％を超えると、膜の機械的強度が不十分となる。In addition, the porosity of the membrane is 30 to 90%, preferably 40 to 90%.
It is 90%. When the porosity is less than 40%, the specific conductivity improves, but when used as an electrode material, the interface with the electrolyte solution decreases, and the application as a battery or an electrochromic device is restricted from a practical standpoint. On the other hand, if the porosity exceeds 90%, the mechanical strength of the membrane will be insufficient.
さらに、本発明においては、特に限定されないが、平均
貫通孔径は、０．００１〜０．７庫、好ましくは、０．
００５〜０．１癖であるのがよい。平均貫通孔径が０．
０ＯＩＩ！ｍ未満では電極活物質の空孔内への充填が幾
何学的制約のために困難となり、０．７ｎを超えると毛
管凝縮作用による溶液の空孔内への充填および漏出防止
が困難となる。Furthermore, in the present invention, although not particularly limited, the average through-hole diameter is 0.001 to 0.7, preferably 0.001 to 0.7.
005-0.1 habit is good. The average through hole diameter is 0.
0OII! If it is less than m, it becomes difficult to fill the electrode active material into the pores due to geometric constraints, and if it exceeds 0.7n, it becomes difficult to fill the pores with the solution and prevent leakage due to capillary condensation.
本発明の導電性多孔膜は、また、１０−５Ｓｃｍ−’以
上、好ましくは１０−”Ｓｅｗｎ−’以上の比導電率を
有する。比導電率が１０−５Ｓｃｍ−’未満では実効抵
抗が大きくなり、実用的でない。例えば、ここで、膜厚
ｌ１Ｍのとき、実効抵抗は、Ｉ Ｉ！Ｗｌ／１０−’Ｓ
ｃｍ−’即ち１０Ωｃｄｌとなる。The conductive porous membrane of the present invention also has a specific conductivity of 10-5 Scm-' or more, preferably 10-"Sewn-' or more. If the specific conductivity is less than 10-5 Scm-', the effective resistance increases. , is not practical.For example, here, when the film thickness is l1M, the effective resistance is II!Wl/10-'S
cm-', that is, 10Ωcdl.
前記の多孔性導電膜は固体高分子材料中に電子導電性材
料を含有する。The porous conductive membrane described above contains an electronically conductive material within a solid polymeric material.
本発明に有用な電子導電性材料としては、各種の金属材
料や半導体材料、酸化物系および硫化物系の電子導電性
材料、およびカーボンもしくはグラファイト材料がある
。これらは、粒子状、繊維状、フィブリル状、ウィスカ
ー状等のいかなる形状にあってもよく、微細なフィブリ
ルもしくはウィスカー状にあるのが好ましい。本発明に
用いる電子導電性材料として特に好ましいものは、アセ
チレンフ゛ラック、ケ・ンチェンフ゛ラック（Ａｋｚｏ
Ｃｈｅｍｉｅ社商標）、カーボンウィスカー、グラフ
ァイトウィスカー、グラファイトフィブリル等がある。Electronically conductive materials useful in the present invention include various metallic and semiconductor materials, oxide-based and sulfide-based electronically conductive materials, and carbon or graphite materials. These may be in any shape such as particles, fibers, fibrils, whiskers, etc., and are preferably in the form of fine fibrils or whiskers. Particularly preferable electronically conductive materials for use in the present invention are acetylene flakes and kenchen flakes (Akzo
Chemie (trademark), carbon whiskers, graphite whiskers, graphite fibrils, etc.
特に、米国Ｈｙｐｅｒｉｏｎ社の開発したＧｒａｐｈｉ
ｔｅ Ｆｉｂｒｉｌｓ（商標）は、中空円柱状構造の直
径３．５〜７０戸ｍ、アスペクト比１００以上のフィブ
リルであり（特開昭６２−５００９４３号公報）、本発
明に用いるのに好適である。In particular, Graphi developed by Hyperion, Inc.
te Fibrils (trademark) is a fibril having a hollow cylindrical structure with a diameter of 3.5 to 70 m and an aspect ratio of 100 or more (Japanese Unexamined Patent Publication No. 62-500943), and is suitable for use in the present invention.
多孔性導電膜を構成する固体高分子材料としてはポリオ
レフィン、ポリカーボネート、ポリエステル、ポリテト
ラフルオロエチレン、ポリメタアクリレート、ポリアセ
タール、ポリスチレン、ポリアミドなとが用いることが
できる。As the solid polymer material constituting the porous conductive film, polyolefin, polycarbonate, polyester, polytetrafluoroethylene, polymethacrylate, polyacetal, polystyrene, polyamide, etc. can be used.
これらのうち好ましい材料の１つは、オレフィンの単独
重合体または共重合体からなる結晶性の線状ポリオレフ
ィンであり、重量平均分子量が５×１０５以上、好まし
くはｌＸｌ０’〜ｌＸｌ０’の超高分子量ポリオレフィ
ンを用いる。ポリオレフィンとしては、ポリエチレン、
ポリプロピレン、エチレン−プロピレン共重合体、ポリ
ブテン−１、ポリ４−メチルペンテン−１などを挙げる
ことができ、これらのうちではポリエチレンおよびポリ
プロピレンが好ましい。ポリオレフィンの重量平均分子
量は、得られる膜の機械的強度に影響する。One of the preferred materials is a crystalline linear polyolefin made of an olefin homopolymer or copolymer, and has a weight average molecular weight of 5 x 105 or more, preferably an ultra-high molecular weight of lXl0' to lXl0'. Use polyolefin. Polyolefins include polyethylene,
Examples include polypropylene, ethylene-propylene copolymer, polybutene-1, poly4-methylpentene-1, and among these, polyethylene and polypropylene are preferred. The weight average molecular weight of the polyolefin influences the mechanical strength of the resulting membrane.
超高分子量ポリオレフィンは、超延伸による極薄で高強
度の膜の調製を可能にする。重量平均分子量が５Ｘ１０
’未満のポリオレフィンを同時に用いることができるが
、重量平均分子量が５Ｘ１０５以上のポリオレフィンを
含まない系では、超延伸により高強度の膜を得ることが
できない。Ultra-high molecular weight polyolefins allow the preparation of ultra-thin, high-strength membranes by ultra-stretching. Weight average molecular weight is 5X10
Although polyolefins having a weight average molecular weight of 5×10 5 or more can be used at the same time, a high-strength film cannot be obtained by ultra-stretching in a system that does not contain a polyolefin having a weight average molecular weight of 5×10 5 or more.
本発明の多孔性導電膜は、上記の電子導電性材料を固体
高分子材料に配合し、製膜することにより得ることがで
きる。電子導電性材料の配合量は、１〜２００重量％、
特に３〜５０重量％であるのが好ましい。この配合量が
１重量％未満では十分な導電性が得られにく（，２００
重量％を超えると実用的に十分な強度の膜を得ることが
困難となる。The porous conductive film of the present invention can be obtained by blending the above electronically conductive material with a solid polymer material and forming a film. The blending amount of the electronically conductive material is 1 to 200% by weight,
In particular, it is preferably 3 to 50% by weight. If this amount is less than 1% by weight, it is difficult to obtain sufficient conductivity (200
If it exceeds % by weight, it becomes difficult to obtain a film with sufficient strength for practical use.
製膜は、例えば、次のようにして行うことができる。超
高分子量ポリオレフィンを含有するポリオレフィンを流
動パラフィンのような溶媒中に１〜５０重量％を加熱溶
解して均一な溶液とし、これに電子導電性材料を均一に
配合せしめる。この溶液からシートを形成し、急冷して
ゲル状シートとする。このゲル状シート中に含まれる溶
媒を必要に応して塩化メチレンのような揮発性溶剤で抽
出処理して、溶媒量を１０〜９０重量％とする。このゲ
ル状シートをポリオレフィンの融点以下の温度で加熱し
、面倍率で１０倍以上に延伸する。この延伸膜中に含ま
れる溶媒を再び塩化メチレンのような揮発性溶剤で抽出
除去し、次いで乾燥する。Film formation can be performed, for example, as follows. A polyolefin containing an ultra-high molecular weight polyolefin is heated and dissolved in an amount of 1 to 50% by weight in a solvent such as liquid paraffin to form a uniform solution, and an electronically conductive material is uniformly blended into the solution. A sheet is formed from this solution and rapidly cooled to form a gel-like sheet. If necessary, the solvent contained in this gel sheet is extracted with a volatile solvent such as methylene chloride to adjust the amount of the solvent to 10 to 90% by weight. This gel-like sheet is heated at a temperature below the melting point of the polyolefin and stretched to an areal magnification of 10 times or more. The solvent contained in this stretched film is extracted and removed again with a volatile solvent such as methylene chloride, and then dried.
多孔性導電膜の空孔中には各種のカソード活物質、例え
ば、二酸化鉛、塩化チオニル、二硫化チタンを固定化し
て使用することができる。しかし、本発明では特に有機
硫黄酸化還元化合物を固定化する。この化合物は前記の
如＜ Ｒ５５Ｒの一般形を有し、２Ｒ５ＳＲ＋２ ｅ−
＝２Ｒ３−の可逆反応を行なうものであるが、このよう
な化合物の例としてはジメルカプトジチアゾール、ジメ
チルエチレンジアミン、トリチオシアヌル酸、ピペラジ
ンおよびそれらの重合体等であり、その他ポリエチレン
イミン誘導体等である。Various cathode active materials, such as lead dioxide, thionyl chloride, and titanium disulfide, can be immobilized in the pores of the porous conductive film. However, in the present invention, in particular, organic sulfur redox compounds are immobilized. This compound has the general form < R55R as described above and 2R5SR+2 e-
=2R3-, and examples of such compounds include dimercaptodithiazole, dimethylethylenediamine, trithiocyanuric acid, piperazine, and polymers thereof, and other polyethyleneimine derivatives.
本発明のＲ３５Ｒの固定化法としては、■溶液状のＲ５
５Ｒ溶媒に溶解させたＲ５５Ｒ１または溶媒中にゾル状
またはゲル状に微分散させたＲ５５Ｒを固体高分子多孔
性薄膜に含浸させるか、塗布またはスプレーした後溶剤
を除去する、■多孔性薄膜の製造工程でＲ５５Ｒの溶液
または、そのゾルまたはゲル状の分散溶液を混合した後
製膜する、■Ｒ５５Ｒの単量体や可溶性プレカーサーを
固体高分子多孔性薄膜に含浸させるか、塗布またはスプ
レーした後、空孔内で反応させる、等の方法を用いるこ
とができる。The method for immobilizing R35R of the present invention includes: (1) R5 in solution form;
Production of a porous thin film by impregnating, coating or spraying R55R1 dissolved in a 5R solvent or R55R finely dispersed in a solvent in the form of a sol or gel into a solid polymer porous thin film, and then removing the solvent. In the process, a film is formed after mixing a solution of R55R or its sol or gel-like dispersion solution. (2) After impregnating, coating or spraying a solid polymer porous thin film with a monomer or soluble precursor of R55R, A method such as causing a reaction within the pores can be used.
電解質としては、有機溶媒にＬｉ塩を溶解した普通のＬ
ｉ−Ｍｎ０□、 Ｌｉ−Ｔｉ５ｚ電池に使用されるもの
やＬｉ塩とポリエチレンオキシド（ＰＥＯ）の混合物を
シートにしたもの、Ｎａ” イオン導電性のβ−アルミ
ナのシートなどが使用される。As an electrolyte, ordinary L with Li salt dissolved in an organic solvent is used.
Used are those used in i-Mn0□ and Li-Ti5z batteries, sheets made of a mixture of Li salt and polyethylene oxide (PEO), and sheets of β-alumina with Na'' ion conductivity.
電池の構成はカソードに多孔性導電膜を用いる以外、慣
用の構成によることができる。本発明のカソードは薄膜
状であるので、好ましい形態として薄膜電池があり、こ
れを構成するために電解質としでも固体高分子多孔性薄
膜の空孔中に電解質を不動化したものを用いると、全固
体型でかつ超薄型の二次電池となる。The structure of the battery can be any conventional structure except for using a porous conductive film for the cathode. Since the cathode of the present invention is in the form of a thin film, a preferred form is a thin film battery, and if an electrolyte immobilized in the pores of a solid polymer porous thin film is used to construct this, the entire This is a solid-state and ultra-thin secondary battery.
（作 用〕
多孔性導電膜の空孔中にカソード°活物質を固定化する
ことにより、活物質を安定に保持した薄膜のカソードが
得られる。(Function) By fixing the cathode active material in the pores of the porous conductive film, a thin film cathode that stably holds the active material can be obtained.
テトラエチルチウラムダイサルファイド（ＴＥＴＤ）を
Ｃ３ＨｗＯＣＨ３に溶解し１５％の溶液をつくる。一方
、重量平均分子量５Ｘ１０’のポリエチレン３．８重量
部、ケッチエンブラック粉末１．２重量部、流動パラフ
ィン９５部を混合・撹拌した後、チッソ雰囲気下オート
クレーブ中で２３０°Ｃ迄昇温した。溶融物を金型に充
填しシート状に成形した後二軸に延伸した。得られたフ
ィルムをペンタンで洗浄し流動パラフィンを除去した。Tetraethylthiuram disulfide (TETD) is dissolved in C3HwOCH3 to make a 15% solution. On the other hand, 3.8 parts by weight of polyethylene having a weight average molecular weight of 5×10′, 1.2 parts by weight of Ketschen Black powder, and 95 parts of liquid paraffin were mixed and stirred, and the mixture was heated to 230° C. in an autoclave under a nitrogen atmosphere. The melt was filled into a mold and formed into a sheet, which was then biaxially stretched. The obtained film was washed with pentane to remove liquid paraffin.
これにより比電導率が５ Ｘ １０−’ Ｓ ｃｒｎ−
’の導電性多孔膜が得られた。This results in a specific conductivity of 5 x 10-' S crn-
'A conductive porous membrane was obtained.
ここで上記のＴＥＴＤ溶液に導電性多孔膜を浸し、真空
とすることで液を完全に膜中に含浸・固定化することが
でき、正極として使用可能となる。電解質にはＣＨ３＋
０ＣｚＨ５±ＣＨ３中に１５−１％のＬｉＣ１，０４を
溶解させた溶液を平均口径０．０１−の微多孔膜に含浸
固定化させたものを用いる。Here, by immersing the conductive porous membrane in the above-mentioned TETD solution and creating a vacuum, the liquid can be completely impregnated and fixed in the membrane, and it can be used as a positive electrode. The electrolyte contains CH3+
A solution prepared by dissolving 15-1% LiC1,04 in 0CzH5±CH3 is impregnated and immobilized on a microporous membrane with an average diameter of 0.01-1.
負極には金属リチウム７０声厚のものを使用し、第１図
のような電池を製作した。第１図において、電解質膜（
膜厚１０趨；４２Ｘ３３＋＋ｕ＋＋） １をリチウム負
極（厚さ７０．ＩＩＴＩＩ ； ４０Ｘ３０ｍｎ＋）
２とＲ５５Ｒ正極（厚さ１００μ；４０Ｘ３０ｍ＋＋＋
） ３とで挟持し、この集合体を金属板からなる容器４
に入れ、シール材５でシールした。電池の厚さは全体で
約４００μで、２ｍＡの放電で約３００ｍＡｈの容量を
有する。A battery as shown in Fig. 1 was manufactured using metallic lithium 70 mm thick as the negative electrode. In Figure 1, the electrolyte membrane (
Film thickness: 10; 42X33++u++) 1: Lithium negative electrode (thickness: 70.IITII; 40X30mn+)
2 and R55R positive electrode (thickness 100μ; 40X30m+++
) 3, and this assembly is placed in a container 4 made of a metal plate.
and sealed with sealant 5. The total thickness of the cell is about 400μ, and it has a capacity of about 300mAh at 2mA discharge.
この電池の放電・充電曲線を第２図に示す。同図の充放
電サイクルを５０回繰り返しても容量の劣化は見られな
かった。これにより、２４ｍＡという大電流を取り出せ
る薄膜２次電池が製作可能となった。The discharge and charge curves of this battery are shown in Figure 2. No deterioration in capacity was observed even after repeating the charge/discharge cycle shown in the figure 50 times. This has made it possible to produce a thin film secondary battery that can draw a large current of 24 mA.
本発明によれば、カソード活物質の保持性に優れた薄膜
状のカソード及び二次電池が捉供される。According to the present invention, a thin film cathode and a secondary battery having excellent cathode active material retention properties are provided.
特にカソード活物質として有機硫黄酸化還元化合物を用
いることにより、高電流密度、小型の二次電池が実現さ
れる。In particular, by using an organic sulfur redox compound as a cathode active material, a high current density, small-sized secondary battery can be realized.
第１図は実施例の二次電池の模式断面図、第２図は実施
例の二次電池の放電・充電特性図である。
１・・・電解質膜、 ２・・・リチウム負極、３
・・・Ｒ５５Ｒ正極、 ４・・・容器、５・・
・シール材。FIG. 1 is a schematic cross-sectional view of the secondary battery of the example, and FIG. 2 is a diagram of the discharge/charging characteristics of the secondary battery of the example. 1... Electrolyte membrane, 2... Lithium negative electrode, 3
...R55R positive electrode, 4...container, 5...
・Seal material.
Claims (1)
〜９０％、比導電率が１０＾−＾５Ｓｃｍ＾−＾１以上
の多孔性導電膜を用いたことを特徴とする二次電池。 ２、カソードの多孔性導電膜の空孔中に有機硫黄酸化還
元化合物を固定化した請求項１記載の二次電池。 ３、電解質が多孔性固体高分子薄膜の空孔中にイオン導
電体を固定化した電解質薄膜である請求項１又は２記載
の二次電池。[Claims] 1. The cathode has a film thickness of 1 to 1000 μm and a porosity of 30
~90% and a specific conductivity of 10^-^5Scm^-^1 or more. A secondary battery characterized by using a porous conductive film. 2. The secondary battery according to claim 1, wherein an organic sulfur redox compound is immobilized in the pores of the porous conductive film of the cathode. 3. The secondary battery according to claim 1 or 2, wherein the electrolyte is an electrolyte thin film in which an ionic conductor is immobilized in the pores of a porous solid polymer thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2054904A JPH03257767A (en) | 1990-03-08 | 1990-03-08 | Secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2054904A JPH03257767A (en) | 1990-03-08 | 1990-03-08 | Secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03257767A true JPH03257767A (en) | 1991-11-18 |
Family
ID=12983596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2054904A Pending JPH03257767A (en) | 1990-03-08 | 1990-03-08 | Secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03257767A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013503439A (en) * | 2009-08-28 | 2013-01-31 | シオン・パワー・コーポレーション | Electrochemical cell having a sulfur-containing porous structure |
-
1990
- 1990-03-08 JP JP2054904A patent/JPH03257767A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013503439A (en) * | 2009-08-28 | 2013-01-31 | シオン・パワー・コーポレーション | Electrochemical cell having a sulfur-containing porous structure |
| US9419274B2 (en) | 2009-08-28 | 2016-08-16 | Sion Power Corporation | Electrochemical cells comprising porous structures comprising sulfur |
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