JPH0332203B2 - - Google Patents
Info
- Publication number
- JPH0332203B2 JPH0332203B2 JP61079206A JP7920686A JPH0332203B2 JP H0332203 B2 JPH0332203 B2 JP H0332203B2 JP 61079206 A JP61079206 A JP 61079206A JP 7920686 A JP7920686 A JP 7920686A JP H0332203 B2 JPH0332203 B2 JP H0332203B2
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- voltage
- sulfolane
- electrolyte
- 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.)
- Expired - Lifetime
Links
- 239000003990 capacitor Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 claims description 3
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical group CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- -1 alkali metal salts Chemical class 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical group CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical group CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000004950 trifluoroalkyl group Chemical group 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
〔産業上の利用分野〕
本発明は電気二重層キヤパシタに関するもので
ある。
〔従来の技術〕
従来電気二重層キヤパシタの電解液としては過
塩素酸、六フツ化リン酸、四フツ化ホウ素又はト
リフルオロメタンスルホン酸のテトラアルキルア
ンモニウム塩、アンモニウム塩、又はアルカリ金
属塩等の炭素プロピレン、γ−ブチロラクトン、
アセトニトリル、ジメチルホルムアミド、アセト
ニトリル、などの有機溶媒に溶解させた電解液が
知られている（特開昭48−50255、特開昭49−
68254、特開昭59−2324097等）。
しかしながら、これら公知の溶媒を使用する場
合には、得られるキヤパシタの耐電圧は充分なも
のではなく、また電圧を印加した状態で高温下に
さらされると、キヤパシタの定格容量が低下して
しまうという問題が残されていた。
〔発明の解決しようとする問題点〕
本発明は、従来技術における上記問題点を解消
しようとするものであり、耐電圧が高くかつ高温
下での容量劣化の少ない電気二重層キヤパシタを
提供しようとするものである。
〔問題点を解決するための手段〕
すなわち、本発明は分極性電極と電解度との界
面で形成される電気二重層を利用する電気二重層
キヤパシタにおいて、該電解液が、スルホラン、
又はその誘導体からなる溶媒に溶質を溶解させた
溶液であることを徴とする電気二重層キヤパシタ
を提供しようとするのである。
本発明において、電解質の溶媒として使用され
るスルホランの誘導体としては、好ましくは３−
メチルスルホラン、２，４−ジメチルスルホラン
などが例示され、これらスルホラン又はその誘導
体はそれぞれ単独に用いることができる。しかし
ながら、本発明では、場合により、これらスルホ
ラン又はその誘導体を混合し混合溶媒として使用
することができる。かくした場合、スルホラン単
独では凝固点が28.5℃と高いが、誘電率が大きい
特性を有し、一方３−メチルスルホランあるいは
２，４−ジメチルスルホランは凝固点が低く、低
温物性がよいため、これらの混合溶媒は、両者の
特性を兼ね備えた性質、即ち、低温特性及び大き
い誘電率をもつことができる。スルホランとその
誘導体が混合される場合、誘導体の混合量は、好
ましくは、20〜70重量％、特には30〜60重量％と
することが、十分な低温特性及び内部抵抗値を付
与するために好ましい。
上記スルホラン又はその誘導体には、もちろん
既知の他の溶媒、例えば、炭酸プロピレン、γ−
ブチロラクトン、アセトニトリルを添加して、そ
の特性を改善することができる。
本発明において、電解液の溶質の種類は特に限
定されることがなく、従来より公知ないしは周知
のものが種々採用可能である。好ましい例として
は、電気化学的に安定な溶質であるアルカリ金
属、アルカリ土類金属、アンモニウム又はラトラ
アルキルアンモニウムなどの４フツ化ホウ酸塩、
６フツ化リン酸塩、過塩素酸塩、６フツ化ヒ素酸
塩、４塩化アルミン酸塩、又はトリフルオロアル
キル（好ましくはメタン）スルホン酸塩などが使
用される。なかでも、溶媒に対する溶解度、電気
導電性、電気化学的安定性の面から、テトラアル
キルアンモニウムの４フツ化ホウ酸塩あるいは６
フツ化リン酸塩は好ましい溶質である。本発明の
電解液中のこれら溶質を好ましくは0.1〜３モル、
特には0.5〜1.5モルの濃度で溶解せしめられる。
〔実施例〕
つぎに、実施例および比較例により本発明をさ
らに具体的に説明する。
なお、以下の実施例および比較例において、試
験装置は下記のようにして組立た。
まず、内面にねじ山を設けたニツケル製円筒形
有底容器中に各々被試験電解液を含浸させた陰極
側活性炭繊維（比表面積2000m2/ｇ、3.14cm2、0.4
mm厚）、ポリプロピレン不織布製セパレータ（4.9
cm2、0.4mm厚）、陽極側活性炭繊維（3.14m2、２mm
厚）を順次重ねて配置する。この際活性炭繊維は
セパレータを挟んで完全に対向させた配置にす
る。
つぎに、この容器に内外両面にねじ山を設けた
ポリテトラフルオロエチレン製リングをねじ込み
活性炭繊維およびセパレータの位置を固定する。
そして、白金リード線付白金網集電体（200メ
ツシユ）を先端に付けたねじ付きポリテトラフル
オロエチレン棒を前記リングの開口部にねじ込
み、白金リード線とニツケル製容器内の導通を
LCRメータ交流二端子法で確認することにより
セツトを完了する。なお、白金リード線は前記棒
の中心に設けた穴を介して外部に引きだしてあ
る。
上記のように組み立てた試験装置を使用し、第
１表に示される溶質と溶媒からなる種々の電解液
を活性炭繊維からなる陽極及び陰極電極に十分に
含浸するようにして使用したキヤパシタについて
特性を評価した。
評価項目は耐電圧の指標となる電解液の分解電
圧、および高温貯蔵後の容量維持率であり、それ
ぞれ以下の手順で測定した。
分解電圧は、試験キヤパシタをセツトした後、
直流電圧を印加して10分後の漏れ電流を測定し、
印加電圧を徐々に増加させたとき漏れ電流が急激
に立ち上る電圧を分解電圧とした。
高温貯蔵後の容量維持率（I0）の測定は次のよ
うに行なつた。まず、試験キヤパシタをセツトし
た後、2.8で１時間定電圧充電を行なう。その
後、1mAで定電流放電し、放電時の端子電圧が
1.0に至るまでの時間を測定し、その値より初
期容量（F0）算出した。
次に同試験セルを2.8の電圧を印加しながら、
85℃の恒温槽中で1000時間貯蔵した後、上記の同
様の方法で貯蔵後の容量（Ｆ）を測定し、高温貯
蔵後の容量維持率、I0＝F/F0×100を算出した。
電解液の種類を変えて試験した結果を第１表に
示す。なお、試験No.10、11、12は、比較のために
従来例を示したものである。表中TEAはテトラ
エチルアンモニウム、TBAはテトラブチルアン
モニウムを表わす。
[Industrial Field of Application] The present invention relates to an electric double layer capacitor. [Prior art] Conventional electrolytes for electric double layer capacitors include carbonaceous materials such as perchloric acid, phosphoric acid hexafluoride, boron tetrafluoride, or tetraalkylammonium salts, ammonium salts, or alkali metal salts of trifluoromethanesulfonic acid. Propylene, γ-butyrolactone,
Electrolytes dissolved in organic solvents such as acetonitrile, dimethylformamide, acetonitrile, etc. are known (Japanese Patent Laid-Open Nos. 48-50255, 1973-
68254, Japanese Patent Application Publication No. 59-2324097, etc.). However, when these known solvents are used, the withstand voltage of the capacitor obtained is not sufficient, and the rated capacity of the capacitor decreases when exposed to high temperatures with voltage applied. Problems remained. [Problems to be Solved by the Invention] The present invention attempts to solve the above-mentioned problems in the prior art, and aims to provide an electric double layer capacitor that has a high withstand voltage and less capacity deterioration at high temperatures. It is something to do. [Means for Solving the Problems] That is, the present invention provides an electric double layer capacitor that utilizes an electric double layer formed at the interface between a polarizable electrode and an electrolyte, in which the electrolyte contains sulfolane,
The purpose of the present invention is to provide an electric double layer capacitor characterized by a solution in which a solute is dissolved in a solvent made of a solute or a derivative thereof. In the present invention, the sulfolane derivative used as the electrolyte solvent is preferably 3-
Examples include methylsulfolane and 2,4-dimethylsulfolane, and each of these sulfolanes or derivatives thereof can be used alone. However, in the present invention, these sulfolane or its derivatives may be mixed and used as a mixed solvent depending on the case. In this case, sulfolane alone has a high freezing point of 28.5°C but has a large dielectric constant, while 3-methylsulfolane or 2,4-dimethylsulfolane have a low freezing point and good low-temperature properties, so a mixture of these The solvent can have properties that combine both properties, ie, low temperature properties and a high dielectric constant. When sulfolane and its derivatives are mixed, the amount of the derivative mixed is preferably 20 to 70% by weight, particularly 30 to 60% by weight, in order to provide sufficient low temperature characteristics and internal resistance value. preferable. The above sulfolane or its derivatives may of course be used with other known solvents, such as propylene carbonate, γ-
Butyrolactone, acetonitrile can be added to improve its properties. In the present invention, the type of solute in the electrolytic solution is not particularly limited, and various conventionally known or well-known solutes can be employed. Preferred examples include tetrafluoroborates such as alkali metals, alkaline earth metals, ammonium or latraalkylammonium, which are electrochemically stable solutes;
Used are hexafluorophosphate, perchlorate, hexafluoroarsenate, tetrachloride aluminate, trifluoroalkyl (preferably methane) sulfonate, and the like. Among them, tetraalkyl ammonium tetrafluoroborate or
Fluorinated phosphate is a preferred solute. These solutes in the electrolyte of the present invention are preferably 0.1 to 3 mol,
In particular, it is dissolved in a concentration of 0.5 to 1.5 molar. [Example] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, in the following Examples and Comparative Examples, the test apparatus was assembled as follows. First, activated carbon fibers on the cathode side (specific surface area 2000 m 2 /g, 3.14 cm 2 , 0.4
mm thickness), polypropylene nonwoven separator (4.9
cm 2 , 0.4mm thick), activated carbon fiber on the anode side (3.14m 2 , 2mm
Thickness) are placed one on top of the other. At this time, the activated carbon fibers are placed completely opposite each other with a separator in between. Next, a ring made of polytetrafluoroethylene having threads on both the inside and outside of the container is screwed into the container to fix the positions of the activated carbon fibers and the separator. Then, a threaded polytetrafluoroethylene rod with a platinum wire mesh current collector (200 mesh) attached to the tip is screwed into the opening of the ring to establish continuity between the platinum lead wire and the inside of the nickel container.
Complete the setup by checking with the LCR meter AC two terminal method. Note that the platinum lead wire is drawn out through a hole provided at the center of the rod. Using the test apparatus assembled as described above, the characteristics of capacitors were determined by sufficiently impregnating the anode and cathode electrodes made of activated carbon fibers with various electrolytes consisting of the solutes and solvents shown in Table 1. evaluated. The evaluation items were the decomposition voltage of the electrolytic solution, which is an indicator of withstand voltage, and the capacity retention rate after high-temperature storage, and each was measured using the following procedure. The decomposition voltage is determined after setting the test capacitor.
Measure the leakage current 10 minutes after applying DC voltage,
The voltage at which the leakage current suddenly rose when the applied voltage was gradually increased was defined as the decomposition voltage. The capacity retention rate (I 0 ) after high-temperature storage was measured as follows. First, after setting the test capacitor, perform constant voltage charging for 1 hour at step 2.8. After that, constant current discharge is performed at 1mA, and the terminal voltage at the time of discharge is
The time taken to reach 1.0 was measured, and the initial capacity (F 0 ) was calculated from that value. Next, while applying a voltage of 2.8 to the same test cell,
After storing for 1000 hours in a constant temperature bath at 85°C, the capacity after storage (F) was measured using the same method as above, and the capacity retention rate after high temperature storage, I 0 = F/F 0 × 100, was calculated. . Table 1 shows the results of tests using different types of electrolyte. Note that Test Nos. 10, 11, and 12 show conventional examples for comparison. In the table, TEA represents tetraethylammonium and TBA represents tetrabutylammonium.
本発明になるキヤパシタは、耐電圧および高温
下での容量劣化の点で従来のものより優れてお
り、その工業的価値はきわめて大である。
The capacitor of the present invention is superior to conventional capacitors in terms of withstand voltage and capacity deterioration under high temperatures, and its industrial value is extremely large.
Claims (1)
二重層を利用する電気二重層コンデンサにおい
て、該電解液が、スルホラン、又はその誘導体か
らなる溶媒に溶質を溶解させた溶液であることを
特徴とする電気二重層キヤパシタ。 ２ スルホランの誘導体が３−メチルスルホラン
もしくは２，４−ジメチルスルホランである特許
請求の範囲第１項記載の電気二重層キヤパシタ。[Claims] 1. An electric double layer capacitor that utilizes an electric double layer formed at the interface between a polarizable electrode and an electrolyte, in which the electrolyte has a solute dissolved in a solvent consisting of sulfolane or a derivative thereof. An electric double layer capacitor characterized in that it is a solution. 2. The electric double layer capacitor according to claim 1, wherein the sulfolane derivative is 3-methylsulfolane or 2,4-dimethylsulfolane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61079206A JPS62237715A (en) | 1986-04-08 | 1986-04-08 | Electric double-layer capacitor |
| US07/035,866 US4725927A (en) | 1986-04-08 | 1987-04-08 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61079206A JPS62237715A (en) | 1986-04-08 | 1986-04-08 | Electric double-layer capacitor |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6133192A Division JPH07101661B2 (en) | 1994-06-15 | 1994-06-15 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62237715A JPS62237715A (en) | 1987-10-17 |
| JPH0332203B2 true JPH0332203B2 (en) | 1991-05-10 |
Family
ID=13683470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61079206A Granted JPS62237715A (en) | 1986-04-08 | 1986-04-08 | Electric double-layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62237715A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6665171B1 (en) | 1999-09-16 | 2003-12-16 | Matsushita Electric Industrial Co., Ltd. | Electrochemical capacitor |
| EP1324358A3 (en) | 2001-12-11 | 2003-12-17 | Asahi Glass Co., Ltd. | Electric double layer capacitor |
| EP1365427B1 (en) | 2002-04-22 | 2008-03-19 | Asahi Glass Co., Ltd. | Electric double layer capacitor |
| WO2005008700A1 (en) | 2003-07-17 | 2005-01-27 | Asahi Glass Company, Limited | Electric double layer capacitor |
| JPWO2008018326A1 (en) | 2006-08-11 | 2009-12-24 | 旭硝子株式会社 | Non-aqueous electrolyte for electric double layer capacitor and electric double layer capacitor using the same |
| US8466324B2 (en) | 2008-11-17 | 2013-06-18 | Sumitomo Seika Chemicals Co., Ltd. | Sulfone compound |
| JP5674390B2 (en) * | 2010-09-13 | 2015-02-25 | 住友精化株式会社 | Sulfone compound and non-aqueous electrolyte using the same |
| CN104067361A (en) | 2012-03-29 | 2014-09-24 | 住友精化株式会社 | Electrolyte solution for electrochemical devices, aluminum electrolytic capacitor, and electric double layer capacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5541015A (en) * | 1978-09-18 | 1980-03-22 | Hitachi Ltd | Signal processing method in high speed facsimile |
-
1986
- 1986-04-08 JP JP61079206A patent/JPS62237715A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5541015A (en) * | 1978-09-18 | 1980-03-22 | Hitachi Ltd | Signal processing method in high speed facsimile |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62237715A (en) | 1987-10-17 |
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