JPH0244105B2 - HISUIYOBAIDENCHI - Google Patents
HISUIYOBAIDENCHIInfo
- Publication number
- JPH0244105B2 JPH0244105B2 JP453883A JP453883A JPH0244105B2 JP H0244105 B2 JPH0244105 B2 JP H0244105B2 JP 453883 A JP453883 A JP 453883A JP 453883 A JP453883 A JP 453883A JP H0244105 B2 JPH0244105 B2 JP H0244105B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- negative electrode
- porous carbon
- metal
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は非水溶媒電池に関し、特に正極材料を
改良した非水溶媒電池に係る。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a non-aqueous solvent battery, and particularly to a non-aqueous solvent battery with an improved positive electrode material.
負極活物質としてリチウム、ナトリウムを用い
た非水溶媒電池はエネルギー密度が大きく、貯蔵
特性に優れ、しかも作動温度範囲が広いという特
長をもち、電卓、時計、メモリのバツクアツプ電
源として多用されている。かかる電池は負極、電
解液、正極から構成されており、一般に負極とし
てリチウムやナトリウムなどのアルカリ金属を、
電解液としてプロピレンカーボネート、γ−ブチ
ロラクトン、ジメトキシエタンなどの非水溶媒中
に過塩素酸リチウム、ホウフツ化リチウムなどの
電解質を溶解してなる溶液を、正極として二酸化
マンガン、フツ化黒鉛等を、夫々用いている。
Nonaqueous solvent batteries that use lithium or sodium as negative electrode active materials have high energy density, excellent storage characteristics, and a wide operating temperature range, and are often used as backup power sources for calculators, watches, and memories. Such batteries are composed of a negative electrode, an electrolyte, and a positive electrode, and generally an alkali metal such as lithium or sodium is used as the negative electrode.
A solution prepared by dissolving an electrolyte such as lithium perchlorate or lithium borofluoride in a nonaqueous solvent such as propylene carbonate, γ-butyrolactone, or dimethoxyethane is used as the electrolyte, and manganese dioxide, graphite fluoride, etc. are used as the positive electrode, respectively. I am using it.
上述した電池の中でも負極にリチウムを用い、
塩化チオニル(SOCl2)を主正極活物質とした、
いわゆるリチウム塩化チオニル系電池は、特にエ
ネルギー密度が大きいため注目されている。こう
した電池は多孔質炭素体及び金属集電体からなる
正極を有し、一般に塩化リチウム(LiCl)及び塩
化アルミニウム(AlCl3)を溶解した塩化チオニ
ル(SOCl2)を電解液として用いている。したが
つて、SOCl2は正極活物質と電解液との双方を兼
用している。 Among the batteries mentioned above, lithium is used for the negative electrode,
Using thionyl chloride (SOCl 2 ) as the main positive electrode active material,
So-called lithium-thionyl chloride batteries are attracting attention because of their particularly high energy density. Such batteries have a positive electrode made of a porous carbon body and a metal current collector, and generally use thionyl chloride (SOCl 2 ) in which lithium chloride (LiCl) and aluminum chloride (AlCl 3 ) are dissolved as an electrolyte. Therefore, SOCl 2 serves both as a positive electrode active material and as an electrolyte.
ところで、SOCl2を正極活物質とする電池にお
いて、負極反応は負極金属が金属イオンとして電
解液中に溶解する反応であり、一方正極反応はそ
の正極の一構成材である多孔質炭素体上で起こ
り、反応生成物が該多孔質炭素体表面に生成する
反応である。しかしながら、アセチレンブラツク
をポリテトラフルオロエチレン等のポリマー結着
剤と共に混合し、所定形状に成形した後、乾燥し
て得た多孔質炭素体からなる正極を有する従来の
電池では、前記反応生成物が該多孔質炭素体上に
作られると、電極反応が著しく阻害され、放電容
量が低下する。しかも、前記電池では、大電流放
電では、低電流放電に比べて放電効率が著しく低
下するという欠点があつた。 By the way, in a battery using SOCl 2 as the positive electrode active material, the negative electrode reaction is a reaction in which the negative electrode metal dissolves in the electrolyte as metal ions, while the positive electrode reaction is a reaction in which the negative electrode metal dissolves on the porous carbon material that is one of the constituent materials of the positive electrode. This is a reaction in which a reaction product is produced on the surface of the porous carbon body. However, in conventional batteries having a positive electrode made of a porous carbon body obtained by mixing acetylene black with a polymer binder such as polytetrafluoroethylene, molding it into a predetermined shape, and drying it, the reaction product is When formed on the porous carbon body, the electrode reaction is significantly inhibited and the discharge capacity is reduced. Moreover, the above-mentioned battery has a drawback in that the discharge efficiency is significantly lower in large current discharge than in low current discharge.
本発明は放電容量及び大電流放電時での放電効
率の優れた非水溶媒電池を提供しようとするもの
である。
The present invention aims to provide a non-aqueous solvent battery with excellent discharge capacity and discharge efficiency during large current discharge.
本発明者らは多種の炭素材の中で、鎖状をなす
粒子の周面に黒鉛結晶薄層が形成された構造のカ
ーボンブラツクは極めて高い導電性、比表面積を
有することに着目し、このカーボンブラツクを主
成分とする多孔質炭素体及び金属集電体からなる
正極を用いることによつて、極めて放電特性の優
れた非水溶媒電池を見い出したものである。
Among various types of carbon materials, the present inventors noticed that carbon black, which has a structure in which a thin graphite crystal layer is formed on the circumferential surface of chain-shaped particles, has extremely high conductivity and specific surface area. By using a positive electrode consisting of a porous carbon body mainly composed of carbon black and a metal current collector, a non-aqueous solvent battery with extremely excellent discharge characteristics has been discovered.
上記正極は例えば以下に示す方法により造られ
る。上記特性のカーボンブラツクにポリテトラフ
ルオロエチレン等のポリマー結着材を添加混合
し、更にエチルアルコール等の有機溶剤を添加し
て充分に撹拌、混練した後、この混練物を金網、
パンチメタル、エキスパンドメタル等の金属集電
体に圧着し、乾燥することにより正極を造る。 The above-mentioned positive electrode is manufactured, for example, by the method shown below. After adding and mixing a polymer binder such as polytetrafluoroethylene to carbon black having the above characteristics, and further adding an organic solvent such as ethyl alcohol and thoroughly stirring and kneading, the kneaded product is mixed with a wire mesh,
A positive electrode is made by pressing onto a metal current collector such as punched metal or expanded metal and drying it.
次に、本発明をリチウム塩化チオニル電池に適
用した例について図面を参照して説明する。
Next, an example in which the present invention is applied to a lithium thionyl chloride battery will be described with reference to the drawings.
図中の1は負極端子を兼ねる上面が開口された
例えばステンレス製の缶体であり、この缶体1の
内面には金属リチウムからなる筒状の負極2が圧
着されている。この負極2の内側の缶体内には正
極3が該負極2内面に配置されたガラス繊維の不
織布からなるセパレータ4を介して設けられてい
る。なお、正極3と缶体1底面との間には絶縁紙
5が介装されている。前記正極3は鎖状をなす粒
子周面に黒鉛結晶薄層が形成された構造のカーボ
ンブラツク(ライオンアグゾ社製商品名;ケツチ
エンブラツク)90重量%とポリテトラフルオロエ
チレン10重量%を混合し、更にエタノールを添加
して混練した後、この混練物をステンレス製網体
からなる金属集電体6と共に該集電体6が内周面
に配置されるように円筒状に成形し、150℃の真
空下で乾燥して同金属集電体6の外周に圧着した
円筒状の多孔質炭素体7を形成することにより造
られる。 Reference numeral 1 in the figure denotes a can made of stainless steel, for example, with an open top that also serves as a negative electrode terminal, and a cylindrical negative electrode 2 made of metallic lithium is crimped onto the inner surface of the can 1. A positive electrode 3 is provided inside the can inside the negative electrode 2 with a separator 4 made of a nonwoven glass fiber fabric disposed on the inner surface of the negative electrode 2 . Note that an insulating paper 5 is interposed between the positive electrode 3 and the bottom surface of the can body 1. The positive electrode 3 is made of a mixture of 90% by weight of carbon black (trade name: KETSUCHEN BLACK, manufactured by Lion Agzo) and 10% by weight of polytetrafluoroethylene, which has a structure in which a thin graphite crystal layer is formed on the peripheral surface of chain-shaped particles. After further adding ethanol and kneading, this kneaded product was formed into a cylindrical shape together with a metal current collector 6 made of a stainless steel net so that the current collector 6 was disposed on the inner peripheral surface, and heated at 150°C. It is manufactured by forming a cylindrical porous carbon body 7 which is dried under vacuum and pressed onto the outer periphery of the same metal current collector 6.
また、前記正極3上方の缶体1内には前記セパ
レータ4に支持された絶縁紙8が配設されてい
る。前記缶体1の上面開口部にはメタルトツプ9
がレーザ溶接等により封着されている。このメタ
ルトツプ9の中心には穴10が開孔されている。
前記缶体1内にはLiAlCl4を溶解した1.8mol濃度
の塩化チオニル(SOCl2)溶液からなる電解液が
前記穴10を通して注入、収容されている。ま
た、前記メタルトツプ9の穴10には正極端子1
1がメタル−ガラスシール材12により電気的に
絶縁され、固定されている。この正極端子11は
その下端に取付けたリード線13を介して前記正
極3の金属集電体6に接続されている。 Further, an insulating paper 8 supported by the separator 4 is disposed inside the can body 1 above the positive electrode 3 . A metal top 9 is provided at the upper opening of the can body 1.
are sealed by laser welding or the like. A hole 10 is made in the center of this metal top 9.
An electrolytic solution consisting of a 1.8 mol thionyl chloride (SOCl 2 ) solution containing LiAlCl 4 dissolved therein is injected into the can body 1 through the hole 10 and housed therein. Further, a positive electrode terminal 1 is provided in the hole 10 of the metal top 9.
1 is electrically insulated and fixed by a metal-glass sealing material 12. This positive electrode terminal 11 is connected to the metal current collector 6 of the positive electrode 3 via a lead wire 13 attached to its lower end.
比較例
カーボンブラツクとして鎖状構造のアセチレン
ブラツクを用いた以外、前記実施例と同様にして
正極を作り、同構成のリチウム塩化チオニル電池
を組立てた。Comparative Example A positive electrode was prepared in the same manner as in the above Example except that acetylene black having a chain structure was used as the carbon black, and a lithium thionyl chloride battery having the same structure was assembled.
しかして、本実施例及び比較例の電池について
常温、300Ωの負荷放電特性を調べたところ、第
2図に示す特性図を得た。なお、第2図中のAは
本実施例の電池における放電特性曲線、Bは比較
例の電池の同曲線、である。この第2図から明ら
かな如く、本発明の電池(図中のA)は放電時間
が従来の電池(図中のB)に比べて著しく長く、
しかも放電電圧が高いことがわかる。このように
本発明の電池が優れた放電特性を有するのは、正
極の多孔質炭素体が鎖状をなす粒子周面に黒鉛結
晶薄層を形成した構造のカーボンブラツクを主成
分とするので、正極の導電性、反応表面積を著し
く向上できるからである。 When the load discharge characteristics of the batteries of this example and comparative example at room temperature and 300Ω were investigated, the characteristic diagram shown in FIG. 2 was obtained. Note that A in FIG. 2 is the discharge characteristic curve of the battery of this example, and B is the same curve of the battery of the comparative example. As is clear from FIG. 2, the battery of the present invention (A in the diagram) has a significantly longer discharge time than the conventional battery (B in the diagram).
Furthermore, it can be seen that the discharge voltage is high. The reason why the battery of the present invention has such excellent discharge characteristics is that the porous carbon body of the positive electrode is mainly composed of carbon black, which has a structure in which a thin graphite crystal layer is formed around the chain-shaped particles. This is because the conductivity and reaction surface area of the positive electrode can be significantly improved.
なお、上記実施例では正極として円筒状のもの
を用いたが、これに限定されない。例えばカーボ
ンブラツクとポリマー結着材との混練物を金属集
電体に圧着して帯状物とし、これを巻回して乾燥
した巻渦状の正極を用いてもよい。 Note that in the above embodiments, a cylindrical positive electrode was used, but the positive electrode is not limited to this. For example, a spiral positive electrode may be used, in which a kneaded mixture of carbon black and a polymer binder is pressed onto a metal current collector to form a band, which is then wound and dried.
以上詳述した如く、本発明によれば放電容量を
大巾に向上し、かつ放電効率の優れた非水溶媒電
池を提供できるものである。
As described in detail above, according to the present invention, it is possible to provide a non-aqueous solvent battery with greatly improved discharge capacity and excellent discharge efficiency.
第1図は本発明の一実施例を示すリチウム塩化
チオニル電池の断面図、第2図は本発明の電池及
び従来の電池における放電時間と端子電圧との関
係を示す特性図である。
1……缶体、2……負極、3……正極、4……
セパレータ、6……金属集電体、7……多孔質炭
素体、9……メタルトツプ、11……正極端子。
FIG. 1 is a sectional view of a lithium thionyl chloride battery showing an embodiment of the present invention, and FIG. 2 is a characteristic diagram showing the relationship between discharge time and terminal voltage in the battery of the present invention and a conventional battery. 1...Can body, 2...Negative electrode, 3 ...Positive electrode, 4...
Separator, 6... Metal current collector, 7... Porous carbon body, 9... Metal top, 11... Positive electrode terminal.
Claims (1)
筒状の負極と、この負極内側の缶体内にセパレー
タを介して配設され、多孔質炭素体及び金属集電
体からなる正極と、 前記缶体内に収容された塩化チオニルを主成分
とし、正極活物質を兼ねる電解液とを具備した非
水溶媒電池において、前記正極の多孔質炭素体と
して鎖状をなす粒子の周面に黒鉛結晶薄層が形成
された構造のカーボンブラツクを主成分とするも
のを用いたことを特徴とする非水溶媒電池。[Scope of Claims] 1. A cylindrical negative electrode made of an alkali metal provided on the inner surface of the can, and a porous carbon body and a metal current collector disposed within the can inside this negative electrode with a separator interposed therebetween. In a nonaqueous solvent battery comprising a positive electrode and an electrolytic solution containing thionyl chloride as a main component and serving as a positive electrode active material, the peripheral surface of chain-shaped particles as a porous carbon body of the positive electrode is provided. A non-aqueous solvent battery characterized by using a battery mainly composed of carbon black having a structure in which a thin graphite crystal layer is formed on the surface.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP453883A JPH0244105B2 (en) | 1983-01-14 | 1983-01-14 | HISUIYOBAIDENCHI |
DE8484100066T DE3485349D1 (en) | 1983-01-14 | 1984-01-04 | NONWATER ELECTROCHEMICAL CELL. |
EP19840100066 EP0118657B1 (en) | 1983-01-14 | 1984-01-04 | Non-aqueous electrochemical cell |
CA000445273A CA1222542A (en) | 1983-01-14 | 1984-01-13 | Non-aqueous electrochemical cell |
US07/129,902 US4767683A (en) | 1983-01-14 | 1987-12-07 | Non-aqueous electrochemical cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP453883A JPH0244105B2 (en) | 1983-01-14 | 1983-01-14 | HISUIYOBAIDENCHI |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59128773A JPS59128773A (en) | 1984-07-24 |
JPH0244105B2 true JPH0244105B2 (en) | 1990-10-02 |
Family
ID=11586816
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP453883A Expired - Lifetime JPH0244105B2 (en) | 1983-01-14 | 1983-01-14 | HISUIYOBAIDENCHI |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0244105B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62249355A (en) * | 1986-04-19 | 1987-10-30 | Hitachi Maxell Ltd | Inorganic nonaqueous electrolyte battery |
US4790969A (en) * | 1987-07-16 | 1988-12-13 | Eveready Battery Company | Dry molded cathode collector for liquid cathode systems |
-
1983
- 1983-01-14 JP JP453883A patent/JPH0244105B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS59128773A (en) | 1984-07-24 |
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