JPH0558229B2 - - Google Patents
Info
- Publication number
- JPH0558229B2 JPH0558229B2 JP17888484A JP17888484A JPH0558229B2 JP H0558229 B2 JPH0558229 B2 JP H0558229B2 JP 17888484 A JP17888484 A JP 17888484A JP 17888484 A JP17888484 A JP 17888484A JP H0558229 B2 JPH0558229 B2 JP H0558229B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- current collector
- battery
- electrode current
- oxyhalide
- 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
- 239000011148 porous material Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- -1 alkaline earth metal salt Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000004020 conductor Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 239000006230 acetylene black Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001291 vacuum drying 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
Description
産業上の利用分野
本発明は、従来の注液式のオキシハライド電池
より高容量で、あらゆるコードレス機器用電源と
して使用可能な注液式のオキシハライド電池に関
するものである。
従来の技術
正極活物質にオキシハライドを用いる非水電池
では、オキシハライドとして塩化チオニル、塩化
スルフリル等を、負極活物質に活性金属であるリ
チウム等を用いる電池が開発されるいる。
このオキシハライド電池は、電池の溶媒が正極
活物質を兼ねるため、エネルギー密度が大きく、
開路電圧は、3.7Vを示すなど、優れた特性を有
するものの、電池長期貯蔵後の放電では、放電初
期に負極上に生成した保護膜のため、電圧遅延が
生ずるという問題がある。この電圧遅延を解決す
るため、電池極板群と、電解液等を添加したオキ
シハライド溶液とを分離しておき、電池使用時に
電池内へオキシハライド溶液を注入し、電池の活
性化をはかる、いわゆる注液式の電池とする方法
が採られている。注液式の電池とすることで貯蔵
時の電池の自己放電等の劣化も抑制され、電池寿
命の極めて長い、優れた電池となる。又、電池を
注液式とすることで、電池内に電解液のオキシハ
ライド溶液を持つ電池では、負極の自己放電を促
進して使えなかつた塩化ガリウムや塩化アルミニ
ウムといつたルイス酸が電解質として使用可能と
なり、高率放電が出来るという利点も有する
（N.Doddapaneni et al，Proc.30th Power
Sources Symposium7−10June 1982、p.201，
Published by The Electrochem.Soc.Inc.）。
オキシハライド電池では正極活物質が液体であ
るため、多孔質の正極集電体中で放電反応を起こ
させる必要がある。そのため正極集電体の多孔
度、細孔分布等の物性は、電池特性に大きく影響
する（S.Szpak et al，J.Power Sources，10
（1983）343）。それにもかかわらず、正極集電体
中での放電反応に必要な大きさの細孔径である有
効細孔径に関して論じた文献及び特許はない。
発明が解決しようとする問題点
以上のように従来明らかにされていなかつた正
極集電体の有効細孔径を解明するとともに、この
結果をもとに従来電池よりも更に高容量の注液式
のオキシハライド電池を得ることを目的とするも
のである。
問題点を解決するための手段
本発明は、塩化ガリウム電解質を用いる注液式
オキシハライド電池を高率放電した時の正極集電
体の有効細孔径を明らかにし、放電反応に有効に
関与する細孔表面積が大きなカーボンを正極集電
体に用いることで、従来のアセチレンブラツクを
正極集電体に用いた電池より、高容量の注液式の
オキシハライド電池を提供するものである。
作 用
凝集状態の違うフアーネスブラツク及び従来の
正極集電体材料であるアセチレンブラツクを用い
て、種々の細孔分布を有する正極集電体を作成
し、電池試験を行なつた。
オキシハライド電池では、放電時、正極集電体
中でオキシハライドの還元反応が起き、反応生成
物のうち、正極活物質で、溶媒でもあるオキシハ
ライドに不溶の塩は、正極集電体内に析出する。
この放電生成物の集電体反応面への析出で放電終
了に至る。
注液式のオキシハライド電池の利点は、他の非
水電池では不可能なほど高率での放電が可能な点
である。
同電池を高率で放電すると、放電反応におい
て、反応種の拡散が支配的となり、正極集電体の
細孔のうち、充分な径を有する細孔のみが反応に
関与する様になると考えられる。
又、オキシハライド電池では、放電容量は、有
効反応表面積の反応生成物での被覆で決定される
ので、放電容量と有効反応表面積との間には相関
がある。そこで、凝集状態の違う種々のカーボン
を正極集電体材料とすることで、細孔分布の異な
る正極集電体を作り、電池試験を行なつて、放電
容量と反応表面積の関係を調べた。本発明は正極
集電体の有効細孔径の結果から、従来のアセチレ
ンブラツクによる正極集電体より大きな有効反応
表面積を有する正極集電体を用いて電池を作るこ
とで、電池特性の改善をはかるものである。
実施例
凝集状態の異なる四種のフアーネスブラツク及
び従来の正極集電体材料であるアセチレンブラツ
クを用いて正極集電体は、ニツケルエキスパンド
集電網にテフロンを11％バインダーとして含むカ
ーボンペーストを塗布し、真空乾燥することによ
り作成した。負極にはリチウムを用い、ニツケル
集電網にリチウム薄膜を圧着して極板とした。セ
パレータは厚さ0.13mm、多孔度92％のガラス繊維
よりなる不織布を使用し、電解質として塩化ガリ
ウムを2M塩化チオニル添加した。
電池構造を第１図に示す。第１図は本発明にな
る電池の一実施例を示すものであり、図において
１は正極集電体、２は正極リード、３はセパレー
タ、４は負極、５はテフロンよりなる極板固定治
具である。正極板は10mm×20mm×0.3mmとし負極
板も同一面積とした。放電は、電池へ電解質を含
む塩化チオニル注液後ただちに85ｍＡ／cm2で端子
電圧2.5Vまで定電流で行なつた。なお、放電容
量は、正極集電体により規制される様リチウム及
び塩化チオニルは過剰に使用した。
本実施例で使用したカーボン及び同カーボンに
より作成した正極集電体の物性を表１に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a liquid injection type oxyhalide battery that has a higher capacity than conventional liquid injection type oxyhalide batteries and can be used as a power source for all cordless devices. BACKGROUND OF THE INVENTION Non-aqueous batteries using oxyhalides as positive electrode active materials have been developed, with thionyl chloride, sulfuryl chloride, etc. as the oxyhalides and lithium, etc. as active metals as negative electrode active materials. This oxyhalide battery has a high energy density because the battery solvent also serves as the positive electrode active material.
Although the battery has excellent characteristics such as an open circuit voltage of 3.7V, there is a problem in that during discharge after long-term storage of the battery, a voltage delay occurs due to the protective film formed on the negative electrode at the beginning of discharge. In order to solve this voltage delay, the battery plate group and the oxyhalide solution containing electrolyte etc. are separated, and when the battery is used, the oxyhalide solution is injected into the battery to activate the battery. A so-called injection type battery is used. By using a liquid injection type battery, deterioration such as self-discharge of the battery during storage is suppressed, resulting in an excellent battery with an extremely long battery life. In addition, by making the battery a liquid injection type, Lewis acids such as gallium chloride and aluminum chloride, which cannot be used as an electrolyte because they promote self-discharge of the negative electrode, can be used as an electrolyte in batteries with an oxyhalide solution as an electrolyte. It also has the advantage of being able to perform high rate discharge (N. Doddapaneni et al, Proc. 30th Power
Sources Symposium7−10June 1982, p.201,
Published by The Electrochem.Soc.Inc.). In oxyhalide batteries, since the positive electrode active material is a liquid, it is necessary to cause a discharge reaction in a porous positive electrode current collector. Therefore, physical properties such as porosity and pore distribution of the positive electrode current collector greatly affect battery characteristics (S.Szpak et al, J.Power Sources, 10
(1983) 343). Nevertheless, there are no literature or patents that discuss the effective pore size, which is the pore size necessary for the discharge reaction in the positive electrode current collector. Problems to be Solved by the Invention As described above, we have clarified the effective pore diameter of the positive electrode current collector, which has not been clarified in the past, and based on this result, we have developed a liquid injection type battery with a higher capacity than conventional batteries. The purpose is to obtain an oxyhalide battery. Means for Solving the Problems The present invention clarifies the effective pore diameter of the positive electrode current collector when a liquid injection type oxyhalide battery using a gallium chloride electrolyte is discharged at a high rate, and clarifies the effective pore diameter of the positive electrode current collector, and clarifies the effective pore diameter of the positive electrode current collector when a liquid injection type oxyhalide battery using a gallium chloride electrolyte is discharged. By using carbon with a large pore surface area for the positive electrode current collector, an injection-type oxyhalide battery with a higher capacity than conventional batteries using acetylene black for the positive electrode current collector is provided. Function Positive electrode current collectors with various pore distributions were prepared using furnace blacks with different agglomeration states and acetylene black, which is a conventional positive electrode current collector material, and battery tests were conducted. In oxyhalide batteries, during discharge, a reduction reaction of oxyhalide occurs in the positive electrode current collector, and among the reaction products, salts that are insoluble in the oxyhalide, which is the positive electrode active material and solvent, are deposited in the positive electrode current collector. do.
The discharge ends when the discharge products are deposited on the current collector reaction surface. The advantage of injection-type oxyhalide batteries is that they can discharge at higher rates than other non-aqueous batteries. When the same battery is discharged at a high rate, diffusion of reactive species becomes dominant in the discharge reaction, and only pores with a sufficient diameter among the pores of the positive electrode current collector become involved in the reaction. . Further, in an oxyhalide battery, the discharge capacity is determined by the coverage of the effective reaction surface area with the reaction product, so there is a correlation between the discharge capacity and the effective reaction surface area. Therefore, by using various carbons with different agglomeration states as positive electrode current collector materials, positive electrode current collectors with different pore distributions were created, and battery tests were conducted to investigate the relationship between discharge capacity and reaction surface area. Based on the results of the effective pore diameter of the positive electrode current collector, the present invention aims to improve battery characteristics by manufacturing a battery using a positive electrode current collector that has a larger effective reaction surface area than the conventional positive electrode current collector made of acetylene black. It is something. Example Using four types of furnace blacks with different agglomeration states and acetylene black, which is a conventional positive electrode current collector material, the positive electrode current collector was made by applying carbon paste containing 11% Teflon as a binder to a nickel expanded current collector net. , was prepared by vacuum drying. Lithium was used for the negative electrode, and a thin lithium film was pressed onto a nickel current collector network to form an electrode plate. The separator used was a nonwoven fabric made of glass fiber with a thickness of 0.13 mm and a porosity of 92%, and 2M thionyl chloride and gallium chloride were added as an electrolyte. The battery structure is shown in Figure 1. FIG. 1 shows an embodiment of the battery according to the present invention. In the figure, 1 is a positive electrode current collector, 2 is a positive electrode lead, 3 is a separator, 4 is a negative electrode, and 5 is a plate fixing jig made of Teflon. It is a ingredient. The positive electrode plate was 10 mm x 20 mm x 0.3 mm, and the negative electrode plate had the same area. Immediately after injecting thionyl chloride containing an electrolyte into the battery, discharging was carried out at a constant current of 85 mA/cm 2 to a terminal voltage of 2.5 V. Note that lithium and thionyl chloride were used in excess so that the discharge capacity was regulated by the positive electrode current collector. Table 1 shows the physical properties of the carbon used in this example and the positive electrode current collector made from the carbon.
【表】
種類の欄のア＝アセチレンブラツク、フア＝フ
アーネスブラツクを表わす。
吸油量およびよう素吸着量は日本工業規格
JISK6221による
吸油量とは、カーボンの凝集の程度を表わす値
で、一定量のカーボン中の空隙を満すのに要する
油の量である。よう素吸着量はカーボンの表面積
を示す。
2M塩化ガリウムを電解質としたリチウム／塩
化チオニル電池の85ｍＡ／cm2での放電試験の結果
を表２に示す。[Table] A=acetylene black and fur=furness black in the type column. Oil absorption and iodine adsorption amount meet Japanese Industrial Standards
According to JISK6221, oil absorption is a value representing the degree of carbon aggregation, and is the amount of oil required to fill the voids in a certain amount of carbon. The amount of iodine adsorption indicates the surface area of carbon. Table 2 shows the results of a discharge test at 85 mA/cm 2 of a lithium/thionyl chloride battery using 2M gallium chloride as an electrolyte.
【表】
単位カーボン重量当りの放電容量と正極集電体
用カーボンのよう素吸着量（比表面積）に相関は
なく、正極集電体内のすべての細孔が放電に関与
しているわけではないことが分かる。そこで正極
集電体の水銀圧入法による細孔体積の結果より各
細孔の表面積を求め、有効細孔径より大きな径の
細孔の積算表面積が単位カーボン重量当りの放電
容量と一次の相関を示す様に有効細孔径を決定し
た。有効細孔径を40ｍμとした時のそれぞれの電
池の単位カーボン重量当り放電容量と有効反応表
面積の関係を第２図に示すが、極めて良い相関を
示す。
以上の結果より、正極集電体の細孔分布を考慮
して有効反応表面積をアセチレンブラツクによる
集電体の50m2／ｇより大きくした正極集電体を用
い電池を組むことで、従来のアセチレンブラツク
を正極集電体に用いた電池より、高容量の塩化ガ
リウム電解質を用いた注液式オキシハライド電池
が製造可能となる。
本実施例ではオキシハライドとして塩化チオニ
ルを用いたが、塩化スルフリルでも同様の効果が
期待できる。
発明の効果
高率放電を要求される塩化ガリウム電解質を用
いる注液式のオキシハライド電池での正極集電体
の有効細孔径は40ｍμ以上であることが分かつ
た。
本発明はこの結果をふまえ従来のアセチレンブ
ラツクを用いた正極集電体の有効反応表面積：50
m2／ｇより広い有効反応表面積を有する正極集電
体を用いることで、従来電池より高容量の注液式
の塩化ガリウム電解質を用いるオキシハライド電
池を提供するものである。本発明電池用正極集電
体には、アセチレンブラツクに代えて高凝集のフ
アーネスブラツクに代表されるカーボンブラツク
が使用可能である。[Table] There is no correlation between the discharge capacity per unit carbon weight and the amount of iodine adsorption (specific surface area) of carbon for the positive electrode current collector, and not all pores in the positive electrode current collector are involved in discharge. I understand that. Therefore, the surface area of each pore was determined from the pore volume results obtained by the mercury intrusion method of the positive electrode current collector, and the cumulative surface area of pores with a diameter larger than the effective pore diameter showed a first-order correlation with the discharge capacity per unit carbon weight. The effective pore diameter was determined as follows. Figure 2 shows the relationship between the discharge capacity per unit carbon weight and the effective reaction surface area of each battery when the effective pore diameter is 40 mμ, and it shows an extremely good correlation. From the above results, we found that by assembling a battery using a positive electrode current collector with an effective reaction surface area larger than 50 m 2 /g of the current collector made of acetylene black, considering the pore distribution of the positive electrode current collector, it is possible to Compared to batteries using black as the positive electrode current collector, it is possible to manufacture injection type oxyhalide batteries using a high-capacity gallium chloride electrolyte. Although thionyl chloride was used as the oxyhalide in this example, similar effects can be expected with sulfuryl chloride. Effects of the Invention It was found that the effective pore diameter of the positive electrode current collector in an injection type oxyhalide battery using a gallium chloride electrolyte that requires high rate discharge is 40 mμ or more. Based on this result, the present invention has developed an effective reaction surface area of a positive electrode current collector using conventional acetylene black: 50
By using a positive electrode current collector having an effective reaction surface area larger than m 2 /g, an oxyhalide battery using an injection type gallium chloride electrolyte having a higher capacity than conventional batteries is provided. In the positive electrode current collector for the battery of the present invention, carbon black, typified by highly agglomerated furnace black, can be used instead of acetylene black.
第１図は本発明になる電池の一実施例を示す断
面図、第２図は従来電池Ａ及び本発明になる電池
Ｂ〜Ｅの単位カーボン重量当り放電容量と正極集
電体の有効反応表面積の関係図である。
１……正極集電体、２……正極リード、３……
セパレータ、４……負極、５……極板固定治具。
FIG. 1 is a cross-sectional view showing an embodiment of the battery according to the present invention, and FIG. 2 is a diagram showing the discharge capacity per unit carbon weight and the effective reaction surface area of the positive electrode current collector of conventional battery A and batteries B to E according to the present invention. It is a relationship diagram. 1... Positive electrode current collector, 2... Positive electrode lead, 3...
Separator, 4... negative electrode, 5... electrode plate fixing jig.
Claims (1)
にカーボンブラツクあるいはカーボンブラツクと
導電体等の複合体を用い、負極活物質に活性金属
を使用し、電解質として前記オキシハライド中に
塩化ガリウムを、あるいは塩化ガリウムとアルカ
リ金属あるいはアルカリ土類金属の塩を添加して
用いる注液式の非水電池において、前記正極集電
体をなすカーボンブラツクの40ｍμ以上の直径を
有する孔の積算表面積が、単位重量当り50m2／ｇ
をこえることを特徴とする非水電池。1. Oxyhalide is used as the positive electrode active material, carbon black or a composite of carbon black and a conductor is used as the positive electrode current collector, an active metal is used as the negative electrode active material, and gallium chloride is used in the oxyhalide as the electrolyte. Alternatively, in an injection type non-aqueous battery using gallium chloride and an alkali metal or alkaline earth metal salt added, the cumulative surface area of the pores having a diameter of 40 mμ or more in the carbon black forming the positive electrode current collector is 50m 2 /g per weight
A non-aqueous battery characterized by exceeding .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17888484A JPS6155867A (en) | 1984-08-27 | 1984-08-27 | Nonaqueous cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17888484A JPS6155867A (en) | 1984-08-27 | 1984-08-27 | Nonaqueous cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6155867A JPS6155867A (en) | 1986-03-20 |
| JPH0558229B2 true JPH0558229B2 (en) | 1993-08-26 |
Family
ID=16056380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17888484A Granted JPS6155867A (en) | 1984-08-27 | 1984-08-27 | Nonaqueous cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6155867A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160896A (en) * | 2013-03-01 | 2013-06-19 | 溧阳市新力机械铸造有限公司 | Preparing method of black hole solution for printed circuit board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2567413A (en) * | 2017-08-15 | 2019-04-17 | Hs Products Ltd | Pocketed spring unit and method and apparatus for forming the same |
-
1984
- 1984-08-27 JP JP17888484A patent/JPS6155867A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160896A (en) * | 2013-03-01 | 2013-06-19 | 溧阳市新力机械铸造有限公司 | Preparing method of black hole solution for printed circuit board |
| CN103160896B (en) * | 2013-03-01 | 2015-06-10 | 溧阳市新力机械铸造有限公司 | Preparing method of black hole solution for printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6155867A (en) | 1986-03-20 |
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