JPH0521073A - Inorganic nonaqueous electrolytic battery - Google Patents
Inorganic nonaqueous electrolytic batteryInfo
- Publication number
- JPH0521073A JPH0521073A JP3201512A JP20151291A JPH0521073A JP H0521073 A JPH0521073 A JP H0521073A JP 3201512 A JP3201512 A JP 3201512A JP 20151291 A JP20151291 A JP 20151291A JP H0521073 A JPH0521073 A JP H0521073A
- Authority
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- Japan
- Prior art keywords
- negative electrode
- height
- positive electrode
- battery
- difference
- 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.)
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Classifications
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- Y02E60/12—
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正極活物質のオキシハ
ロゲン化物が電解液の溶媒を兼ねる無機非水電解液電池
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic non-aqueous electrolyte battery in which an oxyhalide of a positive electrode active material also serves as a solvent for an electrolyte.
【０００２】[0002]
【従来の技術】塩化チオニル、塩化スルフリル、塩化ホ
スホリルなどのオキシハロゲン化物を正極活物質に用
い、アルカリ金属を負極に用い、炭素多孔質成形体を正
極に用い、上記正極活物質のオキシハロゲン化物が電解
液の溶媒を兼ねる無機非水電解液電池は、エネルギー密
度が高く、低温でも作動するなど、優れた特性を有して
いる。2. Description of the Related Art Oxyhalides such as thionyl chloride, sulfuryl chloride and phosphoryl chloride are used as a positive electrode active material, an alkali metal is used as a negative electrode, and a carbon porous molded body is used as a positive electrode. The inorganic non-aqueous electrolyte battery that also serves as a solvent for the electrolyte has excellent characteristics such as high energy density and operation at low temperatures.
【０００３】ところで、この無機非水電解液電池は、そ
の組立工程を図２を参照しつつ説明すると、電池ケース
２の内周面にリチウムなどのアルカリ金属を圧着して負
極１を円筒状に形成し、その内周側にセパレータ４を配
置し、底部絶縁材１１を電池ケース２の底部に配置した
後、中央部に正極３として円柱状の炭素多孔質成形体を
挿入し、その上方から押圧して、炭素多孔質成形体を下
方向に押圧すると共に径方向外方へ膨出させ、その外周
面をセパレータ４の内周面に圧着させる工程を経て、電
池組立が行われていた。The assembly process of this inorganic non-aqueous electrolyte battery will be described with reference to FIG. 2. An alkaline metal such as lithium is pressure-bonded to the inner peripheral surface of the battery case 2 to form the negative electrode 1 into a cylindrical shape. After being formed, the separator 4 is arranged on the inner peripheral side thereof, the bottom insulating material 11 is arranged at the bottom of the battery case 2, and then a cylindrical carbon porous molded body is inserted as the positive electrode 3 in the central portion, and from above, The battery was assembled through the steps of pressing the porous carbon body downward and bulging it outward in the radial direction, and pressing the outer peripheral surface thereof against the inner peripheral surface of the separator 4.
【０００４】そのため、この無機非水電解液電池では、
正極３の高さより負極１の高さを高くする方が電池組立
が行いやすく、その結果、ほとんどの電池が正極３の高
さより負極１の高さの方が高い状態に作製されていた。Therefore, in this inorganic non-aqueous electrolyte battery,
It is easier to assemble the battery when the height of the negative electrode 1 is higher than that of the positive electrode 3, and as a result, most of the batteries are manufactured so that the height of the negative electrode 1 is higher than that of the positive electrode 3.
【０００５】すなわち、押圧前の炭素多孔質成形体の高
さが負極１の高さより高いと、炭素多孔質成形体を上方
から押圧したときに、炭素多孔質成形体が径方向外方に
逃げて短絡発生の原因になるので、押圧前の炭素多孔質
成形体の高さを負極１の高さと同じか、または負極１の
高さより若干低くしておく方が、組立が容易であるから
である。That is, when the height of the carbon porous molded body before pressing is higher than the height of the negative electrode 1, the carbon porous molded body escapes radially outward when the carbon porous molded body is pressed from above. Since it causes a short circuit, it is easier to assemble if the height of the carbon porous molded body before pressing is equal to the height of the negative electrode 1 or slightly lower than the height of the negative electrode 1. is there.
【０００６】その結果、前記のように、ほとんどの電池
が、正極３の高さより負極１の高さが高くなっているの
が現状である。As a result, as described above, in most batteries, the height of the negative electrode 1 is higher than that of the positive electrode 3 under the present circumstances.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、負極１
の高さと正極３の高さとの差が大きくなると、重負荷で
放電した場合、特に放電終期には、負極１のアルカリ金
属のイオン化が電池反応に追いつかなくなり、負極の利
用率が低下する。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
When the difference between the height of the negative electrode 1 and the height of the positive electrode 3 becomes large, the ionization of the alkali metal of the negative electrode 1 cannot catch up with the battery reaction and the utilization factor of the negative electrode decreases, especially when discharged at a heavy load.
【０００８】したがって、本発明は、負極の利用率の低
下を抑制した無機非水電解液電池を提供することを目的
とする。Therefore, it is an object of the present invention to provide an inorganic non-aqueous electrolyte battery in which a decrease in the utilization rate of the negative electrode is suppressed.
【０００９】[0009]
【課題を解決するための手段】本発明は、負極の高さと
正極の高さとの差が負極の高さの１０％以下に規制する
ことによって、負極の利用率の低下を抑制したものであ
る。According to the present invention, the difference between the height of the negative electrode and the height of the positive electrode is regulated to 10% or less of the height of the negative electrode to suppress the decrease in the utilization rate of the negative electrode. ..
【００１０】[0010]
【実施例】つぎに、実施例をあげて本発明をより具体的
に説明する。なお、実施例では、リチウム−塩化チオニ
ル系の無機非水電解液電池について説明するが、本発明
はその場合のみに限られるものではない。EXAMPLES Next, the present invention will be described more specifically by way of examples. In addition, although a lithium-thionyl chloride-based inorganic non-aqueous electrolyte battery is described in Examples, the present invention is not limited to this case.
【００１１】実施例１ 図１に示すような構造で、負極１の高さと正極３の高さ
とが同じ高さのリチウム−塩化チオニル系の無機非水電
解液電池を作製した。この電池の詳細を図１を参照しつ
つ説明する。Example 1 A lithium-thionyl chloride-based inorganic non-aqueous electrolyte battery having a structure as shown in FIG. 1 in which the height of the negative electrode 1 and the height of the positive electrode 3 were the same was produced. Details of this battery will be described with reference to FIG.
【００１２】図中、１は負極、２は電池ケース、３は正
極、４はセパレータ、５は電解液、６は正極集電体、７
は電池蓋である。In the figure, 1 is a negative electrode, 2 is a battery case, 3 is a positive electrode, 4 is a separator, 5 is an electrolytic solution, 6 is a positive electrode current collector, and 7
Is a battery lid.
【００１３】上記電池蓋７は、環状のボディ８と環状の
絶縁層９と中央部の正極端子１０とを有していて、ボデ
ィ８の外周部は電池ケース２の開口端部に溶接されてい
る。そして、１１は底部絶縁材、１２は上部絶縁材であ
る。The battery lid 7 has a ring-shaped body 8, a ring-shaped insulating layer 9 and a positive electrode terminal 10 at the center, and the outer periphery of the body 8 is welded to the open end of the battery case 2. There is. 11 is a bottom insulating material and 12 is an upper insulating material.
【００１４】上記負極１は、厚さ１．０ｍｍのシート状
のリチウムを有底円筒状の電池ケース２の内周面に圧着
することにより形成されていて、円筒状をしており、そ
の高さは３０ｍｍである。The negative electrode 1 is formed by pressing sheet-shaped lithium having a thickness of 1.0 mm onto the inner peripheral surface of a cylindrical battery case 2 having a bottom, and has a cylindrical shape. The length is 30 mm.
【００１５】電池ケース２は、ステンレス鋼製で、その
内周面に負極１のリチウムが圧着することにより、負極
端子としての機能を備えている。The battery case 2 is made of stainless steel, and has a function as a negative electrode terminal when lithium of the negative electrode 1 is pressure-bonded to its inner peripheral surface.
【００１６】上記正極３は、アセチレンブラックを主成
分とし、これに黒鉛とポリテトラフルオロエチレンを添
加した炭素質を主材とする材料の多孔質成形体、いわゆ
る炭素多孔質成形体からなり、円柱状をしていて、その
高さは３０ｍｍである。The positive electrode 3 is made of a so-called carbon porous molded body, which is a porous molded body composed mainly of acetylene black, and a carbonaceous material containing graphite and polytetrafluoroethylene as a main material. It has a columnar shape and its height is 30 mm.
【００１７】セパレータ４は、ガラス繊維不織布からな
り、円筒状をしていて、上記負極１と正極３とを隔離し
ている。The separator 4 is made of glass fiber non-woven fabric and has a cylindrical shape to separate the negative electrode 1 and the positive electrode 3 from each other.
【００１８】電解液５は、塩化チオニルに支持電解質と
してＬｉＡｌＣｌ4（四塩化アルミニウムリチウム）を
１．２モル／リットル溶解した塩化チオニル溶液からな
り、塩化チオニルは上記のように電解液の溶媒であると
ともに正極活物質でもある。The electrolytic solution 5 is a thionyl chloride solution in which 1.2 mol / liter of LiAlCl 4 (lithium aluminum tetrachloride) is dissolved in thionyl chloride as a supporting electrolyte, and thionyl chloride is a solvent of the electrolytic solution as described above. It is also a positive electrode active material.
【００１９】このように塩化チオニルが正極活物質とし
て用いられていることからも明らかであるように、上記
正極３はそれ自身が反応するものではなく、正極活物質
の塩化チオニルと負極１からイオン化して溶出してきた
リチウムイオンとの反応場所を提供するものである。As is clear from the fact that thionyl chloride is used as the positive electrode active material, the positive electrode 3 does not react by itself, but is ionized from the thionyl chloride of the positive electrode active material and the negative electrode 1. It provides a reaction site with the lithium ions that have been eluted.
【００２０】正極集電体６はステンレス鋼棒からなり、
電池蓋７は前記のようにボディ８と絶縁層９と正極端子
１０を有している。The positive electrode current collector 6 is made of a stainless steel rod,
The battery lid 7 has the body 8, the insulating layer 9, and the positive electrode terminal 10 as described above.
【００２１】ボディ８はステンレス鋼で形成されてい
て、その立ち上がった外周部が前記電池ケース２の開口
端部と溶接により接合されている。The body 8 is made of stainless steel, and the raised outer peripheral portion is joined to the open end of the battery case 2 by welding.
【００２２】絶縁層９はボディ８の内周側にガラスで形
成されていて、この絶縁層９はボディ８と正極端子１０
とを絶縁するとともに、外周面でその構成ガラスがボデ
ィ８の内周面に融着し、内周面でその構成ガラスが正極
端子１０の外周面に融着していて、ボディ８と正極端子
１０との間をシールしている。The insulating layer 9 is formed of glass on the inner peripheral side of the body 8. The insulating layer 9 is formed on the body 8 and the positive electrode terminal 10.
And the insulating glass is fused to the inner peripheral surface of the body 8 at the outer peripheral surface, and the constituent glass is fused to the outer peripheral surface of the positive electrode terminal 10 at the inner peripheral surface. The space between 10 and 10 is sealed.
【００２３】正極端子１０はステンレス鋼製で、その一
部は電池組立時はパイプ状をしていて電解液注入口とし
て使用され、その上端部を電解液注入後にその中空部内
に挿入された正極集電体６の上部と溶接して封止するこ
とにより形成されたものである。The positive electrode terminal 10 is made of stainless steel, and a part of the positive electrode terminal 10 has a pipe shape and is used as an electrolyte injection port at the time of assembling the battery. The positive electrode terminal 10 is inserted into the hollow portion after the electrolyte is injected. It is formed by welding and sealing the upper portion of the current collector 6.
【００２４】底部絶縁材１１はガラス繊維不織布からな
り、正極３と負極端子を兼ねる電池ケース２とを絶縁し
ている。また、上部絶縁材１２は上記底部絶縁材１１と
同様のガラス繊維不織布からなり、正極３と負極端子を
兼ねる電池蓋７のボディ８とが直接接触しないように絶
縁している。The bottom insulating material 11 is made of glass fiber non-woven fabric and insulates the positive electrode 3 from the battery case 2 which also serves as the negative electrode terminal. The upper insulating material 12 is made of the same glass fiber non-woven fabric as the bottom insulating material 11 and insulates the positive electrode 3 and the body 8 of the battery lid 7 which also serves as the negative electrode terminal from direct contact.
【００２５】実施例２ 負極１の高さと正極３の高さとの差が負極１の高さの５
％である以外は、実施例１と同様の無機非水電解液電池
を作製した。Example 2 The difference between the height of the negative electrode 1 and the height of the positive electrode 3 is 5 times the height of the negative electrode 1.
An inorganic non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that the content was%.
【００２６】すなわち、この実施例２の電池において
は、負極１の高さが３１．６ｍｍであり、正極３の高さ
が３０ｍｍである。That is, in the battery of Example 2, the height of the negative electrode 1 was 31.6 mm and the height of the positive electrode 3 was 30 mm.
【００２７】実施例３ 負極１の高さと正極３の高さとの差が負極１の高さの１
０％である以外は、実施例１と同様の無機非水電解液電
池を作製した。Example 3 The difference between the height of the negative electrode 1 and the height of the positive electrode 3 is 1 of the height of the negative electrode 1.
An inorganic non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that the content was 0%.
【００２８】すなわち、この実施例３の電池において
は、負極１の高さが３３．３ｍｍであり、正極３の高さ
が３０ｍｍである。That is, in the battery of Example 3, the height of the negative electrode 1 is 33.3 mm and the height of the positive electrode 3 is 30 mm.
【００２９】比較例１ 負極１の高さと正極３の高さとの差が負極１の高さの１
９％である以外は、実施例１と同様の無機非水電解液電
池を作製した。Comparative Example 1 The difference between the height of the negative electrode 1 and the height of the positive electrode 3 is 1 of the height of the negative electrode 1.
An inorganic non-aqueous electrolyte battery similar to that of Example 1 was prepared except that the content was 9%.
【００３０】すなわち、この比較例１の電池は、図２に
示すとおりであり、負極１の高さが３７ｍｍで、正極３
の高さが３０ｍｍであって、負極１の高さが正極３の高
さよりかなり高くなっている。That is, the battery of Comparative Example 1 is as shown in FIG. 2, in which the negative electrode 1 has a height of 37 mm and the positive electrode 3 has a height of 37 mm.
Is 30 mm, and the height of the negative electrode 1 is considerably higher than that of the positive electrode 3.
【００３１】比較例２ 負極１の高さと正極３の高さとの差が負極１の高さの１
５％である以外は、実施例１と同様の無機非水電解液電
池を作製した。Comparative Example 2 The difference between the height of the negative electrode 1 and the height of the positive electrode 3 is 1 of the height of the negative electrode 1.
An inorganic non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that the amount was 5%.
【００３２】すなわち、この比較例１の電池において
は、負極１の高さが３５．３ｍｍであり、正極３の高さ
が３０ｍｍである。That is, in the battery of Comparative Example 1, the height of the negative electrode 1 was 35.3 mm and the height of the positive electrode 3 was 30 mm.
【００３３】つぎに、上記実施例１〜３および比較例１
〜２の電池を２０℃、３００Ω定抵抗で放電して放電電
気量を測定し、負極の理論電気量に対する負極の利用率
を算出した。その結果を表１に示す。Next, the above Examples 1 to 3 and Comparative Example 1
The batteries No. 2 to No. 2 were discharged at a constant resistance of 300Ω at 20 ° C., and the discharge electricity quantity was measured to calculate the utilization rate of the negative electrode with respect to the theoretical electricity quantity of the negative electrode. The results are shown in Table 1.
【００３４】[0034]
【表１】 （注） Ｈ1 ： 負極１の高さ Ｈ2 ： 正極３の高さ[Table 1] (Note) H 1 : Height of negative electrode 1 H 2 : Height of positive electrode 3
【００３５】表１に示すように、（Ｈ1 −Ｈ2 ）／Ｈ1
×１００、つまり、負極１の高さと正極３の高さとの差
が負極１の高さの１０％以下である実施例１〜３の電池
は、負極の利用率が９３％以上であり、負極の利用率の
低下が少なかった。As shown in Table 1, (H 1 -H 2 ) / H 1
× 100, that is, the batteries of Examples 1 to 3 in which the difference between the height of the negative electrode 1 and the height of the positive electrode 3 was 10% or less of the height of the negative electrode 1, the utilization rate of the negative electrode was 93% or more, There was little decrease in the utilization rate of.
【００３６】なお、上記の実施例では、正極活物質とし
て塩化チオニルを用い、負極にリチウムを用いた場合に
ついて説明したが、正極活物質としては、塩化チオニル
以外にも、塩化スルフリル、塩化ホスホリルなどの常温
（２５℃）で液体のオキシハロゲン化物を用いることが
でき、また、負極には、リチウム以外にも、ナトリウ
ム、カリウムなどのアルカリ金属を用いることができ
る。In the above examples, thionyl chloride was used as the positive electrode active material and lithium was used as the negative electrode. However, the positive electrode active material may be sulfuryl chloride, phosphoryl chloride, etc., in addition to thionyl chloride. A liquid oxyhalide at room temperature (25 ° C.) can be used, and an alkali metal such as sodium or potassium can be used for the negative electrode in addition to lithium.
【００３７】また、実施例では、電解液として塩化チオ
ニルにＬｉＡｌＣｌ4 を溶解させたものを用いた場合に
ついて説明したが、電解液には、上記組合せ以外にも、
塩化チオニル、塩化スルフリル、塩化ホスホリルなどの
オキシハロゲン化物にＬｉＡｌＣｌ4 、ＬｉＡｌＢ
ｒ4 、ＬｉＧａＣｌ4 、ＬｉＢ10Ｃｌ10などの支持電解
質を溶解させたものを用いることができる。なお、電解
液の調製にあたっては、ＬｉＡｌＣｌ4 などの支持電解
質は、ＬｉＣｌとＡｌＣｌ3 をオキシハロゲン化物に添
加した電解液中でＬｉＡｌＣｌ4 の形で存在（ただし、
イオン化してＬｉ+ イオンとＡｌＣｌ4 -イオンとで存
在）するようにしてもよい。In the examples, the case where thionyl chloride in which LiAlCl 4 is dissolved was used as the electrolytic solution, but the electrolytic solution is not limited to the above combinations.
For oxyhalides such as thionyl chloride, sulfuryl chloride and phosphoryl chloride, LiAlCl 4 , LiAlB
A solution in which a supporting electrolyte such as r 4 , LiGaCl 4 , or LiB 10 Cl 10 is dissolved can be used. Incidentally, In the preparation of the electrolyte, supporting electrolyte, such as LiAlCl 4 is present in the form of LiAlCl 4 in an electrolytic solution with the addition of LiCl and AlCl 3 in oxyhalide (however,
Ionized to be present as Li + ions and AlCl 4 − ions).
【００３８】さらに、実施例では、電池ケース２に有底
で円筒状のものを用いたが、電池ケース２は角筒状のも
のなど、円筒状以外の形状のものであってもよい。そし
て、実施例では、電池ケース２に円筒状のものを用いた
関係で、負極１やセパレータ４が円筒状で、正極３が円
柱状であるなど、電池の各構成部材が円筒状の電池ケー
ス２に適した形状のものを用いたが、電池ケース２が円
筒状以外の形状のものである場合には、各構成部材は電
池ケース２の形状に適するように作製したものを用いれ
ばよい。Furthermore, in the embodiment, the battery case 2 has a cylindrical shape with a bottom, but the battery case 2 may have a shape other than the cylindrical shape, such as a rectangular tube shape. In the example, the battery case 2 has a cylindrical shape, and the negative electrode 1 and the separator 4 have a cylindrical shape, and the positive electrode 3 has a cylindrical shape. However, when the battery case 2 has a shape other than a cylindrical shape, each component may be manufactured to have a shape suitable for the shape of the battery case 2.
【００３９】また、実施例では、絶縁層９をガラスで構
成したものを用いた場合について説明したが、絶縁層９
はセラミックスで構成したものであってもよい。In the embodiment, the case where the insulating layer 9 is made of glass is used, but the insulating layer 9 is used.
May be made of ceramics.
【００４０】[0040]
【発明の効果】以上説明したように、本発明では、負極
１の高さと正極３の高さとの差を負極１の高さの１０％
以下に規制することによって、負極の利用率の低下の少
ない無機非水電解液電池を提供することができた。As described above, in the present invention, the difference between the height of the negative electrode 1 and the height of the positive electrode 3 is 10% of the height of the negative electrode 1.
By restricting the following, it was possible to provide an inorganic non-aqueous electrolyte battery in which the utilization factor of the negative electrode was less likely to decrease.
【図１】本発明の無機非水電解液電池の一例を示す断面
図である。FIG. 1 is a cross-sectional view showing an example of an inorganic non-aqueous electrolyte battery of the present invention.
【図２】本発明外の無機非水電解液電池の一例を示す断
面図である。FIG. 2 is a cross-sectional view showing an example of an inorganic non-aqueous electrolyte battery outside the present invention.
１ 負極 ２ 電池ケース ３ 正極 ４ セパレータ ５ 電解液 1 Negative electrode 2 Battery case 3 Positive electrode 4 Separator 5 Electrolyte
Claims (1)
活物質および電解液の溶媒とし、 負極１と、正極３と、セパレータ４と、電解液５を有
し、 上記負極１は、有底筒状の電池ケース２の内周面にそっ
て配置された筒状のアルカリ金属からなり、 上記正極３は、上記電池ケース２の中央部に配置された
柱状の炭素多孔質成形体からなり、 上記負極１と正極３との間に、セパレータ４が配置して
いる無機非水電解液電池において、 負極１の高さと正極３の高さとの差が、負極１の高さの
１０％以下であることを特徴とする無機非水電解液電
池。Claim: What is claimed is: 1. An oxyhalide that is liquid at room temperature is used as a positive electrode active material and a solvent for an electrolytic solution, and has a negative electrode 1, a positive electrode 3, a separator 4, and an electrolytic solution 5. Reference numeral 1 denotes a cylindrical alkali metal arranged along the inner peripheral surface of a battery case 2 having a bottomed cylindrical shape, and the positive electrode 3 has a columnar carbon porous material arranged in the central portion of the battery case 2. In the inorganic non-aqueous electrolyte battery, which is formed of a molded body and has a separator 4 disposed between the negative electrode 1 and the positive electrode 3, the difference between the height of the negative electrode 1 and the height of the positive electrode 3 is the height of the negative electrode 1. Of 10% or less of the inorganic non-aqueous electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20151291A JP3031497B2 (en) | 1991-07-15 | 1991-07-15 | Inorganic non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20151291A JP3031497B2 (en) | 1991-07-15 | 1991-07-15 | Inorganic non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0521073A true JPH0521073A (en) | 1993-01-29 |
| JP3031497B2 JP3031497B2 (en) | 2000-04-10 |
Family
ID=16442275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20151291A Expired - Fee Related JP3031497B2 (en) | 1991-07-15 | 1991-07-15 | Inorganic non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3031497B2 (en) |
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|---|---|---|---|---|
| JPH05124198A (en) * | 1991-11-05 | 1993-05-21 | Seiko Epson Corp | Ink jet head and its manufacture |
| JP2000318149A (en) * | 1999-05-10 | 2000-11-21 | Matsushita Electric Ind Co Ltd | Ink jet head |
| JP2002355961A (en) * | 2001-05-31 | 2002-12-10 | Brother Ind Ltd | Ink jet head and ink jet recorder |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP3031497B2 (en) | 2000-04-10 |
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