JP2953144B2 - Separator for alkaline storage battery and its manufacturing method - Google Patents
Separator for alkaline storage battery and its manufacturing methodInfo
- Publication number
- JP2953144B2 JP2953144B2 JP3279230A JP27923091A JP2953144B2 JP 2953144 B2 JP2953144 B2 JP 2953144B2 JP 3279230 A JP3279230 A JP 3279230A JP 27923091 A JP27923091 A JP 27923091A JP 2953144 B2 JP2953144 B2 JP 2953144B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- water repellent
- roll
- storage battery
- alkaline storage
- 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 - Fee Related
Links
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
Landscapes
- Cell Separators (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルカリ蓄電池に用いる
セパレータの改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a separator used for an alkaline storage battery.
【０００２】[0002]
【従来の技術】活物質である水素を多量に電気化学的に
吸蔵・放出しうる水素吸蔵合金は、高エネルギー密度を
有する電極材料として注目され、高容量化を目指す密閉
形アルカリ蓄電池、特に密閉形ニッケル・水素蓄電池へ
の応用が図られている。密閉形ニッケル・水素蓄電池に
おける電極反応は以下に（化１）、（化２）として示す
とおりである。2. Description of the Related Art A hydrogen storage alloy capable of electrochemically storing and releasing a large amount of hydrogen as an active material has attracted attention as an electrode material having a high energy density. It is being applied to nickel-metal hydride storage batteries. The electrode reactions in the sealed nickel-metal hydride storage battery are shown below as (Chemical Formula 1) and (Chemical Formula 2).
【０００３】[0003]
【化１】 Embedded image
【０００４】[0004]
【化２】 Embedded image
【０００５】ここで、Ｍは水素吸蔵合金である。この電
池を過充電すると、正極、負極ではそれぞれ（化３）、
（化４）のガス発生反応が起こる。Here, M is a hydrogen storage alloy. When this battery is overcharged, each of the positive electrode and the negative electrode (Chem. 3)
The gas generation reaction of (Chem. 4) occurs.
【０００６】[0006]
【化３】 Embedded image
【０００７】[0007]
【化４】 Embedded image
【０００８】このとき、電池内圧の上昇を抑制する方法
として（化３）により正極から発生する酸素ガスを負極
に吸蔵されている水素と反応させて水にする方法が採ら
れている。また、（化４）の水素ガス発生を抑制するた
めに、負極の容量を正極の容量よりも大きくする方法が
採られている。しかし、急速充電時には、酸素ガスの発
生速度が、吸収速度を上回り、電池内に酸素ガスが蓄積
して電池内圧が上昇する。上記の不都合を解消するため
に、負極に白金などの貴金属触媒を添加し、酸素ガスの
還元を促進する方法（特開昭６０−１００３８２号）
や、負極に撥水層を設け、酸素ガスの負極上での吸収を
速める（特開昭６１−１１８９６３号）方法などがあ
る。At this time, as a method for suppressing an increase in the internal pressure of the battery, a method is employed in which oxygen gas generated from the positive electrode is reacted with hydrogen stored in the negative electrode to form water according to (Chemical Formula 3). Further, in order to suppress the generation of hydrogen gas in (Chem. 4), a method of increasing the capacity of the negative electrode to the capacity of the positive electrode has been adopted. However, at the time of rapid charging, the generation rate of oxygen gas exceeds the absorption rate, and oxygen gas accumulates in the battery to increase the internal pressure of the battery. In order to solve the above inconvenience, a method of adding a noble metal catalyst such as platinum to the negative electrode to promote the reduction of oxygen gas (Japanese Patent Application Laid-Open No. 60-100382)
Alternatively, there is a method in which a water-repellent layer is provided on the negative electrode to accelerate the absorption of oxygen gas on the negative electrode (Japanese Patent Laid-Open No. 61-18963).
【０００９】[0009]
【発明が解決しようとする課題】しかし、前述した従来
の方法においては、いろいろな問題が存在する。すなわ
ち、負極に貴金属を添加する方法では、材料の高価格化
という問題があった。一方負極に撥水剤を塗布する方法
では、負極表面にのみ撥水剤が存在するため、搬送、切
断、群構成等の各工程で負極表面から撥水剤が脱落する
という問題があった。その結果、負極表面の撥水性が低
下し所定の撥水性が得られずガス吸収能力が低下し電池
内圧が上昇する。そこで、撥水剤の脱落量を補償するた
め負極に接する側のセパレータに撥水剤を塗布する方法
が提案された。セパレータに撥水剤を塗布する方法とし
て、撥水剤をアルコールに分散させ、その分散液をスプ
レーにて噴霧する方法が考えられる。しかし、このスプ
レー方式ではセパレータ表面にのみ撥水剤が存在してい
るため、撥水剤の脱落量が多いという問題点がある。ま
た、この脱落を防ぐため、撥水剤が塗布されたセパレー
タに圧力をかけ固定化しようとするとセパレータ表面の
撥水剤が圧力により成膜化し、セパレータ表面は撥水剤
の成膜作用により、セパレータ中の電解液の吸液量が低
下し電池の内部抵抗が増大する。さらにセパレータのガ
ス透過性が低下し、正極から発生する酸素ガスがセパレ
ータのガス透過性の低下のため負極で吸収されにくくな
り電池内圧が上昇するという問題があった。However, the conventional method described above has various problems. That is, the method of adding a noble metal to the negative electrode has a problem that the material is expensive. On the other hand, in the method of applying the water repellent to the negative electrode, there is a problem that the water repellent drops off from the surface of the negative electrode in each step such as transport, cutting, and group formation because the water repellent exists only on the surface of the negative electrode. As a result, the water repellency of the surface of the negative electrode decreases, the predetermined water repellency cannot be obtained, the gas absorption capacity decreases, and the internal pressure of the battery increases. Therefore, a method of applying a water repellent to the separator in contact with the negative electrode in order to compensate for the amount of the water repellent dropped has been proposed. As a method of applying the water repellent to the separator, a method of dispersing the water repellent in alcohol and spraying the dispersion with a spray can be considered. However, in this spray method, since the water repellent is present only on the separator surface, there is a problem that a large amount of the water repellent falls off. Also, in order to prevent this dropping, when applying pressure to the separator coated with the water repellent to fix it, the water repellent on the separator surface is formed by pressure, and the separator surface is formed by the film forming action of the water repellent, The amount of electrolyte absorbed in the separator decreases, and the internal resistance of the battery increases. Further, the gas permeability of the separator is reduced, and the oxygen gas generated from the positive electrode is less likely to be absorbed by the negative electrode due to the reduced gas permeability of the separator, so that the internal pressure of the battery increases.
【００１０】[0010]
【課題を解決するための手段】この問題を解決するため
に本発明のアルカリ蓄電池用セパレータは撥水剤が塗布
されたセパレータにおいて、その撥水剤７はセパレータ
４の一方の表面から内部まで存在することを特徴とす
る。In order to solve this problem, a separator for an alkaline storage battery according to the present invention is a separator coated with a water repellent, and the water repellent 7 exists from one surface to the inside of the separator 4. It is characterized by doing.
【００１１】前記撥水剤７としては、四フッ化エチレン
六フッ化プロピレン共重合樹脂粉末および四フッ化エチ
レン重合樹脂粉末の少なくとも１種以上が好ましい。The water repellent 7 is preferably at least one of ethylene tetrafluoride hexafluoropropylene copolymer resin powder and ethylene tetrafluoride polymer resin powder.
【００１２】前記セパレータ４に含有される撥水剤７の
量は３．０〜１３．０g/m 2 程度が好ましい。The amount of the water repellent 7 contained in the separator 4 is preferably about 3.0 to 13.0 g / m 2 .
【００１３】セパレータ４はポリプロピレンまたはポリ
エチレンの少なくとも１種以上からなる繊維または不織
布をスルホン化処理したものが好ましい。The separator 4 is preferably a fiber or non-woven fabric made of at least one of polypropylene or polyethylene and subjected to a sulfonation treatment.
【００１４】なおセパレータ４のスルホン化度（炭素原
子数に対する硫黄原子数）は、０．１５×１０-2未満だ
と、撥水性が高すぎるためセパレータ４中の電解液の吸
液量が減少し電池内部抵抗が上昇し、また、０．４０×
１０-2を越えると、セパレータ４の引張強度が低下し電
池の群構成が困難になる。従って、セパレータ４のスル
ホン化度は、０．１５×１０-2〜０．４０×１０-2が好
ましい。If the degree of sulfonation (the number of sulfur atoms with respect to the number of carbon atoms) of the separator 4 is less than 0.15 × 10 −2 , the water repellency is too high, so that the amount of electrolyte absorbed in the separator 4 decreases. The internal resistance of the battery rises,
If it exceeds 10 -2 , the tensile strength of the separator 4 will decrease, and it will be difficult to form a group of batteries. Therefore, the degree of sulfonation of the separator 4 is preferably from 0.15 × 10 −2 to 0.40 × 10 −2 .
【００１５】なおセパレータ４を構成する繊維の構成は
中心がポリプロピレン、周囲がポリエチレンからなり、
その体積割合が４：６〜６：４であるものが好ましい。
ポリエチレンの役割として、セパレータ４製造時、熱風
によりポリエチレンが溶融しセパレータ４繊維間のバイ
ンダーとして働くため、ポリエチレンの体積割合が６割
を越えると、熱風によるポリエチレンの溶融量が多くな
り、その結果セパレータ４繊維間がポリエチレンにより
詰まり、撥水剤７をセパレータ４内部に存在させること
が困難になり、また、ポリエチレンの体積割合が４割未
満になると、セパレータの繊維間のバインダーとしての
機能を満足することができなくなる。The fibers constituting the separator 4 are made of polypropylene at the center and polyethylene at the periphery.
Those having a volume ratio of 4: 6 to 6: 4 are preferred.
As the role of polyethylene, when the separator 4 is manufactured, the polyethylene is melted by the hot air and acts as a binder between the fibers of the separator 4. Therefore, when the volume ratio of the polyethylene exceeds 60%, the amount of the polyethylene melted by the hot air increases, and as a result, the separator The space between the four fibers is clogged with polyethylene, making it difficult for the water-repellent agent 7 to be present inside the separator 4, and when the volume ratio of polyethylene is less than 40%, the separator functions as a binder between fibers. You will not be able to do it.
【００１６】[0016]
【００１７】また、本発明のアルカリ蓄電池用セパレー
タの製造法はセパレータの一方の表面から内部まで撥水
剤が存在するセパレータの製造法であって、撥水剤７を
含有した分散液５を転写するために順方向回転するロー
ル１とロール３の間にセパレータ４を通して分散液５を
塗布する工程において、ロール１とロール３の間のクリ
アランスｘをセパレータ４の厚みｔより小さくし、か
つ、セパレータ４の送り速度ｕに対しロール１の周速度
ｖを大きくすることを特徴とする。The method for producing a separator for an alkaline storage battery according to the present invention is a method for producing a separator in which a water repellent is present from one surface to the inside of the separator, wherein a dispersion 5 containing a water repellent 7 is transferred. In the step of applying the dispersion liquid 5 through the separator 4 between the rolls 1 and 3 which rotate in the forward direction, the clearance x between the rolls 1 and 3 is made smaller than the thickness t of the separator 4, and 4 is characterized in that the peripheral speed v of the roll 1 is increased with respect to the feed speed u of 4.
【００１８】ロール１に転写された分散液５を、セパレ
ータ４に塗布する工程において、セパレータの厚みｔmm
に対し塗布するロール１とロール３の間のクリアランス
ｘmmが０．１×ｔ未満の時、撥水剤７の塗布量を規定量
塗布することが困難になり、また、ｔ以上の時、セパレ
ータ４内部に撥水剤７を擦り込むことが困難になる。従
って、セパレータ４の厚みｔmmに対し塗布するロール１
とロール３の間のクリアランスｘmmは０．１×ｔ≦ｘ＜
ｔの範囲が好ましい。In the step of applying the dispersion liquid 5 transferred to the roll 1 to the separator 4, the thickness of the separator tmm
When the clearance xmm between the rolls 1 and 3 to be applied is less than 0.1 × t, it becomes difficult to apply a predetermined amount of the water repellent 7 and when the clearance is more than t, the separator It becomes difficult to rub the water repellent 7 into the inside 4. Therefore, the roll 1 to be applied to the thickness tmm of the separator 4
The clearance xmm between the roller and the roll 3 is 0.1 × t ≦ x <
The range of t is preferred.
【００１９】ロール１に転写された分散液５を、セパレ
ータ４に塗布する工程において、セパレータ４の送り速
度ｕに対しロール１の周速度ｖがｖ＝ｕ未満の時、セパ
レータ４内部に撥水剤７を擦り込むことが困難になり、
ｖ＝４ｕを越えると撥水剤７の塗布量を規定量塗布する
ことが困難になる。従って、セパレータ４の送り速度ｕ
に対しロール１の周速度ｖはｖ＝ｕ〜４ｕの範囲が好ま
しい。In the step of applying the dispersion liquid 5 transferred to the roll 1 to the separator 4, when the peripheral speed v of the roll 1 is less than v = u with respect to the feed speed u of the separator 4, the inside of the separator 4 has water repellency. It becomes difficult to rub the agent 7,
If v = 4u is exceeded, it becomes difficult to apply a prescribed amount of the water repellent 7. Therefore, the feed speed u of the separator 4
On the other hand, the peripheral speed v of the roll 1 is preferably in the range of v = u to 4u.
【００２０】分散液５の溶媒としてはエチルアルコー
ル、メチルアルコール、イソプロピルアルコールの少な
くとも１種以上からなるものを用いるのが好ましい。As the solvent of the dispersion 5, it is preferable to use one composed of at least one of ethyl alcohol, methyl alcohol and isopropyl alcohol.
【００２１】また、分散液５の濃度について、撥水剤７
の含有量が１０wt％未満だと撥水剤７の塗布量を規定量
塗布することが困難になり、また２０wt％を越えると、
撥水剤７の塗布量を規定量以上塗布することになる。従
って、撥水剤７の含有量は１０〜２０wt％が好ましい。Further, regarding the concentration of the dispersion 5, the water repellent 7
Is less than 10 wt%, it becomes difficult to apply a prescribed amount of the water repellent 7, and if it exceeds 20 wt%,
The application amount of the water repellent 7 is more than the specified amount. Therefore, the content of the water repellent 7 is preferably 10 to 20% by weight.
【００２２】ロール１と該ロール１に分散液５を塗布す
るために逆回転するロール２の間のクリアランスについ
て、クリアランスが２０μm 未満だと撥水剤７の塗布量
を規定量塗布することが困難になり、また、６０μm を
越えると、撥水剤７の塗布量を規定量以上塗布すること
になる。従ってロール１とロール２の間のクリアランス
は２０〜６０μm が好ましい。With regard to the clearance between the roll 1 and the roll 2 which rotates in the reverse direction to apply the dispersion liquid 5 to the roll 1, if the clearance is less than 20 μm, it is difficult to apply a prescribed amount of the water repellent 7 When the thickness exceeds 60 μm, the applied amount of the water repellent 7 is more than a specified amount. Therefore, the clearance between the rolls 1 and 2 is preferably 20 to 60 μm.
【００２３】ロール１の周速度ｖ m/minに対しロール２
の周速度ｗm/minがｗ＝０．１ｖ未満の時、ロール１と
ロール２の間の周速度の差が少ないため分散液５中の撥
水剤７の分散が不足する。またｗ＝０．４ｖを越える
と、分散液５中の撥水剤７の分散は良いがロール１とロ
ール２の間のクリアランスによってできる分散液５の膜
厚が周速度の差が大きいため不安定になり撥水剤７の塗
布量が不安定になる。従って、ロール１の周速度ｖ m/m
inに対し逆回転するロール２の周速度ｗ m/minはｗ＝
０．１ｖ〜０．４ｖの範囲が好ましい。For the peripheral speed v m / min of the roll 1, the roll 2
When the peripheral speed wm / min is less than w = 0.1 v, the dispersion of the water repellent 7 in the dispersion liquid 5 becomes insufficient because the difference in the peripheral speed between the rolls 1 and 2 is small. If w exceeds 0.4 v, the dispersion of the water repellent 7 in the dispersion liquid 5 is good, but the film thickness of the dispersion liquid 5 formed by the clearance between the rolls 1 and 2 is not good because the difference in peripheral speed is large. As a result, the amount of the water repellent 7 applied becomes unstable. Therefore, the peripheral speed v m / m of the roll 1
The circumferential speed w m / min of the roll 2 that rotates in reverse with respect to in is w =
A range of 0.1v to 0.4v is preferred.
【００２４】[0024]
【作用】本発明によれば、撥水剤７が塗布されたセパレ
ータ４において、その撥水剤７はセパレータ４の一方の
表面から内部まで存在することにより、撥水剤７の脱落
量の少ないセパレータとすることができる。したがっ
て、負極表面から撥水剤７が脱落するという問題に対
し、本発明の脱落量の少ないセパレータ４を用いること
により、負極からの撥水剤７の脱落量を補償することが
できる。その結果、負極に所望の撥水性を付与すること
が可能となり内圧の上昇しない電池を提供することがで
きる。スプレー方式による撥水剤のセパレータへの塗布
は、セパレータ表面のみに撥水剤が存在するため接着能
力のない撥水剤は脱落をおこす。その結果、撥水剤量が
減少し、負極に所望の撥水性を付与することが不可とな
りガス吸収能力が低下し、電池内圧が上昇する。またこ
の脱落量を防ぐため、撥水剤が塗布されたセパレータに
圧力をかけ固定化した場合、セパレータ表面の撥水剤が
圧力により成膜化し、セパレータ中への電解液の吸液量
およびガス透過性が低下する。その結果、電池の内部抵
抗の増大をもたらし、また電池内圧が上昇する。そこで
ロール１、３を用いて、分散液５が存在した状態で撥水
剤７をセパレータ４に擦り込みながら塗布することによ
り、セパレータ４表面から内部まで撥水剤７を存在させ
ることができ、撥水剤７の脱落量を減少することができ
る。また、スプレー方式で必要であった固定化工程を除
去できる。その結果、撥水剤７が成膜化することがなく
電池内部抵抗の上昇およびガス透過性の低下を抑制し、
電池内圧を低下させるものである。According to the present invention, in the separator 4 on which the water repellent 7 is applied, the water repellent 7 is present from one surface to the inside of the separator 4, so that the amount of the water repellent 7 which is dropped is small. It can be a separator. Therefore, against the problem that the water repellent 7 drops off from the surface of the negative electrode, the amount of water repellent 7 dropped from the negative electrode can be compensated for by using the separator 4 having a small amount of dropout according to the present invention. As a result, a desired water repellency can be imparted to the negative electrode, and a battery in which the internal pressure does not increase can be provided. When the water repellent is applied to the separator by the spray method, the water repellent having no adhesive ability is dropped because the water repellent is present only on the separator surface. As a result, the amount of the water repellent decreases, the desired water repellency cannot be imparted to the negative electrode, the gas absorbing ability decreases, and the internal pressure of the battery increases. In order to prevent the falling-off amount, when pressure is applied to the separator coated with the water-repellent agent to fix the separator, the water-repellent agent on the separator surface is formed into a film by the pressure, and the amount of electrolyte absorbed into the separator and the gas The permeability decreases. As a result, the internal resistance of the battery increases, and the internal pressure of the battery increases. Then, by applying the water repellent 7 while rubbing the separator 4 with the dispersion liquid 5 using the rolls 1 and 3, the water repellent 7 can be present from the surface of the separator 4 to the inside thereof. The amount of liquid agent 7 falling off can be reduced. Further, the immobilization step required by the spray method can be eliminated. As a result, the water repellent 7 is not formed into a film, thereby suppressing an increase in battery internal resistance and a decrease in gas permeability.
This is to lower the internal pressure of the battery.
【００２５】[0025]
【実施例】以下、本発明をその実施例により説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.
【００２６】本発明のセパレータ４を製造するためのロ
ール方式の転写装置を図１に示す。セパレータ４には繊
維径が９μm で中心がポリプロピレンで周囲がポリエチ
レンでその体積比率が５：５とした不織布を用いた。な
おセパレータ４のスルホン化度は０．２０×１０-2であ
り、厚みは０．１５mmである。撥水剤７としては四フッ
化エチレン六フッ化プロピレン共重合樹脂粉末を用い
た。この撥水剤７をエチルアルコール溶媒に分散させ、
撥水剤７の含有量が１５wt％の分散液５を作成し、分散
液タンク６に入れた。この分散液５を用い、下記の条件
により前記セパレータ４表面にロール方式により塗布し
た。ロール１とロール２の間のクリアランスを４０μm
、ロール１の周速度を１０m/min 、ロール２の周速度
を２m/min 、ロール１とロール３の間のクリアランスを
０．０５mmとした条件の下、図示しない送り装置により
セパレータ４の送り速度５m/min でロール１とロール３
の間を通し、四フッ化エチレン六フッ化プロピレン共重
合樹脂粉末を８．０g/m 2 塗布した。撥水剤７の塗布
後、８０℃の熱風にて５分間乾燥しセパレータ４を得
た。図２に得られたセパレータ４の断面図を示す。本実
施例によるセパレータ４は撥水剤７がセパレータ４表面
から内部まで存在し、撥水剤７の脱落量を減少すること
ができる。FIG. 1 shows a roll type transfer apparatus for producing the separator 4 of the present invention. A non-woven fabric having a fiber diameter of 9 μm, a center in polypropylene, a periphery in polyethylene, and a volume ratio of 5: 5 was used for the separator 4. The degree of sulfonation of the separator 4 is 0.20 × 10 −2 and the thickness is 0.15 mm. As the water repellent 7, a tetrafluoroethylene hexafluoropropylene copolymer resin powder was used. This water repellent 7 is dispersed in an ethyl alcohol solvent,
A dispersion 5 having a water repellent 7 content of 15 wt% was prepared and placed in a dispersion tank 6. This dispersion 5 was applied to the surface of the separator 4 by a roll method under the following conditions. 40 μm clearance between Roll 1 and Roll 2
Under the conditions that the peripheral speed of the roll 1 is 10 m / min, the peripheral speed of the roll 2 is 2 m / min, and the clearance between the rolls 1 and 3 is 0.05 mm, the feeding speed of the separator 4 is not shown in the drawing. Roll 1 and Roll 3 at 5m / min
Then, 8.0 g / m 2 of tetrafluoroethylene hexafluoropropylene copolymer resin powder was applied. After applying the water repellent 7, the separator was dried with hot air of 80 ° C. for 5 minutes to obtain a separator 4. FIG. 2 shows a sectional view of the obtained separator 4. In the separator 4 according to the present embodiment, the water repellent 7 exists from the surface of the separator 4 to the inside thereof, and the amount of the water repellent 7 that is dropped can be reduced.
【００２７】比較例１ 前記実施例と同じセパレータ４、撥水剤７および分散液
５を用い、スプレー方式（スプレーノズル０．７mm、ス
プレー圧力１kg/cm 2 ）にて、８．０g/m 2 塗布し乾燥
しセパレータ４を得た。図３に、得られたセパレータ４
の断面図を示す。本比較例によるセパレータ４は撥水剤
７がセパレータ４表面に存在しているため、撥水剤７が
脱落し易い。COMPARATIVE EXAMPLE 1 Using the same separator 4, water repellent 7, and dispersion liquid 5 as in the above example, 8.0 g / m 2 by a spray method (spray nozzle 0.7 mm, spray pressure 1 kg / cm 2 ). It was applied and dried to obtain a separator 4. FIG. 3 shows the obtained separator 4
FIG. In the separator 4 according to this comparative example, since the water repellent 7 exists on the surface of the separator 4, the water repellent 7 easily falls off.
【００２８】比較例２ 前記実施例と同じセパレータ４、撥水剤７および分散液
５を用い、前記比較例１と同様のスプレー方式にて、
８．０g/m 2 塗布し乾燥した。その後、シリコン製固定
化ロールにより５kg/cm 2 の圧力にて撥水剤７の固定化
を行いセパレータ４を得た。図４に、得られたセパレー
タ４の断面図を示す。本比較例によるセパレータ４は撥
水剤７が固定化により成膜化するため、撥水剤７の脱落
量は固定化しない場合と比較し減少するが、成膜により
セパレータ４のガス透過性が低下する。Comparative Example 2 Using the same separator 4, water-repellent agent 7, and dispersion liquid 5 as in the above-mentioned Example, in the same spraying method as in Comparative Example 1,
8.0 g / m 2 was applied and dried. Thereafter, the water repellent 7 was fixed by a silicon fixing roll at a pressure of 5 kg / cm 2 to obtain a separator 4. FIG. 4 shows a sectional view of the obtained separator 4. In the separator 4 according to the present comparative example, since the water repellent 7 is formed into a film by immobilization, the amount of the water repellent 7 that is dropped is reduced as compared with the case where the water repellent 7 is not fixed. descend.
【００２９】比較例３ 前記実施例と同じセパレータ４、撥水剤７および分散液
５を用い、前記実施例と同じ製造方法で、セパレータ４
に撥水剤７を２．０g/m 2 塗布し乾燥しセパレータ４を
得た。Comparative Example 3 Using the same separator 4, water repellent 7, and dispersion liquid 5 as in the above example, the same method as in the above example was used to produce the separator 4.
2.0 g / m 2 of a water repellent 7 was applied to the mixture and dried to obtain a separator 4.
【００３０】比較例４ 前記実施例と同じセパレータ４、撥水剤７および分散液
５を用い、前記実施例と同じ製造方法で、セパレータ４
に撥水剤７を１４．０g/m 2 塗布し乾燥しセパレータ４
を得た。Comparative Example 4 Using the same separator 4, water-repellent agent 7, and dispersion 5 as in the above-described embodiment, the same method as in the above-described embodiment was used.
14.0 g / m 2 of a water repellent 7 is applied to
I got
【００３１】次に前記セパーレタを用いて円筒密閉形ニ
ッケル水素電池を作成し、特性を試験した。負極に用い
る水素吸蔵合金組成はＭｍＮｉ5-X-Y-Z ＣｏX ＭｎY Ａ
ｌz （Ｘ＝０．７〜０．８，Ｙ＝０．３〜０．４，Ｚ＝
０．３〜０．４）である。この水素吸蔵合金粉末に水を
加えてペースト状にし、公知の多孔度９５％の発泡状ニ
ッケル多孔体へ充填した後、加圧し負極表面に四フッ化
エチレン六フッ化プロピレン共重合樹脂粉末を４g/m 2
塗布し、負極板を作製した。正極は水酸化ニッケルを公
知の多孔度９５％の発泡状ニッケル多孔体へ充填し容量
１４００mAh の正極板を作製した。このようにして得た
負極板と正極板と上記５種類のセパレータを介して渦巻
き状に旋回し負極端子を兼ねるケースに挿入した。なお
セパレータは撥水剤が塗布されいてる面を負極側にし
た。その後、所定量のアルカリ電解液を注液して封口し
円筒密閉形ニッケル水素蓄電池を構成した。Next, a cylindrical sealed nickel-metal hydride battery was prepared using the above separator, and its characteristics were tested. The composition of the hydrogen storage alloy used for the negative electrode was MmNi 5-XYZ Co X Mn Y A
l z (X = 0.7-0.8, Y = 0.3-0.4, Z =
0.3-0.4). Water is added to the hydrogen storage alloy powder to form a paste, which is filled into a known porous nickel porous body having a porosity of 95%, and then pressurized to apply 4 g of ethylene tetrafluoride hexafluoropropylene copolymer resin powder on the negative electrode surface. / m 2
This was applied to produce a negative electrode plate. As the positive electrode, nickel hydroxide was filled into a well-known porous nickel body having a porosity of 95% to prepare a positive electrode plate having a capacity of 1400 mAh. The thus obtained negative electrode plate, positive electrode plate and the above five types of separators were spirally swirled and inserted into a case also serving as a negative electrode terminal. The surface of the separator coated with the water repellent was on the negative electrode side. Thereafter, a predetermined amount of an alkaline electrolyte was injected and sealed to form a cylindrical sealed nickel-metal hydride battery.
【００３２】上記で作製したセパレータおよび円筒密閉
形ニッケル水素蓄電池を次の試験により評価した。The separator and the sealed nickel-metal hydride battery manufactured as described above were evaluated by the following tests.
【００３３】撥水剤を塗布したセパレータを振動試験
器で振動数５回／秒、振幅２mmで１分間振動させ撥水剤
の脱落量を測定した。The separator coated with the water repellent was vibrated at a frequency of 5 times / second at an amplitude of 2 mm for 1 minute using a vibration tester to measure the amount of the water repellent dropped off.
【００３４】作製した電池について電池内圧を測定し
た。電池内圧は、電池ケース底部に１mmφの穴をあけ、
圧力センサーを取り付けた固定装置に電池を固定して測
定した。電池内圧測定時の充電は１ＣｍＡの充電率で正
極容量２００％まで行ない、その時点における電池内圧
をその充電率における電池内圧とした。The internal pressure of the battery was measured. For the battery internal pressure, make a 1mmφ hole in the bottom of the battery case,
The measurement was performed with the battery fixed to a fixing device equipped with a pressure sensor. Charging at the time of measuring the battery internal pressure was performed at a charging rate of 1 CmA to a positive electrode capacity of 200%, and the battery internal pressure at that time was defined as the battery internal pressure at that charging rate.
【００３５】作製した電池について電池内部抵抗を測
定した。〜の試験結果を（表１）に示す。The internal resistance of the battery was measured. The test results are shown in Table 1 below.
【００３６】[0036]
【表１】 [Table 1]
【００３７】（表１）から明らかなように本発明による
ロール方式を用いてセパレータに８．０g/m 2 撥水剤を
塗布したものは、撥水剤の脱落が少なく、電池内圧も４
kg/m 2 と良好であった。As is clear from Table 1, according to the present invention,
8.0g / m on separator using roll methodTwoWater repellent
The applied one has little water repellent falling off and the battery internal pressure is 4
kg / m TwoAnd was good.
【００３８】比較例１はスプレー方式を用いてセパレー
タに同じ８．０g/m2 塗布したものであるが撥水剤の脱
落量が多くその結果、ガス吸収能力が低下し電池内圧が
上昇した。In Comparative Example 1, the same 8.0 g / m 2 was applied to the separator by using the spray method, but the amount of the water repellent dropped out was large, and as a result, the gas absorbing ability was reduced and the internal pressure of the battery was increased.
【００３９】比較例２はスプレー方式を用いてセパレー
タに同じ８．０g/m2 塗布したもので、その後、撥水剤
の脱落量を少なくするために、圧力をかけ固定化を行な
ったものであるが、その結果、比較例１と比べ撥水剤の
脱落量は減少したが、セパレータ表面に撥水剤膜を形成
するため、セパレータ中の電解液の吸液量が低下し電池
の内部抵抗が増大し、放電電位が低下した。さらにセパ
レータのガス透過性が低下し、電池内圧が上昇した。In Comparative Example 2, the same 8.0 g / m 2 was applied to the separator by using a spray method, and thereafter, in order to reduce the amount of the water-repellent agent that had dropped off, the separator was fixed by applying pressure. As a result, as a result, the amount of the water repellent dropped off was smaller than that in Comparative Example 1. However, since the water repellent film was formed on the separator surface, the amount of electrolyte absorbed in the separator was reduced, and the internal resistance of the battery was reduced. Increased, and the discharge potential decreased. Further, the gas permeability of the separator decreased, and the internal pressure of the battery increased.
【００４０】比較例３のロール方式を用いてセパレータ
に２．０g/m 2 塗布したものは、撥水剤の量が少ないた
めガス吸収能力が劣り、電池内圧が上昇した。In the case of applying the separator of 2.0 g / m 2 using the roll method of Comparative Example 3, the gas repelling agent was small, so that the gas absorbing ability was poor and the internal pressure of the battery was increased.
【００４１】比較例４のロール方式を用いてセパレータ
に１４．０g/m 2 塗布したものは、撥水剤の量が多すぎ
るためセパレータ中の電解液の吸液量が減少し電池内部
抵抗が上昇し、放電電位が低下した。When 14.0 g / m 2 was applied to the separator using the roll method of Comparative Example 4, the amount of the electrolyte in the separator was reduced because the amount of the water repellent was too large, and the internal resistance of the battery was reduced. And the discharge potential decreased.
【００４２】以上の結果から、ロール方式を用いて撥水
剤をセパレータの表面から内部まで存在させたものは、
撥水剤の脱落量が少なく、ガス吸収能力が良好で放電特
性にも優れた電池を提供することができる。撥水剤の量
についてはセパレータに３．０〜１３．０g/m 2 塗布し
たものが電池内圧特性の優れた電池を提供することがで
きる。From the above results, the case where the water repellent was present from the surface to the inside of the separator using the roll method was as follows:
It is possible to provide a battery that has a small amount of water repellent falling off, has good gas absorbing ability, and has excellent discharge characteristics. Regarding the amount of the water repellent, a separator coated with 3.0 to 13.0 g / m 2 can provide a battery having excellent battery internal pressure characteristics.
【００４３】[0043]
【発明の効果】以上のように、本発明のアルカリ蓄電池
用セパレータによれば、撥水剤をセパレータの一方の表
面から内部まで存在させることにより、撥水剤のセパレ
ータからの脱落量を減少させ、電池特性の優れたアルカ
リ蓄電池を提供できる。また、本発明のアルカリ蓄電池
用セパレータの製造法によれば前記アルカリ蓄電池用セ
パレータを効率よく製造できる。As described above, according to the alkaline storage battery separator of the present invention, the amount of the water repellent falling off the separator is reduced by allowing the water repellent to be present from one surface to the inside of the separator. Thus, an alkaline storage battery having excellent battery characteristics can be provided. Further, according to the method of manufacturing an alkaline storage battery separator of the present invention, the alkaline storage battery separator can be efficiently manufactured.
【図１】本発明のセパレータの製造に使用するロール方
式の転写装置の断面図FIG. 1 is a cross-sectional view of a roll-type transfer device used for manufacturing a separator of the present invention.
【図２】セパレータにロール方式により撥水剤を塗布し
た時のセパレータの断面図FIG. 2 is a cross-sectional view of the separator when a water repellent is applied to the separator by a roll method.
【図３】セパレータにスプレー方式により撥水剤を塗布
した時のセパレータの断面図FIG. 3 is a sectional view of the separator when a water repellent is applied to the separator by a spray method.
【図４】セパレータにスプレー方式により撥水剤を塗布
し、その後圧力をかけて固定化した時のセパレータの断
面図FIG. 4 is a cross-sectional view of the separator when a water repellent is applied to the separator by a spray method and then fixed by applying pressure.
１ ロール１ ２ ロール２ ３ ロール３ ４ セパレータ ５ 分散液 ６ 分散液タンク ７ 撥水剤 1 Roll 1 2 Roll 2 3 Roll 3 4 Separator 5 Dispersion 6 Dispersion tank 7 Water repellent
───────────────────────────────────────────────────── フロントページの続き (72)発明者 海谷 英男 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 津田 信吾 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平２−68853（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 2/16 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Kamiya 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-2-68853 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 2/16
Claims (15)
その撥水剤７はセパレータ４の一方の表面から内部まで
存在し、かつセパレータ４に含有される撥水剤７の量は
３．０〜１３．０g/m 2 であることを特徴とするアルカリ
蓄電池用セパレータ。1. A separator coated with a water repellent,
The water repellent 7 exists from one surface to the inside of the separator 4, and the amount of the water repellent 7 contained in the separator 4 is
3.0~13.0g / m 2 der Rukoto alkaline storage battery separator according to claim.
ピレン共重合樹脂粉末および四フッ化エチレン重合樹脂
粉末の少なくとも１種以上からなる請求項１記載のアル
カリ蓄電池用セパレータ。2. A water repellent 7 tetrafluoroethylene hexafluoropropylene copolymer resin powder and tetrafluoroethylene polymer resin powder according to claim 1 for an alkaline storage battery separator according consisting of at least one more.
エチレンの少なくとも１種以上からなる繊維または不織
布をスルホン化処理したもので、そのスルホン化度（炭
素原子数に対する硫黄原子数）が０．１５×１０-2〜
０．４０×１０-2である請求項１記載のアルカリ蓄電池
用セパレータ。3. The separator 4 is obtained by sulfonating a fiber or a non-woven fabric made of at least one of polypropylene or polyethylene, and has a degree of sulfonation (the number of sulfur atoms relative to the number of carbon atoms) of 0.15 × 10 −2. ~
Alkaline storage battery separator according to claim 1, wherein the 0.40 × 10 -2.
m で、中心がポリプロピレンで周囲がポリエチレンであ
り、その体積比率が４：６から６：４である請求項１記
載のアルカリ蓄電池用セパレータ。4. The fiber of the separator 4 has a fiber diameter of 3 to 20 μm.
In m, the center is polyethylene surrounding a polypropylene, the volume ratio of 4: 6 to 6: claim 1 Symbol is 4
For alkaline storage batteries.
剤が存在するセパレータの製造法であって、撥水剤７を
含有した分散液５を転写するために順方向回転するロー
ル１とロール３の間にセパレータ４を通して分散液５を
塗布する工程において、ロール１とロール３の間のクリ
アランスｘをセパレータ４の厚みｔより小さくし、か
つ、セパレータ４の送り速度ｕに対しロール１の周速度
ｖが大きくすることを特徴とするアルカリ蓄電池用セパ
レータの製造法。5. A method for producing a separator in which a water repellent is present from one surface to the inside of the separator, comprising: a roll 1 rotating in a forward direction to transfer a dispersion 5 containing a water repellent 7; In the step of applying the dispersion liquid 5 through the separator 4 between the rolls 3, the clearance x between the rolls 1 and 3 is made smaller than the thickness t of the separator 4, and the circumferential speed of the roll 1 is changed with respect to the feed speed u of the separator 4. A method for producing a separator for an alkaline storage battery, wherein the speed v is increased.
ータ４に塗布する工程において、セパレータ４の厚みt
mmに対し分散液５を塗布するロール１とロール３の間の
クリアランスｘmmを０．１×ｔ≦ｘ＜ｔである請求項５
記載のアルカリ蓄電池用セパレータの製造法。6. The step of applying the dispersion liquid 5 transferred to the roll 1 to the separator 4 in the step of coating the separator 4 with a thickness t
Claim clearance xmm between roll 1 and roll 3 for applying the dispersion liquid 5 to mm is 0.1 × t ≦ x <t 5
A method for producing the alkaline storage battery separator according to the above.
ータ４に塗布する工程において、セパレータの送り速度
ｕ m/minに対しロール１の周速度ｖ m/minをｖ＝ｕ〜
４ｕとした請求項５記載のアルカリ蓄電池用セパレータ
の製造法。7. In the step of applying the dispersion liquid 5 transferred to the roll 1 to the separator 4, the peripheral speed vm / min of the roll 1 is set to v = u to the feed speed um / min of the separator.
The method for producing a separator for an alkaline storage battery according to claim 5, wherein the thickness is 4u.
ルアルコール、イソプロピルアルコールの少なくとも１
種以上とした請求項５記載のアルカリ蓄電池用セパレー
タの製造法。8. The solvent of the dispersion 5 is at least one of ethyl alcohol, methyl alcohol and isopropyl alcohol.
6. The method for producing a separator for an alkaline storage battery according to claim 5, wherein the number is at least one kind.
０wt％である請求項５記載のアルカリ蓄電池用セパレー
タの製造法。9. The content of the water repellent 7 in the dispersion 5 is 10 to 2
The method for producing a separator for an alkaline storage battery according to claim 5 , wherein the amount is 0 wt%.
るために逆回転するロール２の間のクリアランスを２０
〜６０μm の範囲とした請求項５記載のアルカリ蓄電池
用セパレータの製造法。10. The clearance between the roll 1 and the roll 2 which rotates in the reverse direction to apply the dispersion liquid 5 to the roll is set at 20.
The method for producing a separator for an alkaline storage battery according to claim 5, wherein the thickness is in a range of from 60 to 60 µm.
２の周速度ｗ m/minをｗ＝０．１ｖ〜０．４ｖとした請
求項５記載のアルカリ蓄電池用セパレータの製造法。11. The method for producing a separator for an alkaline storage battery according to claim 5, wherein the peripheral speed w m / min of the roll 2 is set to 0.1 to 0.4 v with respect to the peripheral speed v m / min of the roll 1.
ロピレン共重合樹脂粉末および四フッ化エチレン重合樹
脂粉末の少なくとも１種以上からなる請求項５記載のア
ルカリ蓄電池用セパレータの製造法。12. The method for producing a separator for an alkaline storage battery according to claim 5, wherein the water repellent 7 comprises at least one of ethylene tetrafluoride hexafluoropropylene copolymer resin powder and ethylene tetrafluoroethylene polymer resin powder.
は３．０〜１３．０g/m2である請求項５記載のアルカリ
蓄電池用セパレータの製造法。13. The method for producing a separator for an alkaline storage battery according to claim 5 , wherein the amount of the water repellent 7 contained in the separator 4 is 3.0 to 13.0 g / m 2 .
リエチレンの少なくとも１種以上からなる繊維または不
織布をスルホン化処理したもので、そのスルホン化度
（炭素原子数に対する硫黄原子数）が０．１５×１０-2
〜０．４０×１０-2である請求項５記載のアルカリ蓄電
池用セパレータの製造法。14. The separator 4 is obtained by sulfonating a fiber or non-woven fabric made of at least one of polypropylene or polyethylene, and has a degree of sulfonation (the number of sulfur atoms relative to the number of carbon atoms) of 0.15 × 10 −2.
To 0.40 × 10 preparation of an alkaline storage battery separator according to claim 5, wherein -2.
μmで、中心がポリプロピレンで周囲がポリエチレンで
あり、その体積比率が４：６から６：４である請求項５
記載のアルカリ蓄電池用セパレータの製造法。15. The fiber of the separator 4 has a fiber diameter of 3 to 20.
6. The composition according to claim 5, in which the center is polypropylene and the periphery is polyethylene, and the volume ratio is from 4: 6 to 6: 4.
A method for producing the alkaline storage battery separator according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3279230A JP2953144B2 (en) | 1991-10-25 | 1991-10-25 | Separator for alkaline storage battery and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3279230A JP2953144B2 (en) | 1991-10-25 | 1991-10-25 | Separator for alkaline storage battery and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05121061A JPH05121061A (en) | 1993-05-18 |
| JP2953144B2 true JP2953144B2 (en) | 1999-09-27 |
Family
ID=17608249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3279230A Expired - Fee Related JP2953144B2 (en) | 1991-10-25 | 1991-10-25 | Separator for alkaline storage battery and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2953144B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4601748B2 (en) * | 1999-12-09 | 2010-12-22 | 日本バイリーン株式会社 | Battery separator |
| JP2001313066A (en) | 2000-04-27 | 2001-11-09 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JP2002033093A (en) | 2000-07-17 | 2002-01-31 | Matsushita Electric Ind Co Ltd | Nickel hydrogen storage battery and manufacturing method for it |
| JP3998446B2 (en) | 2001-10-04 | 2007-10-24 | 松下電器産業株式会社 | Alkaline storage battery |
| JP5100718B2 (en) * | 2009-08-04 | 2012-12-19 | パナソニック株式会社 | Prismatic nickel metal hydride storage battery |
| JP5912464B2 (en) * | 2011-12-02 | 2016-04-27 | 日本バイリーン株式会社 | Production method and production apparatus for porous sheet carrying coating component |
| CN104737357B (en) | 2012-11-28 | 2017-04-19 | 松下知识产权经营株式会社 | Nickel-hydrogen storage battery and battery pack |
-
1991
- 1991-10-25 JP JP3279230A patent/JP2953144B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05121061A (en) | 1993-05-18 |
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