JPS58154171A - Lead-acid battery - Google Patents

Abstract

PURPOSE:To keep good contact between a current collector and a conductive electrolyte-holding layer to increase cycle life performance by forming the conductive electrolyte-holding layer with polytetrafluoroethylene and conductive powder. CONSTITUTION:An electrode group formed by stacking mutually one cathode plate 1 and two anode plates 2 and 2 with an interposed glass fiber separator 4 is inserted into a resin container 5. 10cc of s.g. 1.30 sulfuric acid are poured and impregnated and held in the plates and the separator. Then a container cover 8 having an anode terminal 6 and a cathode terminal 7 is set to form a lead-acid battery having a capacity of 1Ah. At least one electrode of above mentioned electrodes is constructed by arranging a conductive electrolyte-holding layer between an active mass layer and a current collector comprising lead or lead alloy. The conductive electrolyte-holding layer is formed with conductive powder and polytetrafluoroethylene. The quantity of polytetrafluoroethylene is limited to 0.5-20.0wt%.

Description

【発明の詳細な説明】 この発明は鉛蓄電池、特に遊離の電解液が実質的に存在
しないように電解液量を制限した形体のいわゆる、リテ
を一式鉛蓄電池に関するものであシ、電解液の利用率を
改善して電池性能の向上を計るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lead-acid battery, and particularly to a so-called lite lead-acid battery in which the amount of electrolyte is limited so that there is substantially no free electrolyte. This is intended to improve battery performance by improving the utilization rate.

まず、この種電池の放電反応の挙動について説明すると
、放電初期の段階では極板表面における電解液濃度と、
極板に密接せるセパレータに含浸、保持され九電解液濃
度とは同じであるが、放電を開始すると反応は極板表面
から進行する丸め極板表面における電解液濃度が低下し
て濃度勾配が生じ、セパレータに含浸、保持されている
電解液が極板表面に拡散されることになる。つまプ、極
板で消費される電解液量だけセパレータより拡散によっ
て補充されることになる。First, to explain the behavior of the discharge reaction in this type of battery, in the early stage of discharge, the electrolyte concentration on the electrode plate surface changes,
The concentration of the electrolyte is the same as that of the separator impregnated and held in close contact with the electrode plate, but when discharge starts, the reaction proceeds from the surface of the electrode plate.The concentration of the electrolyte decreases on the surface of the rounded electrode plate, creating a concentration gradient. , the electrolytic solution impregnated and held in the separator is diffused onto the surface of the electrode plate. The amount of electrolyte consumed by the electrode plates is replenished by diffusion from the separator.

そして、周知の如く鉛蓄電池における放電反応は陽極板
ではその活物質がＰｂ０宜（二酸化鉛）からＰｂ５Ｏｎ
　（硫酸鉛）へ、を九陰極板ではＰｂ　Ｃ鉛）からＰｂ
日０４に変化する亀のである。ｐｂｏ意あるいはＰｂ活
物質層からなる場合にヰして、１１３Ｂ０４層の孔径が
小なるため、Ｐｂ３Ｏ４が生成するに伴って極板深部へ
の電解液供給が円滑に行なわれず、電解液駿に見合つ大
容量を取出し得ないという不都合があった。As is well known, the discharge reaction in lead-acid batteries is such that the active material on the anode plate changes from Pb0 (lead dioxide) to Pb5On.
(lead sulfate), in nine cathode plates Pb (lead) to Pb
It is a turtle that changes on day 04. In the case of a PBO or Pb active material layer, the pore diameter of the 113B04 layer is smaller, and as Pb3O4 is generated, the electrolyte cannot be smoothly supplied to the deep part of the electrode plate, and the electrolyte flow is not adequate. The disadvantage was that it was not possible to extract a large capacity.

かかる不都合を解消すべく、極板に導電性保液層を配設
して、極板内への電解液供給を容易にし、電解液の利用
率を改善して電池性能の向上を計る提案は＃、、になさ
れている（昭和５６年特許願第１３７９４１号に詳しい
）。In order to solve this problem, there is a proposal to provide a conductive liquid retaining layer on the electrode plate to facilitate the supply of electrolyte into the electrode plate, improve the utilization rate of the electrolyte, and improve battery performance. #, (details in Patent Application No. 137941 of 1982).

しかしながら、上述したものは、電池の過充電等により
、導電性保液層が酸化作用を受け、カーボンブラックな
どの導電性構成部材が膨張し、体積変化しその結果、集
電体と導電層との密着性が低下して、電池特性が劣化す
るという難点があつ九・ 本発明者等は、かかる点に鑑み鋭意検討した結果、導電
性保液層′に４Ｈ＆＝４１４導電性粉末と、ポリテトラ
フルオロエチレンＣ以下、Ｐ、テ、ν・Ｋ、という）−
Ｅ”　ａ　＆することによシ、導電性粉末が過充電等に
：： よる酸化作用のために起こる体積変化を防止抑制する有
効な手段と表ることを見出した。However, in the above-mentioned method, due to overcharging of the battery, etc., the conductive liquid retaining layer is subjected to oxidation, and the conductive constituent members such as carbon black expand and change in volume, resulting in the current collector and the conductive layer The problem is that the adhesion of the battery decreases, resulting in deterioration of the battery characteristics.The inventors of the present invention have made extensive studies in view of this point, and have found that the conductive liquid retaining layer' contains 4H&=414 conductive powder and polyester. Tetrafluoroethylene C (hereinafter referred to as P, Te, ν・K)-
It has been found that conductive powder can be an effective means for preventing and suppressing volume changes caused by oxidation effects such as overcharging.

この発明は上記事実に基づいてなされたもので。This invention was made based on the above facts.

性保液層を、ポリテトラフルオロエチレン（Ｐ、Ｔ・ヒ ν・１・）÷禍会セ央導電性粉末で構成することＫより
、集電体と導電性保液層との密着性を良好に維持し、サ
イクル寿命特性などが向上する鉛蓄電池を提供するもの
である。The adhesiveness between the current collector and the conductive liquid-retaining layer is improved by forming the conductive liquid-retaining layer from polytetrafluoroethylene (P, T, hi ν, 1) ÷ kaikai seo conductive powder. The present invention provides a lead-acid battery that can be maintained well and has improved cycle life characteristics.

豐− 以下、この発明の一実施について詳述する。Toad- Hereinafter, one implementation of this invention will be described in detail.

陽極板甲および陰極板（りは、それぞれ鋳造、打抜きあ
るいはエキスバンド加工により得た鉛−カルシウム合金
を５０Ｘ５０Ｘ２箇および５０×５０×１−の寸法に裁
断しえるものを陽極集電体（ｌ＆）と陰極集電体（３１
）として用い、これら集電体の両面に導電性粉末、例え
ば、カーボンブラックに、Ｐ、？−１，ＩＬ粉末を混合
して、らい潰損等により、せん断力を加えて、このｒ・
テ・シ、ＩＣ・を繊維化せしめてカーボンブラックなど
の導電性粉末を保持させたのち、増粘剤で：：、あるポ
リエチレンオキサイド溶液を用いてペースト状ＫＬｔ４
のを、ローラにより厚み約α５−に圧電した導電性保液
層ｉｌ＋を夫々圧着する。そして、この保液層上Ｋｐｂ
ｏ（−酸化鉛）と水とよシなる活物質ペーストをローラ
により厚＃：１．０■および０，７■に圧延した寸法５
０×５０−のシート状活物質層（１ｂ）および（２ｂ）
を圧着して極板を構成し、それぞれの厚みは２．４箇お
よび１．２■である。Anode plate and cathode plate (respectively, lead-calcium alloy obtained by casting, punching, or expanded band processing can be cut into dimensions of 50 x 50 x 2 and 50 x 50 x 1) as the anode current collector (L&). and cathode current collector (31
), and conductive powder, e.g. carbon black, P, ? -1, IL powder is mixed and shearing force is applied due to leprosy, etc., and this r.
After making the IC into fibers and retaining conductive powder such as carbon black, it is made into paste KLt4 using a certain polyethylene oxide solution with a thickener.
Then, a piezoelectric conductive liquid retaining layer il+ having a thickness of approximately α5− is bonded by a roller. Then, Kpb on this liquid retaining layer
Dimensions 5 are obtained by rolling an active material paste consisting of o (-lead oxide) and water to a thickness of #: 1.0 and 0.7.
0x50-sheet-like active material layers (1b) and (2b)
are crimped to form electrode plates, each having a thickness of 2.4 mm and 1.2 mm.

以上のようにして得た一枚の陽極板（１）と２枚の陰極
板ｌｉｔ　（１１をガラス繊維セパレータ（４）を介し
て交互に積重し走電極群を、樹脂製の電槽（６）内に介
挿し、ついで比重１．３０の硫酸電解液を１０ｃｃ注液
して極板およびセパレータに含浸、保持せしめたの５、
陰、陽極外部端子ｎ１（ｔｌを取付けた電槽蓋（８）を
装着して容量ｌム■の鉛蓄電池を得た。そして、この電
池を化成して使用可能とする。One anode plate (1) and two cathode plates lit (11) obtained as described above are stacked alternately with glass fiber separators (4) interposed between them, and a running electrode group is placed in a resin container ( 6) Then, 10 cc of sulfuric acid electrolyte with a specific gravity of 1.30 was injected to impregnate and hold the electrode plate and separator.
A battery case lid (8) with negative and anode external terminals n1 (tl) attached was attached to obtain a lead-acid battery with a capacity of 1 mm.Then, this battery was chemically converted and made usable.

なお、実施例では、陰、陽極板の双方に導電性保液層を
配設する場合を述べたが、一方の極板にのみ適用しても
差支えない。In the embodiment, a case has been described in which the conductive liquid retaining layer is provided on both the negative and anode plates, but it may be applied only to one of the plates.

第２図は本発明電池に）と、導電性保液層ＫＰ、？・ν
・２・粉末を混合しないことを除いて他は本発明電池と
同様の比較電池（至）および導電性保液層を具備しない
ことを除いて他は本発明電池と同様の比較電池（Ｃ）と
のサイクル寿命特性比較図である。Figure 2 shows the battery of the present invention), conductive liquid retaining layer KP, ?・ν
・2. Comparative battery (C) which is otherwise the same as the battery of the present invention except that no powder is mixed; and comparative battery (C) which is the same as the battery of the present invention except that it does not have a conductive liquid retaining layer. It is a comparison diagram of cycle life characteristics with.

第２図より本発明電池によれば、サイクル特性が安定し
、サイクル寿命が向上していることがわかる＠ 本発明電池が比較電池に比してサイクル寿命特性が向上
するのは、Ｅ　Ｔ、　Ｆ、鳳役末が導電性粉末の過充電
等による酸化作用のために生じる膨張による体積変化を
防止押船し、集電体と導電性保液層の密着性能を良好な
状態で維持できるからである。From FIG. 2, it can be seen that the battery of the present invention has stable cycle characteristics and improved cycle life. The reason why the battery of the present invention has improved cycle life characteristics compared to the comparative battery is that F. This is because the Otori powder prevents volume changes due to expansion caused by oxidation caused by overcharging of the conductive powder, and maintains good adhesion between the current collector and the conductive liquid retaining layer. be.

なお、導電性粉末に混合するＰ、？、ν、ｍ、粉末の量
は、Ｐ、　Ｔ、　？、　Ｌの性質よりα５〜２０．０重
量−が良い。これは、Ｐ、　Ｔ、　？、　Ｉｃ、　＠末
がα５重量−以下であると、Ｆ、　Ｔ−１，ＩＡ、粉末
の結合力が乏しく、導電性粉末を保持することかで１な
（，２０，０重量−以上であると、Ｐ、τ、ｙ、ｍ・の
絶縁性、撥水性により導電性保液層の機能を阻害するか
らである。また、電〜１Ｏ１０参がより好ましい。In addition, P, ? to be mixed into the conductive powder? , ν, m, the amount of powder is P, T, ? , α5 to 20.0 weight is better than the properties of L. This is P, T, ? , Ic, @ If the powder is less than α5 weight, the bonding force of the F, T-1, IA, powder is poor, and it is difficult to hold the conductive powder (if it is more than 20,0 weight) This is because the insulating properties and water repellency of P, τ, y, and m inhibit the function of the conductive liquid retaining layer.Moreover, D to 1O10 are more preferable.

以上説明しえように、本発明電池によれば、極板の活物
質層と集電体との間に配設される導電性保液層を嬌債す
÷導電性粉末ヒ、ポリテトラフルオロエチレンｔ−ａａ
しているので、放電時、極板中心部への電解液供給が容
易に行なわれ、電解液の利用率が改善され電池容量が増
大するとともに、集電体と導電性保液層との密着性を良
好に維持してサイクル寿命特性が向上するなどその工業
的価値は極めて大きい。As can be explained above, according to the battery of the present invention, the conductive liquid retaining layer disposed between the active material layer of the electrode plate and the current collector is divided by conductive powder, polytetrafluorocarbon, etc. ethylene t-aa
During discharge, the electrolyte is easily supplied to the center of the electrode plate, improving the electrolyte utilization rate and increasing the battery capacity, as well as improving the close contact between the current collector and the conductive liquid retaining layer. Its industrial value is extremely great, as it maintains good properties and improves cycle life characteristics.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の一実施例を示す電池の縦断面図、第２
図は本発明電池（Ａ）と、比較電池（ロ）（Ｃ）とのサ
イクル寿命特性比較図である。 ’１）・・・陽極板、（ｌ　ｍ）　＃・＃極集電体、（
ｌｂ）・・・陽極活物質層、（２）・・・陰極板、　（
２ａ）・・・陰極集電体、（２ｂ）・・・陰極活物質１
−１（３）・・・導電性保液層、（４）・・・セパレー
タ、（６）・・・電槽、（８）・・・電槽蓋。FIG. 1 is a vertical cross-sectional view of a battery showing one embodiment of the present invention, and FIG.
The figure is a comparison diagram of the cycle life characteristics of the battery of the present invention (A) and comparative batteries (B) and (C). '1)... Anode plate, (l m) #/# electrode current collector, (
lb)... Anode active material layer, (2)... Cathode plate, (
2a)...Cathode current collector, (2b)...Cathode active material 1
-1 (3)... Conductive liquid retaining layer, (4)... Separator, (6)... Battery container, (8)... Battery container lid.

Claims (1)

【特許請求の範囲】[Claims] （１）　　陰、陽極板と、これら両極板間に介在せるセ
パレータと、前記極板およびセパレータに含浸保持され
遊離の電解液が実質的に存在しないように制限され走置
の電解液とを備え、少なくとも一方の前記極板は活物質
層と鉛又は鉛合金よ）なる集電体との間に導電性保液層
が配設されてなる鉛蓄電池であって、前記導電性保液層
を構構す毒導電性粉末ビポリテトラブルオロエチレンＩ
″槙腺しエチレンの量を、 ０．５〜２０．０重量嘩 にしたことを特徴とする特許請求の範凹第１項記載の鉛
蓄電池。(1) Comprising negative and anode plates, a separator interposed between these plates, and an electrolytic solution that is impregnated and retained in the electrode plates and separator and is restricted so that there is substantially no free electrolyte. , at least one of the electrode plates is a lead-acid battery in which a conductive liquid retaining layer is disposed between an active material layer and a current collector made of lead or a lead alloy; Constructed of poisonous conductive powder bipolytetrofluoroethylene I
The lead-acid battery according to claim 1, wherein the amount of ethylene is 0.5 to 20.0% by weight.