JP2815440B2 - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JP2815440B2 JP2815440B2 JP1342074A JP34207489A JP2815440B2 JP 2815440 B2 JP2815440 B2 JP 2815440B2 JP 1342074 A JP1342074 A JP 1342074A JP 34207489 A JP34207489 A JP 34207489A JP 2815440 B2 JP2815440 B2 JP 2815440B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode plate
- acid battery
- silicon dioxide
- sealed lead
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は密閉形鉛蓄電池に関するものであって、さら
に詳しくは、ペースト式極板の改善に関するものであ
る。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed lead-acid battery, and more particularly to an improvement in a paste-type electrode plate.
従来の技術 従来、この種の密閉形鉛蓄電池は、微細な酸化鉛の粉
（いわゆる鉛粉）に適当量の硫酸を滴下しながら練合し
て出来上がったペーストを鉛又は鉛合金からなる格子に
充填した後に熟成、乾燥したペースト式極板を使用して
おり、極板の寿命、特にサイクル寿命を向上させるため
に、樹脂短繊維をペースト中に添加する方法が採用され
ている。2. Description of the Related Art Conventionally, this type of sealed lead-acid battery has a paste formed by kneading a suitable amount of sulfuric acid into fine lead oxide powder (so-called lead powder) while dropping it into a grid made of lead or a lead alloy. A paste-type electrode plate aged and dried after filling is used. In order to improve the life of the electrode plate, particularly the cycle life, a method of adding short resin fibers to the paste is employed.
さらに、サイクル寿命の向上を目的として、特公昭60
−46778号公報に示されるように、ペースト練合時にフ
ッ素樹脂ディスパージョンを混合することにより活物質
を三次元構造で網状に結びついたフッ素樹脂繊維で囲う
方法が提案されている。Furthermore, in order to improve the cycle life,
As disclosed in JP-46778-A, there has been proposed a method in which a fluororesin dispersion is mixed at the time of kneading a paste to surround an active material with a fluororesin fiber tied in a three-dimensional network.
発明が解決しようとする課題 鉛蓄電池のサイクル寿命の劣化は、充放電時の活物質
の膨張・収縮による正極板の軟化・脱落と、負極板の収
縮が主たる原因である。Problems to be Solved by the Invention Deterioration of the cycle life of a lead storage battery is mainly caused by softening / falling of a positive electrode plate due to expansion / contraction of an active material during charge / discharge and contraction of a negative electrode plate.
これを抑制する方法として前記の特公昭60−46778号公
報で示されるように、ペースト練合時にフッ素樹脂ディ
スパージョンを混合することにより、活物質を三次元構
造で網状をなすフッ素樹脂繊維で囲う方法を採ると、サ
イクル寿命を長く保つ上に有効であるが、次のような問
題点があった。As shown in JP-B-60-46778 as a method for suppressing this, by mixing a fluororesin dispersion at the time of kneading the paste, the active material is surrounded by a fluororesin fiber forming a three-dimensional network. This method is effective for maintaining a long cycle life, but has the following problems.
すなわち、フッ素樹脂は撥水性を有するため、鉛蓄電
池における反応物質の一つである電解液の硫酸もはじく
性質がある。開放（ベント）形鉛蓄電池の場合には電解
液が豊富に存在し、極板周辺の電解液も十分存在するの
で問題とはならないが、充電時に正極から発生する酸素
ガスを、負極で吸収する負極吸収式密閉形鉛蓄電池の場
合、電解液量は制限され、正極・負極板及びセパレータ
中に存在するのみであり、フッ素樹脂の撥水性のため
に、電解液が有効に反応に寄与しにくいという問題点を
生じた。That is, since the fluororesin has water repellency, it has a property of repelling sulfuric acid of the electrolytic solution which is one of the reactants in the lead storage battery. In the case of an open (vented) type lead-acid battery, there is no problem because the electrolyte is abundant and the electrolyte around the electrode plate is also sufficient, but the oxygen gas generated from the positive electrode during charging is absorbed by the negative electrode In the case of a negative electrode absorption type sealed lead-acid battery, the amount of electrolyte is limited and only exists in the positive electrode / negative electrode plate and the separator. Due to the water repellency of the fluororesin, the electrolyte does not effectively contribute to the reaction. The problem arose.
本発明はこのような問題点を解決するもので、寿命、
特にサイクル寿命の延長を図ると同時に活物質の利用率
向上を図ることを目的とするものである。The present invention solves such a problem, and has a long life,
In particular, it aims at extending the cycle life and at the same time improving the utilization rate of the active material.
課題を解決するための手段 これらの問題点を解決するために本発明は、活物質中
に二酸化珪素を含み、なおかつ活物質は互いに三次元構
造で網上に結びついているフッ素樹脂繊維で囲われた極
板を、正極板と負極板のうち少なくとも一方に使用した
ものである。Means for Solving the Problems In order to solve these problems, the present invention is directed to a method in which silicon dioxide is contained in an active material, and the active material is surrounded by a fluororesin fiber which is mutually connected in a three-dimensional structure on a net. The negative electrode plate is used for at least one of a positive electrode plate and a negative electrode plate.
作用 この構成では、ペースト状活物質中に二酸化珪素を添
加することにより、 （１）親水性を有する二酸化珪素が極板活物質中に存在
すること、及び二酸化珪素を添加するとペースト状活物
質が高多孔性になり活物質の見かけ密度が低くなること
から、極板の保液性（極板が吸収しうる電解液量）が向
上する。Action In this configuration, by adding silicon dioxide to the paste-like active material, (1) the presence of silicon dioxide having hydrophilicity in the electrode plate active material; Since the porous material becomes highly porous and the apparent density of the active material becomes low, the liquid retaining property of the electrode plate (the amount of electrolyte that can be absorbed by the electrode plate) is improved.
（２）見かけ密度の低下が活物質重量当たりの表面積の
増大をもたらし、活物質の利用率が向上する。(2) The decrease in apparent density leads to an increase in surface area per active material weight, and the utilization rate of the active material is improved.
（３）さらに、活物質が三次元構造で網状に結びついて
いるフッ素樹脂繊維で囲われてその保持が補強されてい
ることにより、充放電時の活物質の膨張・収縮による軟
化、脱落が抑制され、サイクル寿命の延長を図ることが
できる。(3) Further, since the active material is surrounded by a fluororesin fiber which has a three-dimensional structure and is connected in a net-like manner, and its holding is reinforced, softening and falling off due to expansion and contraction of the active material during charging and discharging are suppressed. Thus, the cycle life can be extended.
実施例 以下、本発明の実施例について説明する。活物質添加
剤として使用した二酸化珪素は市販のもので、粒子径2.
0〜39nm、かさ比重40〜60g/、比表面積130〜380m2/g
の性状のものである。Examples Hereinafter, examples of the present invention will be described. Silicon dioxide used as an active material additive is commercially available and has a particle size of 2.
0~39nm, bulk specific gravity 40~60g /, specific surface area 130~380m 2 / g
Of the nature of.
また、フッ素樹脂であるポリテトラフルオロエチレン
のディスパージョンとしては、市販のもので樹脂分60重
量％で樹脂分に対し６重量％の非イオン界面活性剤とし
てポリオキシエチレンノニフェノールエーテルを含み、
樹脂を水性懸濁液中に保持し、更に長時間の安定を図る
ための増粘剤として、同種の非イオン界面活性剤を添加
して、粘度約25C.P.（25℃）、PH約10としたものを使用
した。Also, as a dispersion of polytetrafluoroethylene which is a fluororesin, a commercially available product containing polyoxyethylene noniphenol ether as a nonionic surfactant having a resin content of 60 wt% and a resin content of 6 wt%,
The same type of nonionic surfactant is added as a thickener to maintain the resin in an aqueous suspension and further stabilize it for a long period of time, with a viscosity of about 25 C.P. 10 was used.
鉛粉10kgに対して、上記市販の二酸化珪素を100g添加
混合した後、市販のポリテトラフルオロエチレンのディ
スパージョンを0.6重量％秤量し、精製水２で希釈し
た希釈液で活物質が均一になるまで練り合わせる。次に
比重1.350（15℃）の希硫酸0.9を添加しながら均等に
なるまで練合すると凝集性のある団子状ペーストができ
る。このペーストを公知の鉛−カルシウム合金製の格子
に充填し、熟成、乾燥すると、活物質が互いに三次元構
造で網状に結びついたフッ素樹脂繊維で囲われた極板と
なる。こうして作成した極板を正極板として12V30Ah/10
HRの負極吸収式密閉形鉛蓄電池を組み立てた。この電池
をＡとする。比較のために二酸化珪素のみを添加して作
成した極板を正極板として用い、Ａと同様に組み立てた
電池をB,フッ素樹脂ディスパージョンのみを添加して作
成した極板を正極板として用い、Ａと同様に組み立てた
電池をＣ、添加剤を全く加えない従来の電池をＤとして
用意した。After adding and mixing 100 g of the above-mentioned commercially available silicon dioxide to 10 kg of lead powder, 0.6 wt% of a commercially available dispersion of polytetrafluoroethylene is weighed, and the active material becomes uniform with a diluent diluted with purified water 2. Knead until well. Next, the mixture is kneaded while adding 0.9 of dilute sulfuric acid having a specific gravity of 1.350 (15 ° C.) until the mixture becomes uniform to form a cohesive dumpling paste. When this paste is filled into a known lead-calcium alloy lattice, aged and dried, an electrode plate surrounded by fluororesin fibers in which the active materials are connected to each other in a three-dimensional structure in a net-like manner. 12V30Ah / 10
A negative electrode absorption type lead storage battery for HR was assembled. This battery is designated as A. For comparison, an electrode plate prepared by adding only silicon dioxide was used as a positive electrode plate, a battery assembled in the same manner as in A was used as a positive electrode plate, and an electrode plate prepared by adding only a fluororesin dispersion was used. A battery assembled in the same manner as A was prepared as C, and a conventional battery without any additive was prepared as D.
このように作成した極板の見掛け密度、保液性及び電
池の10時間率容量の測定結果を第１表に、また、これら
の電池についてサイクル寿命試験を行った結果を第１図
にそれぞれ示す。なお、サイクル寿命試験は、定電流0.
25CA（7.5A）で３時間放電、定電流0.1CA（3A）で９時
間充電を１サイクルとする試験を繰り返し、50サイクル
毎に放電終止電圧10.2Vまで定電流0.25CA（7.5A）で放
電した時の放電容量を測定した。Table 1 shows the measurement results of the apparent density, the liquid retention property and the 10-hour capacity of the battery thus prepared. FIG. 1 shows the results of the cycle life test of these batteries. . The cycle life test was performed at a constant current of 0.
Repeat the test with discharging at 25CA (7.5A) for 3 hours and charging at 9CA (3A) for 9 hours as one cycle. Discharge at constant current of 0.25CA (7.5A) to discharge end voltage of 10.2V every 50 cycles. The discharge capacity at the time of performing was measured.
第１表から明らかなように活物質に二酸化珪素を添加
した電池Ａ、Ｂは無添加の電池C,Dと比較し活物質の見
掛け密度が低く、保液性が向上すると同時に利用率が向
上し、10時間率容量の増加が見られる。 As is clear from Table 1, the batteries A and B in which silicon dioxide was added to the active material had a lower apparent density of the active material than the batteries C and D in which silicon dioxide was not added. However, a 10-hour rate capacity increase is seen.
一方、第１図から明らかなように活物質に二酸化珪素
のみを添加した電池Ｂの寿命は最も短く、フッ素樹脂デ
ィスパージョンを添加した電池Ｃのサイクル寿命は無添
加の電池Ｄよりも長く、さらに二酸化珪素とフッ素樹脂
とを添加した本発明の電池Ａはフッ素樹脂は添加したが
二酸化珪素は無添加の電池Ｃよりも寿命が長い。On the other hand, as is clear from FIG. 1, the life of the battery B in which only silicon dioxide was added to the active material was the shortest, and the cycle life of the battery C in which the fluororesin dispersion was added was longer than that of the battery D in which no addition was made. Battery A of the present invention to which silicon dioxide and a fluorine resin are added has a longer life than battery C to which a fluorine resin is added but silicon dioxide is not added.
これは本発明の電池Ａでは活物質が三次元構造で網状
に結びついたフッ素樹脂繊維で保持補強されると共に、
二酸化珪素を添加することによる極板の保液性向上が、
各サイクルにおける充放電時の液拡散にも寄与したもの
と思われる。This is because, in the battery A of the present invention, the active material is held and reinforced by a fluororesin fiber tied in a network in a three-dimensional structure, and
Improvement of the liquid retention of the electrode plate by adding silicon dioxide
It is considered that this also contributed to liquid diffusion during charge and discharge in each cycle.
なお、活物質当たりの二酸化珪素含有量については、
２重量％以上では活物質間の結合が弱くなり実用に供し
ないし、また0.1重量％以下ではその効果が現れない。In addition, regarding the silicon dioxide content per active material,
When the content is more than 2% by weight, the bonding between the active materials is weakened, which is not practical. When the content is less than 0.1% by weight, the effect is not exhibited.
活物質当たりのフッ素樹脂の含有量については、0.05
重量％以下では網構造がほとんど形成できない。一方、
1.5重量％以上では樹脂量が多くペーストが固くなって
格子への充填が困難になり、内部抵抗が増大して電池特
性が低下する。従って好ましい添加量は活物質当たり0.
05〜1.5重量％の範囲である。For the content of fluororesin per active material, 0.05
When the amount is less than the weight percentage, a net structure can hardly be formed. on the other hand,
If the content is more than 1.5% by weight, the amount of the resin is large and the paste becomes hard, which makes it difficult to fill the lattice, and the internal resistance increases to deteriorate the battery characteristics. Therefore, the preferable addition amount is 0.
It is in the range of 05-1.5% by weight.
本実施例ではこの極板を正極板のみに使用したが負極
板として使用しても有効であり、正極、負極の両方に用
いることも可能である。In this embodiment, this electrode plate is used only as a positive electrode plate, but it is effective to use it as a negative electrode plate, and it is also possible to use it for both a positive electrode and a negative electrode.
発明の効果 本発明の構成により次のような効果が得られる。Effects of the Invention The following effects can be obtained by the configuration of the present invention.
（１）活物質に二酸化珪素を添加したので、二酸化珪素
が持つ親水性と添加による活物質の見掛け密度が低下す
ることから極板の保液性が向上する。(1) Since silicon dioxide is added to the active material, the hydrophilicity of the silicon dioxide and the apparent density of the active material due to the addition are reduced, so that the liquid retaining property of the electrode plate is improved.
（２）活物質の見掛け密度の低下が活物質重量当たりの
表面積の増大をもたらし、保液性増大の効果を合わせて
活物質の利用率が増加する。(2) The decrease in the apparent density of the active material causes an increase in the surface area per weight of the active material, and the utilization rate of the active material increases with the effect of increasing the liquid retention.
（３）さらに、活物質が三次元構造で網状に結びついて
いるフッ素樹脂繊維で囲われて保持補強されていること
により、充放電時の活物質の膨張・収縮による軟化、脱
落が抑制されるとともに、フッ素樹脂が持つ撥水性を相
殺する二酸化珪素添加の保液性向上の効果により、サイ
クル寿命の延長の効果が得られる。(3) Further, since the active material is surrounded and held and reinforced by the fluororesin fibers linked in a three-dimensional structure in a net-like manner, softening and falling off due to expansion and contraction of the active material during charging and discharging are suppressed. At the same time, the effect of improving the liquid retention properties of the addition of silicon dioxide, which offsets the water repellency of the fluororesin, has the effect of extending the cycle life.
第１図は本発明の実施例の電池及び比較電池の充放電サ
イクル寿命結果を示す図である。FIG. 1 is a diagram showing the results of charge / discharge cycle life of a battery of an example of the present invention and a comparative battery.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉山 寛 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 昭58−212077（ＪＰ，Ａ) 特開 平１−302665（ＪＰ，Ａ) 特開 平１−186560（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/14 H01M 4/62────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Sugiyama 1006 Kazuma Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-58-212077 (JP, A) JP-A-1- 302665 (JP, A) JP-A-1-186560 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 4/14 H01M 4/62
Claims (4)
三次元構造で網状に結びついているフッ素樹脂繊維で活
物質が囲われている極板が、正極板と負極板のうち少な
くとも一方に使用されていることを特徴とする密閉形鉛
蓄電池。An electrode plate in which an active material contains silicon dioxide in an active material and is surrounded by a fluororesin fiber which is connected to each other in a three-dimensional structure in a net-like manner, is provided on at least one of a positive electrode plate and a negative electrode plate. A sealed lead-acid battery characterized by being used.
〜２重量％である特許請求の範囲第１項記載の密閉形鉛
蓄電池。2. The content of silicon dioxide is 0.1% of the total amount of the active material.
2. The sealed lead-acid battery according to claim 1, wherein the amount of the lead-acid battery is 2 to 2% by weight.
かさ比重40〜60g/l、比表面積130〜380m2/gである特許
請求の範囲第１項記載の密閉形鉛蓄電池。3. The properties of silicon dioxide are as follows: particle diameter 2.0-39 nm;
2. The sealed lead-acid battery according to claim 1, which has a bulk specific gravity of 40 to 60 g / l and a specific surface area of 130 to 380 m 2 / g.
0.05〜1.5重量％である特許請求の範囲第１項記載の密
閉形鉛蓄電池。4. The content of the fluororesin fiber per active material
2. The sealed lead-acid battery according to claim 1, wherein the content is 0.05 to 1.5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1342074A JP2815440B2 (en) | 1989-12-27 | 1989-12-27 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1342074A JP2815440B2 (en) | 1989-12-27 | 1989-12-27 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03201363A JPH03201363A (en) | 1991-09-03 |
| JP2815440B2 true JP2815440B2 (en) | 1998-10-27 |
Family
ID=18350961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1342074A Expired - Fee Related JP2815440B2 (en) | 1989-12-27 | 1989-12-27 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2815440B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009200042A (en) * | 2008-01-25 | 2009-09-03 | Ntt Data Ex Techno Corp | Positive electrode composition for secondary battery, process for production thereof, and secondary battery using positive electrode composition for secondary battery |
-
1989
- 1989-12-27 JP JP1342074A patent/JP2815440B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03201363A (en) | 1991-09-03 |
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