JP2006059613A - Control valve type lead-acid storage battery - Google Patents
Control valve type lead-acid storage battery Download PDFInfo
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- JP2006059613A JP2006059613A JP2004239009A JP2004239009A JP2006059613A JP 2006059613 A JP2006059613 A JP 2006059613A JP 2004239009 A JP2004239009 A JP 2004239009A JP 2004239009 A JP2004239009 A JP 2004239009A JP 2006059613 A JP2006059613 A JP 2006059613A
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- 239000002253 acid Substances 0.000 title claims abstract description 24
- 238000003860 storage Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 239000003365 glass fiber Substances 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000010030 laminating Methods 0.000 abstract 1
- 238000003466 welding Methods 0.000 abstract 1
- 238000010998 test method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
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- 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
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- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、薄形のセパレータを用いる制御弁式鉛蓄電池に関するものである。 The present invention relates to a control valve type lead storage battery using a thin separator.
制御弁式鉛蓄電池は、安価で信頼性が高いという特徴を有するために、無停電電源装置や電力貯蔵用、自動車用バッテリーなどにおいて広く使用されている。最近、軽量化と高出力化の両方を備えている制御弁式鉛蓄電池が強く求められている。 Control valve-type lead-acid batteries are widely used in uninterruptible power supplies, power storage, automobile batteries, and the like because they have the feature of being inexpensive and highly reliable. Recently, there has been a strong demand for a valve-regulated lead-acid battery that has both light weight and high output.
ここで、軽量化と高出力化の両方を達成するためには、正極板、負極板及びセパレータを薄形化して、それぞれの枚数を増やしたり、捲回式の構造を用いる手法が有力であることが一般的に知られている。すなわち、正極板、負極板及びセパレータを薄くすると、活物質への電解液中の硫酸イオンの拡散性が良好となり、活物質の利用率が向上し、軽量化と高出力化とを図ることができるためである。 Here, in order to achieve both weight reduction and high output, a method of thinning the positive electrode plate, the negative electrode plate, and the separator to increase the number of each, or using a winding structure is effective. It is generally known. That is, when the positive electrode plate, the negative electrode plate, and the separator are thinned, the diffusibility of sulfate ions in the electrolyte to the active material is improved, the utilization factor of the active material is improved, and weight reduction and higher output can be achieved. This is because it can.
また、正極板、負極板及びセパレータを薄形化して対向面積を増加させると、制御弁式鉛蓄電池の内部抵抗が下がり、その結果、電圧特性が改善されることによって高出力化を達成することができる。そこで、最近では、薄く帯状をした正極板と負極板とを捲回する捲回式の構造を用いることによって、高出力化をすることも検討されている。しかしながら、セパレータの薄形化をした場合には、正極板と負極板とが短絡しやすくなるという問題点がある。特に、一旦、過放電がされた後の回復充電時に正極板と負極板とが短絡しやすくなることが知られている。 Moreover, when the positive electrode plate, the negative electrode plate and the separator are thinned to increase the facing area, the internal resistance of the control valve type lead-acid battery decreases, and as a result, the voltage characteristics are improved to achieve high output. Can do. Therefore, recently, it has been studied to increase the output by using a winding type structure in which a positive electrode plate and a negative electrode plate having a thin strip shape are wound. However, when the separator is thinned, there is a problem that the positive electrode plate and the negative electrode plate are easily short-circuited. In particular, it is known that the positive electrode plate and the negative electrode plate are easily short-circuited at the time of recovery charge after being once overdischarged.
ここで、正極板と負極板とが短絡しやすくなる理由は、次のように理解されている。すなわち、上記した正極板、負極板及びセパレータを薄形化したものを積層したり、捲回したりして対向面積を増加させたりすると、電解液量が制限され、正極活物質量や負極活物質量に対して電解液中の硫酸イオンの量が相対的に少なくなるために、過放電された場合に電解液の比重が下がりやすくなるとともに、ｐＨが高くなりやすい。そして、過放電時には電解液のｐＨは中性から弱アルカリ性になる場合もある。 Here, the reason why the positive electrode plate and the negative electrode plate are easily short-circuited is understood as follows. That is, if the above-described positive electrode plate, negative electrode plate, and thinned separator are stacked or wound to increase the facing area, the amount of the electrolyte is limited, and the amount of the positive electrode active material or the negative electrode active material Since the amount of sulfate ions in the electrolytic solution is relatively small with respect to the amount, the specific gravity of the electrolytic solution tends to decrease and the pH tends to increase when overdischarge occurs. And at the time of overdischarge, pH of electrolyte solution may become weak alkaline from neutrality.
この状態で長期間の放置がされた際には、放電により電極板中に生成した硫酸鉛が電解液中に溶解する。この状態から充電をすると、負極側でデンドライト状の鉛結晶が生成したり、充電により電解液の比重が上がるとセパレータ中に硫酸鉛が析出したりする。これらのデンドライト状の鉛結晶や硫酸鉛がさらに充電されると、それぞれ金属鉛（Ｐｂ）或いは酸化鉛（ＰｂＯ２）にまで還元又は酸化されて、セパレータを貫通して正極板と負極板とが短絡をすることになる。 When left in this state for a long period of time, lead sulfate produced in the electrode plate by discharge dissolves in the electrolyte. When charged from this state, dendrite-like lead crystals are formed on the negative electrode side, or lead sulfate is deposited in the separator when the specific gravity of the electrolyte increases due to charging. When these dendritic lead crystals and lead sulfate are further charged, they are reduced or oxidized to lead metal (Pb) or lead oxide (PbO 2 ), respectively, and the positive electrode plate and negative electrode plate penetrate through the separator. A short circuit will occur.
ここで、正極板と負極板との短絡を防止する手法として、セパレータにシリカを添加する手法が検討されている（例えば、特許文献１参照。）。さらに、セパレータにゼオライトを添加する手法も検討されている（例えば、特許文献２参照。）。 Here, as a technique for preventing a short circuit between the positive electrode plate and the negative electrode plate, a technique of adding silica to the separator has been studied (for example, see Patent Document 1). Furthermore, a method of adding zeolite to the separator has been studied (for example, see Patent Document 2).
しかしながら、ガラス繊維を主成分とする薄形のセパレータ中に多量のシリカを添加すると、保持される電解液量が少なくなるという問題点や、セパレータ自身が硬くなるために、正極板や負極板と積層がしにくくなったり、捲回しにくくなったりして、製造が困難になるという問題点が認められている。さらに、上記したような従来のシリカ等を添加する手法では、短絡防止効果が十分ではないという問題点も認められている。 However, when a large amount of silica is added to a thin separator mainly composed of glass fibers, the amount of electrolyte solution to be retained decreases, and the separator itself becomes hard. It has been recognized that it is difficult to laminate and difficult to wind, making manufacturing difficult. Furthermore, the conventional method of adding silica or the like as described above has a problem that the short-circuit prevention effect is not sufficient.
本発明は上記した問題点に鑑みたものであり、薄形のセパレータを用いる制御弁式鉛蓄電池において、製造が容易であるとともに、短絡がしにくくすることを目的としている。 The present invention has been made in view of the above-described problems, and an object of the present invention is to make a control valve type lead-acid battery using a thin separator easy to manufacture and difficult to short-circuit.
上記した課題を解決するために、本発明に係わる制御弁式鉛蓄電池は、粉末状のメソポーラスシリカ又はゼオライトを、ガラス繊維を主成分とするセパレータに混抄させたり、正極板や負極板の表面に存在させたりすることによって短絡を防止するものである。 In order to solve the above-mentioned problems, the valve-regulated lead-acid battery according to the present invention mixes powdered mesoporous silica or zeolite into a separator mainly composed of glass fiber, or on the surface of a positive electrode plate or a negative electrode plate. By making it exist, a short circuit is prevented.
すなわち、請求項１記載の発明は、正極板と負極板とが、ガラス繊維を主成分とするセパレータを介して絶縁されている制御弁式鉛蓄電池において、前記セパレータには、メソポーラスシリカ又はゼオライトが混抄されていることを特徴としている。 That is, the invention according to claim 1 is a control valve type lead-acid battery in which a positive electrode plate and a negative electrode plate are insulated via a separator mainly composed of glass fiber, and the separator is made of mesoporous silica or zeolite. It is characterized by being mixed.
請求項２記載の発明は、正極板と負極板とが、ガラス繊維を主成分とするセパレータを介して絶縁されている制御弁式鉛蓄電池において、前記正極板及び前記負極板の表面には、メソポーラスシリカ又はゼオライトが存在することを特徴としている。 The invention according to claim 2 is a control valve type lead storage battery in which a positive electrode plate and a negative electrode plate are insulated via a separator mainly composed of glass fiber, on the surfaces of the positive electrode plate and the negative electrode plate, It is characterized by the presence of mesoporous silica or zeolite.
本発明を用いると、薄形のセパレータを用いた場合でも、製造が容易であり、且つ、短絡しにくい制御弁式鉛蓄電池の提供することができる。 By using the present invention, it is possible to provide a control valve type lead-acid battery that is easy to manufacture and difficult to short-circuit even when a thin separator is used.
１．制御弁式鉛蓄電池の製造
以下の実施例では、薄形のセパレータを用い、積層式の制御弁式鉛蓄電池を製造して短絡試験をした。なお、特に明記をしない限りでは、正極板や負極板及び制御弁式鉛蓄電池は従来の手法で製造をした。
1. Manufacture of Control Valve Type Lead Acid Battery In the following examples, a laminate type control valve type lead acid battery was manufactured using a thin separator and subjected to a short circuit test. In addition, unless otherwise specified, the positive electrode plate, the negative electrode plate, and the control valve type lead-acid battery were manufactured by conventional methods.
すなわち、酸化鉛と鉛を主成分とするボールミル式鉛粉を所定量の水と希硫酸とで混練して正極用ペースト状活物質を作製する。作製した正極用ペースト状活物質を、幅が４３ｍｍ、長さが６７ｍｍ、厚さが２．７ｍｍの鉛−カルシウム−錫合金製の集電体に充填した。そして、４０℃、湿度９５％の大気中で２４時間放置して熟成をした後に、５０℃で１６時間の乾燥をして未化成のペースト式正極板を作製した。 That is, a ball mill type lead powder mainly composed of lead oxide and lead is kneaded with a predetermined amount of water and dilute sulfuric acid to produce a paste-like active material for a positive electrode. The produced positive electrode paste-like active material was filled into a lead-calcium-tin alloy current collector having a width of 43 mm, a length of 67 mm, and a thickness of 2.7 mm. Then, after aging for 24 hours in an atmosphere of 40 ° C. and 95% humidity, drying was performed at 50 ° C. for 16 hours to produce an unformed pasted positive electrode plate.
酸化鉛と鉛を主成分とするボールミル式鉛粉を従来から使用している添加剤と、所定量の水と希硫酸とで混練して負極用ペースト状活物質を作製する。作製した負極用ペースト状活物質を、幅が４３ｍｍ、長さが６７ｍｍ、厚さが１．６ｍｍの鉛−カルシウム−錫合金製の集電体に充填して未化成のペースト式負極板を作製した。そして、４０℃、湿度９５％の大気中で２４時間放置して熟成をした後に、５０℃で１６時間の乾燥をして未化成のペースト式負極板を作製した。 A ball mill type lead powder mainly composed of lead oxide and lead is kneaded with an additive conventionally used, a predetermined amount of water and dilute sulfuric acid to prepare a paste active material for a negative electrode. The prepared paste-type active material for negative electrode was filled into a current collector made of lead-calcium-tin alloy having a width of 43 mm, a length of 67 mm, and a thickness of 1.6 mm to produce an unformed paste-type negative electrode plate. did. Then, after standing for 24 hours in an atmosphere of 40 ° C. and 95% humidity, aging was performed, followed by drying at 50 ° C. for 16 hours to produce an unformed pasted negative electrode plate.
後述するように、本発明に係わる実施例３，４では、未化成のペースト式正極板及びペースト式負極板の表面に、所定量のメソポーラスシリカ又はゼオライトの粉体を均一に散布し、ローラで加圧してそれぞれ電極板として使用をした。 As will be described later, in Examples 3 and 4 according to the present invention, a predetermined amount of mesoporous silica or zeolite powder is uniformly dispersed on the surface of the unformed paste-type positive electrode plate and paste-type negative electrode plate. Each was used as an electrode plate under pressure.
作製したペースト式正極板が４枚とペースト式負極板が５枚とを、厚みが０．４ｍｍのガラス繊維を主成分とする不織布からなる薄形のセパレータを介して積層し、電極の耳部を溶接して電極群とし、２０ｋｇ／ｄｍ２の群加圧となるようＡＢＳ製の電槽に組み込んだ。これに、電解液を注入し、周囲温度が約２５℃、課電量が２５０％、化成時間が４８時間の条件で電槽化成を行い、公称容量が９Ａｈ−１２Ｖの制御弁式鉛蓄電池を作製した。
２．制御弁式鉛蓄電池の短絡試験
上記した電槽化成の後に、満充電状態にした制御弁式鉛蓄電池を、周囲温度が２５℃、０．２ＣＡ（１．８Ａ）で終止電圧が１０．５Ｖ（１．７５Ｖ／セル）まで放電して初期の放電容量を確認する。続いて、制御弁式鉛蓄電池の正極端子と負極端子との間に、３０Ω、１０Ｗのホーロー抵抗を取り付け、周囲温度が４０℃雰囲気で２週間放置して完全放電をする。次に、周囲温度が２５℃で１４．７Ｖ（２．４５Ｖ／セル）、制限電流が２．７Ａの定電圧充電を１６時間行う。そして、充電状態で制御弁式鉛蓄電池を解体して、セパレータに短絡痕があるか否かを確認した。なお、上記した短絡試験方法は、いわゆる加速試験方法である。
The produced paste type positive electrode plates and four paste type negative electrode plates were laminated through a thin separator made of a nonwoven fabric mainly composed of glass fibers having a thickness of 0.4 mm, and the electrode ears Were welded to form an electrode group, which was assembled in an ABS battery case so as to achieve a group pressure of 20 kg / dm 2 . The electrolytic solution is injected into this, and the battery is formed under the conditions of an ambient temperature of about 25 ° C., an applied amount of 250%, and a formation time of 48 hours, and a control valve type lead storage battery having a nominal capacity of 9 Ah-12 V is produced did.
2. Control valve type lead storage battery short circuit test After the above-mentioned battery case formation, the control valve type lead storage battery, which has been fully charged, has an ambient temperature of 25 ° C., 0.2 CA (1.8 A) and a final voltage of 10.5 V ( 1.75 V / cell) to confirm the initial discharge capacity. Subsequently, a 30Ω, 10 W enamel resistor is attached between the positive electrode terminal and the negative electrode terminal of the control valve type lead-acid battery, and it is left for 2 weeks in an atmosphere of 40 ° C. for complete discharge. Next, constant voltage charging is performed for 16 hours at an ambient temperature of 25 ° C. and 14.7 V (2.45 V / cell) and a limiting current of 2.7 A. And the control valve type lead acid battery was disassembled in the charged state, and it was confirmed whether or not there was a short-circuit trace in the separator. The short circuit test method described above is a so-called accelerated test method.
上記した特許文献１，２等で従来から使用されているシリカは、一般的に乾式シリカ又は湿式シリカと呼ばれている。なお、乾式シリカの一次粒子は小さい（7〜16nm）が、細孔は有していないものである。一方、湿式シリカの一次粒子は大きい（15〜100nm）が、ランダムな細孔を有している。 The silica conventionally used in the above-mentioned Patent Documents 1 and 2 is generally called dry silica or wet silica. The primary particles of dry silica are small (7 to 16 nm) but do not have pores. On the other hand, primary particles of wet silica are large (15 to 100 nm) but have random pores.
本実施例では、粉末状のメソポーラスシリカを使用することを特徴としている。なお、メソポーラスシリカは、原材料組成としてはシリカであるが、表面に立体的で規則的な微細孔を有し、その結果、高い比表面積を有している。 This embodiment is characterized in that powdered mesoporous silica is used. In addition, although mesoporous silica is silica as a raw material composition, it has a three-dimensional regular pore on the surface, and, as a result, has a high specific surface area.
また、本実施例で使用をしている粉末状のゼオライトは、珪素（Ｓｉ）とアルミニウム（Ａｌ）の複合酸化物であり、上記したメソポーラスシリカと同様に比表面積が高いことを特徴としている。
（実施例１）
実施例１として、従来から使用しているガラス繊維製のセパレータの抄造時に、粉末状のメソポーラスシリカ（ＳＩＬＦＡＭ−Ａ型、日本化学工業（株）製）を混抄して、本発明に係わるセパレータを製造した。ここで、メソポーラスシリカは、セパレータを構成するガラス繊維に対して３０質量％添加した。なお、正極板及び負極板として、従来から使用しているものを用いた。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
（実施例２）
実施例２として、従来から使用しているガラス繊維製のセパレータの抄造時に、粉末状のゼオライト（ＨＳ−４０型、日本化学工業（株）製）を混抄して、本発明に係わるセパレータを製造した。ここで、ゼオライトは、セパレータを構成するガラス繊維に対して３０質量％添加した。なお、正極板及び負極板として、従来から使用しているものを用いた。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
（実施例３）
上述した方法で、ペースト式正極板及びペースト式負極板の表面に、粉末状のメソポーラスシリカ（ＳＩＬＦＡＭ−Ａ型、日本化学工業（株）製）をローラで加圧して存在させた。なお、セパレータとして、従来から使用しているガラス繊維製のものを用いた。ここで、ペースト式正極板及びペースト式負極板表面のメソポーラスシリカの量は、セパレータを構成するガラス繊維の質量に対して３０質量％存在させるようにした。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
（実施例４）
上述した方法で、ペースト式正極板及びペースト式負極板の表面に、粉末状のゼオライト（ＨＳ−４０型、日本化学工業（株）製）をローラで加圧して存在させた。なお、セパレータとして、従来から使用しているガラス繊維製のものを用いた。ここで、ペースト式正極板及びペースト式負極板表面のゼオライトの量は、セパレータを構成するガラス繊維の質量に対して３０質量％存在させるようにした。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
（比較例１）
比較例１として、ガラス繊維製のセパレータの抄造時に、従来から使用されている粉末状の乾式シリカをを混抄して製造した。乾式シリカは、セパレータを構成するガラス繊維に対して３０質量％添加した。なお、正極板及び負極板として、従来から使用しているものを用いた。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
（比較例２）
比較例２として、ガラス繊維製のセパレータの抄造時に、従来から使用されているシリカゾル（ＳＴ−４０型、日産化学（株）製）をその表面に吹き付けて、乾燥させて製造した。なお、乾燥後のシリカ質量として、セパレータを構成するガラス繊維に対して３０質量％添加した。正極板及び負極板として従来から使用しているものを用いた。その他の制御弁式鉛蓄電池の製造方法や短絡試験方法は上記したものである。
The powdery zeolite used in this example is a composite oxide of silicon (Si) and aluminum (Al), and is characterized by a high specific surface area, similar to the above-described mesoporous silica.
(Example 1)
As Example 1, powdery mesoporous silica (SILFAM-A type, manufactured by Nippon Chemical Industry Co., Ltd.) was mixed at the time of making a conventionally used glass fiber separator to produce a separator according to the present invention. Manufactured. Here, 30 mass% of mesoporous silica was added to the glass fibers constituting the separator. In addition, what was used conventionally was used as a positive electrode plate and a negative electrode plate. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
(Example 2)
As Example 2, powdery zeolite (HS-40 type, manufactured by Nippon Chemical Industry Co., Ltd.) is mixed at the time of making a conventionally used glass fiber separator to produce a separator according to the present invention. did. Here, 30% by mass of zeolite was added to the glass fiber constituting the separator. In addition, what was used conventionally was used as a positive electrode plate and a negative electrode plate. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
(Example 3)
By the method described above, powdered mesoporous silica (SILFAM-A type, manufactured by Nippon Chemical Industry Co., Ltd.) was present on the surfaces of the paste-type positive electrode plate and the paste-type negative electrode plate by pressing with a roller. In addition, the thing made from the glass fiber conventionally used as a separator was used. Here, the amount of the mesoporous silica on the surface of the paste-type positive electrode plate and the paste-type negative electrode plate was 30% by mass with respect to the mass of the glass fiber constituting the separator. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
(Example 4)
By the method described above, powdery zeolite (HS-40 type, manufactured by Nippon Chemical Industry Co., Ltd.) was present on the surfaces of the paste-type positive electrode plate and the paste-type negative electrode plate by pressing with a roller. In addition, the thing made from the glass fiber conventionally used as a separator was used. Here, the amount of zeolite on the surface of the paste-type positive electrode plate and the paste-type negative electrode plate was 30% by mass with respect to the mass of the glass fibers constituting the separator. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
(Comparative Example 1)
As Comparative Example 1, powdery dry silica, which has been conventionally used, was mixed and manufactured when making a glass fiber separator. 30% by mass of dry silica was added to the glass fiber constituting the separator. In addition, what was used conventionally was used as a positive electrode plate and a negative electrode plate. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
(Comparative Example 2)
As Comparative Example 2, silica sol (ST-40 type, manufactured by Nissan Chemical Co., Ltd.), which has been conventionally used, was sprayed on the surface of the glass fiber separator and made by drying. In addition, 30 mass% was added with respect to the glass fiber which comprises a separator as a silica mass after drying. Conventionally used positive electrode plates and negative electrode plates were used. Other control valve type lead storage battery manufacturing methods and short circuit test methods are as described above.
表１に、上記した６種類の制御弁式鉛蓄電池の短絡試験結果を示す。本発明に係わる制御弁式鉛蓄電池は、短絡痕が認められない。したがって、短絡しにくい制御弁式鉛蓄電池であることがわかる。また、本発明に係わる実施例１，２の制御弁式鉛蓄電池では、比較例１，２の制御弁式鉛蓄電池に比べてセパレータが軟らかく弾力性があり、正極板及び負極板との積層工程やその他の製造工程においても製造が容易であった。 Table 1 shows the short-circuit test results of the six types of control valve type lead-acid batteries described above. The control valve type lead-acid battery according to the present invention does not show short-circuit marks. Therefore, it turns out that it is a control valve type lead acid battery which is hard to short-circuit. Moreover, in the control valve type lead acid batteries of Examples 1 and 2 according to the present invention, the separator is softer and more elastic than the control valve type lead acid batteries of Comparative Examples 1 and 2, and the lamination process with the positive electrode plate and the negative electrode plate It was easy to manufacture in other manufacturing processes.
さらに、上述した実験では積層方式を用いた場合についての短絡試験結果を示したが、本発明を捲回式構造の制御弁式鉛蓄電池に用いた場合でも、製造が容易であることや、同様の短絡防止効果があることも確認された。 Furthermore, although the short circuit test result about the case where a lamination | stacking system was used was shown in the experiment mentioned above, even when it uses this invention for the control valve type lead acid battery of a winding type structure, manufacture is easy, It was also confirmed that there is an effect of preventing short circuit.
本発明を用いると、薄形のセパレータを用いる制御弁式鉛蓄電池において、正極板と負極板との短絡が起こりにくくすることができる。
When the present invention is used, a short circuit between a positive electrode plate and a negative electrode plate can be made difficult to occur in a control valve type lead storage battery using a thin separator.
Claims (2)
前記セパレータには、メソポーラスシリカ又はゼオライトが混抄されていることを特徴とする制御弁式鉛蓄電池。 In the control valve type lead acid battery in which the positive electrode plate and the negative electrode plate are insulated through a separator mainly composed of glass fiber,
A control valve type lead storage battery, wherein the separator is mixed with mesoporous silica or zeolite.
前記正極板及び前記負極板の表面には、メソポーラスシリカ又はゼオライトが存在することを特徴とする制御弁式鉛蓄電池。 In the control valve type lead acid battery in which the positive electrode plate and the negative electrode plate are insulated through a separator mainly composed of glass fiber,
A control valve type lead-acid battery, wherein mesoporous silica or zeolite is present on the surfaces of the positive electrode plate and the negative electrode plate.
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|---|---|---|---|
| JP2004239009A JP2006059613A (en) | 2004-08-19 | 2004-08-19 | Control valve type lead-acid storage battery |
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| JP2004239009A JP2006059613A (en) | 2004-08-19 | 2004-08-19 | Control valve type lead-acid storage battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009148178A1 (en) * | 2008-06-06 | 2009-12-10 | デュポン帝人アドバンスドペーパー株式会社 | Thin tissue material, manufacturing method thereof, and electrical and electronic parts using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009148178A1 (en) * | 2008-06-06 | 2009-12-10 | デュポン帝人アドバンスドペーパー株式会社 | Thin tissue material, manufacturing method thereof, and electrical and electronic parts using same |
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