JP2002141103A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JP2002141103A JP2002141103A JP2000331788A JP2000331788A JP2002141103A JP 2002141103 A JP2002141103 A JP 2002141103A JP 2000331788 A JP2000331788 A JP 2000331788A JP 2000331788 A JP2000331788 A JP 2000331788A JP 2002141103 A JP2002141103 A JP 2002141103A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- acid
- electrode plate
- phenol derivative
- negative electrode
- 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.)
- Pending
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)
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉛蓄電池の高容量
化及び長寿命化に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead storage battery having a higher capacity and a longer life.
【０００２】[0002]
【従来の技術】鉛蓄電池は、コスト及び信頼性の面で優
れていることから、無停電電源装置、自動車用バッテ
リ、電気自動車等の幅広い分野で使用されている。最
近、これらに用いられる鉛蓄電池の高容量化及び長寿命
化が強く望まれている。2. Description of the Related Art Lead-acid batteries are used in a wide range of fields such as uninterruptible power supplies, automobile batteries, and electric vehicles because of their excellent cost and reliability. Recently, there has been a strong demand for higher capacity and longer life of lead storage batteries used in these batteries.
【０００３】鉛蓄電池を高容量化及び長寿命化するに
は、負極板に用いられている活物質を微細化したり多孔
質化したりすることによって、負極板の電極反応面積を
大きくし、その状態を長期間にわたって保持する必要が
ある。In order to increase the capacity and extend the life of a lead-acid battery, the active material used in the negative electrode plate is made finer or porous to increase the electrode reaction area of the negative electrode plate. Need to be maintained for a long time.
【０００４】従来、鉛蓄電池の寿命を延ばすために、負
極用の添加剤として、有機エキスパンダや硫酸バリウム
が利用されている。有機エキスパンダは、活物質の粒子
の粗大化を防止する立場から、また、硫酸バリウムは表
面積の減少を防止する働きがあると考えられている。Conventionally, in order to extend the life of a lead storage battery, an organic expander or barium sulfate has been used as an additive for a negative electrode. Organic expanders are considered to prevent coarsening of active material particles, and barium sulfate is considered to function to prevent a decrease in surface area.
【０００５】なお、上述した有機エキスパンダのうち
で、鉛蓄電池には主にリグニンが用いられている。な
お、リグニンは、製紙工業においてリグノセルロース
（一般の木材等の草木類の構成物質）からパルプ（セル
ロース）を生産する工程の副産物として得ることができ
る。なお、前記リグニンは、木材を形成している細胞と
細胞との間に３次元の網目状に存在しており、細胞間同
士を繋ぐバインダーの働きをするものである。[0005] Among the above-mentioned organic expanders, lignin is mainly used for lead storage batteries. In addition, lignin can be obtained as a by-product of a process of producing pulp (cellulose) from lignocellulose (constituent substance of vegetation such as wood) in the papermaking industry. The lignin is present in a three-dimensional network between cells forming wood, and functions as a binder connecting the cells.
【０００６】製紙工業では、木材を破砕したチップを、
アルカリ蒸解法（クラフト蒸解法とも呼ばれている）や
サルファイト蒸解法により、高温・高圧の条件下で蒸解
・処理して、セルロースとリグニンとに分離している。[0006] In the paper industry, chips obtained by crushing wood are
It is separated into cellulose and lignin by digestion and treatment under conditions of high temperature and high pressure by alkaline cooking method (also called kraft cooking method) or sulfite cooking method.
【０００７】なお、これらの手法で得られたリグニン
（以下、工業リグニンと呼ぶ）において、アルカリ蒸解
法で得られた工業リグニンをクラフトリグニンと呼び、
サルファイト蒸解法で得られた工業リグニンをリグニン
スルホン酸と呼んでいる。[0007] In the lignin obtained by these techniques (hereinafter referred to as industrial lignin), the industrial lignin obtained by the alkaline digestion method is called kraft lignin,
The industrial lignin obtained by the sulfite cooking method is called lignin sulfonic acid.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上述し
た製紙工業における工業リグニンの製造は、高温・高圧
の条件下で行われるので、リグニンの３次元構造の一部
が破壊されている。そして、得られた工業リグニンは、
ランダムにその構造が破壊されると共に、分子レベルに
おいても高度に変性を受けており、それを構成している
官能基の不活性化が起こったり、その安定性が損なわれ
たりしている。However, since the production of industrial lignin in the paper industry described above is performed under high temperature and high pressure conditions, a part of the three-dimensional structure of lignin is destroyed. And the obtained industrial lignin,
The structure is randomly destroyed, and at the molecular level, the protein is highly denatured, and the functional groups constituting it are inactivated or its stability is impaired.
【０００９】これらの工業リグニンを、６０°Ｃを超え
る高温環境下で使用される鉛蓄電池に使用した場合に
は、正極板で分解されたり、電解液として用いられる硫
酸と反応して性能が劣化するなどの理由から、その効果
が短期間に失われるという問題点がある。When these industrial lignins are used in lead-acid batteries used in high-temperature environments exceeding 60 ° C., their performance is degraded by decomposition on the positive electrode plate or by reaction with sulfuric acid used as an electrolyte. For example, the effect is lost in a short time.
【００１０】本発明は上記した事案に鑑み、より優れた
効果を有する有機エキスパンダを用いることによって、
高容量で長寿命な鉛蓄電池を提供することを目的として
いる。The present invention has been made in view of the above-mentioned circumstances, and by using an organic expander having a superior effect,
It aims to provide a high-capacity, long-life lead-acid battery.
【００１１】[0011]
【課題を解決するための手段】上記した課題を解決する
ために本発明では、市販の工業リグニンとフェノール誘
導体との混合物を、リグノセルロース系物質に浸透させ
る。その後、酸を添加し混合・分離して得られた有機エ
キスパンダを負極板やセパレータ中に存在させるもので
ある。In order to solve the above-mentioned problems, according to the present invention, a mixture of a commercially available industrial lignin and a phenol derivative is infiltrated into a lignocellulosic substance. Thereafter, an organic expander obtained by adding an acid, mixing and separating is made to exist in a negative electrode plate or a separator.
【００１２】すなわち、第一の発明は、正極板と負極板
とをセパレータを介して積層した鉛蓄電池であって、前
記負極板、又は、前記負極板及びセパレータに有機エキ
スパンダを含有する鉛蓄電池において、前記有機エキス
パンダは、工業リグニンとフェノール誘導体の混合物
を、リグノセルロース系物質に浸透させた後、酸を添加
し、分離して作製したものであることを特徴とし、第二
の発明は、前記フェノール誘導体として、クレゾールを
用いることを特徴とし、第三の発明は、前記フェノール
誘導体として、ジメトキシフェノールとメトキシフェノ
ールの少なくとも一方、又は、両方を用いることを特徴
とし、第四の発明は、前記フェノール誘導体として、ポ
リフェノール類を用いることを特徴とし、第五の発明
は、前記酸として、６５質量％以上の濃度の硫酸を用い
ることを特徴としている。That is, a first invention is a lead-acid battery in which a positive electrode plate and a negative electrode plate are laminated with a separator interposed therebetween, and wherein the negative electrode plate or the negative electrode plate and the separator contain an organic expander. In, the organic expander is characterized in that a mixture of industrial lignin and a phenol derivative is made by infiltrating a lignocellulose-based substance, then adding an acid, and separating the mixture. The phenol derivative is characterized by using cresol, the third invention is characterized by using at least one of dimethoxyphenol and methoxyphenol, or both, as the phenol derivative, the fourth invention is, According to a fifth aspect of the present invention, a polyphenol is used as the phenol derivative. It is characterized by the use of sulfuric acid mass% or more concentrations.
【００１３】[0013]
【発明の実施の形態】以下に本発明の実施の形態につい
て説明する。リグノセルロース系物質として、広葉樹で
あるブナの木粉を使用した。なお、前記木粉の平均粒子
径は、約０．５ｍｍにした。また、工業リグニンとし
て、日本製紙製のバニレックスＮ（ただし、商品名）を
用いた。Embodiments of the present invention will be described below. As the lignocellulosic material, beech wood powder, which is a hardwood, was used. The average particle diameter of the wood flour was about 0.5 mm. In addition, Nippon Paper's Vanirex N (trade name) was used as the industrial lignin.
【００１４】１．フェノール誘導体が液体の場合の有機
エキスパンダの製造方法 フェノール誘導体として液体のパラ−クレゾールを用い
た。２ｇの工業リグニンを、１０ｍｌのアセトンに溶解
させる。前記ブナの木粉１ｇ当たりに、パラ−クレゾー
ルを１０ｍｌと、前記工業リグニンの溶液を１０ｍｌ加
えて蓋をして、２４時間放置して木粉の内部に十分に浸
透させる。そして、大気中でアセトンを自然気化させ
て、工業リグニンとパラ−クレゾールを浸透した木粉を
得た。1. Production method of organic expander when phenol derivative is liquid Liquid para-cresol was used as the phenol derivative. 2 g of industrial lignin are dissolved in 10 ml of acetone. For 1 g of the beech wood flour, 10 ml of para-cresol and 10 ml of the above-mentioned industrial lignin solution are added, covered, and allowed to stand for 24 hours to allow sufficient penetration into the wood flour. Then, acetone was spontaneously vaporized in the atmosphere to obtain wood flour impregnated with industrial lignin and para-cresol.
【００１５】続いて、７０質量％濃度の硫酸を２０ｍｌ
加えて、６０分間室温で激しく攪拌した。攪拌を停止す
ると、硫酸溶液層とフェノール誘導体溶液層とに分離さ
れる。このうちのフェノール誘導体層を取り出して、過
剰のエチルエーテル溶液に加えて、沈殿物を生成し、該
沈殿物を乾燥させて有機エキスパンダを得た。以下、こ
の有機エキスパンダをＬＣと略称する。Subsequently, sulfuric acid having a concentration of 70% by mass was added in an amount of 20 ml.
In addition, it was stirred vigorously at room temperature for 60 minutes. When the stirring is stopped, the mixture is separated into a sulfuric acid solution layer and a phenol derivative solution layer. The phenol derivative layer was taken out and added to an excess ethyl ether solution to produce a precipitate, and the precipitate was dried to obtain an organic expander. Hereinafter, this organic expander is abbreviated as LC.
【００１６】２．フェノール誘導体が固体の場合の有機
エキスパンダの製造方法 フェノール誘導体として、固体の２−メトキシフェノー
ル、２，６−ジメトキシフェノール、２，６−ジメチル
フェノール、又は、カテコールのいずれかを用いた。２
−メトキシフェノールを使用した場合の一例を以下に示
す。2. Method for producing organic expander when phenol derivative is solid Any of solid 2-methoxyphenol, 2,6-dimethoxyphenol, 2,6-dimethylphenol, or catechol was used as the phenol derivative. 2
An example when -methoxyphenol is used is shown below.
【００１７】２ｇの前記工業リグニンと、０．５ｇのメ
トキシフェノールを、１０ｍｌのアセトンに溶解させ
る。前記ブナの木粉１ｇ当たりに、前記工業リグニンと
２−メトキシフェノールが溶解したアセトン溶液を１０
ｍｌ加えて蓋をして、２４時間放置して木粉の内部に十
分に浸透させる。そして、大気中でアセトンを自然気化
させて、２−メトキシフェノールを浸透した木粉を得
た。2 g of the above industrial lignin and 0.5 g of methoxyphenol are dissolved in 10 ml of acetone. For 1 g of the beech wood flour, an acetone solution containing the industrial lignin and 2-methoxyphenol was dissolved in 10 g.
Add the cap, cover, and allow to stand for 24 hours to allow sufficient penetration into the wood flour. Then, acetone was spontaneously vaporized in the atmosphere to obtain wood powder impregnated with 2-methoxyphenol.
【００１８】続いて、７０質量％濃度の硫酸を２０ｍｌ
加えて、６０分間室温で激しく攪拌した。攪拌を停止し
た後、全反応溶液を過剰な水に投入し、沈殿物を生成
し、該沈殿物を乾燥して有機エキスパンダを得た。以
下、この有機エキスパンダをＬＭＰと略称する。Subsequently, sulfuric acid having a concentration of 70% by mass was added in an amount of 20 ml.
In addition, it was stirred vigorously at room temperature for 60 minutes. After stopping the stirring, the whole reaction solution was poured into excess water to form a precipitate, and the precipitate was dried to obtain an organic expander. Hereinafter, this organic expander is abbreviated as LMP.
【００１９】同様の手法で、他の固体のフェノール誘導
体を用いて有機エキスパンダを作製した。すなわち、固
体のフェノール誘導体として、２，６−ジメトキシフェ
ノールを用いて得た有機エキスパンダをＬＤＭＰと略称
し、２，６−ジメトキシフェノールと２，６−ジメチル
フェノールとの質量比が１：１の混合物を用いて得た有
機エキスパンダをＬＤＭＰ２と略称し、カテコールを用
いて得た有機エキスパンダをＬＫとそれぞれ略称する。In a similar manner, an organic expander was prepared using another solid phenol derivative. That is, an organic expander obtained by using 2,6-dimethoxyphenol as a solid phenol derivative is abbreviated as LDMP, and the mass ratio of 2,6-dimethoxyphenol to 2,6-dimethylphenol is 1: 1. The organic expander obtained using the mixture is abbreviated as LDMP2, and the organic expander obtained using catechol is abbreviated as LK.
【００２０】３．ペースト式負極板の作成 前記した各種の有機エキスパンダ、又は、市販の工業リ
グニン（バニレックスN）を含有するペースト状活物質
を、鉛−カルシウム−錫合金からなる集電体（l６９ｍ
ｍ×w４４ｍｍ×t２．４ｍｍ）に充填した後、熟成（４
５℃,９８ＲＨ％×２４時間）し、乾燥（６０℃×１６
時間）して未化成の負極板とした。そして、前記したそ
れぞれの未化成の負極板を、比重が１．０５０の希硫酸
電解液中で２４時間化成し、既化した負極板とした。3. Preparation of Paste-Type Negative Electrode Plate The above-mentioned various organic expanders or a commercially available industrial lignin-containing paste-like active material (Vanilex N) were mixed with a current collector ( 1 69 m) made of a lead-calcium-tin alloy.
m × w 44 mm × t 2.4 mm) and then aged (4
5 ° C, 98RH% × 24 hours), and dried (60 ° C × 16)
Time) to obtain an unformed negative electrode plate. Each of the unformed negative electrode plates was converted into a diluted sulfuric acid electrolytic solution having a specific gravity of 1.050 for 24 hours to obtain a converted negative electrode plate.
【００２１】 ４．小形制御弁式鉛蓄電池の作製条件及び試験条件 上記した既化した負極板４枚と、従来から使用している
既化した正極板３枚とを、従来から使用している厚さが
１．８ｍｍのガラス繊維製のセパレータを介して積層・
溶接して極板群を組み立て、該極板群をＡＢＳ製の電槽
に組込んで蓋をつけ、電槽内に比重が１．３１（２０°
Ｃ）の希硫酸電解液を５６ｍｌ注液した後、密閉して７
Ａｈ−２Ｖの小形制御弁式鉛蓄電池を作製した。[0021] 4. Fabrication conditions and test conditions of small control valve type lead-acid battery The above-mentioned four conventional negative plates and the three conventional positive plates used conventionally have a thickness of 1. Laminating via 8mm glass fiber separator
The electrode group was assembled by welding, the electrode group was assembled in an ABS battery case, and a lid was attached. The specific gravity was 1.31 (20 °) in the battery case.
After injecting 56 ml of the diluted sulfuric acid electrolyte solution of C), seal
An Ah-2V compact control valve type lead storage battery was manufactured.
【００２２】初期の小形制御弁式鉛蓄電池の放電時間
は、２５℃、２１Ａ(３ＣＡ)の電流値で放電（放電終止
電圧：１．３Ｖ）して測定した。そして、制御弁式鉛蓄
電池の寿命は、加速試験法を用いて測定した。すなわ
ち、前記小形制御弁式鉛蓄電池を６０℃の温度雰囲気中
で２．２７５Ｖ/セルの定電圧で連続過充電を行い、１
ヶ月（実使用での１年に相当）ごとに２５℃まで冷却し
た後、２１Ａ(３ＣＡ)の電流値で放電して放電時間を測
定して、初期の放電時間との比率（％）を比較した。The initial discharge time of the small control valve type lead-acid battery was measured by discharging at 25 ° C. and a current value of 21 A (3 CA) (discharge end voltage: 1.3 V). Then, the life of the control valve type lead storage battery was measured by using an accelerated test method. That is, the small control valve type lead storage battery is continuously overcharged at a constant voltage of 2.275 V / cell in a temperature atmosphere of 60 ° C.
After cooling to 25 ° C every month (corresponding to one year in actual use), discharge at a current value of 21A (3CA), measure the discharge time, and compare the ratio (%) with the initial discharge time did.
【００２３】[0023]
【実施例】（実施例１〜５）酸化鉛（ＰｂＯ）を主成分
とする鉛粉に、上記した手法で作製した各種有機エキス
パンダ（ＬＣ、ＬＭＰ、ＬＤＭＰ、ＬＤＭＰ２、ＬＫ）
を表１に示すように、それぞれ０．２質量％、硫酸バリ
ウムを1質量％を添加し、混合して混合鉛粉を作製す
る。前記鉛粉１００質量部に対して、比重が１．２６の
希硫酸を１０質量部と、水を７質量部を加えて練合し、
負極用のペースト状活物質を作製して負極板に用いた。EXAMPLES (Examples 1 to 5) Various organic expanders (LC, LMP, LDMP, LDMP2, LK) prepared by the above-described method on lead powder containing lead oxide (PbO) as a main component.
As shown in Table 1, 0.2% by mass and 1% by mass of barium sulfate are added and mixed to prepare a mixed lead powder. With respect to 100 parts by mass of the lead powder, 10 parts by mass of dilute sulfuric acid having a specific gravity of 1.26 and 7 parts by mass of water were added and kneaded,
A paste-like active material for a negative electrode was prepared and used for a negative electrode plate.
【００２４】なお、その他の負極板や正極板、小形制御
弁式鉛蓄電池の作製条件及び試験条件は上記したもので
ある。The other conditions for producing and testing the negative electrode plate, the positive electrode plate, and the small control valve type lead storage battery are as described above.
【００２５】（比較例１）フェノール誘導体として液体
のパラ−クレゾールを用いた。ブナの木粉１ｇ当たり
に、パラ−クレゾールを１０ｍｌを加えて蓋をして、２
４時間放置して木粉の内部に十分に浸透させる。そし
て、大気中でアセトンを自然気化させて、クレゾールを
浸透した木粉を得た。すなわち、比較例１では、実施例
１〜５と異なり、木粉にパラ−クレゾールのみを浸透さ
せた。Comparative Example 1 Liquid para-cresol was used as a phenol derivative. For 1 g of beech wood flour, add 10 ml of para-cresol and cover with
Leave for 4 hours to allow sufficient penetration into the wood flour. Then, acetone was spontaneously vaporized in the atmosphere to obtain wood powder impregnated with cresol. That is, in Comparative Example 1, unlike in Examples 1 to 5, only para-cresol was permeated into wood flour.
【００２６】続いて、７０質量％濃度の硫酸を２０ｍｌ
加えて、室温で６０分間激しく攪拌した。攪拌を停止す
ると、硫酸溶液層とフェノール誘導体溶液層とに分離さ
れる。このうちのフェノール誘導体層を取り出して、過
剰のエチルエーテル溶液に加えて、沈殿物を生成し、該
沈殿物を乾燥させて有機エキスパンダを得た。以下、こ
の有機エキスパンダをＬＣ０と略称する。Subsequently, sulfuric acid having a concentration of 70% by mass was added in an amount of 20 ml.
In addition, the mixture was vigorously stirred at room temperature for 60 minutes. When the stirring is stopped, the mixture is separated into a sulfuric acid solution layer and a phenol derivative solution layer. The phenol derivative layer was taken out and added to an excess ethyl ether solution to produce a precipitate, and the precipitate was dried to obtain an organic expander. Hereinafter, this organic expander is abbreviated as LC0.
【００２７】酸化鉛（ＰｂＯ）を主成分とする鉛粉に、
前記した手法で作製した有機エキスパンダ（ＬＣ０）を
０．２質量％、硫酸バリウムを1質量％を添加し、混合
して混合鉛粉を作製する。前記鉛粉１００質量部に対し
て、比重が１．２６の希硫酸を１０質量部と、水を７質
量部を加えて練合し、負極用のペースト状活物質を作製
して負極板に用いた。A lead powder mainly composed of lead oxide (PbO)
0.2% by mass of the organic expander (LC0) produced by the above-described method and 1% by mass of barium sulfate are added and mixed to produce a mixed lead powder. To 100 parts by mass of the lead powder, 10 parts by mass of dilute sulfuric acid having a specific gravity of 1.26 and 7 parts by mass of water were added and kneaded to prepare a paste-like active material for a negative electrode, and the negative electrode plate was formed. Using.
【００２８】なお、その他の負極板や正極板、小形制御
弁式鉛蓄電池の作製条件及び試験条件は上記したもので
ある。The manufacturing conditions and test conditions for the other negative and positive electrode plates and the compact control valve type lead-acid battery are as described above.
【００２９】（比較例２）酸化鉛（ＰｂＯ）を主成分と
する鉛粉に、上記した市販の工業リグニンを０．２質量
％、硫酸バリウムを1質量％を添加し、混合して混合鉛
粉を作製する。前記鉛粉１００質量部に対して、比重が
１．２６の希硫酸を１０質量部と、水を７質量部を加え
て練合し、負極用のペースト状活物質を作製して負極板
に用いた。Comparative Example 2 To a lead powder mainly composed of lead oxide (PbO) was added 0.2% by mass of the above-mentioned commercially available industrial lignin and 1% by mass of barium sulfate. Make the powder. To 100 parts by mass of the lead powder, 10 parts by mass of dilute sulfuric acid having a specific gravity of 1.26 and 7 parts by mass of water were added and kneaded to prepare a paste-like active material for a negative electrode, and the negative electrode plate was formed. Using.
【００３０】なお、その他の負極板や正極板、小形制御
弁式鉛蓄電池の作製条件及び試験条件は上記したもので
ある。The other conditions for producing and testing the negative electrode plate, positive electrode plate, and small control valve type lead-acid battery are as described above.
【００３１】表１に、上記した各種小形制御弁式鉛蓄電
池の試験結果を示す。本発明を用いた実施例１〜５は、
比較例１、２と比べて初期の放電時間が長く、長寿命で
あることがわかる。Table 1 shows the test results of the various small-size control valve type lead-acid batteries described above. Examples 1 to 5 using the present invention are:
It can be seen that the initial discharge time is longer and the life is longer as compared with Comparative Examples 1 and 2.
【００３２】実施例１と比較例1とを比較することによ
り、木粉にあらかじめ工業リグニンとクレゾール（フェ
ノール誘導体）を含浸させた後に硫酸で抽出した有機エ
キスパンダを用いると、好ましいことがわかる。この理
由としては定かではないが、抽出される有機エキスパン
ダの分子量が影響しているためと考えられる。Comparison between Example 1 and Comparative Example 1 shows that it is preferable to use an organic expander obtained by impregnating wood flour with industrial lignin and cresol (a phenol derivative) in advance and then extracting with sulfuric acid. Although the reason for this is not clear, it is considered that the molecular weight of the extracted organic expander has an effect.
【００３３】また、実施例１〜５を比較すると、フェノ
ール誘導体にメトキシ基を有する実施例２〜４や、２個
以上のフェノール基（ＯＨ基）を有するもの実施例５
が、メトキシ基の無い実施例１に比べて好ましいことが
わかる。In addition, when Examples 1 to 5 are compared, Examples 2 to 4 having a methoxy group in the phenol derivative and Example 5 having two or more phenol groups (OH groups) are shown.
Is more preferable than that of Example 1 having no methoxy group.
【００３４】[0034]
【表１】 [Table 1]
【００３５】（実施例６）アセトンに、フェノール誘導
体を用いて作製した有機エキスパンダ（ＬＣ）を1質量
％溶解し、この溶液を前記セパレータに１ｇ/ｃｍ2染み
こませた後、大気中で乾燥させてアセトンを除去した。
このＬＣを含浸したセパレータと、実施例１で作成した
負極板を用いて小形制御弁式鉛蓄電池を作製した。その
他の正極板や、小形制御弁式鉛蓄電池の作製条件及び試
験条件は上記したものである。Example 6 1% by mass of an organic expander (LC) prepared using a phenol derivative was dissolved in acetone, and this solution was impregnated with 1 g / cm 2 into the separator. Dry to remove acetone.
Using the separator impregnated with this LC and the negative electrode plate prepared in Example 1, a small control valve type lead storage battery was produced. The manufacturing conditions and test conditions for other positive electrode plates and small control valve type lead-acid batteries are as described above.
【００３６】表２に、実施例６を用いた小形制御弁式鉛
蓄電池の試験結果を示す。本発明を用いると、小形制御
弁式鉛蓄電池をさらに長寿命化できることがわかる。Table 2 shows the test results of the compact control valve type lead-acid battery using the sixth embodiment. It is understood that the use of the present invention can further extend the life of the small-sized control valve type lead storage battery.
【００３７】[0037]
【表２】 [Table 2]
【００３８】上述した実施例では、小形制御弁式鉛蓄電
池に使用した場合について例示したが、本発明は鉛蓄電
池の用途や形状等に限定されることなく、上述した特許
請求の範囲において用いることができる。また、使用す
る酸として、６５質量％の濃度の硫酸を用いた場合も同
様の結果が得られた。In the above-described embodiment, the case where the present invention is used for a small control valve type lead-acid battery has been described. However, the present invention is not limited to the use and shape of the lead-acid battery, but may be used in the above-described claims. Can be. Similar results were obtained when sulfuric acid having a concentration of 65% by mass was used as the acid to be used.
【００３９】[0039]
【発明の効果】上述したように、本発明を用いることに
よって、高容量で長寿命な鉛蓄電池を提供することがで
きるため工業上優れたものである。As described above, by using the present invention, it is possible to provide a high-capacity, long-life lead-acid battery, which is industrially excellent.
フロントページの続き Ｆターム(参考） 5H021 BB09 EE09 EE11 EE31 HH01 5H028 AA08 BB03 BB06 EE06 EE08 HH01 HH03 5H050 AA02 AA07 BA09 CB15 DA19 EA12 EA26 GA10 HA10 Continued on the front page F term (reference) 5H021 BB09 EE09 EE11 EE31 HH01 5H028 AA08 BB03 BB06 EE06 EE08 HH01 HH03 5H050 AA02 AA07 BA09 CB15 DA19 EA12 EA26 GA10 HA10
Claims (5)
層した鉛蓄電池であって、前記負極板、又は、前記負極
板及びセパレータに有機エキスパンダを含有する鉛蓄電
池において、前記有機エキスパンダは、工業リグニンと
フェノール誘導体の混合物を、リグノセルロース系物質
に浸透させた後、酸を添加し、分離して作製したもので
あることを特徴とする鉛蓄電池。1. A lead-acid battery in which a positive electrode plate and a negative electrode plate are stacked with a separator interposed therebetween, wherein the negative electrode plate or the negative electrode plate and the separator contain an organic expander. Is a lead-acid battery produced by infiltrating a mixture of industrial lignin and a phenol derivative into a lignocellulosic substance, adding an acid, and separating the mixture.
を用いることを特徴とする請求項１に記載の鉛蓄電池。2. The lead-acid battery according to claim 1, wherein cresol is used as the phenol derivative.
フェノールとメトキシフェノールの少なくとも一方、又
は、両方を用いることを特徴とする請求項１記載の鉛蓄
電池。3. The lead-acid battery according to claim 1, wherein at least one or both of dimethoxyphenol and methoxyphenol are used as the phenol derivative.
ール類を用いることを特徴とする請求項１記載の鉛蓄電
池。4. The lead-acid battery according to claim 1, wherein polyphenols are used as said phenol derivative.
酸を用いることを特徴とする請求項１〜４のいずれか１
項に記載の鉛蓄電池。5. The method according to claim 1, wherein sulfuric acid having a concentration of 65% by mass or more is used as said acid.
The lead storage battery according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000331788A JP2002141103A (en) | 2000-10-31 | 2000-10-31 | Lead-acid battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000331788A JP2002141103A (en) | 2000-10-31 | 2000-10-31 | Lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002141103A true JP2002141103A (en) | 2002-05-17 |
Family
ID=18808083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000331788A Pending JP2002141103A (en) | 2000-10-31 | 2000-10-31 | Lead-acid battery |
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| Country | Link |
|---|---|
| JP (1) | JP2002141103A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006114313A (en) * | 2004-10-14 | 2006-04-27 | Matsushita Electric Ind Co Ltd | Lead storage battery |
-
2000
- 2000-10-31 JP JP2000331788A patent/JP2002141103A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006114313A (en) * | 2004-10-14 | 2006-04-27 | Matsushita Electric Ind Co Ltd | Lead storage battery |
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