JPH097630A - Lignin compound for adding lead acid battery, method for producing the same, and lead acid battery - Google Patents
Lignin compound for adding lead acid battery, method for producing the same, and lead acid batteryInfo
- Publication number
- JPH097630A JPH097630A JP7159011A JP15901195A JPH097630A JP H097630 A JPH097630 A JP H097630A JP 7159011 A JP7159011 A JP 7159011A JP 15901195 A JP15901195 A JP 15901195A JP H097630 A JPH097630 A JP H097630A
- Authority
- JP
- Japan
- Prior art keywords
- lignin compound
- negative electrode
- functional group
- acid battery
- electrode plate
- 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.)
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鉛蓄電池添加用リグニ
ン化合物及びその製造方法並びに鉛蓄電池に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lignin compound for adding a lead storage battery, a method for producing the same, and a lead storage battery.
【０００２】[0002]
【従来の技術】鉛蓄電池の負極活物質は放電生成物（Ｐ
ｂＳＯ4 ）から充電生成物（Ｐｂ）に変化する際に収縮
するために、活物質粒子の表面積が小さくなる。また活
物質が収縮する割合は、活物質層の内部と表面部とで異
なる。そのため、鉛蓄電池で充放電を繰り返すと負極活
物質層内の導電性が低下して、鉛蓄電池の放電特性が低
下したり、寿命が短くなるという問題があった。そこ
で、負極活物質にＢａＳＯ4 やリグニン化合物からなる
表面積低下防止剤を添加して、鉛蓄電池の放電特性やサ
イクル寿命を向上させることが提案された。2. Description of the Related Art A negative electrode active material of a lead-acid battery is a discharge product (P
When the charge product (Pb) changes from bSO 4 ) to shrinkage, the surface area of the active material particles decreases. The rate of contraction of the active material differs between the inside and the surface of the active material layer. Therefore, when charge and discharge are repeated in the lead storage battery, there is a problem that the conductivity in the negative electrode active material layer is lowered, the discharge characteristics of the lead storage battery are lowered, and the life is shortened. Therefore, it has been proposed to add a surface area reduction inhibitor made of BaSO 4 or a lignin compound to the negative electrode active material to improve the discharge characteristics and cycle life of the lead storage battery.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、リグニ
ン化合物の中には、−ＣＯＯＨ、−ＳＯ3 Ｈ等の水素過
電圧を低下させる作用をする官能基が含まれている。こ
れらの官能基は、−ＣＯＯ−＋Ｈ＋、−ＳＯ3 −＋Ｈ＋
のように解離するため、マイナスの電荷を帯びた官能基
に活物質のＰｂ 2＋が吸着して、水素過電圧が低下す
る。したがって、このような官能基の量が多いと、負極
板の水素過電圧が低下し、電池の充電受入れ性が低下す
るという問題があった。However, the lignin compound contains a functional group such as --COOH or --SO 3 H, which acts to reduce the hydrogen overvoltage. These functional groups, -COO - + H +, -SO 3 - + H +
As described above, Pb 2+ of the active material is adsorbed on the negatively charged functional group, and the hydrogen overvoltage decreases. Therefore, when the amount of such a functional group is large, there is a problem that the hydrogen overvoltage of the negative electrode plate is lowered and the charge acceptability of the battery is lowered.
【０００４】本発明の目的は、水素過電圧を低下させる
ことのない鉛蓄電池添加用リグニン化合物を提供するこ
とにある。An object of the present invention is to provide a lignin compound for adding a lead storage battery which does not reduce hydrogen overvoltage.
【０００５】本発明の他の目的は、鉛蓄電池の過放電特
性を高めることができる鉛蓄電池添加用リグニン化合物
を提供することにある。Another object of the present invention is to provide a lignin compound for adding a lead storage battery which can enhance the over-discharge characteristics of the lead storage battery.
【０００６】本発明の他の目的は、水素過電圧を低下さ
せることのない鉛蓄電池添加用リグニン化合物を簡単に
製造する方法を提供することにある。Another object of the present invention is to provide a method for easily producing a lignin compound for adding a lead storage battery which does not reduce hydrogen overvoltage.
【０００７】本発明の更に他の目的は、水素過電圧及び
過放電特性の高い鉛蓄電池を提供することにある。Still another object of the present invention is to provide a lead storage battery having high hydrogen overvoltage and overdischarge characteristics.
【０００８】[0008]
【課題を解決するための手段】本発明は、鉛蓄電池添加
用リグニン化合物を改良の対象とする。本発明では、水
素過電圧を低下させる作用をする官能基（以下、水素過
電圧低下官能基と言う）を含むリグニン化合物と、水素
過電圧低下官能基と反応して水素過電圧低下官能基を含
む沈殿物を生成しかつ鉛蓄電池の負極板及び電解液中に
存在しても電池性能を低下させることのないアルカリ溶
液との混合液から前述の沈殿物を除去したものにより鉛
蓄電池添加用リグニン化合物を構成する。The present invention is directed to an improvement of a lignin compound for adding a lead storage battery. In the present invention, a lignin compound containing a functional group that acts to reduce hydrogen overvoltage (hereinafter referred to as hydrogen overvoltage reducing functional group) and a precipitate containing a hydrogen overvoltage reducing functional group by reacting with the hydrogen overvoltage reducing functional group. A lignin compound for addition to a lead storage battery is formed by removing the above-mentioned precipitate from a mixed solution of an alkaline solution that does not deteriorate the battery performance even if it is produced and exists in the negative electrode plate of the lead storage battery and the electrolyte solution. .
【０００９】リグニン化合物としては、下記化１式に示
す骨格を有するリグニンスルホン酸、や下記化１式及び
化２式に示す骨格を有するチオリグニン等がある。Examples of the lignin compound include lignin sulfonic acid having a skeleton represented by the following chemical formula 1 and thiolignin having a skeleton represented by the following chemical formulas 1 and 2.
【００１０】[0010]
【化１】 Embedded image
【化２】 鉛蓄電池添加用リグニン化合物を製造するには、まず水
素過電圧低下官能基を含むリグニン化合物と、水素過電
圧低下官能基と反応して水素過電圧低下官能基を含む沈
殿物を生成しかつ鉛蓄電池の負極板及び電解液中に存在
しても電池性能を低下させることのないアルカリ溶液と
を混合して混合液を作る。次にこの混合液から沈殿物を
除去するいわゆるアルカリ処理をリグニン化合物に施
す。また沈殿物を生成するのに用いたアルカリ溶液はリ
グニン化合物と分離する必要はない。Embedded image In order to produce a lignin compound for adding a lead storage battery, first, a lignin compound containing a hydrogen overvoltage-reducing functional group is reacted with a hydrogen overvoltage-reducing functional group to form a precipitate containing the hydrogen overvoltage-reducing functional group, and a negative electrode of the lead storage battery is produced. A mixed solution is prepared by mixing the plate and an alkaline solution which does not deteriorate the battery performance even when present in the electrolytic solution. Next, the lignin compound is subjected to a so-called alkaline treatment for removing precipitates from this mixed solution. Also, the alkaline solution used to form the precipitate need not be separated from the lignin compound.
【００１１】アルカリ溶液としては、コロイダルシリ
カ、水酸化ナトリウム（ＮａＯＨ）溶液等を用いるのが
好ましい。コロイダルシリカはシリカ分散用にＮａ＋等
のアルカリ金属イオンが表面に付着しており、アルカリ
性を示す。As the alkaline solution, colloidal silica, sodium hydroxide (NaOH) solution or the like is preferably used. Colloidal silica has alkali metal ions such as Na + attached to the surface for silica dispersion, and thus exhibits alkalinity.
【００１２】鉛蓄電池添加用リグニン化合物は、鉛蓄電
池の負極板の活物質及び電解液の少なくとも一方に添加
する。The lignin compound for adding a lead storage battery is added to at least one of the active material and the electrolytic solution of the negative electrode plate of the lead storage battery.
【００１３】特に鉛蓄電池添加用リグニン化合物を電解
液中に添加すると、負極板から電解液中へのリグニン化
合物の溶出が減少し、電解液中から負極板へのリグニン
化合物の吸着力が増加する利点がある。Particularly, when a lignin compound for adding a lead-acid battery is added to the electrolytic solution, the elution of the lignin compound from the negative electrode plate into the electrolytic solution is reduced, and the adsorption power of the lignin compound from the electrolytic solution to the negative electrode plate is increased. There are advantages.
【００１４】[0014]
【作用】水素過電圧低下官能基を含むリグニン化合物と
アルカリ溶液とを混合すると、−ＣＯＯ−＋Ｈ＋、−Ｓ
Ｏ3 −＋Ｈ＋のように解離した水素過電圧低下官能基の
−ＣＯＯ−、−ＳＯ3 −がＮａ＋等のアルカリ金属イオ
ンと結び付く。そのため、−ＣＯＯ−、−ＳＯ3 に活物
質のＰｂ 2＋に吸着するのを防ぐことができる。また解
離したＨ＋はアルカリ溶液中のＯＨ−と結び付いて水
（Ｈ2 Ｏ）になる。また一部の水素過電圧低下官能基は
硫酸カルシウム、シュウ酸カルシウム等のの沈殿物にな
る。そのため、本発明のリグニン化合物を鉛蓄電池の負
極板等に添加すると、負極板の水素過電圧を低下させる
ことなく、電池の充電受入れ性を向上させることができ
る。SUMMARY OF] when mixing the lignin compound and an alkali solution containing hydrogen overvoltage lowering functional group, -COO - + H +, -S
Dissociated hydrogen overvoltage-reducing functional groups such as O 3 − + H + , —COO − , and —SO 3 − are bound to alkali metal ions such as Na + . Therefore, -COO -, it can be prevented from being adsorbed on Pb 2+ of the active material in the -SO 3. Further, the dissociated H + combines with OH − in the alkaline solution to become water (H 2 O). Further, some hydrogen overvoltage lowering functional groups become precipitates of calcium sulfate, calcium oxalate and the like. Therefore, when the lignin compound of the present invention is added to the negative electrode plate or the like of a lead storage battery, the charge acceptance of the battery can be improved without lowering the hydrogen overvoltage of the negative electrode plate.
【００１５】また、本発明のリグニン化合物を鉛蓄電池
の負極板等に添加すると、電池性能を低下させることの
ないアルカリ溶液も一緒に負極板等に添加される。例え
ば、Ｎａ＋等のアルカリ金属イオンがリグニン化合物に
含まれる場合には、電池の過放電特性を高めることがで
きる。また電解液（希硫酸）中には分散し難いリグニン
化合物をアルカリ溶液と一緒に添加することにより、電
解液中にリグニン化合物を分散させることができる。When the lignin compound of the present invention is added to the negative electrode plate or the like of a lead storage battery, an alkaline solution that does not deteriorate the battery performance is also added to the negative electrode plate or the like. For example, when an alkali metal ion such as Na + is contained in the lignin compound, the overdischarge characteristics of the battery can be improved. Further, by adding a lignin compound that is difficult to disperse in the electrolytic solution (dilute sulfuric acid) together with the alkaline solution, the lignin compound can be dispersed in the electrolytic solution.
【００１６】[0016]
（実施例１）本実施例では、負極活物質にアルカリ処理
したリグニン化合物を添加した。まず上記化学式１に示
す骨格を有するリグニンスルホン酸をコロイダルシリカ
からなるアルカリ溶液中に分散させ、これを常温で撹拌
した。これにより硫酸カルシウム（ＣａＳＯ4 ）及びシ
ュウ酸カルシウム（ＣＯＯＨ−Ｃａ−ＣＯＯＨ）の沈殿
物が生成される。次にこれらの白い沈殿物をろ過により
除去してリグニン化合物溶液を完成した。ここで用いた
リグニンスルホン酸は、後にリグニン化合物を添加する
負極活物質の鉛粉に対して０．５重量％となる量とし、
コロイダルシリカは、該コロイダルシリカ中のＳｉＯ2
が負極活物質の鉛粉に対して１．０重量％となる量とし
た。リグニンスルホン酸とコロイダルシリカ中のＳｉＯ
2 との好ましい混合重量割合は１：８〜１：２０であ
る。コロイダルシリカのＳｉＯ2 の混合重量割合が上記
量を下回るとリグニンスルホン酸を十分にアルカリ処理
することができない。コロイダルシリカのＳｉＯ2 の混
合重量割合が上記量を上回ると、後の工程で活物質ペー
ストを作る際に、多量のＳｉＯ2 が活物質ペーストに混
入することになり、活物質ペーストが固くなるおそれが
ある。Example 1 In this example, an alkali-treated lignin compound was added to the negative electrode active material. First, lignin sulfonic acid having the skeleton shown in the chemical formula 1 was dispersed in an alkaline solution made of colloidal silica, and this was stirred at room temperature. This produces calcium sulfate (CaSO 4 ) and calcium oxalate (COOH-Ca-COOH) precipitates. Next, these white precipitates were removed by filtration to complete the lignin compound solution. The amount of lignin sulfonic acid used here is 0.5% by weight with respect to the lead powder of the negative electrode active material to which a lignin compound is added later,
The colloidal silica is SiO 2 in the colloidal silica.
Was 1.0 wt% with respect to the lead powder of the negative electrode active material. SiO in lignin sulfonic acid and colloidal silica
The preferred mixing weight ratio with 2 is 1: 8 to 1:20. If the mixing weight ratio of SiO 2 of colloidal silica is less than the above amount, the lignin sulfonic acid cannot be sufficiently alkali-treated. If the mixing weight ratio of SiO 2 of the colloidal silica exceeds the above amount, a large amount of SiO 2 will be mixed into the active material paste when the active material paste is made in a later step, and the active material paste may become hard. There is.
【００１７】次に、このリグニン化合物溶液３．２重量
％と鉛粉８０重量％と比重１．３００（２０℃）の希硫
酸８重量％と水８．８重量％とを混練して活物質ペース
トを作った。負極活物質の鉛粉とリグニン化合物溶液と
の好ましい混合重量割合は１：０．０１８〜１：０．０
８である。次に活物質ペースト１５０ｇをＰｂ−Ｃａ合
金の格子体からなる集電体に充填して、未乾燥極板を作
った。そして未乾燥極板を熟成した後にこれを比重１．
０５０の希硫酸（４０℃）中で対極（正極板）に対して
２５０％の課電量で４０時間化成して負極板を作った。
次に負極板と公知の正極板と電解液とを組み合わせて２
Ｖ−１０Ａｈの密閉形鉛蓄電池を作った。Next, 3.2% by weight of this lignin compound solution, 80% by weight of lead powder, 8% by weight of dilute sulfuric acid having a specific gravity of 1.300 (20 ° C.) and 8.8% by weight of water were kneaded, and the active material was kneaded. Made a paste. The preferable mixing weight ratio of the lead powder of the negative electrode active material and the lignin compound solution is 1: 0.018 to 1: 0.0.
8 Next, 150 g of the active material paste was filled in a current collector composed of a Pb-Ca alloy lattice to prepare a undried electrode plate. Then, after aging the undried electrode plate, it has a specific gravity of 1.
A negative electrode plate was prepared by conducting chemical conversion in 050 diluted sulfuric acid (40 ° C.) at a charge amount of 250% for 40 hours with respect to the counter electrode (positive electrode plate).
Next, combine the negative electrode plate, the well-known positive electrode plate, and the electrolyte solution to
A sealed lead acid battery of V-10Ah was made.
【００１８】（実施例２）本実施例では、負極活物質と
電解液の両方にアルカリ処理したリグニン化合物を添加
した。本実施例でも、アルカリ処理用のアルカリ溶液と
してコロイダルシリカを用いて作った。リグニン化合物
の添加量は電解液の硫酸に対して０．０５重量％となる
量であり、コロイダルシリカは該コロイダルシリカ中の
ＳｉＯ2 が電解液の硫酸に対して１．０重量％となる量
とした。その他は実施例１と同様に製造した。リグニン
化合物の添加量は、後に組み合わせる負極板中に存在す
るリグニンの理論量の５０％以上の量とする必要があ
る。これは極板の化成中に負極活物質中のリグニンの約
５０％が電解液中に溶出するためである。なおリグニン
スルホン酸とコロイダルシリカのＳｉＯ2 との好ましい
混合重量割合は１：８〜１：２０である。コロイダルシ
リカのＳｉＯ2 の混合重量割合が上記量を下回るとリグ
ニンスルホン酸を十分にアルカリ処理することができな
い。コロイダルシリカのＳｉＯ2 の混合重量割合が上記
量を上回ると、多量のＳｉＯ2 が電解液に混入すること
になり、電解液が固くなるおそれがある。Example 2 In this example, an alkali-treated lignin compound was added to both the negative electrode active material and the electrolytic solution. Also in this example, colloidal silica was used as the alkaline solution for the alkaline treatment. The amount of the lignin compound added is 0.05% by weight with respect to the sulfuric acid of the electrolytic solution, and the colloidal silica is such that SiO 2 in the colloidal silica is 1.0% by weight with respect to the sulfuric acid of the electrolytic solution. And Others were manufactured similarly to Example 1. The added amount of the lignin compound needs to be 50% or more of the theoretical amount of lignin present in the negative electrode plate to be combined later. This is because about 50% of lignin in the negative electrode active material is eluted into the electrolytic solution during formation of the electrode plate. Incidentally preferred mixing weight ratio of the SiO 2 of lignin sulfonic acid and colloidal silica is 1: 8 to 1: 20. If the mixing weight ratio of SiO 2 of colloidal silica is less than the above amount, the lignin sulfonic acid cannot be sufficiently alkali-treated. If the mixing weight ratio of SiO 2 of the colloidal silica exceeds the above amount, a large amount of SiO 2 will be mixed into the electrolytic solution, and the electrolytic solution may become hard.
【００１９】そして、このリグニン化合物溶液を比重
１．３０３（２０℃）の希硫酸及び水中に添加して電解
液を作った。電解液の硫酸とリグニン化合物溶液との好
ましい混合重量割合は３５：１〜７５：１である。次に
実施例１で用いた負極板と公知の正極板と電解液とを組
み合わせて２Ｖ−１０Ａｈの密閉形鉛蓄電池を作った。
正極板は実施例１で用いたものと同じ正極板を用いた。Then, this lignin compound solution was added to dilute sulfuric acid having a specific gravity of 1.303 (20 ° C.) and water to prepare an electrolytic solution. A preferable mixing weight ratio of the sulfuric acid of the electrolytic solution and the lignin compound solution is 35: 1 to 75: 1. Next, the negative electrode plate used in Example 1, a known positive electrode plate, and an electrolytic solution were combined to form a sealed lead acid battery of 2V-10Ah.
As the positive electrode plate, the same positive electrode plate as that used in Example 1 was used.
【００２０】（実施例３）本実施例では、負極活物質に
アルカリ処理を施さないリグニン化合物を添加し、電解
液にアルカリ処理したリグニン化合物を添加した。本実
施例では、リグニン化合物にアルカリ処理を施さず、そ
の他は実施例１で用いた負極板と同様の方法で製造した
負極板を用いる。また、実施例２で用いたアルカリ処理
したリグニン化合物を添加した電解液を用いる。そし
て、公知の正極板とを組み合わせて２Ｖ−１０Ａｈの密
閉形鉛蓄電池を作った。なお正極板は実施例１で用いた
ものと同じ正極板を用いた。Example 3 In this example, a lignin compound not subjected to alkali treatment was added to the negative electrode active material, and an alkali-treated lignin compound was added to the electrolytic solution. In this example, the lignin compound was not subjected to an alkali treatment, and the negative electrode plate manufactured by the same method as that of the negative electrode plate used in Example 1 was used. Further, the electrolytic solution containing the alkali-treated lignin compound used in Example 2 is used. Then, a known positive electrode plate was combined to make a sealed lead acid battery of 2V-10Ah. The same positive electrode plate as that used in Example 1 was used as the positive electrode plate.
【００２１】（比較例１）本比較例では、負極活物質及
び電解液にアルカリ処理を施さないリグニン化合物を添
加した。本比較例では、リグニン化合物にアルカリ処理
を施していない点を除いて、その他は実施例１で用いた
負極板と同様の方法で製造した負極板と、アルカリ処理
を施さずに、その他は実施例２で用いた電解液と同様の
方法で製造した電解液と、公知の正極板とを組み合わせ
て２Ｖ−１０Ａｈの密閉形鉛蓄電池を作った。なお正極
板は実施例１で用いたものと同じ正極板を用いた。(Comparative Example 1) In this comparative example, a lignin compound not subjected to alkali treatment was added to the negative electrode active material and the electrolytic solution. In this comparative example, except that the lignin compound was not subjected to alkali treatment, the negative electrode plate manufactured by the same method as the negative electrode plate used in Example 1 was used except that the lignin compound was not subjected to alkali treatment. An electrolytic solution produced in the same manner as the electrolytic solution used in Example 2 and a known positive electrode plate were combined to form a sealed lead acid battery of 2V-10Ah. The same positive electrode plate as that used in Example 1 was used as the positive electrode plate.
【００２２】次に上記各電池に０．２５Ｃで２時間の放
電と２．４５Ｖ（０．３ＣＡカット）で８時間の充電と
１時間の休止とを繰り返す充放電を行って各電池のサイ
クル寿命特性を調べた。図１はその測定結果を示してい
る。本図より実施例１〜３の電池はサイクル寿命が延び
ており、特に負極板と電解液の両方にアルカリ処理した
リグニン化合物を添加した実施例２の電池は大幅にサイ
クル寿命が延びるのが分る。Next, each battery was charged and discharged by repeatedly discharging it for 2 hours at 0.25 C, charging it for 2.45 V (0.3 CA cut) for 8 hours, and suspending it for 1 hour. The characteristics were investigated. FIG. 1 shows the measurement result. It can be seen from the figure that the batteries of Examples 1 to 3 have a long cycle life, and in particular, the battery of Example 2 in which the alkali-treated lignin compound is added to both the negative electrode plate and the electrolytic solution has a significantly long cycle life. It
【００２３】次に各電池に６０℃雰囲気中において２．
２３Ｖの設定電圧で０．２５Ｃ放電（Ｆ．Ｖ．１．７
Ｖ）のトリクルユースを行い、各電池のトリクル寿命特
性を調べた。図２はその測定結果を示している。本図よ
り実施例１〜３の電池はトリクル寿命が延びており、特
に負極板と電解液の両方にアルカリ処理したリグニン化
合物を添加した実施例２の電池は大幅にトリクル寿命が
延びるのが分る。Then, each battery was subjected to 2.
0.25C discharge (F.V.1.7 at a set voltage of 23V)
The trickle use of V) was performed to examine the trickle life characteristics of each battery. FIG. 2 shows the measurement results. From this figure, the batteries of Examples 1 to 3 have a longer trickle life, and in particular, the battery of Example 2 in which the alkali-treated lignin compound is added to both the negative electrode plate and the electrolytic solution is found to have a significantly longer trickle life. It
【００２４】実施例１〜３の電池がサイクル寿命及びト
リクル寿命を延ばせるのは、水素過電圧低下官能基を除
去したことにより負極板の水素過電圧が高くなって、電
池の充電特性が向上したためである。特に、アルカリ処
理したリグニン化合物を電解液中に添加すると、負極板
からリグニン化合物の溶出が低減して効果が高くなる。The batteries of Examples 1 to 3 can extend the cycle life and the trickle life because the hydrogen overvoltage of the negative electrode plate was increased and the charging characteristics of the batteries were improved by removing the hydrogen overvoltage lowering functional group. . In particular, when the alkali-treated lignin compound is added to the electrolytic solution, the elution of the lignin compound from the negative electrode plate is reduced and the effect is enhanced.
【００２５】本発明は、水酸化ナトリウム（ＮａＯＨ）
からなるアルカリ溶液によりアルカリ処理を施してもよ
い。ＮａＯＨを用いる場合は、上記化学式１に示す骨格
を有するリグニンスルホン酸を１／１０ＮのＮａＯＨか
らなるアルカリ溶液中に分散させ、これを撹拌すればよ
い。そして、溶液中に生じた白い沈殿物をろ過により除
去する。リグニンスルホン酸は、後にリグニン化合物を
添加する負極活物質の鉛粉に対して０．５重量％となる
量とし、ＮａＯＨは１．０重量％となる量である。アル
カリ溶液としてＮａＯＨを用いる場合には、硫酸との中
和反応が生じるので、通常の比重よりも高比重の硫酸を
用いるのが好ましい。ＮａＯＨを用いた場合も、コロイ
ダルシリカを用いた場合と同様の効果を示すことが試験
により確認できた。The present invention relates to sodium hydroxide (NaOH)
You may perform alkali treatment with the alkali solution consisting of. When NaOH is used, ligninsulfonic acid having the skeleton represented by the chemical formula 1 may be dispersed in an alkaline solution composed of 1/10 N NaOH and stirred. Then, the white precipitate generated in the solution is removed by filtration. The amount of lignin sulfonic acid is 0.5% by weight, and the amount of NaOH is 1.0% by weight, based on the lead powder of the negative electrode active material to which the lignin compound is added later. When NaOH is used as the alkaline solution, it is preferable to use sulfuric acid having a higher specific gravity than usual because a neutralization reaction with sulfuric acid occurs. It was confirmed by a test that the same effect as when colloidal silica was used was also obtained when NaOH was used.
【００２６】本実施例では、リグニン化合物としてリグ
ニンスルホン酸を用いたが、チオリグニン等の他のリグ
ニン化合物を用いた場合でも、本発明を適用できる。In this example, lignin sulfonic acid was used as the lignin compound, but the present invention can be applied to the case of using other lignin compounds such as thiolignin.
【００２７】また、アルカリ溶液としては、鉛蓄電池の
負極板及び電解液中に存在しても電池性能を低下させる
ことのないものであればよく、コロイダルシリカ、水酸
化ナトリウム（ＮａＯＨ）溶液以外のものも用いること
ができる。特にＮａ＋を含有するアルカリ溶液が好まし
い。As the alkaline solution, any alkaline solution may be used as long as it does not deteriorate the battery performance even if it exists in the negative electrode plate of the lead acid battery and the electrolytic solution. Other than colloidal silica and sodium hydroxide (NaOH) solution. Things can also be used. Particularly, an alkaline solution containing Na + is preferable.
【００２８】以下、明細書に記載した複数の発明の中で
いくつかの発明についてその構成を示す。The constitution of some of the inventions described in the specification will be shown below.
【００２９】（１） リグニンスルホン酸と、コロイダ
ルシリカからなるアルカリ溶液とを前記リグニンスルホ
ン酸と前記コロイダルシリカ中のＳｉＯ2 との混合重量
割合が１：８〜１：２０になるように混合して混合液を
作り、前記混合液から沈殿物を除去して鉛蓄電池添加用
リグニン化合物を作り、前記鉛蓄電池添加用リグニン化
合物を前記負極板の活物質中に、前記負極活物質の鉛粉
と前記リグニン化合物溶液との混合重量割合が１：０．
０１８〜１：０．０８になるように添加して負極活物質
の活物質ペーストを作り、この活物質ペーストを用いて
鉛蓄電池用負極板を製造する方法。(1) Lignin sulfonic acid and an alkaline solution containing colloidal silica are mixed so that the mixing weight ratio of the lignin sulfonic acid and SiO 2 in the colloidal silica is 1: 8 to 1:20. A mixed solution is prepared by removing a precipitate from the mixed solution to prepare a lignin compound for adding a lead storage battery, the lignin compound for adding a lead storage battery in the active material of the negative electrode plate, and lead powder of the negative electrode active material. The mixing weight ratio with the lignin compound solution was 1: 0.
A method for producing a negative electrode plate for a lead storage battery by using the active material paste to make an active material paste of the negative electrode active material.
【００３０】（２） リグニンスルホン酸と、コロイダ
ルシリカからなるアルカリ溶液とを前記リグニンスルホ
ン酸と前記コロイダルシリカ中のＳｉＯ2 との混合重量
割合が１：８〜１：２０になるように混合して混合液を
作り、前記混合液から沈殿物を除去して鉛蓄電池添加用
リグニン化合物を作り、前記鉛蓄電池添加用リグニン化
合物を希硫酸中に、負極活物質中に添加するリグニン化
合物の量の５０％以上の量を添加してなるリグニン化合
物溶液電解液の製造方法。(2) Lignin sulfonic acid and an alkaline solution containing colloidal silica are mixed so that the mixing weight ratio of the lignin sulfonic acid and SiO 2 in the colloidal silica is 1: 8 to 1:20. A mixed solution is prepared by removing the precipitate from the mixed solution to prepare a lead-acid battery addition lignin compound, and the lead-acid battery addition lignin compound in diluted sulfuric acid, the amount of the lignin compound added to the negative electrode active material. A method for producing a lignin compound solution electrolyte, which comprises adding an amount of 50% or more.
【００３１】[0031]
【発明の効果】本発明によれば、リグニン化合物中から
水素過電圧低下官能基を除くことができるため、本発明
のリグニン化合物を鉛蓄電池の負極板等に添加すると、
負極板の水素過電圧の低下を防いで電池の充電受入れ性
を向上させることができる。According to the present invention, since the hydrogen overvoltage lowering functional group can be removed from the lignin compound, when the lignin compound of the present invention is added to a negative electrode plate of a lead acid battery,
It is possible to prevent a decrease in hydrogen overvoltage of the negative electrode plate and improve charge acceptance of the battery.
【００３２】また、本発明のリグニン化合物を鉛蓄電池
の負極板等に添加すると、アルカリ溶液も一緒に負極板
等に添加されるので、アルカリ金属塩（Ｎａ＋等）によ
り電池の過放電特性を高めることができる。また電解液
（希硫酸）中には分散しにくいリグニン化合物をアルカ
リ溶液と一緒に添加することにより、電解液中にリグニ
ン化合物を分散させることができる。When the lignin compound of the present invention is added to the negative electrode plate or the like of a lead storage battery, the alkaline solution is also added to the negative electrode plate or the like. Therefore, the alkaline metal salt (Na + or the like) improves the overdischarge characteristics of the battery. Can be increased. Also, by adding a lignin compound that is difficult to disperse in the electrolytic solution (dilute sulfuric acid) together with the alkaline solution, the lignin compound can be dispersed in the electrolytic solution.
【図１】 試験に用いた電池のサイクル寿命特性を示す
図である。FIG. 1 is a diagram showing cycle life characteristics of a battery used in a test.
【図２】 試験に用いた電池のトリクル寿命特性を示す
図である。FIG. 2 is a diagram showing a trickle life characteristic of a battery used in a test.
Claims (4)
基を含むリグニン化合物と、前記官能基と反応して前記
官能基を含む沈殿物を生成しかつ鉛蓄電池の負極板及び
電解液中に存在しても電池性能を低下させることのない
アルカリ溶液との混合液から前記沈殿物が除去されてな
る鉛蓄電池添加用リグニン化合物。1. A lignin compound having a functional group that acts to reduce hydrogen overvoltage, and a lignin compound that reacts with the functional group to form a precipitate containing the functional group and is present in the negative electrode plate of the lead acid battery and the electrolytic solution. A lignin compound for addition to a lead storage battery, which is obtained by removing the precipitate from a mixed solution with an alkaline solution that does not deteriorate the battery performance even if it is used.
基を含むリグニン化合物と、前記官能基と反応して前記
官能基を含む沈殿物を生成しかつ鉛蓄電池の負極板及び
電解液中に存在しても電池性能を低下させることのない
アルカリ溶液とを混合して混合液を作り、 前記混合液から前記沈殿物を除去して鉛蓄電池添加用リ
グニン化合物を製造することを特徴とする鉛蓄電池添加
用リグニン化合物の製造方法。2. A lignin compound containing a functional group that acts to reduce hydrogen overvoltage, and a lignin compound that reacts with the functional group to form a precipitate containing the functional group and is present in the negative electrode plate and the electrolytic solution of a lead acid battery. A lead acid battery characterized by producing a lignin compound for adding a lead acid battery by mixing with an alkaline solution that does not deteriorate the battery performance to form a mixed solution and removing the precipitate from the mixed solution. A method for producing a lignin compound for addition.
たは水酸化ナトリウム溶液である請求項２に記載の鉛蓄
電池添加用リグニン化合物の製造方法。3. The method for producing a lignin compound for adding a lead storage battery according to claim 2, wherein the alkaline solution is colloidal silica or sodium hydroxide solution.
ン化合物が負極板の活物質及び電解液の少なくとも一方
に添加されていることを特徴とする鉛蓄電池。4. A lead acid battery, wherein the lignin compound for adding a lead acid battery according to claim 1 is added to at least one of an active material of a negative electrode plate and an electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7159011A JPH097630A (en) | 1995-06-26 | 1995-06-26 | Lignin compound for adding lead acid battery, method for producing the same, and lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7159011A JPH097630A (en) | 1995-06-26 | 1995-06-26 | Lignin compound for adding lead acid battery, method for producing the same, and lead acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH097630A true JPH097630A (en) | 1997-01-10 |
Family
ID=15684300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7159011A Withdrawn JPH097630A (en) | 1995-06-26 | 1995-06-26 | Lignin compound for adding lead acid battery, method for producing the same, and lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH097630A (en) |
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|---|---|---|---|---|
| JP2002117856A (en) * | 2000-10-10 | 2002-04-19 | Yuasa Corp | Negative electrode board for control valve type lead storage battery |
| WO2002039519A1 (en) * | 2000-11-09 | 2002-05-16 | Yuasa Corporation | Negative electrode active material, process for its production and lead storage battery |
| JP2007165273A (en) * | 2005-11-17 | 2007-06-28 | Gs Yuasa Corporation:Kk | Anode for lead acid storage battery, and the lead acid battery using the anode |
| WO2020013112A1 (en) | 2018-07-09 | 2020-01-16 | 日本製紙株式会社 | Organic anti-shrinkage agent for lead storage battery |
| JP2021111492A (en) * | 2020-01-08 | 2021-08-02 | 古河電池株式会社 | Liquid type lead storage battery |
| WO2021182364A1 (en) | 2020-03-09 | 2021-09-16 | 日本製紙株式会社 | Organic shrink-proofing agent for lead acid storage batteries, and method for producing same |
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-
1995
- 1995-06-26 JP JP7159011A patent/JPH097630A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002117856A (en) * | 2000-10-10 | 2002-04-19 | Yuasa Corp | Negative electrode board for control valve type lead storage battery |
| WO2002039519A1 (en) * | 2000-11-09 | 2002-05-16 | Yuasa Corporation | Negative electrode active material, process for its production and lead storage battery |
| US7022433B2 (en) | 2000-11-09 | 2006-04-04 | Gs Yuasa Corporation | Negative active material, method of manufacturing its material, and lead acid battery |
| JP2007165273A (en) * | 2005-11-17 | 2007-06-28 | Gs Yuasa Corporation:Kk | Anode for lead acid storage battery, and the lead acid battery using the anode |
| WO2020013112A1 (en) | 2018-07-09 | 2020-01-16 | 日本製紙株式会社 | Organic anti-shrinkage agent for lead storage battery |
| US11251434B2 (en) | 2018-07-09 | 2022-02-15 | Nippon Paper Industries Co., Ltd. | Organic expander for lead storage battery |
| JP2021111492A (en) * | 2020-01-08 | 2021-08-02 | 古河電池株式会社 | Liquid type lead storage battery |
| WO2021182364A1 (en) | 2020-03-09 | 2021-09-16 | 日本製紙株式会社 | Organic shrink-proofing agent for lead acid storage batteries, and method for producing same |
| CN114335756A (en) * | 2021-01-11 | 2022-04-12 | 骆驼集团襄阳蓄电池有限公司 | Electrolyte, manufacturing method thereof and lead-acid storage battery prepared from electrolyte |
| CN114335756B (en) * | 2021-01-11 | 2023-07-14 | 骆驼集团襄阳蓄电池有限公司 | Electrolyte, manufacturing method thereof and lead-acid storage battery prepared from electrolyte |
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