JP3196556B2 - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JP3196556B2 JP3196556B2 JP04290495A JP4290495A JP3196556B2 JP 3196556 B2 JP3196556 B2 JP 3196556B2 JP 04290495 A JP04290495 A JP 04290495A JP 4290495 A JP4290495 A JP 4290495A JP 3196556 B2 JP3196556 B2 JP 3196556B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- conductive material
- active material
- barium
- conductivity
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は鉛蓄電池の活物質導電性
向上に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improving the conductivity of an active material of a lead storage battery.
【０００２】[0002]
【従来の技術】鉛蓄電池は二次電池として比較的安価で
安定な性能を有しているため一般に普及している。また
近年ではポータブル機器や電動車の電源に用いられるサ
イクル使用の移動用電源、コンピューターなどのバック
アップに用いる据え置き用電源としても普及してきた。2. Description of the Related Art Lead storage batteries are widely used because they have relatively low cost and stable performance as secondary batteries. In recent years, it has also been widely used as a portable power supply for use in portable devices and electric vehicles, and a stationary power supply used as a backup for computers and the like.
【０００３】近年、自動車用の無公害対策として電気自
動車が脚光を浴びている。またポータブル機器のコード
レス化も進んでおり、これにつれて電源として価格の安
い鉛蓄電池の高性能化への要望が高まってきている。こ
の鉛蓄電池の高性能化にはとりわけ高エネルギー密度
化、長寿命化が大きな課題となっている。In recent years, electric vehicles have been spotlighted as non-pollution measures for vehicles. In addition, the trend toward cordless portable devices is progressing, and with this trend, demands for higher performance of inexpensive lead-acid batteries as power sources are increasing. In order to improve the performance of the lead storage battery, it is particularly important to increase the energy density and extend the service life.
【０００４】これらの課題は活物質の導電性によるとこ
ろが大きい。鉛蓄電池は正極に二酸化鉛（ＰｂＯ2）、
負極に鉛（Ｐｂ）、電解液に硫酸（Ｈ2ＳＯ4）水溶液を
用いておりその電池放電反応は以下に示す通りである。[0004] These problems largely depend on the conductivity of the active material. Lead acid batteries use lead dioxide (PbO 2 ) as the positive electrode,
Lead (Pb) is used for the negative electrode, and sulfuric acid (H 2 SO 4 ) aqueous solution is used for the electrolytic solution. The battery discharge reaction is as follows.
【０００５】 正極：PbO2＋2H+＋H2SO4＋2e-→PbSO4＋2H2O 負極：Pb＋SO4 2-→PbSO4＋2e- 上記の反応式から明らかなように、正極、負極とも活物
質が硫酸鉛（ＰｂＳＯ 4）に変化していく。硫酸鉛は
鉛、二酸化鉛に比べ電気抵抗がはるかに大きくほとんど
導電性をもたない。そのため放電反応が進むにつれて極
板自身の導電性が劣化してくる。このようなことが、電
池電圧の低下ならびに活物質利用率の低下につながって
いる。また、充電時はこの硫酸鉛を正極では二酸化鉛に
負極では鉛に変化させるため極板の導電性の悪さは、充
電効率の低下につながる。このように、極板の導電性の
悪さが鉛蓄電池の高エネルギー密度化や長寿命化への大
きな課題となっている。[0005] Positive electrode: PbOTwo+ 2H++ HTwoSOFour+ 2e-→ PbSOFour+ 2HTwoO Negative electrode: Pb + SOFour 2-→ PbSOFour+ 2e- As is clear from the above reaction formula, both the positive electrode and the negative electrode
The quality is lead sulfate (PbSO Four). Lead sulfate
Electric resistance is much higher than lead and lead dioxide, almost
It has no conductivity. As the discharge reaction progresses,
The conductivity of the plate itself deteriorates. Such a thing
Of battery voltage and active material utilization rate
I have. During charging, this lead sulfate is converted to lead dioxide at the positive electrode.
Since the negative electrode changes to lead, the poor conductivity of the electrode plate
This leads to a decrease in power efficiency. Thus, the conductivity of the electrode plate
Badness is the key to increasing the energy density and extending the life of lead-acid batteries
Has become a critical issue.
【０００６】これらの課題を解決するための方策として
従来種々の導電材を添加する手法が提案されている。一
例として鉛酸バリウム（ＢａＰｂＯ3）という材料が導
電材として近年注目を集めている（例えば特開平４−２
０６２６８号公報、「Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ，Ｓ
ｏｃ」１３９（１９９２）第４１〜４３頁）。鉛酸バリ
ウムは比較的良導電性を示すと言われており、硫酸中で
安定であり且つ充放電でほとんど変化しないという性質
を持つ。そこで、この鉛酸バリウムを活物質ペーストに
混合、分散することで極板に導電性を持たせ電気抵抗を
低減させようというものである。As a measure for solving these problems, there has been proposed a method of adding various conductive materials. As an example, a material called barium plumbate (BaPbO 3 ) has attracted attention as a conductive material in recent years (for example, see Japanese Patent Application Laid-Open No. Hei 4-2).
No. 06268, J. Electrochem, S
oc "139 (1992) pp. 41-43). Barium plumbate is said to have relatively good conductivity, and is stable in sulfuric acid and hardly changes during charge and discharge. Then, by mixing and dispersing the barium lead acid into the active material paste, the electrode plate is made conductive and the electric resistance is reduced.
【０００７】[0007]
【発明が解決しようとする課題】上記のように鉛酸バリ
ウムの導電材を活物質中に添加することによって導電性
を向上させる手法において、その導電材自身の導電性が
鉛蓄電池の充放電性能を大きく左右する。しかし鉛酸バ
リウムは金属並みの導電性を持つとはいえ、金属鉛や二
酸化鉛に比べるとやはり導電性は低い。そのため鉛酸バ
リウムに換わる、さらに高導電性能を持ち活物質利用率
の優れた導電材が必要である。SUMMARY OF THE INVENTION As described above, in a technique for improving conductivity by adding a barium lead oxide conductive material to an active material, the conductivity of the conductive material itself is determined by the charge / discharge performance of a lead-acid battery. Greatly affect However, although barium plumbate has the same conductivity as metal, it still has lower conductivity than metal lead or lead dioxide. Therefore, there is a need for a conductive material having a higher conductivity and an excellent utilization rate of the active material in place of barium plumbate.
【０００８】本発明は、このような課題を解決するもの
で、導電性が高く、活物質利用率ならびにサイクル寿命
の優れた鉛蓄電池用の導電材を見出すことを目的とす
る。An object of the present invention is to solve such a problem, and an object of the present invention is to find a conductive material for a lead storage battery having high conductivity, excellent active material utilization rate and excellent cycle life.
【０００９】[0009]
【課題を解決するための手段】これらの課題を解決する
ため本発明は、鉛蓄電池において正，負極の少くとも一
方にペロブスカイト構造を持ち、化学式がＢａＰｂ1-x
Ｏ3（０＜ｘ≦０．０５）なる導電材を添加させるとい
う構成を備えたものである。In order to solve these problems, the present invention relates to a lead-acid battery having at least one of a positive electrode and a negative electrode having a perovskite structure and a chemical formula of BaPb 1-x
It has a configuration in which a conductive material of O 3 (0 <x ≦ 0.05) is added.
【００１０】さらに導電材の添加量が活物質の鉛換算重
量に対して２〜１０重量％の範囲とするものである。Further, the amount of the conductive material to be added is in the range of 2 to 10% by weight based on the weight of the active material in terms of lead.
【００１１】[0011]
【作用】鉛酸バリウムの結晶構造は図１に示すように、
Ａサイトにバリウムイオンが位置し、Ｂサイトに鉛イオ
ン、立方体の１２の稜の中心に酸素イオンが存在するい
わゆるペロブスカイト構造をしている。本発明の導電材
料はこのペロブスカイト構造はそのままに、Ｂサイトの
鉛の一部が欠損し空孔となった構造を持つ。[Action] The crystal structure of barium plumbate is shown in FIG.
It has a so-called perovskite structure in which barium ions are located at the A site, lead ions are located at the B site, and oxygen ions are present at the center of the 12 ridges of the cube. The conductive material of the present invention has a structure in which part of lead at the B site is lost to form pores, while maintaining this perovskite structure.
【００１２】これは鉛酸バリウムのＢサイトの鉛イオン
欠損するとそれにつれて相対的にバリウムイオンが増加
することになる。するとバリウムイオンに関与する酸素
の割合が増加し、結果として鉛イオンの（５ｄ）10閉核
構造からの電子の一部欠損が生じるか、もしくは酸素２
Ｐ軌道にホールが生じる。このように電子の不足してい
る鉛イオンまたは酸素イオンが導電性を向上させる原因
と思われる。[0012] This is because, when lead ions are deficient at the B site of barium plumbate, barium ions are relatively increased. Then, the proportion of oxygen involved in barium ions increases, and as a result, a partial loss of electrons from the (5d) 10 closed nucleus structure of lead ions occurs, or oxygen 2
A hole occurs in the P orbit. It is considered that lead ions or oxygen ions, which lack electrons, cause the improvement in conductivity.
【００１３】本発明による材料を導電材として活物質中
に添加すると、従来の鉛酸バリウムを添加する場合に比
べ活物質利用率およびサイクル寿命が向上する。When the material according to the present invention is added to the active material as a conductive material, the active material utilization and the cycle life are improved as compared with the case where barium plumbate is conventionally added.
【００１４】[0014]
【実施例】以下、本発明の一実施例を説明する。An embodiment of the present invention will be described below.
【００１５】ペロブスカイト構造を持つ鉛酸バリウムで
は単位格子の中心はバリウムイオンであるが、本発明品
ではペロブスカイト構造はそのままに鉛の一部（５％以
下）を抜き取り空孔とする。この構造を化学式で表すと
次のようになる。In barium plumbate having a perovskite structure, the center of the unit cell is a barium ion. In the present invention, however, a part (5% or less) of lead is extracted from the perovskite structure as it is to form a hole. This structure is represented by the following chemical formula.
【００１６】 ＢａＰｂ1-xＯ3（０＜ｘ≦０．０５） (ａ) ここで本発明の導電材は二酸化鉛と硝酸バリウムとのモ
ル数比を種々変化させ、酸素雰囲気中で５００〜８００
℃にて約８時間焼成して作製した。BaPb 1-x O 3 (0 <x ≦ 0.05) (a) Here, the conductive material of the present invention is obtained by changing the molar ratio of lead dioxide to barium nitrate in various ways, and 800
It was manufactured by firing at about 8 hours.
【００１７】本実施例での鉛蓄電池の活物質ペーストは
次のように作製した。まず酸化度７０％〜８０％の鉛粉
６ｋｇに希硫酸（比重：１．２０、２０℃）１．４ｌを
徐々に加えながら練合し活物質ペーストを作製する。そ
して本発明の導電材（(ａ)式：ｘ＝０．０３）と従来の
導電材（鉛酸バリウム）をそれぞれ鉛換算重量に対し
て、０、２、５、７、１０、１５ｗｔ％添加したものを
作りさらに練合した。この時の導電材は１００ｍｅｓｈ
以下に粉砕している。それぞれのペーストをシール電池
用の鋳造格子に充填しこの極板を正極として化成した。
なお極板のサイズは縦４０ｍｍ×横１３ｍｍ．厚さ１．
３ｍｍであり、この極板に充填されたペースト重量は約
２．３ｇであった。The active material paste for the lead-acid battery in this embodiment was prepared as follows. First, 1.4 l of dilute sulfuric acid (specific gravity: 1.20, 20 ° C) is gradually added to 6 kg of lead powder having an oxidation degree of 70% to 80% to prepare an active material paste. Then, the conductive material of the present invention (formula (a): x = 0.03) and the conventional conductive material (barium plumbate) are added in an amount of 0, 2, 5, 7, 10, and 15 wt%, respectively, based on the weight in terms of lead. Was made and further kneaded. The conductive material at this time is 100 mesh
It is crushed below. Each paste was filled in a casting grid for a sealed battery, and this electrode plate was formed as a positive electrode.
The size of the electrode plate is 40 mm long × 13 mm wide. Thickness 1.
3 mm, and the weight of the paste filled in this electrode plate was about 2.3 g.
【００１８】充填電気量は各ペーストに含まれる鉛原子
のモル数を計算し、それらが化成により全て二酸化鉛に
変化したとして算出した。この充填電気量を基準とし
０．２Ｃおよび１Ｃの定電流放電によって放電容量を調
べた。その結果を（表１）（表２）に示す。なお、対極
には、正極容量に対して２倍の容量を持つシール電池用
の負極を用い正極容量制限によって性能が劣化するよう
に調整した。The amount of electricity charged was calculated by calculating the number of moles of lead atoms contained in each paste, and assuming that all of them were converted to lead dioxide by formation. The discharge capacity was examined by constant current discharge at 0.2 C and 1 C based on the charged amount of electricity. The results are shown in (Table 1) and (Table 2). As a counter electrode, a negative electrode for a sealed battery having twice the capacity of the positive electrode capacity was used, and the performance was deteriorated due to the positive electrode capacity limitation.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】（表１）（表２）から明らかなように、本
発明の導電材を添加した極板は従来の導電材（鉛酸バリ
ウム）を添加したものに比べ利用率およびサイクル寿命
が向上している。As is clear from Tables 1 and 2, the electrode plate to which the conductive material of the present invention is added has an improved utilization factor and cycle life as compared with the conventional electrode material to which the conductive material (barium lead oxide) is added. are doing.
【００２２】そして導電材添加量が２％より優位性が現
われ、７〜１０％の範囲で利用率，サイクル寿命共にピ
ーク値を示している。１０％以上添加しても利用率，サ
イクル寿命は向上せず、逆に活物質量が減少するため放
電容量が劣化する。The superiority appears when the amount of the conductive material added is 2%, and both the utilization factor and the cycle life show peak values in the range of 7 to 10%. Even if 10% or more is added, the utilization factor and the cycle life are not improved, and conversely, the discharge capacity is deteriorated because the amount of the active material is reduced.
【００２３】以上の結果より総合的にみて、導電材添加
量は２〜１０ｗｔ％の範囲が良好であり更に７〜１０ｗ
ｔ％が優れている。In view of the above results, the amount of the conductive material added is preferably in the range of 2 to 10 wt%, and more preferably 7 to 10 w%.
t% is excellent.
【００２４】次に(ａ)式で表される本発明の導電材でｘ
の値を変化させた場合の活物質利用率とサイクル寿命の
性能を（表３）に示す。導電材の添加量は鉛換算重量に
対して７ｗｔ％であり、極板のサイズや試験方法などは
上記と同様である。Next, with the conductive material of the present invention represented by the formula (a), x
(Table 3) shows the performance of the active material utilization rate and the cycle life when the value of was changed. The amount of the conductive material added is 7 wt% with respect to the lead conversion weight, and the size of the electrode plate and the test method are the same as described above.
【００２５】[0025]
【表３】 [Table 3]
【００２６】（表３）から分かるように、０＜ｘ≦０．
０５であれば利用率、サイクル寿命共に改善されてお
り、従来の鉛酸バリウム（即ち表３のｘ＝０の場合）に
比べて優位性が明らかである。As can be seen from Table 3, 0 <x ≦ 0.
In the case of 05, both the utilization factor and the cycle life are improved, and the superiority is clear as compared with the conventional barium lead oxide (that is, when x = 0 in Table 3).
【００２７】なお、ｘの値が０．０５を超えるとペロブ
スカイトとしての構造を保てなくなり、導電性が急激に
劣化するため利用率が低下するものと思われる。When the value of x exceeds 0.05, the structure as a perovskite cannot be maintained, and the conductivity is rapidly deteriorated, so that the utilization factor is considered to be reduced.
【００２８】なお本実施例では導電材を正極中に添加し
たが、負極あるいは正極、負極両方に添加しても同様の
効果が得られた。In this example, the conductive material was added to the positive electrode. However, the same effect was obtained by adding the conductive material to the negative electrode or both the positive electrode and the negative electrode.
【００２９】[0029]
【発明の効果】以上のように、本発明の導電材は従来の
導電材として提案されている鉛酸バリウムに比べ活物質
利用率ならびにサイクル寿命の向上に効果がある。As described above, the conductive material of the present invention is more effective in improving the utilization rate of the active material and the cycle life than barium plumbate proposed as a conventional conductive material.
【図１】鉛酸バリウムの結晶構造を示す図FIG. 1 is a diagram showing the crystal structure of barium plumbate
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−225711（ＪＰ，Ａ) 特開 平４−206268（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/62 H01M 4/14 - 4/23 C04B 35/00 H01B 1/16 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-225711 (JP, A) JP-A-4-206268 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/62 H01M 4/14-4/23 C04B 35/00 H01B 1/16
Claims (2)
ある鉛蓄電池であって、正，負極の少くとも一方にペロ
ブスカイト構造を持ち、化学式がＢａＰｂ1-xＯ3（Ｏ＜
ｘ≦０．０５）なる導電材を添加した鉛蓄電池。1. A lead-acid battery in which the negative electrode active material is lead and the positive electrode active material is lead dioxide, wherein at least one of the positive and negative electrodes has a perovskite structure and the chemical formula is BaPb 1-x O 3 (O <
(x ≦ 0.05).
に対して２〜１０重量％の範囲である請求項１記載の鉛
蓄電池。2. The lead-acid battery according to claim 1, wherein the amount of the conductive material added is in the range of 2 to 10% by weight based on the weight of the active material in terms of lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04290495A JP3196556B2 (en) | 1995-03-02 | 1995-03-02 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04290495A JP3196556B2 (en) | 1995-03-02 | 1995-03-02 | Lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08241718A JPH08241718A (en) | 1996-09-17 |
| JP3196556B2 true JP3196556B2 (en) | 2001-08-06 |
Family
ID=12649028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04290495A Expired - Fee Related JP3196556B2 (en) | 1995-03-02 | 1995-03-02 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3196556B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3035433B1 (en) | 2014-12-18 | 2020-02-19 | GS Yuasa International Ltd. | Lead-acid battery |
-
1995
- 1995-03-02 JP JP04290495A patent/JP3196556B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08241718A (en) | 1996-09-17 |
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