JPS60121673A - Active substance of positive pole for lead storage battery - Google Patents
Active substance of positive pole for lead storage batteryInfo
- Publication number
- JPS60121673A JPS60121673A JP58228527A JP22852783A JPS60121673A JP S60121673 A JPS60121673 A JP S60121673A JP 58228527 A JP58228527 A JP 58228527A JP 22852783 A JP22852783 A JP 22852783A JP S60121673 A JPS60121673 A JP S60121673A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- positive electrode
- active material
- positive pole
- active substance
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は鉛蓄電池用正極活物質に関し、詳しくは鉛酸化
物にチタン酸またはその焼成物を添加することにより鉛
蓄電池の放電容量を向上させた鉛蓄電池用正極活物質に
関する。Detailed Description of the Invention The present invention relates to a positive electrode active material for lead-acid batteries, and more specifically, a positive electrode active material for lead-acid batteries whose discharge capacity is improved by adding titanic acid or a fired product thereof to lead oxide. Regarding.
従来、鉛蓄電池の正極活物質としては純鉛の酸化物をペ
ースト状に練合したものが主に用いられており、電池性
能はこの正極活物質の機能により影響されることがよく
知られ、正極活物質の利用率向上のための種々の方法が
種々検討されているが、その電気エネルギー利用率は未
だ５０％程度に止まっているのが現状である。Traditionally, the positive electrode active material for lead-acid batteries has mainly been a paste of pure lead oxide, and it is well known that battery performance is affected by the function of this positive electrode active material. Although various methods have been studied to improve the utilization rate of positive electrode active materials, the current state is that the electric energy utilization rate is still only about 50%.
一般に、鉛蓄電池は重量が大きく、かつ寸法も大きいと
いう問題点があり、従来の性能を維持しつつ軽量化およ
び小型化することが強く要望されている。また同様に、
鉛蓄電池にあっては同程度の重囲および寸法を維持しつ
つ、放電容量を高めることも要望されている。In general, lead-acid batteries have problems in that they are large in weight and size, and there is a strong demand for reductions in weight and size while maintaining conventional performance. Similarly,
For lead-acid batteries, it is also desired to increase the discharge capacity while maintaining the same degree of bulk and size.
本発明は、上記のような実情を鑑みてなされたものであ
り、保有する電気エネルギーを有効に活用できる利用率
の高い鉛蓄電池用正極活物質を提供することを目的とす
る。The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a positive electrode active material for a lead-acid battery that has a high utilization rate and can effectively utilize the electric energy it possesses.
鉛蓄電池にあっては、その充放電サイクルにおいて、良
好な活物質と起電反応に有用な量の電解液の補給退散が
円滑に行なわれることとが相まって電池の性能を向上さ
せることはよく知られていることである。It is well known that the performance of lead-acid batteries is improved by a combination of a good active material and smooth replenishment and withdrawal of an amount of electrolyte useful for electromotive reactions during the charge/discharge cycle. This is what is happening.
本発明者らは、電気利用率の高い正極活物質を得るとい
う上記目的に沿ってに鋭意検討した結果、鉛蓄電池用正
極活物質として、鉛酸化物にチタン酸またはその焼成物
を添加量ることによって上記の目的が達成されることを
見出し本発明に到達しｌこ 。As a result of intensive studies in line with the above-mentioned objective of obtaining a positive electrode active material with a high electricity utilization rate, the present inventors discovered that titanic acid or a fired product thereof is added to lead oxide as a positive electrode active material for lead-acid batteries. The inventors have discovered that the above object can be achieved by doing so, and have arrived at the present invention.
すなわち、本弁明は鉛酸化物にチタン酸またはその焼成
物を添加することを特徴とする鉛蓄電池用正極活物質に
ある。That is, the present invention resides in a positive electrode active material for a lead-acid battery, which is characterized in that titanic acid or a fired product thereof is added to lead oxide.
本発明の正極活物質に使用する鉛酸化物としては、一般
に、酸化鉛７０〜９０重量％、残部金属鉛３０〜１０重
量％からなる、いわゆる［鉛粉Ｊが好適に用いられ、そ
の他には一酸化鉛（ＰｂＯ）、鉛丹（Ｐｌ）３０４）、
亜酸化鉛（Ｐｂ２０）等の酸化物も利用できる。As the lead oxide used in the positive electrode active material of the present invention, so-called [lead powder J], which is generally composed of 70 to 90% by weight of lead oxide and 30 to 10% by weight of metallic lead, is preferably used; Lead monoxide (PbO), red lead (Pl) 304),
Oxides such as zinc oxide (Pb20) can also be used.
本発明の正極活物質において、チタン酸またはその焼成
物の添加量を、鉛酸化物総量に対し、好ましくは０．１
〜ｓ、ｏ重量％、さらに好ましくは０．５〜３．０型口
％とすることにより、正極活物質の電気１ネルギー利用
率を有効に向上させることができる。正極活物質中のチ
タン酸またはその焼成物の添加量が上記範囲未満では電
気エネルギー利用率を向上させる効果が不充分であり、
また上記範囲を越えて含有すると有効活物質量が相対的
に減少するため逆に性能が低下する。なお、チタン酸ま
たはその焼成物の粒子径が鉛酸化物の粒子径よりも大き
すぎる場合には添加効果が減少するので、鉛酸化物粒子
径に近い大きさにすることが望ましい。In the positive electrode active material of the present invention, the amount of titanic acid or its fired product added is preferably 0.1 with respect to the total amount of lead oxide.
By setting it to s, o weight %, more preferably 0.5 to 3.0 weight %, the electric energy utilization rate of the positive electrode active material can be effectively improved. If the amount of titanic acid or its fired product added in the positive electrode active material is less than the above range, the effect of improving the electrical energy utilization rate is insufficient,
Furthermore, if the content exceeds the above range, the effective amount of active material will be relatively reduced, resulting in a decrease in performance. Note that if the particle size of titanic acid or its fired product is too larger than the particle size of lead oxide, the effect of addition will be reduced, so it is desirable to make the particle size close to the lead oxide particle size.
本発明の正極活物質において、鉛酸化物に加えてチタン
酸またはその焼成物を添加することにより活物質の電気
エネルギー利用率が向上する理由としては、そのペース
トとした正極活物質の多孔度が増加したためと考えられ
る。つまり、本発明のチタン酸またはその焼成物を添加
する正極活物質のペーストは、チタン酸またはその焼成
物を添加せず、鉛酸化物のみを用いた従来の正極活物質
のペーストに比べ、約５．０〜８．０％程度多孔度が増
加しており、これにより電解液としての希硫酸がペース
ト内へ、より容易に侵入または退散し得ることによるも
のと推察される。In the positive electrode active material of the present invention, the reason why the electrical energy utilization rate of the active material is improved by adding titanic acid or a fired product thereof in addition to lead oxide is because of the porosity of the positive electrode active material made into a paste. This is thought to be due to an increase. In other words, the positive electrode active material paste to which titanic acid or its fired product of the present invention is added is approximately The porosity increases by about 5.0 to 8.0%, and it is presumed that this is because dilute sulfuric acid as an electrolytic solution can more easily enter or escape into the paste.
以下、実施例および比較例により本発明を具体的に説明
する。Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
実施例１ ＋１３よび比交例１
通常のボールミル法により得られる鉛粉１Ｇｇに対し、
チタン酸（Ｈ４１−！ Ｏｎ ）を ｉ、ｏ重量％添加
し、メノウ乳鉢によって十分に混合した。Example 1 +13 and proportional example 1 For 1 Gg of lead powder obtained by the normal ball mill method,
Titanic acid (H41-!On) was added i,o wt % and thoroughly mixed in an agate mortar.
この混合物に、比重１．２の希硫酸２．３ ＩＩＪおよ
び純水１．５７を添加し°（１０分間よく混練して、ペ
ースト状物質を得た。To this mixture were added 2.3 IIJ of dilute sulfuric acid with a specific gravity of 1.2 and 1.57 J of pure water (kneaded thoroughly for 10 minutes to obtain a paste-like material).
このペースト状物質を格子状（縦４！ＩＩＩＩＩＲＸ横
５８ｍｍ ＞の鉛合金ＩＩＡ極ａｔ（Ｓｂ２，５重量％
含有）に塗布し、しかる後、高温多湿雰囲気中（８０〜
９０℃）にて１６時間熟成した。This paste-like material was formed into a grid (length: 4! III RX x width: 58 mm) lead alloy IIA electrode at (Sb2, 5% by weight)
After that, it is applied in a high temperature and humid atmosphere (80~
90° C.) for 16 hours.
この正極板を通常のガラスマットとセパレーターで挾み
、これに通常用いられる負極板を組合ねけ′Ｃ、プラス
デック製の電槽に挿入した素電池を作成し、比重１．１
の希硫酸を注入したのち、０．２Ａの電流を４０時間通
して化成を行なった。This positive electrode plate was sandwiched between an ordinary glass mat and a separator, and a commonly used negative electrode plate was combined with it.C, a unit cell was created by inserting it into a Plus Deck battery case, and the specific gravity was 1.1.
After injecting dilute sulfuric acid, chemical conversion was performed by passing a current of 0.2 A for 40 hours.
さらに、この化成後の電解液比重を１．２８ 、液温を
２０℃に調整し、電池（Δ）を作成した〈実施例１〉。Furthermore, the electrolytic solution specific gravity after chemical formation was adjusted to 1.28, and the solution temperature was adjusted to 20° C., and a battery (Δ) was prepared (Example 1).
また、鉛粉にチタン酸を添加しないことを除いて上記の
操作と全く同じ方法で電池（Ｂ）を作成したく比較例１
）。In addition, we would like to create a battery (B) in exactly the same manner as the above procedure except that titanic acid is not added to the lead powder. Comparative Example 1
).
この電池＜Ａ）および（Ｂ）について、放電（０，４Ａ
定電流）および充電（０，２Ａ定電流）によるサイクル
を繰り返す電池試験を行なった場合の充放電サイクル４
０回までの毎回の放電時間の累削を第１表に示す。なお
、放電終止電圧は１．７ｖに設定した。For this battery <A) and (B), the discharge (0,4A
Charging/discharging cycle 4 when conducting a battery test that repeats cycles with constant current) and charging (0.2A constant current)
Table 1 shows the cumulative discharge time for each discharge up to 0 times. Note that the discharge end voltage was set to 1.7V.
第１表
この結果から、正極活物質中にチタン酸を添加しなかっ
た電池（Ｂ）に比し、チタン酸を添加した電池（Ａ）の
方が放電時間が長く優れていることがわかる。Table 1 The results show that the battery (A) with titanic acid added has a longer discharge time and is superior to the battery (B) with no titanic acid added to the positive electrode active material.
１１Ｆ
実施例１において鉛粉に添加したチタン酸に代えて、チ
タン酸焼成物、を用いた以外は実施例１と同様な方法′
Ｃ電池（Ｃ）を作成した。なａ５、チタンＭ焼成物は、
チタン酸を炉内温度５５０℃に設定した通常の電気炉中
に４時間保持覆ることにより製造した。11F The same method as in Example 1 except that a fired titanic acid was used instead of the titanic acid added to the lead powder in Example 1.
A C battery (C) was created. A5, titanium M fired product is
It was produced by keeping titanic acid covered in a normal electric furnace set at an internal temperature of 550° C. for 4 hours.
この電池（Ｃ）につき実施例１と同様に電池試験を行な
った。充放電サイクル４０回までの放電時間の累８１を
第２表に示づ。なＪ３、参考のため前記の比較例１の電
池（Ｂ）の結果も併せて示す。A battery test was conducted on this battery (C) in the same manner as in Example 1. Table 2 shows the cumulative discharge time up to 40 charge/discharge cycles. For reference, the results of the battery (B) of Comparative Example 1 are also shown.
第２表
以上の結果から、正極活物質中にチタン酸焼成物を添加
した電池（Ｃ）は、チタン酸焼成物を添加しなかった電
池（８）に比べ、放電時間が長い未」Ｕ１旦二」と
チタン酸の添加ｍを変向する以外は実施例１の電池（Ａ
）の作成方法と同様の方法によって、電池（Ｄ）〜（Ｇ
）を作成した。From the results in Table 2 and above, the battery (C) in which the fired titanate was added to the positive electrode active material had a longer discharge time than the battery (8) in which the fired titanate was not added. The cell of Example 1 (A
) Batteries (D) to (G
)It was created.
この電池−（Ｄ）〜（Ｇ）の終止電圧１．１ｖまでの全
容量放電を繰り返し、４０サイクル目における放電持続
時間の累計値を比較した。結果を第３表に示す。なお、
参考として前記の実施例１および比較例１の結果も第３
表に示した。Full capacity discharge of these batteries (D) to (G) to a final voltage of 1.1 V was repeated, and the cumulative discharge durations at the 40th cycle were compared. The results are shown in Table 3. In addition,
For reference, the results of Example 1 and Comparative Example 1 are also
Shown in the table.
第３表
この結果から、正極活物質の鉛酸化物中にチタン酸を添
加する場合、添加口が０．５重量％付近から効果が見ら
れるが、５．０重量％付近では逆に効果が低減づ゛るの
で、添加範囲は０．５〜３，０型開％程度が特に好まし
いことがわかる。Table 3 From the results, when titanic acid is added to the lead oxide of the positive electrode active material, an effect is seen when the addition port is around 0.5% by weight, but the opposite effect is observed when the addition port is around 5.0% by weight. It can be seen that the addition range is particularly preferably about 0.5 to 3.0 mold open% because the mold opening percentage decreases.
以上説明したように、鉛酸化物にチタン酸またはその焼
成物を含有さぜる本発明の鉛蓄電池用正極活物質は、従
来の正極活物質より電気エネルギー利用率が高いことか
ら、鉛蓄電池の正極活物質として好適に用いられ、本発
明の正極活物質を用いた鉛蓄電池は放電容量が大幅に向
上する。As explained above, the positive electrode active material for lead-acid batteries of the present invention, which is a mixture of lead oxide and titanic acid or its fired product, has a higher electrical energy utilization rate than conventional positive electrode active materials. It is suitably used as a positive electrode active material, and a lead-acid battery using the positive electrode active material of the present invention has a significantly improved discharge capacity.
特許出願人 三井金属鉱業株式会社 代理人 弁理士 伊東辰雄 代理人 弁理士 伊東哲也Patent applicant: Mitsui Metal Mining Co., Ltd. Agent: Patent Attorney Tatsuo Ito Agent: Patent Attorney Tetsuya Ito
Claims (1)
とを特徴とする鉛蓄電池用正極活物質。 ２、前記チタン酸またはその焼成物の添加ｍが鉛酸化物
総量に対して０．５〜５．０重量％であることを特徴と
する特許請求の範囲第１項に記載の鉛蓄電池用正極活物
質。[Claims] 1. A positive electrode active material for a lead-acid battery, characterized in that titanic acid or a fired product thereof is added to lead oxide. 2. The positive electrode for a lead-acid battery according to claim 1, wherein the addition m of the titanic acid or its fired product is 0.5 to 5.0% by weight based on the total amount of lead oxide. active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58228527A JPS60121673A (en) | 1983-12-05 | 1983-12-05 | Active substance of positive pole for lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58228527A JPS60121673A (en) | 1983-12-05 | 1983-12-05 | Active substance of positive pole for lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60121673A true JPS60121673A (en) | 1985-06-29 |
Family
ID=16877808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58228527A Pending JPS60121673A (en) | 1983-12-05 | 1983-12-05 | Active substance of positive pole for lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60121673A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016072105A (en) * | 2014-09-30 | 2016-05-09 | パナソニックＩｐマネジメント株式会社 | Lead storage battery |
-
1983
- 1983-12-05 JP JP58228527A patent/JPS60121673A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016072105A (en) * | 2014-09-30 | 2016-05-09 | パナソニックＩｐマネジメント株式会社 | Lead storage battery |
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