JPH09147841A - Negative electrode plate for lead acid battery and its manufacture - Google Patents
Negative electrode plate for lead acid battery and its manufactureInfo
- Publication number
- JPH09147841A JPH09147841A JP7307462A JP30746295A JPH09147841A JP H09147841 A JPH09147841 A JP H09147841A JP 7307462 A JP7307462 A JP 7307462A JP 30746295 A JP30746295 A JP 30746295A JP H09147841 A JPH09147841 A JP H09147841A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- active material
- negative electrode
- lead
- 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.)
- Granted
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)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、通信用、非常用電
源、携帯用機器などの分野に使用される鉛蓄電池に使用
される負極板とその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode plate used in a lead storage battery used in the fields of communication, emergency power supply, portable equipment and the like, and a manufacturing method thereof.
【0002】[0002]
【従来の技術】従来の鉛蓄電池用負極板は、金属鉛粒子
(鉛粉)にリグニン等を添加して活物質ペーストとし、
このペーストを集電体に充填して作製される。該鉛蓄電
池用負極板を用いて作製された鉛蓄電池は、長期間放置
しておくと、熱サイクルによって硫酸鉛の溶解析出が繰
り返され、導電性を有しない硫酸鉛の結晶が徐々に成長
し、遂には充電できなくなるというサルフェーション現
象が生じる。この現象は、特に密閉形鉛蓄電池に多く、
短寿命の原因になっている。この対策として、従来、カ
ーボン粉末を活物質に混合して負極板を作製していた。
しかし、このような負極板を用いた鉛蓄電池は、充放電
を繰り返していくうちに、徐々にその効果がなくなり、
前記サルフェーション現象による短寿命を防ぐことが出
来なかった。2. Description of the Related Art A conventional negative electrode plate for a lead storage battery is prepared by adding lignin to metallic lead particles (lead powder) to prepare an active material paste.
It is prepared by filling a current collector with this paste. If the lead storage battery prepared using the negative electrode plate for lead storage battery is left for a long period of time, the dissolution and precipitation of lead sulfate is repeated by a thermal cycle, and a lead sulfate crystal having no conductivity gradually grows. Finally, a sulfation phenomenon occurs where the battery cannot be charged. This phenomenon is especially common in sealed lead-acid batteries,
It is a cause of short life. As a countermeasure against this, conventionally, a carbon powder is mixed with an active material to produce a negative electrode plate.
However, the lead-acid battery using such a negative electrode plate gradually loses its effect as charging and discharging are repeated.
The short life due to the sulfation phenomenon could not be prevented.
【0003】[0003]
【発明が解決しようとする課題】本発明は上記問題点に
鑑みてなされたものであって、その目的とするところは
サルフェーション現象の起こりにくい鉛蓄電池用負極板
とその製造方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a negative electrode plate for a lead storage battery in which sulfation phenomenon hardly occurs and a method for manufacturing the same. is there.
【0004】[0004]
【課題を解決するための手段】上記目的を達成するため
に本発明は、活物質粒子群の表面に導電性に優れたカー
ボンまたはグラファイト粒子の皮膜を水ガラスでもって
結着させたものであって、前記カーボンまたはグラファ
イト粒子の粒子径は、0.3〜1.0μmであることが
好ましい。また、本発明の方法は、カーボン粒子または
グラファイト粒子を水ガラス溶液に懸濁して得たものに
鉛粉を加えて練り合わせた後、乾燥して粉末を得、次い
で、該粉末に希硫酸を加えて練りあわせて活物質ペース
トを作製し、次いで、該ペーストを集電体に充填するこ
とを特徴とするものである。In order to achieve the above object, the present invention is to bind a film of carbon or graphite particles having excellent conductivity to the surface of an active material particle group with water glass. The particle size of the carbon or graphite particles is preferably 0.3 to 1.0 μm. In addition, the method of the present invention is a method in which lead powder is added to a product obtained by suspending carbon particles or graphite particles in a water glass solution, kneaded, and dried to obtain a powder, and then dilute sulfuric acid is added to the powder. It is characterized by kneading and kneading to prepare an active material paste, and then filling the current collector with the paste.
【0005】[0005]
【作用】従来のカーボンまたはグラファイト粉末を添加
した活物質ペーストの鉛粉粒子3は、図2に示すよう
に、複数の活物質粒子1が集合した活物質粒子群にカー
ボンまたはグラファイト粒子2が機械的に接触しただけ
で、一部の前記粒子2が活物質粒子群に接触せずにい
た。しかし、本発明の活物質ペーストは、図1に示すよ
うに、活物質粒子群にカーボンまたはグラファイト粒子
2が水ガラスによって結着しているので、結着面での放
電反応が起きにくく、周囲の硫酸鉛の結晶が粗大化する
のを抑制する。また、硫酸鉛の結晶が粗大化しても結晶
中にカーボンまたはグラファイト粒子2が取り込まれる
ので、導電性が保持される。As shown in FIG. 2, the lead powder particles 3 of the conventional active material paste to which the carbon or graphite powder is added have the carbon or graphite particles 2 mechanically formed in the active material particle group in which a plurality of active material particles 1 are aggregated. However, some of the particles 2 did not come into contact with the active material particle group. However, in the active material paste of the present invention, as shown in FIG. 1, since the carbon or graphite particles 2 are bound to the active material particle group by water glass, the discharge reaction on the binding surface is unlikely to occur, and Suppresses the coarsening of lead sulfate crystals. Further, even if the crystal of lead sulfate is coarsened, the carbon or graphite particles 2 are taken into the crystal, so that the conductivity is maintained.
【0006】[0006]
【発明の実施の形態】以下、本発明の実施形態について
説明する。 (実施形態1)平均粒子径0.3μmのカーボン粒子を
水ガラス溶液に加え、固形分が20〜40%含む懸濁液
を作製し、この懸濁液をカーボン粒子が鉛粉に対し2.
0質量%含むように鉛粉と混合し、乾燥した。乾燥はバ
インダーである水ガラスの固化を確実にするために、通
常より高温の200℃で1時間行った。乾燥した鉛粉を
粉末とし、これに通常の手段で水と硫酸を加えて練り合
わせて活物質ペーストを得た。このペーストを集電体に
充填し、熟成、乾燥工程を経て、通常の方法で化成して
負極板を作製した。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. (Embodiment 1) Carbon particles having an average particle diameter of 0.3 [mu] m are added to a water glass solution to prepare a suspension containing 20 to 40% of solid content, and the suspension has carbon particles based on lead powder.
It was mixed with lead powder so as to contain 0 mass% and dried. The drying was performed at 200 ° C., which is higher than usual, for 1 hour in order to ensure the solidification of the binder water glass. Dried lead powder was made into powder, and water and sulfuric acid were added thereto by a conventional means and kneaded to obtain an active material paste. This paste was filled in a current collector, and after aging and drying steps, chemical conversion was carried out by a usual method to produce a negative electrode plate.
【0007】こうして得た負極板は、図1のように、複
数の活物質粒子1が集合した二次粒子群表面にカーボン
粒子2が付着している。このカーボン粒子2はバインダ
ーにより一種のネットワーク構造体を形成しているの
で、熱サイクルによる溶解析出によって硫酸鉛結晶粒子
が粗大化しても、ネットワークは容易に破壊されず、従
って導電性が失ないにくい。In the negative electrode plate thus obtained, as shown in FIG. 1, carbon particles 2 are attached to the surface of the secondary particle group in which a plurality of active material particles 1 are aggregated. Since the carbon particles 2 form a kind of network structure by the binder, even if the lead sulfate crystal particles become coarse due to the dissolution and precipitation due to the thermal cycle, the network is not easily broken and therefore the conductivity is not easily lost. .
【0008】(実施形態2および3)平均粒子径1.0
および5.0μmのカーボン粒子をそれぞれ水ガラスに
加えた他は、実施形態1と同様にして実施形態2と実施
形態3の負極板を作製した。次に、実施形態1〜3の負
極板を用いてそれぞれの電池A〜Cを組立て、放電容量
試験を実施し、放電後の作用活物質中に占める硫酸鉛の
割合と放電時間を調査した。試験条件は、周囲温度50
℃とし、1/128C(Cは10時間定格容量の値)の
低率放電を終止電圧が0Vになるまで実施して硫酸鉛の
割合を調査した後、10時間率電流で放電電気量の1.
5倍に相当する電気量になるまで充電し、その後5時間
率の放電容量試験を実施し、終止電圧が1.7Vになる
までのそれぞれの時間を測定した。その結果を表1に示
す。(Embodiments 2 and 3) Average particle size 1.0
And negative electrode plates of Embodiments 2 and 3 were produced in the same manner as in Embodiment 1, except that carbon particles of 5.0 μm and 5.0 μm were added to the water glass. Next, the batteries A to C were assembled using the negative electrode plates of Embodiments 1 to 3, a discharge capacity test was carried out, and the ratio of lead sulfate in the active material after discharge and the discharge time were investigated. The test condition is ambient temperature 50
C., a low rate discharge of 1/128 C (C is the value of the rated capacity for 10 hours) is performed until the cutoff voltage reaches 0 V, and the proportion of lead sulfate is investigated. .
The battery was charged until the amount of electricity corresponded to 5 times, and then a discharge capacity test was performed at a rate of 5 hours, and each time until the final voltage reached 1.7 V was measured. Table 1 shows the results.
【0009】(実施形態4〜6)平均粒子径0.3、
1、5μmのグラファイト粒子をそれぞれ水ガラスに加
えた他は、実施形態1と同様にして実施形態4〜6の負
極板を作製した。次に、実施形態4〜6の負極板を用い
て電池D〜Fを組立て、電池A〜Cと同様の放電容量試
験を実施し、硫酸鉛の割合と放電時間を調査した。その
結果を表1に示す。(Embodiments 4 to 6) Average particle diameter 0.3,
Negative electrode plates of Embodiments 4 to 6 were produced in the same manner as in Embodiment 1 except that graphite particles of 1 and 5 μm were added to water glass. Next, Batteries D to F were assembled using the negative electrode plates of Embodiments 4 to 6, the same discharge capacity test as Batteries A to C was performed, and the ratio of lead sulfate and the discharge time were investigated. Table 1 shows the results.
【0010】(従来形態)平均粒子径0.3μmのカー
ボン粒子を鉛粉に対して2.0質量%加えて混合し、そ
の後、水と希硫酸を加えて混練して活物質ペーストを作
製し、このペーストを実施形態1と同様な集電体に充填
して従来と同じ構成の負極板を作製した。次に、この負
極板を用いて実施形態1と同様な電池Gを組立て、電池
A〜Fと同様の放電試験を実施し、硫酸鉛の割合と放電
時間を調査した。その結果を表1に示す。(Conventional embodiment) Carbon particles having an average particle diameter of 0.3 μm were added to 2.0 mass% of lead powder and mixed, and then water and diluted sulfuric acid were added and kneaded to prepare an active material paste. Then, this paste was filled in a current collector similar to that of Embodiment 1 to fabricate a negative electrode plate having the same structure as the conventional one. Next, using this negative electrode plate, a battery G similar to that of Embodiment 1 was assembled, a discharge test similar to batteries A to F was performed, and the proportion of lead sulfate and the discharge time were investigated. Table 1 shows the results.
【0011】[0011]
【表1】 [Table 1]
【0012】表1より本発明品は、従来品に比べ硫酸鉛
の割合が少なく、放電容量が優れることがわかる。従っ
て、本発明は従来品に比べサルフェーション現象が起こ
り難く、充電回復性能が優れる。It can be seen from Table 1 that the product of the present invention has a smaller proportion of lead sulfate than the conventional product and is excellent in discharge capacity. Therefore, according to the present invention, the sulfation phenomenon is less likely to occur and the charge recovery performance is superior to the conventional products.
【0013】なお、本発明に係るカーボンまたはグラフ
ァイトの平均粒子径を0.3μm未満にすると、硫酸の
保持性が悪くなり、ペーストの流動性が低下し、充填が
困難となるので、多くのカーボンまたはグラファイトを
添加できなくなり、前記平均粒子径を1.0μmより大
きくすると、放電容量が従来品と略同等になるので、平
均粒子径は0.3〜1.0μmが好ましい。また、本発
明は実施形態に限定されるものではなく、電池の用途に
応じて添加比率や平均粒子径は種々変更することができ
る。When the average particle size of the carbon or graphite according to the present invention is less than 0.3 μm, the retention of sulfuric acid is deteriorated, the fluidity of the paste is lowered, and the filling becomes difficult. Alternatively, if graphite cannot be added and the average particle size is larger than 1.0 μm, the discharge capacity becomes substantially the same as that of the conventional product, so the average particle size is preferably 0.3 to 1.0 μm. Further, the present invention is not limited to the embodiment, and the addition ratio and the average particle diameter can be variously changed depending on the application of the battery.
【0014】[0014]
【発明の効果】上記の如く本発明によれば、 (1)硫酸鉛の溶解析出が繰り返えされても、導電性を
有する硫酸鉛の結晶が粗大化するのを抑制し、サルフェ
ーション現象による鉛蓄電池の短寿命を防止できる。 (2)また、硫酸鉛の粗大化が起こっても、活物質とカ
ーボンまたはグラファイト層の微細ネットワークに粗大
化した硫酸鉛が取り込まれるので、放電後にも活物質層
ので導電性が維持され、鉛蓄電池の充電受入れ性が優れ
る。As described above, according to the present invention, (1) it is possible to prevent the crystal of lead sulfate having conductivity from being coarsened even by repeated dissolution and precipitation of lead sulfate, and to prevent the sulfation phenomenon. The short life of lead acid batteries can be prevented. (2) Further, even if lead sulfate coarsens, the coarse lead sulfate is taken into the fine network of the active material and the carbon or graphite layer, so that the electrical conductivity of the active material layer is maintained even after discharge, and lead The charge acceptance of the storage battery is excellent.
【図1】本発明に係る鉛粉粒子の模式図である。FIG. 1 is a schematic view of lead powder particles according to the present invention.
【図2】従来の鉛粉粒子の模式図である。FIG. 2 is a schematic view of a conventional lead powder particle.
1 活物質粒子 2 カーボンまたはグラファイト粒子 3 鉛粉粒子 1 Active material particles 2 Carbon or graphite particles 3 Lead powder particles
Claims (3)
質粒子群の表面に、カーボン粒子またはグラファイト粒
子(2)と水ガラスとからなる層を付着した鉛粉粒子
(3)からなる活物質ペーストを集電体に充填したこと
を特徴とする鉛蓄電池用負極板1. Lead powder particles (3) having a layer of carbon particles or graphite particles (2) and water glass attached to the surface of an active material particle group in which a plurality of active material particles (1) are aggregated. A negative electrode plate for a lead storage battery, characterized in that a current collector is filled with an active material paste
子の粒子径が0.3〜1.0μmであることを特徴とす
る請求項1記載の鉛蓄電池用負極板2. The negative electrode plate for a lead storage battery according to claim 1, wherein the carbon particles or the graphite particles have a particle diameter of 0.3 to 1.0 μm.
水ガラス溶液に懸濁して得たものに鉛粉を加えて練り合
わせた後、乾燥して粉末を得、 次いで、該粉末に希硫酸を加えて練りあわせて活物質ペ
ーストを作製し、 次いで、該ペーストを集電体に充填することを特徴とす
る、鉛蓄電池用負極板の製造方法。3. Lead powder is added to a product obtained by suspending carbon particles or graphite particles in a water glass solution and kneaded, and then dried to obtain a powder. Then, dilute sulfuric acid is added to the powder and kneaded. A method for producing a negative electrode plate for a lead storage battery, which comprises: producing an active material paste by filling the current collector with the paste.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30746295A JP3575145B2 (en) | 1995-11-27 | 1995-11-27 | Negative electrode plate for lead storage battery and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30746295A JP3575145B2 (en) | 1995-11-27 | 1995-11-27 | Negative electrode plate for lead storage battery and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09147841A true JPH09147841A (en) | 1997-06-06 |
JP3575145B2 JP3575145B2 (en) | 2004-10-13 |
Family
ID=17969369
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30746295A Expired - Fee Related JP3575145B2 (en) | 1995-11-27 | 1995-11-27 | Negative electrode plate for lead storage battery and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3575145B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120115031A1 (en) * | 2010-11-05 | 2012-05-10 | Cabot Corporation | Lead-acid batteries and pastes therefor |
CN102522531A (en) * | 2011-12-14 | 2012-06-27 | 深圳市雄韬电源科技股份有限公司 | Carbonaceous lead powder, its preparation method, battery lead paste and its application |
US20120248383A1 (en) * | 2011-04-04 | 2012-10-04 | Cabot Corporation | Lead-acid batteries and pastes therefor |
CN107887595A (en) * | 2016-09-29 | 2018-04-06 | 深圳市雄韬电源科技股份有限公司 | Improve the cathode lead plaster and preparation method of lead acid battery charge ability to accept |
CN113646933A (en) * | 2020-12-31 | 2021-11-12 | 宁德新能源科技有限公司 | Pole piece, electrochemical device and electronic device |
-
1995
- 1995-11-27 JP JP30746295A patent/JP3575145B2/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120115031A1 (en) * | 2010-11-05 | 2012-05-10 | Cabot Corporation | Lead-acid batteries and pastes therefor |
US9112231B2 (en) * | 2010-11-05 | 2015-08-18 | Cabot Corporation | Lead-acid batteries and pastes therefor |
US20120248383A1 (en) * | 2011-04-04 | 2012-10-04 | Cabot Corporation | Lead-acid batteries and pastes therefor |
US9281520B2 (en) * | 2011-04-04 | 2016-03-08 | Cabot Corporation | Lead-acid batteries and pastes therefor |
CN102522531A (en) * | 2011-12-14 | 2012-06-27 | 深圳市雄韬电源科技股份有限公司 | Carbonaceous lead powder, its preparation method, battery lead paste and its application |
CN107887595A (en) * | 2016-09-29 | 2018-04-06 | 深圳市雄韬电源科技股份有限公司 | Improve the cathode lead plaster and preparation method of lead acid battery charge ability to accept |
CN113646933A (en) * | 2020-12-31 | 2021-11-12 | 宁德新能源科技有限公司 | Pole piece, electrochemical device and electronic device |
CN113646933B (en) * | 2020-12-31 | 2024-02-13 | 宁德新能源科技有限公司 | Pole piece, electrochemical device and electronic device |
Also Published As
Publication number | Publication date |
---|---|
JP3575145B2 (en) | 2004-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5156935A (en) | Lead-acid battery | |
JP6524610B2 (en) | Positive electrode active material for non-aqueous secondary battery and method for producing the same | |
JP2009048800A (en) | Manufacturing method for paste type positive electrode plate | |
JP2001229920A (en) | Method of manufacturing sealed lead acid battery | |
JP2004199950A (en) | Manufacturing method of positive electrode plate for lead-acid storage battery | |
JP2003123760A (en) | Negative electrode for lead-acid battery | |
JPH09245770A (en) | Non-aqueous electrolyte battery | |
JP5017746B2 (en) | Control valve type lead acid battery | |
JP3575145B2 (en) | Negative electrode plate for lead storage battery and method for producing the same | |
JP2000251896A (en) | Lead-acid battery and its manufacture | |
JPH1069900A (en) | Pole plate for lead-acid battery | |
JP3835093B2 (en) | Sealed lead acid battery | |
JP2949773B2 (en) | Lead storage battery | |
JP2002100347A (en) | Lead-acid battery | |
JP2004055309A (en) | Manufacturing method of pasty active material for positive electrodes, and lead storage battery using it | |
JP4066509B2 (en) | Manufacturing method of lead acid battery | |
CN116404101B (en) | Negative pole piece, battery pack and electric equipment | |
JPH11162456A (en) | Lead-acid battery | |
JP2004055417A (en) | Manufacturing method of pasty active material for positive electrode and lead storage battery using it | |
CN108075116B (en) | Lead-acid storage battery cathode lead plaster and lead-acid storage battery | |
JP2003086178A (en) | Sealed lead-acid battery and method of manufacturing the same | |
JP2006202584A (en) | Lead-acid battery and its manufacturing method | |
JPS61264675A (en) | Positive plate of clad type lead-acid battery | |
JPH0414758A (en) | Lead-acid accumulator | |
JP4501246B2 (en) | Control valve type stationary lead acid battery manufacturing method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040312 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040330 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040615 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040628 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080716 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080716 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090716 Year of fee payment: 5 |
|
LAPS | Cancellation because of no payment of annual fees |