JP2002231247A - Control valve type lead storage battery - Google Patents
Control valve type lead storage batteryInfo
- Publication number
- JP2002231247A JP2002231247A JP2001021180A JP2001021180A JP2002231247A JP 2002231247 A JP2002231247 A JP 2002231247A JP 2001021180 A JP2001021180 A JP 2001021180A JP 2001021180 A JP2001021180 A JP 2001021180A JP 2002231247 A JP2002231247 A JP 2002231247A
- Authority
- JP
- Japan
- Prior art keywords
- control valve
- type lead
- valve type
- negative electrode
- 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.)
- Pending
Links
- 238000003860 storage Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006230 acetylene black Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002142 lead-calcium alloy Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、制御弁式鉛蓄電池
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a control valve type lead storage battery.
【０００２】[0002]
【従来の技術】制御弁式鉛蓄電池は安価で信頼性が高い
という特徴を有するため、無停電電源装置や電力貯蔵用
として使用されている。最近、制御弁式鉛蓄電池の長寿
命化が強く要求されている。2. Description of the Related Art Controlled valve type lead-acid batteries are characterized by being inexpensive and highly reliable, and are therefore used for uninterruptible power supplies and for power storage. Recently, there has been a strong demand for a longer life of a control valve type lead storage battery.
【０００３】これらの制御弁式鉛蓄電池は、図１に示す
ように、ペースト式の正極板1及び負極板2を、ガラス繊
維を主成分とする不織布製のセパレータ3を介して積層
し、前記正極板1及び負極板2の耳部18を溶接してストラ
ップ6を有する極板群を作製し、該極板群を電槽4に挿入
し、蓋5を取りつけて作成するものである。As shown in FIG. 1, these control valve type lead-acid batteries are formed by laminating a paste type positive electrode plate 1 and a negative electrode plate 2 via a non-woven fabric separator 3 mainly composed of glass fiber. The electrode plates having the straps 6 are produced by welding the ears 18 of the positive electrode plate 1 and the negative electrode plate 2, the electrode plates are inserted into the battery case 4, and the lid 5 is attached thereto.
【０００４】そして、制御弁式鉛蓄電池は、前記ペース
ト式正極板1、ペースト式負極板2及びセパレータ3に、
電解液として希硫酸を染み込ませた状態で使用してい
る。[0004] The control valve type lead-acid battery includes the paste-type positive electrode plate 1, the paste-type negative electrode plate 2, and the separator 3,
It is used with dilute sulfuric acid impregnated as electrolyte.
【０００５】制御弁式鉛蓄電池の寿命要因の一つに、充
放電を繰り返すと負極板が充電されにくくなり、放電生
成物である硫酸鉛が負極の活物質中に次第に蓄積して放
電容量が低下するという現象がある。したがって、制御
弁式鉛蓄電池を長寿命化するには、負極板の充電受け入
れ特性を向上させることが重要である。[0005] One of the life factors of a control valve type lead-acid battery is that it becomes difficult to charge the negative electrode plate when charging and discharging are repeated, and lead sulfate, which is a discharge product, gradually accumulates in the active material of the negative electrode to reduce the discharge capacity. There is a phenomenon that it decreases. Therefore, in order to extend the life of the control valve type lead-acid battery, it is important to improve the charge receiving characteristics of the negative electrode plate.
【０００６】負極板の充電受け入れ特性を向上させるに
は、負極活物質中に電子伝導性を有し、電気化学的に安
定な物質を添加すると効果があることが知られている。
そして、負極活物質中にカーボンブラックを添加する方
法が特開昭63-187559号公報によって、カーボンウイス
カを添加する方法が特開平06-140043号公報によって、
それぞれ開示されている。It is known that the addition of an electrochemically stable material having electron conductivity to the negative electrode active material is effective in improving the charge receiving characteristics of the negative electrode plate.
A method for adding carbon black in the negative electrode active material is disclosed in JP-A-63-187559, and a method for adding carbon whiskers is described in JP-A-06-140043.
Each is disclosed.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、前記カ
ーボンブラックやカーボンウイスカなどの市販の炭素粉
末を、そのまま使用して制御弁式鉛蓄電池を製造した場
合には、それらの粉末の製品ロットによって制御弁式鉛
蓄電池の寿命特性にも影響することが認められていた。However, when a commercially available carbon powder such as carbon black or carbon whisker is used as it is to manufacture a control valve type lead-acid battery, the control valve is controlled depending on the product lot of the powder. It has been recognized that this also affects the life characteristics of the lead-acid battery.
【０００８】そして、電力貯蔵用の制御弁式鉛蓄電池の
ような、多数のセルを直列に接続して使用する場合に
は、１個の制御弁式鉛蓄電池の劣化によってシステム全
体の寿命となるため特に問題となっていた。本発明の目
的は、炭素粉末を負極活物質中に添加して作製する制御
弁式鉛蓄電池を長寿命化することである。When a large number of cells are connected in series, such as a control valve type lead-acid battery for power storage, the life of the entire system is shortened by the deterioration of one control valve type lead-acid battery. This was a particular problem. An object of the present invention is to extend the life of a control valve type lead storage battery manufactured by adding carbon powder to a negative electrode active material.
【０００９】[0009]
【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、本発明は還元処理を施したアセチレンブラック
やグラファイトなどの炭素粉末を負極活物質中に含有さ
せることを特徴としている。In order to solve the above-mentioned problems, the present invention is characterized in that a carbon powder such as acetylene black or graphite that has been subjected to a reduction treatment is contained in a negative electrode active material.
【００１０】すなわち、第一の発明は、ペースト式負極
板を用いる制御弁式鉛蓄電池において、前記ペースト式
負極板の活物質層に、還元処理をした炭素粉末を含有す
ることを特徴としている。That is, a first aspect of the present invention is a control valve type lead-acid battery using a paste-type negative electrode plate, wherein the active material layer of the paste-type negative electrode plate contains reduced carbon powder.
【００１１】第二の発明は、前記炭素粉末は、アセチレ
ンブラック又は天然鱗片状黒鉛を水素で還元処理をした
ものであることを特徴としている。The second invention is characterized in that the carbon powder is obtained by reducing acetylene black or natural flaky graphite with hydrogen.
【００１２】[0012]
【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。Embodiments of the present invention will be described below.
【００１３】１．炭素粉末 炭素粉末としてアセチレンブラック（導電性トーカブラ
ック＃５５００、三菱化学製）と、天然鱗片状黒鉛（Ｃ
Ｂ−１００、日本黒鉛製）を用いて実験した。後述する
実施例１、２において使用した炭素粉末は、前記したア
セチレンブラック又は天然鱗片状黒鉛を、以下の手法で
還元処理したものである。1. Carbon powder Acetylene black (conductive Toka Black # 5500, manufactured by Mitsubishi Chemical Corporation) and natural flaky graphite (C
B-100, manufactured by Nippon Graphite). The carbon powder used in Examples 1 and 2 described below is obtained by reducing the above-mentioned acetylene black or natural flaky graphite by the following method.
【００１４】すなわち、アセチレンブラック又は天然鱗
片状黒鉛の粉末１ｇをアルミナ製のボートに載せ、オー
トクレーブ（ＴＡＳ−１型、耐圧硝子工業製）の反応容
器内に収納する。そして、大気圧のもとで水素ガスを１
０ｍｌ／ｍｉｎで流しながら３００℃に加熱し、５時間
保持して還元処理を行った。That is, 1 g of acetylene black or natural flaky graphite powder is placed on an alumina boat and placed in a reaction vessel of an autoclave (TAS-1 type, manufactured by Pressure Glass Corporation). Then, one hydrogen gas is added under atmospheric pressure.
The mixture was heated to 300 ° C. while flowing at 0 ml / min, and kept for 5 hours to perform a reduction treatment.
【００１５】２．負極板の作製 一酸化鉛を７０〜８０質量％含む鉛粉１ｋｇに、該鉛粉
質量に対してリグニン粉末を０．２質量％、硫酸バリウ
ム粉末を１．５質量％、後述する実施例の炭素粉末を１
質量％、比重が１．３０の硫酸を７０ｃｃと適量の水を
加えて混練し、従来の手法で負極用のペースト状活物質
を作製した。2. Preparation of negative electrode plate In 1 kg of lead powder containing 70 to 80% by mass of lead monoxide, 0.2% by mass of lignin powder and 1.5% by mass of barium sulfate powder with respect to the mass of the lead powder were used. 1 carbon powder
A 70% by mass sulfuric acid having a specific gravity of 1.30 and an appropriate amount of water were added and kneaded, and a paste-like active material for a negative electrode was prepared by a conventional method.
【００１６】作製した負極用ペースト状活物質を、w５
８ｍｍ × 1１１４ｍｍ × t１．０ｍｍの鉛−カルシウ
ム合金製の格子体に充填し、４０℃、相対湿度９５％の
雰囲気中で４０時間熟成・乾燥して未化成のペースト式
負極板を作製した。[0016] The negative electrode for a paste active material that was produced, w 5
An 8 mm × 1 114 mm × t 1.0 mm grid made of a lead-calcium alloy was filled, aged in an atmosphere of 40 ° C. and a relative humidity of 95% for 40 hours, and dried to prepare an unformed paste negative electrode plate. .
【００１７】３．制御弁式鉛蓄電池の作製 前記未化成のペースト式負極板が４枚と、従来から使用
している未化成のペースト式正極板が３枚とを、ガラス
繊維製のリテーナを介して積層・溶接して極板群を組み
立て、それをＡＢＳ製の電槽に組み込み、比重が１．３
０（２０℃）の希硫酸電解液を注入する。その後、充電
量が２５０％、化成時間が４８時間、周囲温度が４０℃
の条件で電槽化成して、１３Ａｈ−２Ｖの制御弁式鉛蓄
電池をそれぞれ３６セル作製した。3. Fabrication of a control valve type lead-acid battery Lamination and welding of the four unformed paste-type negative electrode plates and three conventionally used unformed paste-type positive electrode plates via a glass fiber retainer To assemble the electrode group, assemble it into an ABS battery case, and have a specific gravity of 1.3.
A dilute sulfuric acid electrolyte of 0 (20 ° C.) is injected. Thereafter, the charge amount is 250%, the formation time is 48 hours, and the ambient temperature is 40 ° C.
, And 36 cells of 13 Ah-2V controlled valve type lead-acid batteries were produced.
【００１８】３．充放電試験 作製した制御弁式鉛蓄電池は、０．１ＣＡ（１．３Ａ）
で放電（２５℃、放電終止電圧：１．７５Ｖ）して、初
期の放電容量を測定して異常がないことを確認する。3. Charge / discharge test The produced control valve type lead-acid battery was 0.1 CA (1.3 A)
(25 ° C., discharge end voltage: 1.75 V), and the initial discharge capacity is measured to confirm that there is no abnormality.
【００１９】その後、作製した制御弁式鉛蓄電池を満充
電状態にし、１４４セル（３６セル×４）を直列に接続
し、０．２５ＣＡ（１．７５Ａ）で２．８時間放電した
後、２．４５Ｖ/セルの定電圧充電で前記放電量の１０
２％を充電するサイクル寿命試験を実施した。そして、
充放電サイクル数が２０００サイクルに達した時点で、
一部の制御弁式鉛蓄電池は０．１ＣＡ（１．３Ａ）で放
電（２５℃、放電終止電圧：１．７５Ｖ）して放電容量
を測定して、初期の放電容量との比率を算出した。一
方、他の制御弁式鉛蓄電池は充電状態を解体し、負極活
物質中に含まれる硫酸鉛量（質量％）を測定した。Thereafter, the control valve type lead-acid storage battery was fully charged, 144 cells (36 cells × 4) were connected in series, and discharged at 0.25 CA (1.75 A) for 2.8 hours. .45V / cell at a constant voltage of 10
A cycle life test of charging 2% was performed. And
When the number of charge / discharge cycles reaches 2000,
Some control valve-type lead-acid batteries were discharged at 0.1 CA (1.3 A) (25 ° C., discharge end voltage: 1.75 V), the discharge capacity was measured, and the ratio to the initial discharge capacity was calculated. . On the other hand, the charge state of other control valve type lead storage batteries was disassembled, and the amount (% by mass) of lead sulfate contained in the negative electrode active material was measured.
【００２０】[0020]
【実施例】以下に、実施例についてより詳細に説明す
る。EXAMPLES Examples will be described below in more detail.
【００２１】（実施例１）上記した還元処理したアセチ
レンブラックを用いてペースト式負極板を作製した。そ
の他の制御弁式鉛蓄電池の作製条件や試験条件は、上記
したものである。(Example 1) A paste-type negative electrode plate was produced using the above-mentioned reduced acetylene black. Other manufacturing conditions and test conditions for the control valve type lead-acid battery are as described above.
【００２２】（実施例２）上記した還元処理した天然鱗
片状黒鉛を用いてペースト式負極板を作製した。その他
の制御弁式鉛蓄電池の作製条件や試験条件は、上記した
ものである。(Example 2) A paste-type negative electrode plate was prepared using the above-mentioned reduced natural flake graphite. Other manufacturing conditions and test conditions for the control valve type lead-acid battery are as described above.
【００２３】（比較例１）上記した還元処理をしていな
いアセチレンブラックを用いてペースト式負極板を作製
した。その他の制御弁式鉛蓄電池の作製条件や試験条件
は、上記したものである。Comparative Example 1 A paste type negative electrode plate was prepared using acetylene black not subjected to the above-mentioned reduction treatment. Other manufacturing conditions and test conditions for the control valve type lead-acid battery are as described above.
【００２４】（比較例２）上記した還元処理していない
天然鱗片状黒鉛を用いてペースト式負極板を作製した。
その他の制御弁式鉛蓄電池の作製条件や試験条件は、上
記したものである。(Comparative Example 2) A paste-type negative electrode plate was prepared using the above-mentioned natural flake graphite that had not been subjected to a reduction treatment.
Other manufacturing conditions and test conditions for the control valve type lead-acid battery are as described above.
【００２５】表１に、各種負極板を用いた制御弁式鉛蓄
電池について、２０００サイクル時点での放電容量と初
期の放電容量との比率（％）及び、充電状態での負極活
物質中に含まれる硫酸鉛量を測定した結果を示す。Table 1 shows the ratio (%) between the discharge capacity at the time of 2000 cycles and the initial discharge capacity of the control valve type lead-acid battery using various negative plates, and included in the negative electrode active material in the charged state. 4 shows the results of measuring the amount of lead sulfate.
【００２６】本発明を用いると、サイクル寿命特性が大
幅に向上している。本発明を用いると、負極板の充電受
け入れ特性が向上して硫酸鉛量が残存しにくくなってお
り、その結果、サイクル寿命特性が向上したものと考え
られる。When the present invention is used, the cycle life characteristics are greatly improved. It is considered that when the present invention is used, the charge receiving characteristics of the negative electrode plate are improved and the amount of lead sulfate is less likely to remain, and as a result, the cycle life characteristics are improved.
【００２７】[0027]
【表１】 [Table 1]
【００２８】なお、炭素粉末として、ケッチェンブラッ
クや活性炭などを用いた場合でも同様の良好な効果を得
ることができた。また、還元処理の方法については、ア
ルゴンなどの不活性ガス雰囲気中で１０００〜１２００
℃に加熱したり、硫酸ヒドラジンなどの水溶性還元剤と
反応させた場合でも同様の効果を得ることができた。Similar good effects could be obtained when Ketjen Black or activated carbon was used as the carbon powder. Regarding the method of the reduction treatment, 1000 to 1200 in an inert gas atmosphere such as argon.
The same effect could be obtained when the mixture was heated to ℃ or reacted with a water-soluble reducing agent such as hydrazine sulfate.
【００２９】[0029]
【発明の効果】上述したように、本発明を用いると長寿
命な制御弁式鉛蓄電池を提供できるため、工業上きわめ
て優れたものである。As described above, the use of the present invention makes it possible to provide a long-lived control valve type lead-acid battery, which is extremely excellent in industry.
【図１】制御弁式鉛蓄電池の内部構造の概略図である。FIG. 1 is a schematic view of the internal structure of a control valve type lead storage battery.
１：正極板、２：負極板、３：セパレータ、４：電槽、
５：蓋、６：ストラップ、１７：端子、１８：耳部1: positive electrode plate, 2: negative electrode plate, 3: separator, 4: battery case,
5: lid, 6: strap, 17: terminal, 18: ear
Claims (2)
電池において、前記ペースト式負極板の活物質層に、還
元処理をした炭素粉末を含有することを特徴とする制御
弁式鉛蓄電池。1. A control valve type lead storage battery using a paste type negative electrode plate, wherein the active material layer of the paste type negative electrode plate contains reduced carbon powder.
は天然鱗片状黒鉛を水素で還元処理をしたものであるこ
とを特徴とする請求項１記載の制御弁式鉛蓄電池。2. The control valve type lead storage battery according to claim 1, wherein the carbon powder is obtained by reducing acetylene black or natural flaky graphite with hydrogen.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001021180A JP2002231247A (en) | 2001-01-30 | 2001-01-30 | Control valve type lead storage battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001021180A JP2002231247A (en) | 2001-01-30 | 2001-01-30 | Control valve type lead storage battery |
Publications (1)
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| JP2002231247A true JP2002231247A (en) | 2002-08-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001021180A Pending JP2002231247A (en) | 2001-01-30 | 2001-01-30 | Control valve type lead storage battery |
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